PETROLEUM COKE EFFECTS ON REFRACTORY

INTRODUCTION In the recent past, Petroleum Coke has been used to supplement the primary fuel source (coal) in most North American cement manufacturing facilities. Within the last few years a number of plants have progressed from burning a low percentage of Coke (10-25%) to 100% Coke and other alternative fuels.

The driving factor in the utilization of Coke as a fuel has been based on economics and essentially the Coke BTU / Coal BTU price ratio. The lower coke price combined with the higher BTU content has made coke a very attractive method to reduce energy expense. However, as every major cement manufacturer has experienced, the fuel price is only one factor in the overall economics in the decision to burn alternative fuels. Included in the overall economics: Increase in NOx emissions pet cokes increased BTU value causes higher in-flame temperatures and therefore creates higher NOx emissions. Higher NOx levels may require the use of SNCR or other NOx control technologies to stay within regulatory emission limits. Power increase on Finish mills (kWh/ton) Due to longer burning zone (less volatile fuel), clinker crystal size is smaller and more difficult to grind Increase of specific heat consumption (MMBtu/ton KK) Higher oxygen levels require more secondary air to be heated, therefore increasing the specific heat consumption. Power increase on Preheater (kWh/ton) higher load on ID fan and cooler fans to maintain adequate feed shelf oxygen to prevent significant buildup Fan Limitations if the plant is ID fan limited, production is lost due to maintaining higher feed shelf oxygen levels. Change in Kiln Feed to Clinker Factor since pet coke has a very low ash content compared to coal, more kiln feed will be required per ton of clinker. Kiln Feed composition changes The increase in sulfur and reduced ash content may require kiln feed composition changes and

possibly raw material additions to optimize clinker chemistry and the sulfur/alkali ratio. Maintenance Costs Pet coke, besides being more abrasive, requires higher fineness levels which leads to increased maintenance costs on coal mill rollers, ducts, liners, etc. and more expensive materials may need to be installed. Fuel addition for flame stabilization some plants have seen the need to burn natural gas or fuel oil at times to control the flame and promote combustion which causes system fluctuations. Refractory reliability and service life may be compromised.

This article will focus only on the refractory reliability and service life aspect of burning Coke in an effort to provide our customers some insight into the refractory economics of pet coke as a source of alternative fuel. REFRACTORY FAILURES Refractory failures are generally very difficult to identify the root cause failure mechanism. The main reasons are: Very few people truly understand the non-linear properties of the refractory, the thermo-chemical reactions of the refractory with the process environment and the thermo-mechanical interactions of the refractory and steel shell. Correct information regarding the service conditions of the existing refractory is rarely compiled by the plant. There are so many variables that could affect the brick reliability during a typical campaign that it would be impossible to isolate the direct effect of any. Most refractory (especially kiln brick) failures are a result of a complex combination of multiple variables. Therefore, this article will not be able to pinpoint the exact cause-and-effect of fuel changes but will rather try to isolate a few of the most relevant issues and make recommendations on how to extend the refractory reliability. SPECIFIC VARIABLES Sulfur / Alkali The most obvious affects of burning Pet Coke on cement plant refractory have been the destructive forces of sulfur / alkali. These destructive forces are seen in brick spalling, brick capping, shell corrosion, anchor corrosion, alkali penetration, expansive refractory reactions and direct damage from buildup removals. Depending on the fuel sources, pet coke can have anywhere from 1-7 wt% more sulfur and is typically in the 4-6% range. This change in fuel composition creates a large change in the sulfur / alkali ratio and the resulting cycles.

