Monolithic refractory composition

BACKGROUND OF THE INVENTION
This invention relates to compositions particularly suited for the formation of refractory monoliths, and in particular to such a composition for forming a ramming mix for use as a cooler plate packing material in blast furnaces.
Monolithic or monolith forming refractories are special mixes or blends of dry granular or stiffly plastic refractory materials, with which virtually joint free linings are formed. They embrace a wide range of mineral compositions and vary greatly in their physical and chemical properties. In various types of furnaces, monolithic refractories are used to advantage over brick construction. The use of monolithic refractories enables the installation to be made in a relatively short period of time whereby any delays resulting from a required manufacture of special brick shapes may be avoided. Further, the use of monolithic refractories frequently eliminate difficult brick laying tasks. The use of monolithic refractories is of particularly importance in the maintenance of furnaces. Substantial repairs may be made with a minimum loss of time, and in some instances, even during continued operation of the furnace.
A ramming mix is one type of composition typically used to create a monolith. One application of a ramming mix involves the use thereof as a cooler plate packing material in blast furnaces. Requirements for the ramming mix to satisfy the needs of this particular application include relatively high thermal conductivity, a dried cold crushing strength of at least 1000 psi, reheat stability at 1000.degree. F., ramming mix or platic consistency, a relatively high degree of water insolubility, and a curing temperature not exceeding 250.degree. F. Although some ramming mixes satisfy one or more of the required properties, the ramming mix of the present invention satisfies all of the properties. Further, the present ramming mix is sold as a single component and has a four-month shelf life.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide a ramming mix particularly suitable for use as a cooler plate packing material in blast furnaces and having the following properties:
(1) relatively high thermal conductivity;
(2) dried cold crushing strength of at least 1000 psi;
(3) reheat stability at 1000.degree. F. (linear shrinkage not exceeding 1.5%);
(4) ramming mix or plastic consistency;
(5) a relatively high degree of water insolubility; and
(6) a curing temperature not exceeding 250.degree. F.
The above objective is attained in a monolithic refractory batch composition comprising, by weight, 50-75% relatively large grain flake graphite; 5-30% relatively micronized flake graphite; approximately 20% ball clay, said batch further containing, based on its total weight, 10-25% liquid phenolic resin in combination with an alcoholic solvent, and 0.5-2% resin curing agent.

DESCRIPTION OF THE PREFERRED EMBODIMENT
A commercial need was identified for a refractory to be used as a packing material for a blast furnace shell and cooler plate, having the following properties:
(1) thermal conductivity of 75 Btu/ft.sup.2 --Hr..degree.F/in. at 1500.degree. F. (in the "fast" direction);
(2) dried cold crushing strength of at least 1000 psi;
(3) reheat stability at 1000.degree. F.; and
(4) ramming mix or plastic consistency.
As used herein, the term "fast" direction is the measurement of conductivity in a direction taken perpendicular to that in which the material is pressed in applying the same, while the "slow" direction corresponds to measurement of the thermal conductivity in the direction taken parallel to that in which the material is pressed or rammed.
Initially, it is presupposed that a monolith refractory based on silicon carbide and/or flake graphite could be produced to meet the above requirements. Initial work included evaluation of a series of bench scale mixes consisting of silicon carbide, graphite and clay. This was done to determine the effect, if any, that the addition or elimination of graphite to a commercial ramming mix would have on the Mix's plastic consistency. Referring to Tables I and II, poor plastic properties and reduced crushing strength in Mixes E, E-1 and F corresponded to the inclusion of flake graphite in amounts exceeding 12.5%. Mix A had the highest cold crushing strength (900 psi) after drying. The thermal conductivity of a ramming mix containing 10% flake graphite, was 45.8 Btu/ft.sup.2 --Hr..degree./in. at 1500.degree. F. in the "fast" direction. Consequently, it was assumed that the thermal conductivity of Mixes D through G would not meet the desired goal of at least 75 Btu/ft.sup.2 --Hr..degree.F./in.
