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Controlling the processing parameters affecting the refractory requirements for

Peirce-Smith converters and anode refining vessels

Conference Paper · January 2005

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CONTROLLING THE PROCESSING PARAMETERS AFFECTING THE
REFRACTORY REQUIREMENTS FOR PEIRCE-SMITH CONVERTERS
AND ANODE REFINING VESSELS

A. J. Rigby

RHI Canada Inc., 4355 Fairview Street

Burlington, ON, L7L 2A4, Canada

Keywords: Refractories, tuyeres, optical process control, porous plugs, burners

Abstract

Refractory linings in converters or anode furnaces used to over-oxidize the blister copper will
suffer rapid deterioration due to prolonged contact with copper oxide-rich slag. Nitrogen
stirring with COP KIN® porous plugs and use of SEMTECH OPC in converters and anode
refining vessels can reduce considerably both refractory wear and processing times. In addition
careful control of the vessel atmosphere and the use of real-time optical process control
minimize both the slag volume and contact time with the vessel refractory.

1. Introduction

It is generally accepted industry-wide that the integrity of a refractory lined vessel is

determined by an inextricable combination of refractory brick quality, the caliber of the lining
design and installation, and the severity of the process inflicted upon the high wear areas of the
vessel lining. Over the past several years, there has been a concentrated attempt to optimize the
microstructural, chemical, and fracture properties of the refractories used in non-ferrous
pyrometallurgical vessels. Furthermore, lining design concepts involving larger and longer
brick and the extent and positioning of expansion allowance have been extensively trialled. All
these efforts have provided some significant, but not startling, improvements 1-5. The simple
fact is that a vessel lining composed of bricks with an optimized microstructure and chemical
inertness, even when installed with a well-conceived design, can rapidly deteriorate if the
process parameters are not sensibly controlled.
 It is the intent of this paper to emphasize that close control of the converting and fire-refining
processes will result in both exceptional vessel integrity and reduced processing costs. By
prudent use of high velocity burners in conjunction with nitrogen stirring with COP KIN®
porous plugs and SEMTECH OPC systems, it is currently feasible to provide a system with
comprehensive PLC real-time process control.

2. Refractory Quality

Molten copper has little if no affinity for refractory oxide furnace linings. Channel induction
furnaces used to melt cathode copper are lined with inexpensive fireclay products and operate
continuously without repair for up to four years. However, these furnaces utilize a layer of
charcoal or low sulphur coke to eliminate any possibility of forming copper oxide slag by
contact of the molten bath with oxygen in the atmosphere.

Converting and anode refining is conducted by injecting air into the molten matte and blister
copper for the very purpose of generating iron and copper oxide slags. These slags must be
contained by a refractory which, by its mineralogical formulation, is optimized for chemical
inertness.

Magnesia-chrome bricks with approx. 60% MgO have been found to have this chemical
inertness in part due to the fact that by high-temperature firing (~1720ºC) the MgO portion of
the product has been pre-reacted and saturated with iron and chromic oxide. Further reaction of
the brick with the iron oxide formed during converting will not take place at working
temperatures normally encountered (~1260ºC). Copper with over 0.1% O2 can penetrate
magnesia-chrome bricks readily and lead to severe bloating and spalling as in-situ oxidation
takes place.

The mineralogical composition of suitable magnesia-chrome products is of utmost importance,

however, these bricks must be manufactured in a large format up to 600mm long and possess
tight dimensional tolerances (± 0.7mm). Large hydraulic presses are undeniably a prerequisite
for manufacturing bricks of this size and consistency.

A typical magnesia-chrome product suitable for the bottom and roof areas of converting and
anode vessels need not be especially formulated for environments where high stresses or
corrosion by slag is expected.

