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Typical Range
20 to 90 HGI
3.5% to 7%
3.5% TO 12 %
0.5% to 1.5%
100 5000 ppm
3 mm to 200 mm
32.5-33.5 x 106 Joules/kg
Fuel Specification
35 to 55 HGI
As low as possible
6% or less
As low as possible
Not a constraint
100% less than 50 mm
32.5 x 106 Joules/kg
There are several types of pet coke, the nomenclature dependent on source and to some degree common usage. The
characteristics and the ability of the process to absorb sulphur and metals, not the name, determine use as a fuel.
Grinding to a high fineness, a minimum of 90% passing 200 USS mesh per ASTM E-11 or a BSI or Tyler mesh of
200 is needed. This average particle size is 75 microns and the energy content of this reduced moisture, less than
1.0%; ground pet coke is increased to 34.8 x 106 Joules/kg.
CHEMICAL IMPACTS AND EMISSIONS
Chemical Impacts
The primary concern in substituting pet coke for natural gas and fuel oil is in increased operating costs in the
chemical recovery cycle and emissions, principally NOx, SO2 and high volatility metals. Effects to the chemical
recovery cycle are addressed in four areas:
Lime kiln.
Slaker.
Causticizer.
Post white liquor or dead load.
Lime Kiln
There have been different opinions where the sulphur reports when pet coke is fired in a lime kiln. Some published
emissions factors indicate at least 97% of the sulphur, generated as SO2, is converted to calcium sulfate by anhydrite
reaction with the lime. A similar high conversion, approaching 100%, has been reported by some pulp and paper
mills after actual testing. Mills evaluating pet coke firing in lime kilns should be able to consider a sulphur
conversion to calcium sulfate in the high 90% range. Items such as the length and diameter of the kiln and whether
NCGs or SOGs are also burned affect the degree of sulphur conversion.
The generation of calcium sulfate will displace some calcium oxide production. Fuel per ton of product will remain
the same but fuel needed per ton of calcium oxide will increase due to this reduced availability. Various opinions
have been expressed, some based on theoretical analyses, how much additional lime product needs to be processed.
Real mill data indicates a mill will need to process about 3.5% more lime product and makeup lime requirements
will increase.
Two other lime kiln concerns that have been expressed are ring formation and reduced refractory life due to the
vanadium content of the pet coke. Burning pet coke will aggravate ring and ball formation. The sulphur is oxidized
to SO2 and reacts with lime and residual sodium (which readily converts to Na2O in the kiln) to form CaSO4 and
Na2SO4. The sulfate deposits can form rings in the kiln, which can form blockages although there is a tendency for
these rings to stabilize. This stabilization reduces the frequency rings have to be shot out with a kiln gun.
However, there are other items that also influence ring formation. There are mills that have two kilns burning pet
coke, one of which sees ring and ball formations, the other does not.
Vanadium can reduce refractory life. In alumina based refractory the concentration of the vanadium and hot face
refractory temperature determine if reduced refractory life will be seen. Mills burning pet coke that use higher
service temperature low cement castable refractory in the kiln hot zone have not reported any refractory issues.
One additional lime kiln system related concern is about outages required to remove calcium sulfate deposits in a
scrubber. This has not been a significant issue to-date.
Slaker
The calcium sulfate produced in the lime kiln has a low solubility in the slaker. Calcium sulfate will carry over to
the Causticizer.
Although a lot is not known about vanadium in the liquor cycle it is felt vanadium and nickel, the principle heavy
metal elements, are controlled by elimination in the grits of the Slaker and the green liquor dregs system. Purging
lime mud on a steady basis can also help and this purge is necessary to keep the inerts in the lime at a reasonable
level (85-88%). Although these activities help purge the vanadium a significant amount has been found in the white
liquor at one mill.
Causticizer
Calcium sulfate carried over from the Slaker will react, over time, with sodium carbonate to form calcium carbonate
and sodium sulfate. The disassociation constant of calcium sulfate is about ten times less than that of calcium
carbonate. Sodium sulfate generation results in a reduction of sodium hydroxide formation or a make-up caustic
requirement.
The impact is mill specific depending on existing sources of sulphur, sources and cost of caustic and other factors. If
the mill is burning a relatively high sulphur fuel oil and the pet coke is low in sulphur, the impact may be negligible.
Those mills using waste caustic, for which they are paid a disposal fee or receive at no cost, have an advantage. The
advantage or lack thereof is dependent upon the sulphur content of the displaced fuel.
Dead load
Sodium sulfate generated reports to the white liquor as dead load. This impacts the solids to the recovery boiler and
the solids to the evaporator increase.