TABLE I__________________________________________________________________________ Mix Designation: A A-1 A-2 B B-1 C C-1 D__________________________________________________________________________Mix:Silicon Carbide -8/+16 mesh 40%-16/+30 mesh 5%-30/+50 mesh 10%-50/+100 mesh 5%Silicon Carbide DCF 30 30 35 25 25 20 20 151631 Flake Graphite -- -- -- -- -- -- -- 10Mexaloy Graphite -- -- -- -- -- -- -- --M & D Ball Clay 10 -- -- 15 -- 20 -- 15Jackson Ball Clay -- 10 -- -- 15 -- 20 --SPV Volclay -- -- 5 -- -- -- -- --Plus Additions:Silicanit 2%Water (for pressing) 7.3 6.8 8.8 7.7 7.8 8.1 8.0 8.6Water (for storage) 10.3 7.9 9.8 12.7 10.8 9.6 9.0 10.6Bulk Density, pcf (Av. 3)After Heating 18 Hrs. at 250.degree. F.: 156 158 150 155 155 154 152 147After Heating 5 Hrs. at 2000.degree. F.:* 156 156 149 152 152 150 148 144Apparent Porosity, % (Av. 3) 20.1 19.4 23.0 20.9 20.7 21.6 22.7 22.6After Heating 5 Hrs. at 2000.degree. F.:*Reheat 2000.degree. F. (Av. 3)*Linear Change: -0.3. -0.2 +0.2 .+-.0.2 .+-.0.3 .+-.0.3 -0.3 -0.3Volume Change: -0.8 -0.2 -0.2 -0.4 -0.3 -0.3 -0.7 -0.8Cold Crushing Strength, psi 900 890 740 730 740 640 600 630After Heating 18 Hrs. at 250.degree. F.Workability (Storage Data) 40 40 35 37 43 37 39 3314# wt. as Made for PressingTempered for Storage 43 50 50 50 45 43 44 46 (5# wt.) (5# wt.) (5# wt.)After One Week 29 26 32 56 31 31 30 33 (5# wt.) (5# wt.)After One Month 42 21 24 55 50 24 23 33After Two Months 33 22 25 49 39 21 19 33After Three Months 37 16 24 44 35 18 15 38__________________________________________________________________________ *Reducing conditions.
TABLE II__________________________________________________________________________ Mix Designation: D-1 D-2 E E-1 E-2 F G__________________________________________________________________________Silicon Carbide -8/+16 mesh 40%-16/+30 mesh 5%-30/+50 mesh 10%-50/+100 mesh 5%Silicon Carbide DCF 15 20 12.5 12.5 15 15 151631 Flake Graphite 10 -- 12.5 12.5 -- 15 --Mexaloy Graphite -- 10 -- -- 15 -- 15M & D Ball Clay -- -- 15 -- -- 10 10Jackson Ball Clay 15 -- -- 15 -- -- --SPV Volclay -- 10 -- -- 10 -- --Plus Additions:Silicanit 12%Carboxymethyl Cellulose -- -- -- -- -- 0.75 0.75Water (for pressing) 8.5 9.7 8.5 8.6 10.0 12.6 13.5Water (for storage) 10.0 11.2 10.0 10.1 11.1 14.6 15.5Bulk Density, pcf (Av. 3)After Heating 18 Hrs. at 250.degree. F.: 146 144 145 144 140 131 125After Heating 5 Hrs. at 2000.degree. F.:* 143 142 142 141 137 129 124Apparent Porosity, % (Av. 3) 22.8 23.8 23.2 23.1 25.1 30.1 32.1After Heating 5 Hrs. at 2000.degree. F.:*Reheat 2000.degree. F. (Av. 3)*Linear Change: -0.2 -0.4 .+-.0.2 -0.2 -0.2 -0.1 .+-.0.4Volume Change: -0.5 -0.5 -0.4 -0.7 -0.4 -0.5 -0.4Cold Crushing Strength, psi 600 750 540 510 600 560 280After Heating 18 Hrs. at 250.degree. F.Workability (Storage Data) 35 30 32 39 32 35 3514 # wt. as Made for PressingTempered for Storage 50 43 43 50 46 46 46After One Week 43 36 26 36 38 36 38After One Month 34 33 29 39 38 52 50After Two Months 31 32 28 34 35 60+ 60+After Three Months 30 32 28 35 37 -- --__________________________________________________________________________ *Reducing conditions.
