Properties of Refractories HEAT TRANSMISSION Thermal Conductivity When a furnace is heated, thermal energy flows into the refractory structure, causing a temperature difference to develop between inside and outside surfaces of walls and roofs, Part of this thermal energy is stored in the refractory structure and its foundation, and part flows through the walls, roofs, and hearths, and is lost to the outside air by radiation and convection. The amount of heat which escapes in this manner is often of considerable importance in the economy of the process. In estimating the quantities of heat flowing through the parts ofa furnace, use is made of a coefficient known as the thermal conductivity, or K-value, of each material involved in the construction. The thermal conductivity value differs not only for different materials, but Usually also for the same material at different temperatures. ‘The coefficient of thermal conduc tivity (K) is defined as the quantity of heat that will flow across unit area in unit time, ifthe temperature gradient across this area is unity. As applied to refractories, the thermal conductivity represents the amount of heat, in British Thermal Units (BTU’s), which will flow through the refractory per FIGURE 3.15 Apparatus for Measuring Thermal Conductivity While in Operation hour, per square foot of surface, per degree F temperature difference between the hotter and cooler faces, and per one inch of thickness. The water calorimeter method Uses. test panel, as shown in Figure 3.15, which hasa top and bottom surface measuring approximately 18"x 13'/2". The panel is heated from above using electrically heated silicon carbide elements which are controlled to give a constant temperature. After the panel reaches thermal equilibrium {Usdally in 2 to lohous) avonstant temperature gradient through the test panel exists, At this time, the tempera- ture gradient is determined using thermocouples which are embedded in the top and botiom of the center brick of the test panel. The heat fluxis, determined using a water calorimeter Which is located beneath the panel, TABLE 3.12 _K Values for Refractory Brick at Various Mean Temperatures, Btu « in/ft? + h «°F Mean temperature, °F ee eee EEE eee eee eet ‘Type of brick 600 1200 1500 1800 2200 2600 Fieclay Superduty a8 a9 10.2 105 114 128 High-duty at 83 as BT 92 10.0 High-alumina 60% class. 13.0 129 13.4 13.3 144 187 70% class 158 144 14a 143 146 149 85% class 184 162 169 175 196 22.9 90% class, 219 185 178 176 179 sas Corundum class 348 226 20.7 187 179 183 Silica (superciuty) 9.0 10.4 11.0 118 135 16.1 Basic Magnesite, fred 73.2 39 36.1 B17 30.8 92.3 Magnesite-chrome, fred 479 152 147 442 147 16.2 Magnesite-chrome, unbumed 18.4 172 187 145 147 16.0 Chrome, fired 152 15.0 181 145 133, 129 Chrome-magnesite, fired 118 123 124 125 325 136 Magnesite-carbon 150.0 1150 108.0 100.0 95.0 90.0 Silicon carbide 112 1120 107.5 103.0 97.0 94.6 Zircon 224 165 166 166 168 17.9 Conversion Factor: 1 Btu + invit'+h =F = 0.144 Wim + K HARBISON-WALKER PR-27Properties of Refractories and the thermal conductivity is calculated according to the following equation: K = Qa/aT where: K = thermal conductivity, BIU-in/tt-he-*F (W/mK) d= thickness of test brick, in (mn) Q = heat flux through test brick, BTU/ft-hr (W/m) AT = temperature gradient through test brick, °F (0) ‘The thermal conductivity is reported at the mean temperature of the test brick ‘The measured thermal conduc- tivities of various refractories are given in Table 3.12 and Figures 3.16, 3.17 and 3.18. These data were determined at the Harbison-Walker Garber Research Center using the ‘water calorimeter apparatus which is described in ASTM Method C 201 Typically, thermal conductivity of ‘a material is measured at several temperatures. ASTM Method C 202 details the preferred method for fired refractories and suggests a minimum of four test temperatures. ASTM Method C 417 describes the preferred method for unfired refractories and suggests a minimum of seven points, four ascending in temperature and three descending in temperature. A special test procedure, ASTM Method €767, provides a means for measur- ing the thermal conductivity of carbon-bearing refractories; special precautions for preventing oxidation Of the test panel are described. Major factors which affect the thermal conductivity ofa refractory material are the mineral composition, the amount of amorphous material (lass or liquid) which it contains, its porosity, and its temperature. For ‘materials which have similar mineral- ‘gical compositions, the proportion of pore space is unquestionably the most important factor affecting the amount of heat which will flow through itat a given temperature. Within the PR-28 HARBISON-WALKER 2 BTU-INFt?