The sulfur to alkali ratio is a calculation used to assure that the raw mix has enough alkali to help absorb the sulfur into the meal. Prior to switching to an alternative fuel such as pet coke, this ratio has been set as a quality control number based on a mix design allowing for optimum production, stability, and quality. With limited raw material options specific to the plant, a limited alkali level also exists in order to maintain the desired mix design. With a substantial increase to fuel sulfur levels, this ratio will inevitably change and the flexibility will be limited. Once the amount of alkali sulfates that can be produced is exhausted, excess sulfur needs to be removed from the system with free lime as calcium sulfate which is promoted at higher oxygen levels. Most plants burning pet coke have severe sulfur buildup problems revealing the sulfur is not being adequately removed from the system. The result of skewed sulfur / alkali ratios or insufficient process parameters can cause sulfur cycles. Sulfur will volatilize in the burning zone and condense in the calcining zone (typically feed shelf / riser area) due to being absorbed by the calcium oxide (free lime). The sulfur cycles can get more complex as the volatile sulfur percentage increases. The most obvious effects of the high concentration of sulfur is in the amount and hardness of the coating, sulfur ring formation and tower buildups. These affects all contribute to a reduction in gas flow, which without adjustment, causes reduced oxygen levels and a worsening effect. Even plants with alkali bypass lines, the amount of sulfur is difficult to minimize. It is estimated that a minimum of 15% flow is required to the Bypass to reduce the sulfur compared to only about 2% to reduce chlorides to a refractory acceptable level. Coating Stability Most plants strive to achieve a 1 year campaign on their kiln brick. This goal has become increasing difficult to achieve by burning alternative fuels such as Pet Coke. The variation of fuel has compromised the kiln coating stability and thus the kiln brick reliability. Transition and burning zone brick life is directly proportional to the stability of the coating. Every instance that coating is dropped from an area of brick, the brick is subjected to an instant thermal shock and resulting compressive stress thermal shock wave. When the direct convective and radiant heat hits the newly

exposed brick and if the brick hotface has room to expand (strain) the brick will immediately shear or spall. If the brick has no room to expand the thermal expansion is induced into the brick as residual stress and creep. This type of damage is usually deeper into the brick (10-15% of brick thickness) and spalls within a few thermal cycles. Also when the coating falls, the brick is directly exposed to the process heat and environment. This allows the volatiles (sulfur / alkali) to condense on the surface and penetrate deeper into the brick. Due to the higher temperature at the brick hotface and the additional elements available to react with, a liquid phase will result on the brick surface and destroy the brick properties in all affected areas. Upon repeated exposure the liquid phase will penetrate deeper into the brick. It is also possible that if a liquid phase is formed and then quenched, a slick glass will form and no coating will be able to adhere to the brick. Changes in the mix or process (fuel / flame) can cause the coating to lose its adherence. The excessive buildups caused by the sulfur / alkali ratio can also cause thermal cycling as they change the process characteristics. The buildups can choke off air / heat and change flame patterns. A thermal shock condition can exist when a buildup, coating or sulfur ring falls and again abruptly changes the process condition. Water blasting the Riser causes direct refractory damage, process changes and thermal changes. Tower buildups should be avoided at all costs.

Another thermal cycle that affects the coating stability is fluctuations of the flame front and burning zone. The grinding and burning characteristics of coke are significantly different than coal and generally result in slow ignition (burning zone length increased and moved uphill) and higher flame temperatures to make up for less efficient combustion. Difficulties with Coke combustion are a generally recognized fact in the cement industry with solutions slow coming. The results of flame fluctuations can be readily seen in kilns as multiple sulfur rings, sulfur balls, burnt out brick in the #2 tire neighborhood and nose ring brick problems. Direct Refractory Damage Direct refractory damages are of a physical nature due to mechanical forces. These damages and the failure analysis are usually easily identified and corrected in a timely manner. Examples of direct damage include the following: Misaligned kiln, kiln shell damage, incorrect shimming of the kiln tires, direct flame impingement of a misaligned burner, over-