Referring to Table III, there is shown the results of the testing of a second series of mixes. The second series of mixes, labeled H through L, were made from a batch including silicon carbide, clay and increased amounts of either Mexaloy, micronized amorphous, or micronized flake graphite. These mixes also contained a powdered pitch addition to improve crushing strength after drying. Mixes I, K and L included micronized flake graphite. These mixes required additional quantities of water for forming the monolith and consequently, the density of the monolith was significantly reduced. The thermal conductivity of Mix H and J was determined to be 30 Btu/ft.sup.2 --Hr..degree.F./in. in the "slow" direction. None of these mixes proved commercially acceptable.
TABLE III__________________________________________________________________________ Mix Designation: H I J K L__________________________________________________________________________Mix:Silicon Caribde -8/+16 mesh 40% 40% 40% 40% 28%-16/+30 mesh 5 5 10 5 10-30/+50 mesh 10 10 5 10 4-50/+100 mesh -- 5 -- 5 --Silicon Carbide, DCF -- 5 -- -- --Ashbury Micronized Graphite #505 30 -- -- -- 30Ashbury Micronized Graphite #FG -- 20 -- 27 10Mexaloy Graphite -- -- 40 -- --Powdered Pitch 10 10 10 10 8M & D Ball Clay 5 5 5 --SPV Volclay -- -- -- 3 --Plus Additions:Silicanit 2%Water (for pressing) 10 12 12 14 14Water (for storage) 13 21 16 23 23Bulk Density, pcf (Av. 3) As Made: 134 127 134 120 124After Heating 18 Hrs. at 250.degree. F.: 124 116 120 107 110After Heating 5 Hrs. at 2000.degree. F.:* 118 112 114 -- --Method of Forming: 21/8" .times. 2 1/2" Cylinders Pressed at 1000 psiCold Crusing Strength, psi (Av. 3)After Heating 18 Hrs. at 250.degree. F. 930 650 950 370 690After heating 18 Hrs. at 400.degree. F. 1380 1190 1120 670 1090Workability (Storage Data) 29 35 42 25 295# wt. as Made:After One Week 25 30 41 24 23After One Month 49 62 27 19 20 (14# wt.)After Two Months 40 20 60 17 50 (14# wt.) (14# wt.) (14# wt.)__________________________________________________________________________ *Reducing conditions.
Additional mixes were prepared (M, N, O, P and R) as indicated in Table IV. These mixes were prepared as resin bonded, flake graphite plastics. These mixes contained 80 to 100% flake graphite (Asbury 3166A and Asbury micronized FG) with additions of alumina (M) or ball clay (N, O and P). The resin required to bring these mixes to a plastic consistency ranged from 35 to 50%. These mixes were pressable, but laminations and severe cracking occurred after drying of the pressed specimen.
TABLE IV______________________________________ Mix Designation: M N O P R______________________________________Mix:Asbury 3166A 50% 55% 60% 55% 60%GraphiteAsbury Micronized 30 30 30 30 410Flake Graphite, FGM & D Ball Clay -- 15 10 15 --A-17 Alumina 20 -- -- -- --Plus Additions:ML-53 Resin 35 35 -- -- --RL-2302 Resin -- -- -- 50 50RM 441 Resin -- -- 35 -- --Stadex 4.0 4.0 4.0 4.0 4.0Darvon C 0.10 0.10 0.10 0.10 0.10Method of Forming: Six inch bars were pressed at 1000 psiObservation: None of these mixes had good compaction properties and laminations resulted after pressing.Bulk Density, pcf 100 93 102 100 93After Drying 18Hrs. at 500.degree. F.______________________________________
Additional mixes (X, Y and Z) were prepared as ramming mixes having reduced binder additions. These mixes are described in detail in Table V. Mixes Y and Z (100% flake graphite) contained reduced amounts of liquid resin, while Mix X contained water. Mix Y, having the 20% addition of ball clay, provided a mix with the best rammability. The thermal conductivity of Mix Y in the "slow" direction was 55.0 Btu/ft.sup.2 --Hr..degree.F./in. at 1500.degree. F. In contrast, Mix X had a thermal conductivity value of 35.0 Btu/Ft.sup.2 --Hr..degree.F./in. at 1500.degree. F. in the "slow" direction. The thermal conductivity for Mix Y was also determined in the "fast" direction. This was done by continuously ramming a large block of material and then cutting nine-inch straights from the block. The thermal conductivity was measured perpendicular to the direction of ramming. The thermal conductivity value for Mix Y in the "fast" direction was 82.6 Btu/Ft..sup.2 --Hr..degree.F./in. at 1500.degree. F. This represents a difference of 27.5 Btu/Ft..sup.2 --Hr..degree.F./in. over the thermal conductivity value of the same mix in the "slow" direction.