The highly stressed converter tuyere line area does demand an engineered product with a
specifically designed mineralogy and microstructure. It is thought that a co-sintered grain
constituted to engender ductility to the brick would best suit an area where stresses can be
absorbed than a brick with brittle fracture characteristics at converting temperatures
(see Figure 1).
 Figure 1. Characteristics of brittle versus ductile fracture of
magnesia-chrome brick at 1250ºC

In anode vessels where copper oxide penetration resistance takes precedence, the bricks are
formulated to provide for the lowest permeability and porosity. A class of super dense products
containing co-sintered grain and/or rebonded fused grain possessing extremely low
permeabilities and porosities in addition to high thermal conductivities are a natural choice in
high wear areas of anode vessels.

3. Lining Design Concepts

A well-engineered design for a converter or anode vessel will effectively zone the high wear
areas with suitable products and ensure the lining is in excellent thermal contact with the vessel
steel shell. Maximizing the thermal contact aids in producing a steep thermal profile, which
minimizes the penetration of the hot face of the lining, subsequently reducing the corrosion rate
of the brick. In some cases, a graphite-containing mastic should be employed to safeguard
against air gaps between the cold face of the brick and the steel shell.

However, in many areas of these processing vessels, the localized heat loss will be sufficient to
produce a build-up of frozen slag/matte and/or copper metal, which lowers the effective
working volume of the vessel. The lining in this instance should be effectively insulated to
allow the working hot face of the lining to operate at a higher temperature. Microporous
insulation has been shown to alleviate frozen magnetite deposition in several areas of
converting and anode vessels.6
3.1 Converter Lining Design

The wear mechanisms of the tuyere lines of Peirce-Smith and Hoboken converters are a subject
of endless debate and speculation. However, in recent published papers 3,4, there has been an
indication that one of the primary factors in the deterioration of tuyere lines is due to the batch
operation of the converting process.

The cooling of the brick in the tuyere line during out-of-stack times leads to shrinkage of the
brick and resultant opening of the joints. Subsequently, on re-entry of the tuyere line into the
bath, the joints become penetrated with matte and re-expansion of the brick is prevented. It is
thought that this regular cycle of exiting the batch for slag skimming and replenishment of
matte and re-entering for further blowing leads to a gradual “ratcheting” of the tuyere brick
lining. If no expansion allowance is furnished between the endplate and the endwall of the
lining, then the generation of damaging compressive stress is unavoidable.

It is recommended that in the tuyere lines if Peirce-Smith and Hoboken converters, a 60% MgO
magnesia-chrome brick manufactured with a co-sintered grain will provide the optimum
resistance to the many stressors in this environment. These stressors include cycling
temperatures, compressive stresses, punching impacts, and fayalite slag contact. The co-
sintered produce exhibits superior flexibility at copper making temperature to resist fracture and
spalling, in addition to relatively low permeability and porosity to afford resistance to
penetration and corrosion by converter slags.

3.2 Anode Vessel Design

For anode vessels where cycling temperatures are not a serious issue, the rebonded fused grain
or super dense co-sintered products can be expected to perform incomparably with the
combination of lowest permeability and porosity in the 60% MgO magnesia-chrome class.
These dense, high thermal conductivity products are appropriately zoned at the slaglines,
taphole, tuyere area (up to 2 metres above the tuyere pipe), blister copper impact area, and
mouth.

There is no doubt that nitrogen stirring with porous plugs has proven to be an extremely useful
technology in the anode refining vessel and computer modeling is advantageous in developing a
lining design. The stirring action of the plugs avoids excessive wear of the slagline by reducing
the volume and temperature of the copper oxide slag generated in the oxidation cycle of the
process.

The tuyere area of the anode vessel should be designed to incorporate some form of replaceable
insert to allow for extended campaign life. This insert often takes the form of a smaller
diameter stainless steel pipe or a refractory sleeve, which can be conveniently replaced from
outside the vessel while the vessel remains hot on standby (Figure 2).

By zoning in this fashion, the wear of the vessel can be balanced and allow for campaign lives
of up to 5 years before a complete repair is required.
 Figure 2. Stainless steel pipe insert used to keep air injection away from brickwork.

