CA1208018A

CA1208018A - Method and apparatus for producing a dried coal fuel having a reduced tendency to spontaneously ignite from a low rank coal

Info

Publication number: CA1208018A
Application number: CA000492918A
Authority: CA
Inventors: Donald K. Wunderlich
Original assignee: Atlantic Richfield Co
Current assignee: Atlantic Richfield Co
Priority date: 1981-12-21
Filing date: 1985-10-11
Publication date: 1986-07-22
Also published as: CA1208435A; AU6782987A; AU6783287A; AU578553B2; AU573470B2

Abstract

ABSTRACT

A method and apparatus for producing a dried particulate coal fuel having a reduced tendency to spon-taneously ignite from particulate low rank coal. Features of the apparatus include coal-deactivating fluid contact-ing apparatus and dried coal oxidation appartus A method for deactivating partially dried coal by oxidation is also disclosed.

Description

:~08~

METHOD AND APPARATUS FOR PRODUCING A DRIED COAL FUEL HAVING A
REDUCED TENDENCY TO SPONTANEOUSLY IGNITE FROM A LOW RP~K COAL

'rhis invention relates to methods and apparatus for producing a dried particulate coal fuel having a reduced tendency to spontaneously ignite from a particulate low rank coal.
In many instances, coal as mined contains undesirably high quantities of water for transportation and use as a fuel.
This problem is common to all coals, although in higher grade coals, such as anthracite and bituminous coals, the probIem is less severe because the water content of the coal is normally - lower and the heating value of such coals is higher. The situation is different with respect to lower grade coals such as sub-bituminous, lignite and brown coals. Such coals, as produced, typically contain from about 25 to about 65 weight percent water.
While many such coals are desirable as fuels because of their relatively low mining cost and since many such coals have a relatively low sulfur content, the use of such lower grade coals as fuel has been greatly inhibited by the fact that as produced, they typically contain a relatively high percentage of water.
Attempts to dry such coals for use as a fuel have been inhibited by the tendency of such coals after drying to undergo spontaneous ignition and combustion in storage, transit or the like.
The drying required with such low rank coals is a deep drying process for the removal of surface water plus the large quantities of interstitial water present in such low rank coals. By contrast, when higher grade coals are dried, the drying is commonly for the purpose of dr~ing the surface water from the coal particle surfaces but not interstitial water, since the interstitial water content of the higher rank coals is relatively low. As a result, short residence times in the drying zone are normally used, and the interior portions of the coal particles are not heated, since such is not necessary for surface drying. Typically, the coal leaving the 9l5~

dryer in such surEace water drying processes is at a tempera-ture below about 110F. (45 C.). sy contrast, processes for the removal of interstitial water require longer residence times and result in heating the interior portions of the coal particles. The coal leaving a drying process for the removal of interstitial water will typically be at a tempera-ture from about 130 to about 250 F (54 -to 121 C~). When such processes for the removal of interstitial water are applied to low rank coals, the resulting dried coal has a strong tendency to spontaneously ignite especially at the high discharge temperatures, upon storage, during transpor-tation and the like.
As a result, a continuing effort has been directed to the development of improved methods whereby such lower grade coals can be dried and thereafter safely transported, stored and used as fuels. In accordance with copending Canadian Patent Application No. 429,071 filed May 27, 1983, such coals may be dried to produce a stable, storable dried coal product by a method comprising:
a. charging particulate low rank coal to a coal drying zone;
b. contacting the particulate low rank coal with a hot gas in the coal drying zone to produce a dried coali c. recovering -the dried coal from the coal drying zone;
d. charging the dried coal to a coal cooling zone;
and e. cooling the dried coal in the coal cooling zone to a temperature below about 100 F. (38 C.) to produce a 30 cooled, dried coal.
In some instances, such cooled, dried coals may still have a tendency to spontaneously ignite, even though '~ZO~