For bleached mills this increased sodium sulfate dead load from pet coke might be offset by a reduced introduction
of salt cake to the black liquor. For brown mills the increased sulphidity may be desirable.
Emissions
NOx Emissions
NOx formation in kiln flames is by both thermal and fuel routes. In natural gas fired kilns, NOx formation is through
the thermal route as fuel nitrogen is absent. Because natural gas flame temperatures are typically higher than those
generated by pet coke, coal and fuel oil, NOx formation is significant. Additional mechanisms that contribute to
thermal NOx formation are in-flame oxygen concentration (due to primary air levels and fuel-air mixing rates) and
the residence time in the high temperature zones of the kiln. .
Due to the 1% to 5% nitrogen in pet coke, one can predict 50% to 100% conversion to NOx emissions from this
source. There are opportunities to control or reduce NOx emissions from lime recovery kilns.
Decreasing the primary air flow through the kiln burner to 10% to 15% of the total combustion air will
lower NOx.
Managing the excess kiln oxygen at a level just below the onset of significant carbon monoxide generation
would reduce NOx concentration and increase fuel efficiency.
The contribution of the swirl air component of the primary air can affect NOx concentrations.
The use of Computational Fluid Dynamics (CFD) modeling of pet coke firing and experience of burner
manufacturers specific to pet coke firing with access to actual kiln measurements will ensure that NOx emissions are
minimized and, where possible, remain within required mill limits. The use of CFD modeling of pet coke firing
could in the future ensure that NOx emissions are minimized. CFD is currently the only tool available to predict
NOx in lime recovery kilns and will ultimately be used to provide the best predictions for permitting. However, it is
yet to be validated with mill data and, hence, is still work-in-progress.
Because of limitations in design and lack of experience of solid fuel firing, conversion to pet coke and the
application of optimized multi-fuel burners from an experienced burner manufacturer are recommended to control
the increases in NOx emissions.
SO2 Emissions
Sulphur input to the kiln occurs through fuel (Pet Coke and Fuel Oil), NCGs, and SOGs. As previously mentioned,
an order of 97% of the sulphur is captured by the lime in the kiln with the remaining removed in the scrubber and to
some extent in the ESP. Those kilns with only an ESP are likely to emit some SO2, although if they are presently
firing high sulfur fuel oil, there may be no increase.
Particulates
There is some indication that those kilns with only scrubbers could experience an increase in particulates from firing
pet coke. Historically, low energy types of scrubbers were characterized as being less efficient than high energy
scrubbers. There are now low pressure drop multi-stage scrubbers that are very efficient in removing particulate.
Metals
The low volatility metals report to the Slaker grits and green liquor dregs in the slaker. The higher volatility metals
condense and are captured in the feed end of the kiln or scrubber. Some are retained in the white liquor.
ENGINEERING DESIGN OF PET COKE GRINDING SYSTEMS
There are 3 distinct areas of engineering expertise required for the introduction of pet coke to a kiln:
Pet Coke receiving from the refinery, unloading and storage.
Pet Coke grinding, transportation and storage of the finely ground product, weigh feeding and transport to
the burner.
Burner design and operation.
Solid Fuels such as coal and pet coke have been fired in cement and commercial lime kilns for over 70 years. The
technology is well established and experience with these systems is employed in the engineering design of firing pet
coke in pulp and paper mill lime kilns. The challenge is coming up with a lower cost system than is typically found
in the other industries because capacities of pulp and paper mill lime kilns vary and are typically much smaller. The
elements of the system are:
Unloading rail cars or trucks of pet coke received from the refinery.
If required, crushing the pet coke to minus 50 mm.
Conveying this raw pet coke to a storage bin.
Withdrawing of the pet coke from the bin and weigh feeding to the grinding mill.
Drying and grinding in the grinding mill.
Collecting the ground pet coke in a fabric filter.
A hot air supply for drying the pet coke in the mill.
Conveying ground pet coke from the fabric filter to a storage bin.
Weigh Feeding ground pet coke out of the bin.
Conveying the ground pet coke to the kiln burner.
Firing the pet coke through a multi-channel burner designed for pet coke.
Power and Controls to regulate the system.
Fire and Deflagration suppression and control systems.
In the past few years in the United States some major energy services companies have built large pet coke grinding
facilities. These facilities receive raw pet coke, grind it to the desired fineness, store it, and ship it to different pulp
and paper mills. While regenerative limekilns at pulp and paper mills are candidates for pet coke firing, some mills
with a single lower capacity kiln may be borderline for an investment in a grinding circuit. Reasons for this
borderline status could include a relatively low pet coke usage and a high internal rate of return threshold. Some
mills in this category opt to receive ground pet coke rather than raw pet coke. Eliminating the grinding mill reduces
the capital investment but at the expense of a higher cost for the ground pet coke.