+°F+Hr SUPERDUTY FIRECLAY HIGH FIRED SUPERDUTY FIRECLAY SEMI-SILICA 300 6000012001500 ‘Mean Temperature, °F 1800 2100 2400 FIGURE 3.16 Approximate Thermal Conduetivities of Fireclay Brick 2 8 BTU- INL °F Hr T 90% ALUMINA, SILICA | CHROME, FIRED CHROME-MAGNESITE, FIRED 300 600 900 1200-1500 Mean Temperature, °F 1800 2100 2400 FIGURE 3.17 Approximate Thermal Conductivties of Various Refractory BrickProperties of Refractories pt {|_| {||| | MAGNESITE CARBON (20% ©) | £5 BTU-INFt? =F Hr gs 8 I ® | MAGNESITE CHROME - FIREC 300 600 900-1200 1500 t@00 2100-2400 ‘Mean Temperature, °F 160 140 120 100 60 FIGURE 3.18 Approximate Thermal Conduetivties of Various Relractory Brick 4 3000 IF BTU. INFt? «°F + Hr 00 1000 1500 2000 2500 Mean Temperature, °F FIGURE 9.19 Approximate Thermal Conductivities of Insulating Firebrick temperature range seen in most applications, thermal conductivity lecreases with increasing porosity At atmospheric temperatures, the thermal conductivity of glass is considerably lower than that of crystalline material of the same composition. With rising tempera: tures, the conductivity of glasses tends to increase, while that of crystalline ‘material tends to decrease. However, in refractory bodies consisting of crystal aggregates with a limited amount of glass, the temperature effects are difficult to predict. The conductivity of a refractory in service at high temperature is often changed somewhat, either by an increase in the amount of glass or liquid it contains, or by devitification of any glass it may contain, The thermal conductivity of refractories which are highly porous increases significantly with increases in temperature, This behavior is primarily due to increasing heat radiation across pores. Figure 3.19 shows thermal conductivity curves for several insulating firebrick which are prime examples. High thermal conductivity is desirable for refractories used in constructions requiring efficient transfer of heat through brickwork, as in retorts, muffles, byproduct coke oven walls, and recuperators, In most types of vessels, however, low thermal conductivity is desirable for heat conservation, but is usually less important than other properties of the refractories Heat Flow In furnaces which operate ata con- stant temperature for long periods of time, two stages of heat flow behavior ‘occur. During the first stage, called unsteady state or transient heat flow, the refractories store a portion of the absorbed heat, and the remainder is lost to the surroundings, Since refractories retain additional heat, the temperatures within the lining change with time. ‘After a long period of time, which depends on the thickness and compo- sition of the lining, refractories no longer store any of the incoming heat, and all of the absorbed heat is lost to HARBISON-WALKER PR-29Properties of Refractories the surroundings. This marks the beginning of the second stage which is known as steady state or equilibrium heat flow. Since the refractories are not storing additional heat, the temperatures within the lining are constant with time, ‘The amount of heat flowing through a refractory wall in service "under equilibrium conditions is directly proportional to (1) the thermal conductivity (K) of the material the temperature drop, (T,-T,) from the hot face to the cold face; (3) the area (A) of the wall; and ) the time (t). The heat flow is inversely proportional to the thickness (d) of the wall. These relations are expressed by the well-known formula Q = KyTpat/d The calculation of heat flow rates through a refractory lining under unsteady state conditions is rather complicated and, in most cases, requires a complex computer model to provide accurate results. A brief description ofthe principtes will be discussed in a later section, However, itis appropriate at this point to introduce a material property, called thermal diffusivity, which is used for such calculations. Thermal diffusivity is defined by: a = K/Cp where: & = thermal diffusivity, f2/hr (m/sec) K = thermal conductivity, BIU/ft-hrF (W/m-K) C= specific heat, BTU/Ib- O/Ke-®) p= bulk density, Ibs/ft g/m) ‘Thermal diffusivity indicates the rate at which thermal energy diffuses through a material, The rate of heat flow in refractory constructions can be calculated only approximately for several reasons: + Theaccuracy of methods used to ‘measure thermal conductivity is unconfirmed. PR-30 HARBISON-WALKER + The temperatures of the hotter and cooler faces of the refractory wall or roof are rarely known with exactness, + The conductivity of a refractory ‘may be altered in service by mineral changes in the refractory, by vitrification of the refractory, orby absorption of slags, metals, or other materials, ©The thickness of a furnace lining ‘may not remain constant during ‘operation. The lining may become thinner because of wear and transmit more heat; or it may become thicker, because of the formation of a solid coating (as in rotary cement kilns), and transmit less heat. + The rate of heat flow is influenced by the pressure of the furnace gases and by the permeability of the refractory. A positive pressure tends to force hot gases out through the walls, while a negative pressure tends to draw cold air from the surroundings into the furnace. + The rate of heat flow may be influenced by the thickness of the joints and gaps between lining, components and by the character of the bonding mortar, if used. Other important factors which affect the amount of heat flowing through refractory linings include the emissivity of the refractory or the ‘metal shell; the kind of gases within the furnace; and the extemal convec- tion currents, Effect of Gases In furnaces which contain highly porous refractories, the type of atmosphere can have an appreciable effect on the heat Joss through the lining. This is especially ‘true of atmospheres with a high hydrogen content. Many atmospheres in petro- chemical processing vessels and most protective atmospheres (including dissociated ammonia, exothermic gases and endothermic gases) contain substantial percentages of hydrogen. ‘The conductivity of hydrogen, which is approximately seven times that of air, must be taken into consideration {n calculating heat losses through the refractory walls of vessels such as controlled-atmosphere heat-treating furnaces, coal gasifier vessels, and cat-crackers. ‘A study using a verified com- puter mociel compared the effects of various gases on heat transfer through coal gasifier lining.* ‘The lining consisted of 4/2 inches of a dense castable (porosity = 23%) backed up by 7'/s inches of a light- weight castable (porosity = 50%), and a hot face temperature assumed to be 1500°F (816°C). The heat fluxes calculated for six atmospheres are shown in Table 3.13. The hydrogen atmosphere caused a 68% increase in the heat flux as compared to the air atmosphere. The coal gas atmospheres (15% and 48% HL.) caused increases of 200% and 41%. The carbon dioxide and steam atmospheres showed only minor effects. TABLE 3.13 Effect of Gases on Heat Flux of Coal Gasifier Lining Heat Flux ‘Atmosphere (BTUhr-ft) Air 543, Carbon Dioxide 538 Goal Gas 1 (15% H,) 654 Coal Gas 2 (48% H:) 768 Steam 568 Hydrogen 310 ‘Mean Thermal Conductivity ‘Thermal conductivity values calcu- lated using the water calorimeter ‘apparatus are mean values, since a temperature gradient through the sample must exist. Therefore, thermal conductivity versus temperature curves generated by this method represent a series of mean conductivi- ties, The conductivity curve only represents true conductivities if it isa straight line. Even if thermal conduc~ tivity is represented by a curved line, however, the deviation from true values is usually less than the errors of observation. "Connected Block and Eifective Conductivity (CONBEC) Computer Program to Predict, Heat Flow Through Multicomponent Refractory Lines Gasifier Vesse! Walls, US, Depurtment of Energy, Washington, DC. pp. S11 through 517,Properties of Refractories For the water calorimeter method, the “within laboratories” variation is approximately plus or minus 5%, and the “between laboratories” variation is Of the order of plus or minus 10%. However, there may be even greater variations between materials of the same class but of different manufac- ture. For example, a variation in the degree of firing will usually result in some change in