TABLE V______________________________________ Mix Designation: X Y Z______________________________________Mix:Asbury 3166A 40% 50% 50%Flake GraphiteAsbury Micronized 30 30 50Flake Graphite FGM & D Ball Clay 20 20 --Powdered Pitch 10 -- --Plus Additions:RM441 Liquid Resin -- 21 30Water 18 -- --Stadex 4 4 4Darvon C 0.10 0.10 0.10Bulk Density, pcf(Av. 3) As Made:After Heating 18 Hrs. 110 117 102at 500.degree. F.After Heating 5 Hrs. 90 108 86at 1500.degree. F.*Forming Pressure, psi: 1000 2000 1000Appearance After Some lamina- Good com- SevereForming: tions oc- paction laminations curred in properties occurred in shape pressed 9" straightsCold Crushing Strength 650 1310 440psi (Av. 3) After Heat-ing 18 Hrs. at 500.degree. F.:Linear Change, %After Heating 18 Hrs. -0.8 -0.4 --at 500.degree. F.After Heating 5 Hrs. -- -1.2 --at 1500.degree. F.:*Observed StorageBehavior:After 1 week Good Good --After 1 month Good Good --After 2 months -- Good --Bulk Density, pcf (Av. 3) -- 103 --After RammingContinuously:After Ramming and -- 93 --Heating 18 Hrs.at 500.degree. F.Appearance afterRamming And Drying at500.degree. F. (Mix Y only) Cut samples from large rammed blocks were essentially lamination free. The brick were submitted for Thermal Conductivity Determination in the "Fast Direction".______________________________________ *Reducing conditions.
After heating at 1500.degree. F., Mix Y had a linear change of -1.2% and a volume change of -3.8%. Table VI illustrates a comparison of the thermal conductivity between mixes H, J, X and Y.
Based upon the test work, it was determined that Mix Y would represent the best candidate for a graphite based high conductivity ramming mix. A sample of the mix was tested, with the evaluation of the test indicating that the mix was commercially satisfactory in all respects, except that it had a relatively high degree of water solubility and required a higher than desired resin curing temperature of 500.degree. F. It was decided to conduct additional testing to develop a high thermal conductivity mix having a high degree of water insolubility and a curing temperature of about 250.degree. F. Mix Y was used as the starting basis for the additional test work.
TABLE VI__________________________________________________________________________Thermal Conductivity on Selected Mixes*Mix Designation:H J X Y YSlow Direction Slow Direction Slow Direction Slow Direction Fast DirectionMean Thermal Mean Thermal Mean Thermal Mean Thermal Mean ThermalTempera- Conduc- Tempera- Conduc- Tempera- Conduc- Tempera- Conduc- Tempera- Conduc-ture (.degree.F.) tivity ture (.degree.F.) tivity ture (.degree.F.) tivity ture (.degree.F.) tivity ture (.degree.F.) tivity__________________________________________________________________________ 323 23.73 323 25.40 311 24.59 306 50.16 311 84.891065 26.03 1050 27.51 1146 26.74 1154 46.0 1165 82.581805 33.98 1792 33.30 1781 38.94 1838 56.66 689 85.941455 31.56 1445 32.07 1426 36.59 1471 56.44 225 88.961089 28.86 1089 30.07 1044 35.05 1088 55.04 720 26.88 717 27.96 660 36.00 699 54.19 243 24.48 249 25.96 224 34.94 236 56.23__________________________________________________________________________ *Argon Atmosphere Btu/Ft.sup.2 -Hr. .degree.F./in.