the tendency to spontaneously ignite has been reduced by cool-ing the dried coal. In accordance with the presen-t invention, the tendency of the dried coal to spontaneously ignite is further reduced by a controlled oxidation step. In such instances, it is desirable to adjust the water content of the dried coal to a value somewhat greater than that desired in the dried oxidized coal product so that a portion of the drying may be accomplished in the oxidation zone. The controlled oxidation i,s readily accomplished in an apparatus and method as set forth more particularly hereinafter.
The dried and oxidized coal product can be further deactivated by contacting the particulate coal product with a suitable deactivating fluid to further reduce the tendency of the dried coal to spontaneously ignite.
One such deactiva-ting fluid comprises a special de-activating oil composition having in combination four charac--teristics. The special oil comprises a virgin vacuum reduced crude oil having a minimum characterization factor of l0.8, a minimum flash point of 400F., and a 5~ point above 900F.
The dried coal particles may also be deactivated with a water-base dispersion or emulsion of latex paint type solids.
The dried coal is r~adily contacted with deactivating fluid in the apparatus more fully described hereinafter.
Figure l is a schematic diagram of a coal drying system;
Figure 2 is a schematic diagram of a system embody-ing the method of the present invention;
Figure 3 is a schematic diagram of an oxidizer vessel suitable for use in the practice of the method of the present invention;

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Figure 4 is a schematic diagram of an apparatus suitable for use in intimately contacting particulate coal and a deacti-vating fluid; and, Figure 5 is a schematic diagram of a further embodiment of an apparatus suitable for use in contacting particulate coal and a deactivating fluid.
In the description of the Figures, the same numbers will be used to refer to the same or similar components throughout.
Further, it should be noted that in the description of the Figures, reference will be made to lines generally rather than attempting to distinguish between lines as conduits, conveyors or the like as required for the handling of particulate solid materials.
In Figure 1, a run of mine coal stream is charged through a line 12 to a coal cleaning or preparation plant 10 from which a coal stream is recovered through a line 14 with a waste stream comprising gangues and the like being recovered and passed to discharge through a line 11. In some instances, it may not be necessary to pass the run of mine coal to a coal cleaning or processing plant prior to charging it to the process of the present invention, although in many instances, such may be desir-able. The coal stream recovered from preparation plant 10 through line 14 is passed to a crusher 16 where it is crushed to a suit-able size and passed through a line 18 to a hopper 20. While a size consist less than about two inches, i.e. two inches by zero may be suitable in some instances, typically a size consist of about one inch by zero or about three-quarters inch by zero will be found more suitable. The particulate coal in hopper 20 is fed through a line 22 into a dryer 24. In dryer 24, the coal moves across dryer 24 above a grate 26 at a rate determined by the desired residence time in dryer 24. A hot gas is passed _~_ upwardly through the coal moving across grate 26 to dry the coal. The hot gas is produced in Figure 1 by injecting air through a line 30 to combust a stream of coal fines injected through a line 34. The co~bustion of the coal fines generates hot gas at a temperature suitable for drying the coal. As will be obvious to those skilled in the art, the temperature can be varied by diluting the air or the hot gas with a non-combustible gas such as the exhaust gas from the dryer, by the use of alternate fuels, by the use of oxygen enriched streams or the like. Clearly, alternate fuels, i.e. liquid or gaseous fuels could be used instead of or in addition to the finely divided coal, although it is contemplated that in most instances, a stream of finely divided coal will be found most suitable for use as a fuel to produce the heated gas. Ash is recovered from dryer 24 through a line 36. In Figure 1, a combustion zone 28 is provided beneath grate 26 to permit the proauction of the hot gas in dryer 24, although it will be readily understood that the hot gas could be produced outside dryer 24 or the like. The exhaust gas from dryer 24 is passed to a cyclone 40 where finely divided solids, typically larger than about 100 Tyler mesh, are separated from the exhaust gas and recovered through a line 44. The exhaust gas, which may still contain solids smaller than about lOO Tyler mesh, is passed through a line ~2 to a fine solids recovery section 46 where finely divided solids, which will typically consist primarily of finely divided coal are recovered through line 34 with all or a portion of the finely divided coal being recycled back to combustion zone 28. The purified exhaust gas from fine solids recovery section 46 is passed through a line 48 to a gas cleanup section 50 where sulfur compounds, light hydro-carbon compounds, and the like are removed from the exhaust gasin line 48, as necessary to produce a flue gas which can be :120~