Basics of Grinding Pet Coke
Pet coke and other solid fuel grinding systems are typically configured in one of three ways:
The direct grinding and firing is a system in which the solid fuel is swept out of the grinding mill by the primary air
and piped directly to the burner. The I.D. fan is often coupled to the drive shaft of the mill but can be independently
driven. The semi-direct system installs a cyclone downstream of the mill followed by the I.D. fan. This fan
discharges the air to two paths, one to the cyclone discharge and the burner, the other back to the inlet of the mill.
The solid fuel is discharged from the cyclone through a rotary feeder/airlock into the pipe and is blown to the burner
either by the I.D. Fan or a primary air fan depending on burner requirements. In both systems, hot air for drying is
typically drawn from the kiln hood. The indirect system has a fabric filter in place of the cyclone and a ground solid
fuel storage bin and weigh feeding system to meter fuel to the burner. Direct grinding systems result in 30%-40%
primary air. A semi-direct system reduces primary air to 15%-20% and indirect systems offer a further reduction to
12% to 15%. The indirect system offers much better flame and firing control and less NOx formation.
In firing lime recovery kilns with pet coke, the indirect system is used because the amount of air to the burner has to
be restricted, the system has to respond to a fuel trip and the re-start of firing after a fuel trip has to be quick and
safe. In both direct and semi-direct systems the grinding mill shuts down on a fuel trip. Re-start is an involved and
slow process.
In all of the above systems, the classic belt type weigh feeder is used to convey pet coke or other solid fuel to the
grinding mill and a rotary airlock at the mill inlet limits ambient air infiltration. In lime recovery applications, hot air
for drying comes from a natural gas or No.6 oil fired hot air generator.
Types of Grinding Mills
There are four types of grinding mills that can be used. They are summarized along with their characteristics in table
II.
Roller Mills
Characteristics
Highest purchase and installation cost.
Much lower efficiency.
Limited drying capacity.
Requires separate classifier and extensive materials handling systems.
Lowest cost option. Reconditioned equipment with capacities suitable for
lime recovery kilns readily available.
Retrofitted with modern dynamic classifiers to achieve required pet coke
fineness.
Efficient Grinding Power, Acceptable Drying Capacity.
Built-in high performance dynamic classifiers provide superior drying
capacity and pet coke fineness control.
Most Efficient Grinding Power, greatest drying capacity.
Typically run for a year between maintenance shutdowns.
Higher cost than other types of roller mills, longer delivery times.
Lowest cost option of new mills.
Efficient Grinding Power, good drying capacity.
Now available with modern dynamic classifiers.
Fabric Filters
Essentially there are two types that are used, the classic pulse jet and the newer medium pressure controlled air jet
cleaning units. The critical consideration is whether to apply the 3.4 bar (50 psi) rated versions or filters with
explosion vent panels to comply with safety requirements. The filters must be insulated in locations where
temperatures can drop below 10o C.
Ground Pet Coke Conveying
The finely ground pet coke collected in the filter is pneumatically conveyed to the ground pet coke storage bin.
Conveying can usually be done with an eductor type system because the grinding rates are modest, the storage bin is
typically located near the firing floor, and conveying pressures typically do not exceed 1000 mm wc. Conveying
velocity and conveying air to pet coke ratios are critical parameters. Where possible, elbows should be long sweep
type. Pipe runs should be a combination of horizontal and vertical runs. If the lower cost option of a centrifugal
blower is selected, provision to monitor pipeline air velocity and adjust the blower speed to maintain constant
velocity is necessary. The alternative is a Positive Displacement blower.
Ground Pet Coke Storage
Capacity, appropriate fire and deflagration protection, and attention to discharge flowability are the key parameters.
The planned mill operating program, adequate time for mill and fabric filter maintenance and available excess
capacity dictate bin capacity. Ground pet coke has difficult flow characteristics, which dictate bin discharge
geometry. Explosion vents are an economical means to comply with fire and deflagration regulations; however fire
suppression requires either CO2 or other approved systems.
Ground Pet Coke Weigh Feeding and Conveying
There are four systems in use for ground solid fuel weigh feeding, which are summarized in Table III.
Characteristics
2%, typically better, accuracy, reliable
1% accuracy claimed, prone to flushing, requires
weigh bin on load cells for calibration.