4.0 Process Control Parameters

It is thought that overheated copper oxide slags contribute to the accelerated deterioration of the
vessel lining integrity of converters and anode vessels. Thus, a prioritized assessment of the
specific process parameters leading to the generation of oxidised copper should be conducted.

4.1 Smelter Matte Metallurgy

Treating matte that is contaminated with elements such as lead, bismuth, arsenic, or antimony
inevitably requires over-oxidation in the converting and/or refining vessels. In either case, the
highly oxidizing environment produces large volumes of copper-oxide slag.

In some smelters where strict environmental restrictions prevail, the blister copper must also be
transferred to the anode with little or no sulphur for removal. In both of these cases, blister
copper is normally “over-oxidised” to ~1.0% 02/0.005%S.
It is evident that the individual tuyere pipes will often suffer severe burn-back. Injected tuyere
air now intermixes with matte/blister copper in close proximity to the brick hot face, developing
a corroded, flared appearance (figure 3).

Figure 3. Flared tuyeres corroded deep into the refractory

brickwork by contact for extended time with copper oxide slag.

Tuyere lines from converters treating the blister copper to over-oxidation can seldom produce
more than 25,000 T.
Converters that process matte from comparatively uncontaminated concentrates have the
capability to transfer the blister copper with a lower oxygen content (<0.4% O2, 0.08%S). The
tuyere pipes in these converters tend to remain proud of the surrounding brickwork
(figure. 4) and can provide for campaigns in excess of 60,000 T blister copper.

Figure 4. Pipes still slightly proud of the brickwork in

converter tuyere line producing relatively low oxygen blister copper.
4.2 Secondary Burners

4.2.1 Converters

The efficient use of high-velocity natural gas burners will undoubtedly have a beneficial impact
upon both the refractory life of the converter and anode vessel 12. There is a considerable
amount of anecdotal evidence that the use of endwall burners is treated simply as a cost to be
avoided due to the rising cost of natural gas. Indeed, since it is often stated that in addition to
being costly to operate, the burners are rendered useless by the splash from the tuyere action.

Modern burner systems for use in converters are designed to be easily retractable during the
blowing cycles and re-inserted between cycles. These burners will surely reduce build-up,
especially in Hoboken converters where the siphon or goose neck is prone to closing up. In
addition, the singular most beneficial consequence of a secondary burner is to retain the
working temperature of the tuyere line brick in between cycles. The resultant lack of
temperature cycling reduces joint opening and penetration by matte and eliminates the
“ratcheting” of the tuyere brickwork onto the endplates of the converter. The brickwork suffers
much less compressive stressing and spalling, especially in the centre of the tuyere line opposite
the mouth where the worst wear normally occurs.

4.2.2 Anode Vessels

High velocity burners with or without oxygen enrichment provide a primary source of heat in
anode vessels to prepare the copper for casting. With the advent of nitrogen stirring with
porous plugs, the burners perform an equally important role of establishing a suitable
atmosphere above the bath. During desulphurization, the air/oxygen/fuel ratio should be pre-
determined to run lean in fuel to produce an oxygen-rich environment to help with removal of
sulphur.

Deoxidation should be performed with an oxygen/fuel ratio with excess fuel to allow for
improved removal of oxygen from the molten bath surface.

Essentially, porous plugs demand the use of a well-designed and controlled burner system since
the stirring action in the presence of a continuously oxidizing environment will ultimately work
against the reductant injected through the tuyeres and culminate in much higher natural gas
consumption. The free-board atmosphere of an anode vessel must be carefully controlled for
optimum process performance.