discharged to the atmosphere. The purified gas is dis,charged via a line 51 with the contaminates recovered from the exhaust gas being recovered through a line 76 and optionally passed to a flare, a wet scrubber or the like. The handling of the process gas discharge is not considered to constitute a part of the pre-sent invention, and the cleanup of this gaseous stream will not be discussed further. The fine coal stream recovered through line 34 may in some instances constitute more coal fines than are usable in cornbustion zone 28. In such instances, a fine coal product can be recovered through a line 54. In other instances, the amount of coal fines recovered may not be sufficient to provide the desired temperature in the hot gas used in dryer 24.
In such instances, additional coal fines may be added through a line 52.
The dried coal product recovered from dryer 24 is recovered via a line 38 and combined with the solids recovered from cyclone 40 through line 44 and passed to a hopper 116 ~rom which dried coal is ~ed via a line 78 to a cooler 80. In cooler ~0, the dried coal moves across cooler 80 above a grate 82. A
cool gas is introduced through a line 86 into a distribution chamber 84 beneath grate 82 and passed upwardly through the dried coal to cool the dried coal. The exhaust gas from cooler 80 is passed to a cyclone 90 where solids generally larger than about 100 Tyler mesh are separated and recovered through a line 94 with the exhaust gas being passed through a li,ne 92 to fine solids recovery section 46. ~ptionally, the gas recovered through line 92 could be passed to combustion chamber 28 for use in producing the hot gas required in dryer 24. The cooled dried coal is recovered through a line 96 and combined with the solids recovered from cyclone 90 to produce a dried coal product. The tendency of such dried low rank coals to spontaneously ignite is ~;ZO8~

inhibited greatly by cooling such coals after drying. In some instances, no further treatment may be necessary to produce a dried coal product which does not have an undue tendency to spontaneously ignite upon transportation and storage. In other instances, it will be necessary to treat the dried coal product further. In such instances, the dried coal product may be coated with a suitable deactivating fluid in a mixing zone 100. The deactivating 1uid is introduced through a line 102 and intimately mixed with the cooled dried coal in mixing zone 100 to produce a coal product, recovered through a line 104, which has a reduced tendency to spontaneously ignite under normal storage and trans-portation conditions. While the dried coal is mixed with deacti-vating fluid a~ter cooling in Figure 1, it should be understood that the dried coal can be mixed with the deactivating fluid at higher temperatures before cooling although it is believed that normally the mixing is preferably at temperature no higher than about 200 F. (93 C.).
While cool gas alone may be used in cooler 80, an improvement is accomplished by the use of water injection in cooler 80. The water is added through a line 106 and a spray system 108 immediately prior to passing the dried coal into cooler 80 or through a spray system 110 which adds the water to the dried coal immediately after injecting the coal into cooler 80. Either or both types of systems may be used. In any event, it is highly desirable that the water be sprayed uni~ormly over the coal surface. An important limitation, however, is that the amount of water added is only that amount required to achieve the desired cooling of the dried coal by evaporation. The water is very finely sprayed onto the coal, and is controlled to an amount such that the added water is substantially completely evaporated from the coal prior to discharge of the cooled dried 12~80~L~

coal via line ~6. In many areas of the country, relatively dry air is available for use in such cooling applications. For instance, in Wyoming, a typical summer air condition is about 90 F. (32~ C.) dry bulb and about 65 F. (18 C.) wet bulb tem-perature. Such air is very suitable for use in the cooler as described. While substantially any cooling gas could be used, the gas used will normally be air. Air is injected in an amount suffi-cient to fluidize or semi-fluidize the dried coal moving along grate 82 and in an amount sufficient to prevent the leaking of water through grate 82. The flow is further controlled to a level such that the velocity above the coal on grate 82 is insufficient to entrain any liquid water in the exhaust stream flowing to cyclone 90. Desirably, the air flow is at a rate such that the air leaving the cooler is no more than about 85 percent saturated with water. A preferred range is from about 50 to about 85 percent saturation. Such determinations are readily within the skill of those in the art and need not be discussed in detail since the flow rates will vary depending upon the amount of cooling required.
In a further variation, the water may, in some instances, be introduced as a fine mist beneath grate 82 via a spray system 109 and carried into the coal rnoving along grate 82 with the cooling gas or sprayed directly into the coal via a spray system 111. In such instances, similar considerations apply~ and only that amount of water is added which is required to accomplish the desired temperature reduction in the coal on grate 82. The use of water as set forth above results in a reduced horsepower requirement for the blowers (not shown~ for cooler 80 and in a reduced air flow. The use of water as set forth herein would at first appear undesirable and impractical since the coal has just been dried, and it would appear to be an exercise in futility to --8~