The Coriolis and Pfister feeders offer the highest accuracy but at a considerable cost, up to about 8-10 times the cost
of a weigh bin on load cells system. Mills should determine if this high level of accuracy is justified or required to
operate their lime recovery kilns effectively.
ENGINEERING DESIGN OF MULTI-FUEL BURNERS
Lime recovery kilns present a significant challenge to burning pet coke or other solid fuels. Due to the low volatile
content of pet coke, the distinct flame characteristics and the need for NOx control, the burner selection is critical.
There are a very limited number of suppliers with the expertise to meet the challenges of lime recovery kilns.
The heat flux profile for pet coke differs significantly from natural gas and to a lesser extent fuel oil, which must be
taken in to account when designing the firing system. In lime recovery kilns, particularly those without coolers,
secondary air temperatures are relatively low. This makes pet coke, with its low volatiles content, slow to ignite.
Due to its high ignition temperature, >1000 C, and the fact lime recovery kilns operate at a lower temperature than
cement or pebble lime kilns, a co-fuel such as natural gas or oil is needed to stabilize and maintain combustion..
Flame Emissivity
Radiation is the dominant mechanism of heat transfer in the burning zone of a rotary kiln, with over 95% of the heat
transferred in this way. The rate at which heat is transferred to the bed or from a flame is controlled predominantly
by the radiant exchange in the combustion chamber. The factors that affect this exchange are the temperatures,
emissivity and relative geometry of the flame and surroundings.
The emissive properties of a flame are a function of the concentrations of the spectrally emissive and absorptive
gases (CO2, CO, H2O) from the combustion process, and the particulates burden in the flame. Flames in rotary kilns
fired with pet coke have a high particulates burden and hence a high emissivity, while natural gas flames have a low
particulates burden and low emissivity. Natural gas flames are therefore at a disadvantage because the low
emissivity results in a peak heat flux further down the kiln (Figure 1). Physical modeling of the fuel/air mixing and
mathematical modeling of the heat transfer along with an optimized burner design can minimize this effect, but not
eliminate it; everything else being equal, a pet coke flame will produce a more effective combustion profile,
compared to natural gas.
1 1 .4
Natural Gas
# 6 Fue l O i l
75% Pet Coke: 25% Gas
8 .5
5 .7
2 .8
21
15
18
Burner Design
For any given kiln, the flame length and heat transfer are determined by the fuel characteristics, the fuel/air mixing
rate and the quantity of excess air. The fuel/air mixing rate is primarily dependent on the ratio of the burner
momentum and that of the secondary air.
Aerodynamic and combustion modeling is the best method for assessing optimal burner engineering given the
unique design characteristics of each kiln and the specific firing properties of the fuels used. In lime kilns, the high
temperatures in the burning zone allow combustion to take place immediately where fuel and oxygen meet. Flame
shape is controlled by the rate of mixing of fuel and air rather than the kinetic rates of reaction.
Pet coke requires less air for combustion due to its lower hydrogen content in the fuel. This ultimately leads to
lower kiln gas volume flows and lower feed-end temperatures. Due to improved heat transfer from pet coke firing,
lower overall fuel requirements and a further reduction in the flue gas volume are realized. The combined effect is
to reduce load on the kiln ID fan - an important feature for ID fan limited kilns.
STEPS TO IMPLEMENT A PET COKE GRINDING AND FIRING SYSTEM
A Feasibility or Planning Study is the preferred first step to determine if a grinding circuit or a ground pet coke
system is the economically preferred solution. Some mills have decided to proceed directly with detailed
engineering for a ground pet coke system without a planning or feasibility study to justify the investment due to
anticipated very favorable economics. Otherwise, the objectives of this study are to:
Evaluate the type and capacity of grinding mill and system applicable to the Pulp and Paper Mill.
Evaluate the pet coke receiving and unloading system and storage requirements.
Prepare conceptual arrangements and determine the capital cost. This capital cost will include the ground
pet coke system, which is a part of the grinding circuit.
Determine the pet coke supply cost and operating and maintenance costs so the Rate of Return can be
established.
Determine the emissions characteristics and parameters for permit application.
Following evaluation of this study and a decision to go forward with either a ground pet coke system or a raw pet
coke handling and grinding system, the next step is the environmental permit application.
Once the permit application is submitted and Management has confidence a permit will be forthcoming, a Process
Audit by the Burner Manufacturer is needed. This will establish important kiln operating features, potential fuel
savings, assessment of effects on the pulping process and other factors.