firing a burner, sulfur ring buildups, abrasion in high wear areas and normal wear and tear of the system. Direct Refractory Damages that are related to fuel variations might include: Excessive temperatures (due to coke combustion) in the burning zone brick which show 1 to 2 of severe penetration of high liquid phase is an indication of excessive temperature. This can be accompanied with thick coating and extremely hard to remove (also indicating high liquid phase). Deep cobbling of brick is a result of excessive temperatures which left residual stress in the brick. Water blasting damages due to thermal shock and scaling refractory from the walls due to the excessive buildups caused by the pet coke sulfur / alkali. Corrosion Sulfur / Alkali present in concentrated amounts due to the cycles will tend to penetrate the porosity of the refractory in every area where volatile alkalis are present. The salts in a vaporized form will penetrate through and around the hot face refractory until the temperature gradient through the refractory reaches the condensation point of the salt. The metal anchor will be at a slightly lower temperature than the immediate surrounding refractory and will likely precipitate the salt first. The temperature gradient across the refractory interface will likely precipitate the salt into the interface or into the porosity of the insulation. Once precipitated the salts could form a low melting point eutectic with the anchor and refractory. This is seen as a black tarnish and corrosion on all the anchors. The carburisation and sulphidation of the anchor is likely the result of the condensation of sulfur salts (namely Potassium Sulfate) on the anchor at the interface between the hot face and insulation These alkalis can also react with refractory components to form expansive phases and react with the steel shell in an acid-type corrosion reactions. Refractory Materials In general, most cement plant refractory (basic and alumina) should be fairly resistant to the environment created by alternative fuels. The additional sulfur and burning characteristics of Pet Coke can affect the refractory life. Under ideal conditions, the cement process could alleviate most of these affects. But since ideal conditions are rare, the conditions that these fuels create do have a pronounced affect on the refractory as described above. The following refractory upgrades are recommendations made to alleviate these detrimental affects on the actual refractory products. AZS castables have been found to offer excellent buildup resistance in cement application. The AZS grain imparts great thermal shock (water blasting) resistance, low thermal expansion, low thermal conductivity and excellent abrasion resistance. The AZS fused grain products are an upgrade over the products with just the Zircon additive. Numerous trials

have shown that it is more effective to utilize an AZS refractory rather than Silica Carbide. The AZS refractory has shown as good if not better results for buildup resistance, lower conductivity for better designs, and better resistance to alkali/steam reactions that limit the service life of Silicon Carbide. Standard 50-70% alumina products can be upgraded with a zircon flour addition of 4-8% in the matrix. The zircon addition can fill interstices sites within the refractory matrix and impart a non-wetting type property to the system to help repeal alkali impregnation. This type of product is recommended not only in buildup areas of the Tower but also in the Cooler and Tertiary Air Ducts. Denser spinel kiln brick with less porosity / permeability are being evaluated to help decrease kiln shell corrosion. The trade off is that this type of brick will generally have a higher modulus of elasticity and may not lead to shorter term reliability. Monolithic materials with high percentage of calcium alumina cement should be avoided in any application above 1400 deg. F. Any firebrick should be of the high-fired variety to avoid expansive reactions.

Rather than upgrading the refractory anchors with high nickel (Inconel) or grade 321 (not readily available) alloys, it is recommended to engineer the lining system and control the alkali condensation point. This can usually be accomplished by manipulating the insulation thickness and in some cases of severe shell corrosion a membrane may be required. PROCESS RECOMMENDATIONS The refractory upgrades mentioned above will not be enough to combat the affects of fuel changes and plant process issues will also have to be addressed. These may include any number of the following. Control the Sulfur / Alkali ratio. Determine if mix changes can optimize this ratio. Note that it is reported that the additional sulfur introduced by coke will only form Aphihitacite (3K2SO4-NaSO4) and none of the other calcium or sodium compounds. Increase oxygen to promote sulfur removal in buildup areas (i.e. Feed Slopes) Develop a more relevant ratio (such as feed shelf SO 3 to clinker SO3 ratio) to determine the maximum sulfur allowable for a particular mix. Control Flame / Burning Zone / Excessive Temperature Evaluate flame shape, temperature, and stability. Install better temperature measurement device at Feed End Examine Coke grinding to ensure efficient combustion Control Buildups

If the Sulfur / Alkali ratio and oxygen levels are controlled the amount of buildup should also be controlled. Minimizing any chlorides in the process will help eliminate buildups. Optimize the mix, fuel and bypass to eliminate chlorides. Sustain a minimum oxygen level in buildup areas (typically 3.5% at a minimum) Maximize Air Cannons usage and minimize water blasting.

CONCLUSION It is estimated that the annual budget for refractory repairs will increase about 20% in all plants burning over 20% petroleum coke as fuel. This annual percentage could be substantially more as the plant struggles through the learning curve with the alternative fuels or as the described corrosion mechanisms continue to deteriorate the plant refractory and supporting systems. We highly recommend that any plant burning alternative fuels or experiencing refractory problems contact a refractory contractor which specializes in refractory reliability. The contractor should have the capabilities to analyze your plant, process, refractory and all the thermo-chemical and thermo-mechanical interactions that can lead to refractory failures. Inferno can assist the plant in all aspects of solving any refractory problems. We can identify all the areas that will require attention, schedule and budget for the repairs, design and engineer the refractory, and manage the entire outage(s).