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reapply water to the dried coal. Surprisingly, it has been found that the use of relatively small amounts of water as required for the evaporative cooling does not result in the retention of the water in the coal, but rather the water is readily removed by evaporation with the net result being a cooling of the coal particles without the absorption of any substantial portion of the water added in cooler 80. While Applicant does not wish to be bound by any particular theory, it appears that when water contacting for short times is used, the water does not diffuse back into the coal, but rather is readily evaporated to cool the surface. Accordingly, the use of the improvement of the present invention, i.e., the addition of water to the dried coal in cooler 80, has resulted in a substantial reduction in t~e volume of air required and an increase in the efficiency of operation of cooler 80. Such volume reductions result in substantial reductions in the power requirements to cooler 800 In some instances, the power requirements could be reduced by up to 50 percent of the power required for drying with air alone. Lower temperatures in the cooled coal can be achieved in a given cooling zone where the air volumes are limited by use of evaporative cooling. Typical residence times in cooler B0 may be of the order of two minutes, and it is highly desirable that the water be applied in the first one minute of residence time in cooler 80, so that the water may be substantially completely evaporated before discharging the dried coal product through line 96.
Typically, amounts of water from about 0.3 to about 0.8 lbs. of water per ton of dried coal per ~ F of desired tem-perature reduction are suitable.
Example: 150 tons per hour of hot (200 F.) dried coal (5 weight percent water) is to be cooled to 90 Fo (32 C.) using direct evaporative cooling. Ambient air at 80 F. (26. 5b C . ) _9_ ::LZ~8~

and 30% relative humidity is available, and water is available at 80 F. (26.5~ C.) The water is sprayed onto the coal, and air is passed upwardly through the coal. Air is used at the rate of 600,000 lbs. of air per hour and water is sprayed onto the dried coal at the rate of 8,023 lbs. per hour. The resulting exhaust stream is at 90 F. (32 C.) and is 68~ saturated with water.
The coal is cooled to 90 F. (32 C.). A residence time of two minutes is suitable. When a slotted grate conveyer is used, a pressure drop of 12 inches of water across the grate is considered suitable. At this pressure drop, the flcw rate through the slots is desirably about 300 feet per second to achieve the desired pressure drop and prevent the passage of water throuqh the slots. In the example given, the slot area required is 8.7 ft.2. A bed depth of 4 ft. is used in the example, and it is assumed that the bed is 50% expanded or fluidized.
The area in the exhaust zone in cooler 80 above the cooler grate may need to be larger than grate `32 in some instances to prevent the entrainment of water in the exhaust gas.
In the operation of dryer 24, the discharge temperature of the dried coal is typically from about 130 to about 250 F.
(54 to 121 C.) and is preferably from about 190 to about 220 F.
(88 to 104 C.). The hot gas is passed upwardly through the coal on grate 26 at a suitable rate to maintain the coal in a fluidized or semi-fluidized condition above grate 26. The residence time is chosen to accomplish the desired amount of drying and is readily determined experimentally by those skilled in the art based upon the particular type of coal used and the like. For instance, when drying sub-bituminous coal, an initial water con-tent of about 30 weight percent is common. Desirably, such coals are dried to a water content of less than about 15 weight percent and preferably from about S to about 10 weight percent. Lignite ~10-~2~