thermal conductivity. For temperatures up to about 2000°F (1090°C), the K-values given in charts and tables represent laboratory determinations, For temperatures above 2000°F (1090°O), they are mainly extrapolations; and above 2400°F (1320°C) are likely to have a lower degree of accuracy. Calculated thermal data for walls 13'/: inches thick with a hot face temperature of 2600°F (1430°C) are given in Table 3.14, Unfired Refractories ‘The estimation of heat flow through unfired refractories is complicated. ‘Chemically-bonded brick, magnesite- carbon brick, and monolithic refracto- ries, which fall in this category, begin to undergo physical and chemical changes almost as soon as they are initially heated in service. These changes have a pronounced and complex effect on the thermal condue- tivity of the refractories. Consider the case of a wall built of «a cement-bonded castable material ‘which is heated in service above 2000°F (109°C) on one side and exposed to the outside air on the other. Before heat is applied, the complete wall hasa strong hydraulic bond throughout its entire thickness, When the furnace is fired, a tempera- ture difference develops between the intetior and exterior surfaces. In any part of the wall heated above about 400°F (205°C), the chemically com- bined water is gradually driven off. In any part above 1900°F to 2000°F (980°C to 1090°O),a second change, the development of a ceramic bond, takes place. Consequently, by the time the wall has reached essential thermal equilibrium and no further appre- ‘Gable changes are occurring, the wall has a well-developed zoned structure. In the first or coolest zone, where the maximum temperature is below TABLE 3.14 Approximate Thermal Data for Walls 13" Inches Thick with Hot-Face Temperature of 2600°F Cold-Face Heat Flow per Square ‘Type of Brick Temperature Foot of Wall per Hour Fiedlay. High-Duty 265°F 1490 BTU 70% Alumina 490°F 1650 BTU FORSTERITE L 00°F 1720 BTU Sica 05°F 1790 BTU Chrome 565° 2280 BTU 90% Alumina KORUNDAL 560° 2200 8TU KORUNDAL XD 620°F 2790 BTU Magnesite (82% MgO) 750° 4990 BTU Tt re-tre szvte) Thermal conductity E | B- zone [Zone 2 {+ 2ore3 a T Combined water wdc | § Sommtmtt § | mieten r 2 border formed £ : 4 tion kvave | 2 | com kane | | lank vase & eI a a a FIGURE 3.20. Variations in thermal conductivity through a castable wall heated from one side only. 400°F (205°C), the refractory retains its hydraulic bond and the thermal conductivity is relatively high. Inthe second or middle zone, the hydraulic and chemical bonds have been destroyed, but the temperature is not high enough for the development of a ceramic bond. Here, the strength is moderate and the conductivity is relatively low. In the third or highest tempera- ture zone, where the minimum temperature is above 1800°F (80°C), sintering reactions have taken place Which form a strong permanent ceramic bond. The thermal conductivity is much higher than that in the middle zone, The conditions described above are illustrated schematically in Figure 320, which shows that each zone has its own thermal conductivity characteristics, Depending on the particular construc- tion and the operations temperature, a ‘monolithic component could consist of (Dall three zones; 2) the unaffected portion alone (Zone 1); (3) the portion with a ceramic bond alone (Zone 3); or @)a combination of any two adjacent zones, HARBISON-WALKER PR-31Properties of Refractories Similar phenomena occur during measurements of thermal conduc: tivity of unfired materials using the water calorimeter method. Since the calculated thermal conductivity data represent mean values over, in some cases, a relatively large temperature ifforential, they must be interpreted carefully. Figures 3.21 and 322 give thermal conductivity curves for a ‘wide range of unfired refractories. PR-32 HARBISON-WALKER, 190% Alumina Castable | Eee ee 60% Alumina Castable Low Cement Superduty Firecay Castable BTU-INIFt? °F - Hr Vitreous Silica Castable | Fireclay Castable ° 200 600 1009) 1400 12002200 Mean Temperature, °F FIGURE 3.21 Approximate Thermal Conductiites of Untired Refractories 6 185% Alumina Brick (Unburned) Hf ' | 90% Alumina Chrome Plastic 30 75% Alumina Brick (Unburned) {50% Alumina Plastic it {60% Alumina Plastic 2200 200 600 7000 1400 1800 ‘Mean Temperature, °F FIGURE 3.22 Approximate Thermal Conductiities of Unfired Refractories