Table VII illustrates the test work conducted on additional mixes AA-EE. A resorcinol type resin and various powdered phenolic resins were added to the mixes in an attempt to achieve the best water insoluble cure. Water solubility was measured by determining the weight loss of cured samples that were exposed to boiling water for six hours. Initial tests indicated that Mix EE, which contained RL-2302 resin manufactured by Borden Chemical Company (RL-2302 resin was formerly sold as ML-25R resin), showed the best water insolubility (lowest weight loss). RL-2302 resin is a phenolic resin which can be thermoset by the addition of a curing agent. As curing agent either hexamethylenetetramine ("hexa") or stadex were used. The curing agents caused the resin to thermoset at relatively low temperatures at about 250.degree. F. An alcoholic solvent such as ethylene glycol was also used in some instances.
TABLE VII______________________________________ Mix Designation: AA BB CC DD EE______________________________________Mix:Asbury 3166A 50 50 50 50 50Flake GraphiteAsbury FG110 30 30 30 30 30Micronized Flake GraphiteM & D Ball Clay 20 20 20 20 20Plus Additions:RM441 Resin (65% solids) 25 -- -- -- --RL-2304 Resin -- 22 -- -- --SD 5132 Powdered Resin -- -- 10 -- --SD 5144 Powdered Resin -- -- -- 15 --RL-2302 Resin -- -- -- -- 22Ethylene Glycol -- 8 -- -- 12Water -- -- 20 20 --Hexa 1.6 1.4 1.0 -- 1.8Stadex -- -- -- 4.0 --Method of Forming: 1.5" .times. 1.5" Dia Cylinders Were Pressed at 1000 psiBulk Density, pcf After 117 116 107 106 115Pressing at 1000 psi:After Drying 18 109 108 -- -- 108Hrs. at 180.degree. F.After Drying 12 -- 107 -- -- 108Hrs. at 250.degree. F.*Cold Crushing Strength psiAfter Drying18 Hrs. at 180.degree. F.: -- 1190 -- -- 1050After Drying18 Hrs. at 250.degree. F.: -- 1420 -- -- 1370Water Solubility Test, %Weight LossAfter Drying at 180.degree. F. and 6.3 4.2 Dissolved 2.4Boiling 6 Hrs.After Drying at 250.degree. F. and 4.5 2.8 2.5 3.5 2.3Boiling 6 Hrs.______________________________________
Additional tests were conducted as illustrated in Table VIII with newly prepared mixes FF-JJ. These mixes were all made with RL-2302 resin. In these mixes, the amount of Asbury FG micronized graphite was varied in the mix to determine the effect on rammability, pore size, and ultimately, thermal conductivity. A Mercury porosimetry test, conducted on Mixes GG, II and JJ, determined that Mix II had the smallest average pore diameter (5 microns). The thermal conductivity of Mix II was determined perpendicular to the direction of ramming (high thermal conductivity value or "fast" direction) and parallel to the direction of ramming (low thermal conductivity value or "slow" direction).