coals often contain in the vicinity of about 40 weight percent water and are desirably dried to less than about 20 weight percent water with a range from about 5 to about 20 weight percent water being preferred. Brown coals may contain as much as, or in some instances even more than about 65 weight percent water. In many instances, it may be necessary to treat such brown coals by other physical separation processes to remove portions of the water before drying is attempted. In any event, these coals are desirably dried to a water content of less than about 30 weight percent and preferably to about 5 to about 20 weight percent. The determination of the residence time for such coals in dryer 24 may be determined experimentally by those skilled in the art for each particular coal. The determination of a suitable residence time is dependent upon many variables and will not be discussed in detail.
The water contents referred to herein are determined by ASTM D3173-73 entitled "Standard Test Method for Moisture in the Analysis Sample of Coal and Coke", published in the 1978 Annual Book of ASTM Standards, Part 26.
The discharge temperature of the dried coal from dryer 24 is readily controlled by varying the amount of coal fines and air injected into dryer 24 so that the resulting hot gaseous mixture after combustion is at the desired temperature. Ternpera-tures beneath grate 26 should be controlled to avoid initiating spontaneous combustion of the coal on grate 26. Suitable temper-atures for many coals are from about 250 to about 950 F. (104 to 570 C.).
In the operation of cooler 80 as discussed above, the temperature of the dried coal charged to cooler 80 in the the process shown in Figure 1 is typically that of the dried coal discharged from dryer 24 less process heat losses. The temper-ature of the dried coal is desirably reduced in cooler 80 to a ~2~0~

temperature below about 100 F. (38 C.) and preferably below about 80 F. (27 C.). The cool gas is passed upwardly through the coal on grate 82 at a suitable rate to maintain the coal in a fluidized or semi-fluidized condition above grate 82. The residence time, amount of cooling air, cooling water and the like may be determined experimentally by those skilled in the art. Such determinations are dependent upon the amount of cooling required and the like. As well known to those skilled in the art, after drying, lower rank coals are very susceptible to spontaneous ignition and combustion upon storage, in transit or the like.
While such is the case, it is highly desirable that such coals be available for use more widely than is possible at the present.
The high moisture content of these fuels results in excessive shipping costs, due at least in large measure to the excessive amount of water which is subject to freight charges and similarly results in lower heating values for the coals since a substantial portion of the coal is water rather than combustible carbonaceous material. The lower heating value results in a limited use for the coals since many furnaces are not adapted to burn such lower heating value coals. By contrast, when the water content is reduced, the heating value is raised since a much larger portion of the coal then comprises combustible carbonaceous material.
As a result, it is highly desirable that such coals be dried prior to shipment.
In many instances, it has been found that cooling such dried coals to a temperature below about 100~ F. (38 C.), and preferably below about 80 F. (27 C.), is sufficient to inhibit spontaneous ignition of tlle dried coal. Not all dried low rank coals will be found to be sufficiently non-reactive to permit storage and transportation without further treatment after cooling, but in many instances, such dried low rank coals are ~o~

sufficiently non-reactive after cooling that spontaneous ignition is avoided. It has been observed that spontaneous ignition of such dried low rank coals is further inhibited by the use of a suitable deactivating fluid to further reduce the tendency of the dried coal to spontaneously ignite as discussed more fully hereinafter. The deactivating fluid is desirably applied by intimately mixing it with the dried coal to pro-duce a dried coal product having a reduced tendency toward spontaneous combustion. The use of the deactiva-ting fluid also reduces the dusting tendencies of the dried coal.
In accordance with this invention, the tendency of the dried coal to spontaneously ignite is reduced by the use of a controlled oxidation step after the coal drying operation and prior to cooling the dried coal. Such a variation is shown in Figure 2 where the dried coal is passed through line 38 to a coal oxidizer vessel 60. The dried coal is charged to oxidizer 60 and passes downwardly through oxidizer 60 from its upper end 62 to its lower end 64 at a rate controlled to obtain the desired residence time. The flow of dried coal downwardly through oxidizer 60 is controlled by a grate 66 which supports the coal in oxidizer 60 and accomplishes the removal of controlled amounts of dried oxidized coal through line 78. A free-oxygen containing gas such as air is in~ected into oxidizer 60 through a line 68 and an air distribu-tion system 70 as shown more fully in Figure 3. Air distribution system 70 comprises a plurality of lines 122 having suitable openings (not shown) positioned along their length for the discharge of air into oxidizer 60 with lines 122 being posi-tioned beneath shields 120. Shields 120 serve to prevent clogging of the air discharge openings in lines 122 and to prevent damage to lines 122 by the downcoming coal. Spaces 124 between shields 120 are provided for the passage of coal between shields 120 and spaces 124 are typically sized to be at least three times the diameter of the largest coal particles expected in width. Oxidizer 60 also includes a coal distribution system 112 which may be of a variety of configurations known to those skilled in the art for the uniform distribution of parti-culate solids. Exhaust gases are recovered from oxidizer 60 through a line 72 and as shown in Figure 2 passed to gas cleanup section ~0 for processing prior to discharge. Grate 66 may be of a variety of configurations known to those skilled in the art for supporting and removing controlled amounts of a parti-culate solids stream passing downwardly through a reaction zone to result in uniform downward movement of particulate solids through the reaction zone.
The grate shown in Figure 3 comprises retarder plates 121 positioned across the bottom of oxidizer 60 and pusher bars 123 to remove desired quantities of dried oxidized coal while supporting dried coal in oxidizer 60. Diverter plates are,shown as shields 120 for air injection lines 122. A star feeder or the like 125 is included in line 78 to prevent the flow of air through line 78 as the dried oxidized coal is withdrawn. In the operation of grate 66, coal is pushed off retarder plates 121 by movement of pusher bars 123 which are moved reciprocally to push desired quantities of coal off retarder plates 121. Air could be injected at a higher point in oxidizer 60 or at a plurality of points, but it is presently preferred that substantially all the air be injected near the bottom of oxidizer 60.
The oxidization of the dried coal in oxidizer 60 results in a further reduction in the tendency of the dried coal to spon-taneously ignite. The dried oxidized coal is cooled in cooler 80 as described in conjunction with Figure 1 and may be usable as a stable product without the need for mixing with a deactivating fluid.

