AUTHOR: J.

BOLEBRUCH TITLE: Key factors in selecting refractories SOURCE: Hydrocarbon Processing (International edition) 86 no3 65-6 Mr 2007 COPYRIGHT: The magazine publisher is the copyright holder of this article and it is reproduced with permission. Further reproduction of this article in violation of the copyright is prohibited. To contact the publisher: http://www.gulfpub.com Longer campaigns, higher temperatures and more oxygen all add up to increased wear and tear on process vessels and equipment, and make proper material selection even more critical. Unanticipated failure in refractory lined vessels or failure of critical pieces of equipment, whatever the material of construction, can have expensive and tragic consequences. The same refractory lining designs that have performed admirably in service for years may not be suited to the new realities of the process industries. Higher temperatures can require higher duty compositions, and at the very least, exacerbate the differences in thermal expansion between refractory and steel as the insulated vessel walls remain the same temperature, while the hot face of the refractory can be seeing considerably higher temperatures than previously. Also, processes utilizing oxygen enrichment can operate more unstably, causing large temperature swings, which in turn stresses the refractory as it is forced to expand and contract repeatedly. This highlights the point that refractory linings are dynamic bodies, expanding and contracting with swings in operating temperature, and, as such, should be treated with careful consideration. Large refractory bodies will thermal fatigue and crack over time as the number of thermal cycles they see increases. Mitigating fatigue. This type of fatigue can be mitigated through material selection-choosing refractory compositions that have lower coefficients of thermal expansion, or by physical means such as segmenting linings to discourage the transmission of stresses across entire bodies. Most refractory linings in process vessels are composed of a single or double layer of castable refractory. These linings are typically secured to the vessel wall via a series of metallic hangers that are welded to the shell, forming fields of metal fingers protruding from the wall in a variety of shapes and lengths. These lengths of steel serve to "knit" together the castable, providing a physical means of holding it together and keeping it attached to the steel shell of the process vessel. Unfortunately, metal has a much higher coefficient of thermal expansion than ceramic, and in particular, in applications where temperatures are very high and the hangers come close to the surface, there is potential for the hangers to actually force the refractory to crack as they expand at nearly twice the rate of the refractory for a given operating temperature. In addition to expansion from a purely temperature-related mechanism, many process vessels contain corrosive or oxidizing atmospheres that can penetrate far enough into refractory linings to attack the metallic hangers, cause swelling and further exacerbate the cracking problem. Why then are monolithic refractories used so extensively? Because they are relatively inexpensive and easy to install for experienced refractory contractors. They also adapt to nearly any shape or size without a requirement for tooling up front. The process industries are in business to make money, and to expect them to spend any more money on refractory materials than is absolutely necessary is just not realistic. Process examples. Many processes are pushing the envelope to the point where the costs of unexpected downtime and damaged equipment can, and do, greatly outweigh the incremental up-front cost of an engineered lining.