TABLE VIII______________________________________ Mix Designation: FF GG HH II JJ______________________________________Mix:Asbury 3166A 55 60 65 70 80Flake GraphiteAsbury FG110 25 20 15 10 --Micronized FlakeGraphiteM & D Ball Clay 20 20 20 20 20Plus Additions:RL-2302 Resin 22 22 18 16 14Ethylene Glycol 7 2.5 3 3 2.5Hexa 1.8 1.8 1.8 1.5 1.2Method of Forming: 1.5" .times. 1.5" Dia Cylinders Were Pressed at 100 psiBulk Density, pcfAfter Ramming and -- -- -- 112 98Drying at 250.degree. F.After Pressing at 112 114 116 117 121100 psi:After Drying 18 108 111 112 113 116Hrs. at 180.degree. F.After Drying 18 108 110 112 112 111Hrs. at 250.degree. F.*After Heating -- -- -- 109 --5 Hrs. at 1000.degree. F.Apparent Porosity, % -- 15.6 15.6 17.1 17.0After Ramming andDrying 18 Hrs.at 250.degree. F.Average Pore Dia., -- 8.5 -- 5.0 6.3Microns (MercuryPorosimetry)After Ramming andDrying 18 Hrs. at250.degree. F.Cold CrushingStrength psiAfter Drying 1070 1850 1840 1740 1930at 180.degree. F.After Drying 1550 1920 2160 1800 2720250.degree. F.Linear Change, %After Drying at -- -0.7 -0.2 -0.3 -0.6250.degree. F.After Heating -- -- -- -1.0 --5 Hrs. at 1000.degree. F.,ReducingVolume Change, %After Drying at -- -0.7 -0.2 -0.2 -0.3250.degree. F.After Heating 5 Hrs. -- -- -- -3.0 --at 1000.degree. F., ReducingWater Solubility% Weight LossAfter Drying at 2.1 3.8 4.8 4.9 4.6180.degree. F., andBoiling 6 Hrs.After Drying at 1.3 0.7 0.7 0.6 0.4250.degree. F., andBoiling 6 Hrs.______________________________________
Table IX illustrates the comparative testing conducted on these mixes.
Mix II had the best ramming and compaction properties compared to other mixes. Its degree of water insolubility after curing at 180.degree. F. and 250.degree. F. was improved compared to previously developed mixes. The thermal conductivity of this material was 168.3 Btu/Ft.sup.2 --Hr..degree.F./in. compared to 84.9 Btu/Ft.sup.2 --Hr..degree.F./in. for previously developed Mix Y ("fast" direction). Mix JJ had a thermal conductivity of 69.4 Btu/Ft.sup.2 --Hr..degree.F./in. Mix II had improved thermal conductivity compared to mixes Y and JJ due to better ramming properties, increased rammed density, and smaller average pore size. Mix II therefore achieved the best overall commercial characteristics as a ramming mix for packing around blast furnace cooler plates. Mix II has high conductivity, high cold crushing strength (in excess of 1500 psi after heating at 250.degree. F.), a high degree of water insolubility and good ramming properties.
TABLE IX__________________________________________________________________________Thermal Conductivity (Argon Atmosphere)Mix Designation:Y* Y* II** II** JJ**Fast Direction Slow Direction Fast Direction Slow Direction Fast DirectionMean Thermal Mean Thermal Mean Thermal Mean Thermal Mean ThermalTempera- Conduc- Tempera- Conduc- Tempera- Conduc- Tempera- Conduc- Tempera- Conduc-ture (.degree.F.) tivity ture (.degree.F.) tivity ture (.degree.F.) tivity ture (.degree.F.) tivity ture (.degree.F.) tivity__________________________________________________________________________311 84.9 306 50.2 312 168.3 309 54.2 310 69.41165 82.6 1154 46.0 1201 139.6 1180 50.5 1226 65.5689 85.9 699 54.2 709 143.0 709 53.7 733 69.3225 89.0 236 56.2 258 152.0 244 55.6 242 76.7__________________________________________________________________________ *Test Samples were cured at 500.degree. F. **Test Samples were coked at 1000.degree. F. ***Test Samples were cured at 250.degree. F.
Table X illustrates the Taylor Standard Series screen analysis of Mix II.
TABLE X______________________________________Mix Designation: II______________________________________Screen Analysis% Held on8 mesh10 mesh14 --20 --28 2 235 848 2865 22 58100 10150 -- 10200 2270 --325 -- 2Minus 325 mesh 28 28______________________________________
While the preferred embodiment of the present invention has been described and illustrated, the invention should not be limited thereto, but may be otherwise embodied within the scope of the following claims.

Number	Name	Date
3303031	Shields	Feb 1967
3637412	Felice et al.	Jan 1972
3954695	Cleland	May 1976
4083716	Yoshida	Apr 1978
4108675	Tomita et al.	Aug 1978
4296793	Yasinsky et al.	Oct 1981

Monolithic refractory composition

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