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In the oxidation of the dried coal in oxidizer 60, a continuing problem is the tendency for the coal to become progres-sively hotter as it oxidizes. Such is undesirable since the higher temperatures are not required for deactivation of the coal and increase the load on the cooler and result in the consumption of more of the coal product in oxidizer 60. From about 6 to about 25 lbs. of oxygen per ton of dried coal may be used although a preferred range is from about 6 to about 15 lbs. of oxygen per ton of coal. The use of such amounts of oxygen results in the liberation of substantial quantities of heat. To maintain tem-perature stability in oxidizer 60, it has been found desirable to restrict the drying in dryer 24 to somewhat less than is desired in the final dried coal product. In other words, less drying is accomplished in dryer 24 than is desired in the dried oxidized coal product. In many instances, it will be desirable to leave from about 1 to about 5 weight percent water (based on the weight of the coal) above that amount of water desired in the final dried oxidized product in the dried coal stream when it is to be oxidized. The presence of the additional water results in cooling the dried coal during oxidization by evaporation of the water. The amount of water left in contemplation of the oxidation oxidization step is desirably the amount required to remove the heat generated by the desired oxidization by evaporation. In most instances, it will be found desirable to leave from about 1 to about 3 weight percent water above that amount required in the dried product in the dried coal stream passed to oxidizer 60 when from 6 to about 15 lbs. of oxygen per ton of coal is used.
Suitable coal outlet temperatures from oxidizer 60 are from about 175 to about 225 F. (80 to 107 C.). Desirably the net temperature increase in the coal temperature in oxidizer 60 is small. ~hile higher temperatures may occur locally in oxidizer 60, it is preferred that the coal discharge temperature be from ~zo~