4.3 COP KIN® Porous Plug Technology

Porous plugs are routinely used in Peirce-Smith converters and anode vessels for affecting
metallurgical efficiencies and process control 7,8. In Peirce-Smith converters, the stirring action
of the plugs leads to better deslagging, a lowering of the copper oxide slag volume, combined
with a lower final oxygen content in the blister copper for the same or lower sulphur content 9.
Published data has proven that nitrogen stirring with porous plugs eliminates the temperature
stratification with the molten copper bath within anode refining vessels 10. In addition, nitrogen
stirring improves heat transfer from the bath and eliminates frozen copper build-up at the base
of the endwalls of these vessels.

Some of the most interesting data indicates that both sulphur removal and subsequent oxygen
reduction times can be dramatically reduced using nitrogen stirring 11. Trials with porous plug
stirring at LG NIKKO, Onsan, Korea, demonstrated that the sulphur level had been reduced
sufficiently after 225 minutes of oxidation. In essence, the trial showed that desulphurization
had been completed 175 minutes earlier than a typical charge. Furthermore, the deoxidation
time would have been drastically reduced by up to 50% had the desulphurization been
terminated and deoxidation initiated in a timely fashion.

With reference to the overall beneficial effect of nitrogen stirring on refractory performance, it
is unquestionable that slag volume generation and temperature will be considerably reduced.
The anode tuyere areas, taphole, and bath line zones will survive longer and ultimately prolong
the campaign life of the anode vessel.

4.4 SEMTECH OPC (Optical Process Control) System

Essentially, a converter operator is constantly faced with large variations in matte volume, cold
dope and scrap from one process cycle to the next. To determine the status of the converting
cycle, an operator still must rely to a large extent on the colour and shape of the off-gas flame
and the visual appearance of a bar sample. The increasing use of higher matte grades and
oxygen enrichment to improve the productivity has rendered the converting process even less
forgiving to operator error. To add to the complexity of the process control, in many plants the
implementation of tight emission restrictions has enforced enclosed off-gas systems, severely
limiting the operator’s ability to observe the off-gas flame. However, since 1994, the
SEMTECH OPC system13 has provided the operator with continuous information on the
instantaneous status of the process in each converting vessel.

Light emitted from the off-gas flame is composed partially of discrete characteristic radiation
from excited molecules in the vapour phase. The very presence of these molecules and their
concentration is generally dictated by the oxygen potential inside the molten bath.
The online relation between the vapour pressures of PbO, PbS, and CuOH above the bath of a
Peirce-Smith converter is illustrated in Figure 5.

Figure 5. Plot of SEMTECH OPC readings during two

successive slag blows and one copper blow illustrating precision of endpoint detection.

Towards the end of the slag-making step as the last remnants of the iron in the matte are
oxidised, the vapour pressure of the PbS decreases and that of the PbO increases. Close to the
end of the copper making step, CuH radicals are generated indicating precisely the oxygen and
sulphur levels in the bath.

The SEMTECH OPC system can be used to monitor real-time bath oxidation and reduction
processes in converters and anode vessels. Thus, an optical spectroscopic technique using
mouth off-gas analysis is effective in pinpointing the exact stage of oxidation in the converter
bath
 Figure 6. Plot of CuH against time to show real-time oxygen-in
-copper determination of SEMTECH OPC in anode vessel.

In anode vessels, the deoxidation stage can be terminated at the exact oxygen-in-copper content
require by the refinery (fig 6.)

Smelters routinely using an OPC system for controlling the production in their Peirce-Smith
converters have reported a number of direct consequences of the implementation of OPC
technology

. In addition to a substantial reduction of the total cycle time and/or increased blister-copper
output/cycle, it is reported that a considerable reduction in the magnetite levels of converting
slags and, as a result, a concomitant reduction in copper losses to slag of up to 30%.
Furthermore, the reduction of copper oxide slag volume by more than 30%, a refractory lining
improvement of 10%, and a reduced variation of the final oxygen and arsenic levels of the
blister copper are reported.