Four to six months prior to award of a permit, which will allow construction to begin, specifications and purchase of
equipment and engineering design must begin. Construction will begin about three months after the start of
engineering design and typically can be completed in about four months. You start construction at your own risk if
you do not have a permit in hand. Some states will not allow construction to begin by not issuing a construction
permit until the environmental permit is issued.
Prior to start up, operator and maintenance training is required. Some mills insist on preparing an Operating and
Maintenance Manual. This is very helpful in the training program and in subsequent operations.
During the first 12 to 24 hours of start up, one can expect to operate at a 25-50% replacement of natural gas or No.6
fuel oil with pet coke. As the operators gain more confidence the substitution rate is raised to 80-85+%. We do not
expect lime recovery kilns to achieve 100% firing of pet coke that is routine in the higher temperature cement and
commercial dolomite lime kilns. Can other solid fuels, such as coal, be fired in lime recovery kilns? This is quite
possible. Remember the make-up lime you currently buy has been produced from coal and pet coke fired kilns.
CONCLUSION
The use of ground pet coke as a fuel for regenerative lime kilns offers pulp and paper mills a lower and more stable
fuel cost in comparison to natural gas or fuel oil. However, this savings in fuel cost needs to be reduced by
individual mill specific costs that address the undesirable effects resulting from burning pet coke. Lime kiln
availability will decrease by 3-4 % and burning ground pet coke will aggravate ball and ring formation. If NCGs
and SOGs are also burned ball and ring formation can become worse.
Sulfur will be added to the chemical recovery cycle. Every ton of sulfur added to the system via the pet coke route
will require 2.3 tons NaOH addition to the liquor system. In brown mills this increased sulfur load may be
beneficial. Mills that adhere to following the basic chemistry balances for controlling the increased sulfur load have
seen the best savings due to lower or reduced costs to control the increased sulfidity. Regardless of the cost of
resolving dead load and other adverse process impacts substantial fuel cost savings exist. No mill that has converted
to burn ground pet coke has stopped.
ACKNOWLEDGMENTS
The authors wish to acknowledge the assistance of the following in the preparation of this paper: Mr. Richard
Manning, Director, Kiln Flame Systems Ltd., High Wycombe, UK and Mr. John D, Macfadyen, PE and President,
Phoenix Process Engineering, Inc., St. Peters, MO USA.
Topics
Technical Aspects of Pet Coke Substitution
Background
Conversion of Ground Pet Coke System to an Indirect
Grinding and Firing System
Types of Grinding Mills
Types of Weigh Feed Systems
Pneumatic Conveying Issues
Importance of Burner Design to Pet Coke
Substitution Rate
Emissions and Operating Issues
The Engineering Process
Engineering Design and Construction Services
Project Management
Green Coke
Fuel Coke
Delayed Process Coke
Flexicoke
Fluid Coke
Characteristics
Ball mills, ring roller mills, and vertical roller mills have
all been used
Targeted fineness is > 90% passing 200 mesh (75
micron)
Grinding mill capacity is dependent on solid fuel
hardness of grind (HGI), desired fineness of grind,
moisture content, degree of wear on grinding
components, and classifier efficiency
Roller Mill
Pfister Feeder
11.4
Natural Gas
#6 Fuel Oil
75% Pet Coke: 25% Gas
8.5
5.7
2.8
12
15
18
NATURAL GAS
# 6 OIL
PETCOKE
Emissions
For natural gas firing, fuel NOx is absent and all NOx is
produced through the thermal NOx route
In high temperature environments, >1600 C, thermal
NOx is generally the dominant reaction
Higher nitrogen solid fuels do not necessarily translate
into a proportionate increase is NOx emissions,
compared to natural gas, due to the lower flame
temperatures
There will be an increase in NOx emissions
Solid fuels will introduce SO2, most of which is absorbed
in the kiln
Lime kilns with caustic wet scrubbers have the highest
capture rate of SO2
Construction Services
Conclusions
Sulphur will be added to the chemical recovery cycle. Mills
that adhere to following the basic chemistry balances for
controlling the increased sulfur load have seen the best
savings due to lower or reduced costs to control the sulphidity.
In brown mills this increased sulphur may help.
Every ton of sulphur added to the system via the pet coke
route will require 2.3 tons NaOH addition to the liquor system.
Burning pet coke will aggravate ball and ring formation in lime
recovery kilns. If NCGs and SOGs are also burned ball and
ring formation can become worse.
However, pet coke still provides a substantial fuel savings,
even after costs have been assigned to resolve dead load and
other adverse process impacts.
No mill that has converted to burning pet coke has stopped
burning it.