Consider, for example, the Claus sulfur recovery process. In the Claus process, hydrogen sulfide (H[sub2]S) is combusted in a refractory-lined thermal reactor at temperatures in the low-to-mid 2,000E H[sub2]S is extremely corrosive by itself, but increasingly, oxygen enrichment is being used, which forces the temperatures up to, and sometimes above, 3,000E Further, oxygen enrichment tends to lead to greater swings in temperature as air, with its large percentage of inert nitrogen, is replaced with much more combustible oxygen and smaller changes to process parameters have greater impact on the business end. Consequently, many cases over the past few years, particularly in Claus units with a combination of large-diameter tubesheets and high operating temperatures/oxygen enrichment, have had tubesheet refractory failures in some cases leading to the destruction of the entire waste heat boiler. In almost every case, the failure mode was cracking of the monolithic refractory, caused either by repeated thermal cycles or corrosion of the hangers buried in the refractory and the subsequent shearing off of the tube ferrules that protect the waste heat boiler tube ends, leading to significant corrosion of large areas of the tubesheet and the tube-to-tubesheet welds, and immediate failure. Enough installations of precast hex-head ferrules over the past few years show, that when properly designed, a segmented lining can not only safely protect a tubesheet in these difficult environments, it can also extend the length of the campaign. There are a couple of reasons for this. A segmented lining, by definition, is comprised of a series of smaller precast shapes that are designed to expand at operating temperature and form what is in effect a monolithic face, but also to contract upon cool-down, returning to their status as individual components, thus preventing the accumulation and transmission of stresses across the larger body. There is a good reason why sidewalks have expansion joints, and the temperature swings there amount to maybe a hundred degrees! Additionally, use of a precast, prefired lining allows for incorporating refractory fiber insulation that cannot tolerate the moisture present when monolithic refractories are applied. A precast liner, designed as part of a two-piece system including a fiber component, will have much greater insulating value than a two-piece monolithic castable lining consisting of a lower density insulating castable and a high-duty castable on the face. This permits the design of thinner, more dynamic linings, with much less mass than castin-place systems. Less refractory mass means less energy used to heat the lining and more going directly to the process. Inspection of vessel walls is simplified since parts or all of a segmented system may be removed and reinstalled without having to jackhammer an entire lining out and recast it, allowing days for subsequent cure-out. There are other applications where this approach has shown merit. Often waste heat boilers in applications such as nitric acid, ammonia, syngas, etc., are lined with castable refractory-often cast in place over stainless steel ferrules. Metallic ferrules do not provide the thermal insulation ceramic ones do, and are often viewed as sacrificial, merely protecting boiler tubes from corrosion, or metal dusting, doing nothing to protect the tube-to-rubesheet welds from the effects of thermal cycling and heat flux. This example raises an equally important point. Upon reading the title of this article, "Key factors in selecting refractories," many would tend to assume that it was intended to refer to the replacement of one refractory material with another. This is not necessarily the case. It is simply that most people are comfortable using refractory materials in certain areas, while immediately going to a metallic solution for a traditionally metallic application, even if the part is considered to be sacrificial and is regularly replaced in service. Inconels and other high-alloy steels are used in many process plant areas, and can experience accelerated chemical attack or loss of strength due to the higher temperatures and more aggressive processes.

Thermocouple tubes, sparger nozzles, spent acid nozzles and the like, are frequently fabricated from various grades of stainless alloys. Premature failure of the components and subsequent shutdown to replace them compound the already high cost of fabricated components. In many cases a ceramic or refractory can be used to do the job and, if designed properly, could have considerably longer life and resulting lower cost. Advanced ceramics have greater strength and impact resistance. Many "conventional" refractory compositions such as aluminas and spinels would not be appropriate for such structural requirements, but a series of advanced ceramics could fit the bill (Figs. 1,2 and 3). Compositions such as reaction-bonded silicon carbide, silicon nitride and zirconia all have the strength and impact resistance to serve admirably in some of the mentioned applications. Traditionally, these advanced compositions have been very expensive, but emerging applications such as armor have increased the volumes of these materials processed, and that has led, in some cases, to substantial decreases in cost. Process engineers have been tasked repeatedly over the past few years to increase efficiencies and yield, while reducing cost at the same time. Because of this, anything that did not directly relate to more product out the door was not a priority. This has begun to change as more rigorous conditions, brought on by intensified processes, have begun to adversely affect the life of conventionally applied refractory materials. ADDED MATERIAL J. BOLEBRUCH, Blasch Precision Ceramics, Albany, New York Jeffrey Bolebruch graduated in 1985 from the United States Military Academy at West Point with a BS degree in environmental engineering. He received an MBA degree from Marist College in Poughkeepsie, New York in 2004. Mr. Bolebruch joined Blasch Precision Ceramics in 1990 as technical sales representative, becoming market manager, then senior market manager, responsible for sales to the chemicall petrochemical market He holds five US patents, including two relating to Claus technology and presented, "The Successful Use of 1-Piece Hex or Square Head Ferrules in Claus Sulfur Recovery Units," at the Sulphur 2006 Conference in Vienna. FIG. 1 Ceramic hex-head ferrules fit together like building blocks, with expansion spaces in between. When the ferrules are at operating temperature they expand closing the spaces. FIG. 2 Ceramic ferrules offer several times the service life of metal ferrules in hostile environments. FIG. 3 Hexagonal ceramic blocks interlock to stay in the same geometric relationship to each other regardless of expansion and contraction caused by thermal cycling.