In the anode vessel during deoxidation, the optical process parameter can be calibrated to an
extraordinary precision to terminate the process at the optimum oxygen-in-copper content for
casting.
 5. Summary

A novel approach to controlling the process parameters of converting and fire refining of
copper has been proposed. By using a PLC system to combine the real-time SEMTECH OPC,
the metallurgical benefits of nitrogen stirring with an optimized series of COP KIN® porous
plugs and a well-controlled burner system, it is expected that processing times and costs can be
dramatically reduced in anode refining vessel. (see fig. 7).

Figure 7. Schematic of anode vessel indicating the use of burner

control, nitrogen stirring with COP KIN® porous plugs and SEMTECH OPC

Queneau and Marcuson14 aptly described the knowledge required by the operator to fulfil his
task adequately “ The operator needs to know not only what was going on in the closed
vessel, but what is going on and what will be going on”

Process control at this level of precision will reduce the volume, temperature, and contact time
of the copper oxide slag in both the converter and anode linings and produce impressive lining
performance gains.
 References

1. H.M. Mikami and A.G. Sidler. “Mechanisms of Refractory Wear in Copper Converters.”
Trans. Met. Soc. AIME 227 (1963), 1229-244.

2. A.J. Rigby. “Wear Mechanisms of Refractory Linings of Converters and Anode

Furnaces.” Converting, Fire Refining and Casting. J.D. McCain and J.M. Floyd 1994
TMS Annual Meeting, San Francisco, California 1994, 155-168.

3. J.Suarez and F. Alvarado. “Refractory Performance in Peirce-Smith Converters at SPCC-

Ilo Smelter” UNITECR 2001 Proceedings Cancun , Mexico

4. T.W. Gonzales, A.J. Rigby, and O. Pasca. “Refractory Performance in Peirce-Smith

Converters at BHP San Manual Smelter.” Copper 99 - Vol. V, Smelting Operations and
Advances Oct. 10-13, 1999, Phoenix, Arizona, U.S., 447-456.

5. T.W. Gonzales, D. Snashell, O. Pasca, and Robert David. “Converter Operation at BHP
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6. Iain B. Mackenzie, O. Pasca, A. Enriques and A.J. Rigby. “Use of Microporous

Insulation in Copper Holding Furnaces at BHP San Manual Smelter.” Copper 99 – Vol.
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7. A. Filzwieser, S. Wallner, K. Caulfield and A.J. Rigby. “The COP KIN® System –
Performance and Benefits – World Wide Overview.” Copper 2003, Vol. IV
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Newman.

8. A. Filzwieser, J. Kleicker, K. Caulfield and S. Wallner. “The COP KIN® System –

Fundamentals and Modelling.” Copper 2003, Vol. IV Pyrometallurgy of Copper (Book
1), Santiago, Chile, 429-441, Ed. Diaz, Kapusta and Newman.

9. T. Prietl, A. Filzwieser and S.Wallner.“ Productivity Increase in a Peirce-Smith Converter

using the COP KIN® and OPC system” TMS 2005 Converting and Fire-Refining, San
Francisco (This Volume)

10. C. Acura and M. Sherington. “Efficiency of Porous Plugs in Fire Refining of Crude
Copper.” Yazawa International Symposium, Vol. 2, March 2-6, 2003, High Temperature
Metal Production, 265-279 TMS 2003.

11. S-S Lee, B-S Kim, and S-R Choi. “Application of the Porous Plug System in the Anode
Furnace at Onsan Smelter.” Yazawa International Symposium, Vol. 2, March 2-6, 2003,
High Temperature Metal Production, 447-457 TMS 2003.
 12. J. Hugens and J. Kondziela. “Natural Gas Firing of Copper Melting and Smelting
Operations.” Yazawa International Symposium, Vol. 2, March 2-6, 2003, High
Temperature Metal Production, 615-629 TMS 2003.

13. W. Persson, W. Wendt and S. Demetrio.J “Use of optical on-line production control in
copper smelters.” Copper 99 Vol. V, Smelting Operations and Advances, Phoenix, AZ,
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