akout 175 to about 225 F. (80 to 107 C.). The coal inlet temperature can vary but it is expected that in many instances the dried coal will be charged to the oxidizer at temperatures near the discharge temperature.
It will be noted by reference to the amounts of water to be removed by evaporation in the oxidation vessel that the desired amount of drying is much less than required to produce a dried low rank coal product. Accordingly, the controlled oxida-tion step is not suited to function as the primary drying step, but rather is suitably used following a coal drying step. The reactivity of the dried coal is then suitable for deactivation by the controlled oxidation step and the major portion of the water has been removed.
The aried oxidized product recovered from cooler 80 in many instances will be usable as a dried coal product as recovered.
In other instances, it may be desirable that a suitable deactivating fluid be mixed with the dried o~idized coal product either before or after cooling the dried oxidized coal to produce a stable storable fuel.
The intimate mixing of the dried coal and deactivating fluid is readily accomplished in a vessel such as shown in Figure 4. In Figure 4, the dried coal product or oxidized dried coal is charged to a contacting vessel 140 through a line 146 with the contacted coal being recovered through a line or discharge 148.
In contact vessel 140, the deactivating fluid is maintained as a finely divided mist by spraying the deactivating fluid into vessel 140 through spray mist injection means 150 which, as shown in Figure 4, are nozzles 152. Clearly, vessel 140 can be of a variety of configurations, and any reasonable number of mist nozzles 152 can be used. It is, however, necessary that the residence time between the upper end 142 of contacting vessel 140 and the lower end 144 of vessel 140 be sufficient that the lZV~ L8 coal is intimately contacted with the deactivating fluid as it passes through vessel 140. Deactivating fluid is injected into vessel 140 through lines 158 which supply nozzles 152. Optionally a diverter 143 may be positioned to disrupt the flow of the coal to facilitate contact with the deactivating fluid.
A further embodiment of a suitable contacting vessel is shown in Figure 5. The contacting vessel shown in Figure 5 is positioned on a storage hopper 162 and includes on its inner walls a plurality of projections 154, which serve to break up the smooth fall of particulate coal solids through vessel 140 thereby facili-tating intimate contact of the particulate solids with the deacti-vating fluid mist present in vessel 140. Projections 154 may be of substantially any effective shape or size. Mist injection means 150 as shown in Figure 5 comprise tubes 156 positloned beneath projections 154. Tubes 156 include a plurality of mist injection nozzles 152. Mist injection nozzles 152 could also be positioned i~ the walls of vessel 140. Further, a deflector 160 is provided near lower end 144 of vessel 140 to further deflect the stream of particulate coal solids as they are discharged from vessel 140.
A tube 156 including mist nozzles 152 is positioned beneath deflector 160.
In the operation of the vessels shown in Figures 4 and 5, a particulate coal stream is introduced into the upper portion of the vessels 140 and passes downwardly through vessel 140 by gravity flow i~ continuous contact with a finely divided mist of a suitable deactivating fluid. The residence time is highly variable depending upon the size of the stream passed through vessel 140 the presence or absence of projections in vessel 140 and the like.
The contact time and amount of mist are adjusted to obtain a de-sired quantity of deactivating fluid in intimate mixture with the coal. Desirably, the coal is charged to the mist zone at a temper-ature from about 70 to about 110 F. ~about 20 to about 45 C.).

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A special deactivating oil composition which is effec-tive as a deactivating fluid is a virgin vacuum reduced crude with a 5% point above 900 F. (485 C.), a characterization factor of 10.8 or greater, and a minimum flash point of 400 F. (205 C.).
The term flash point is well known and will not be further described.
It is important to note that the special deactivating oil composition is obtained by vacuum reducing virgin crude oil under conditions such that the five percent point is above 900 F.
Virgin crude oil is an oil or oil cut as produced from a petroleum reservoir and that has not been subjected to any appreciable thermal treatment that would produce cracked material.
The special oil composition is obtained by vacuum reduction of crude oil under conditions such that the five percent point is above 900 F. as determined from test values obtained on virgin crude oil in accord with the procedures described in ~STM
D1160-77, entitled "Standard Method for Distillation of Petroleum Products at Reduced Pressures", published in the 1978 Annual Book of ASTM Standards, Part 23. For example, crude oils were vacuum reduced at different cut points ranging between 600 F. and 1000 F.
and then applied to dried coal. The oxidation rate constants before and after applying the reduced oil were measured. In general, it was foun~ that at 600 F., the degree of deactivation was unsuitable, and that at 800 F., the degree of deactivation was only marginally successful at best; but that at 1000 F., the oil was fully satisfactory.
The characterization factor is a special physical pro-perty of hyarocarbons defined by the relationship:
K Tb G
where ~ = Characterization factor.
Tb = Cubic averaye boiling point R.
G = Specific gravity 60 F./60 F.
R = F. ~ ~60.
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The cubic average boiling point is determined in accor-dance with the calculations mentioned in an article entitled "Boiling Points and Critical Properties of Hydrocarbon Mixtures", by R. L. Smlth and K. M. Watson, appearing in Industrial and Engineering Chemistry, Volume 29, pages 1408-1414, December 1937, and using the ten, thirty, fifty, seventy, and ninety percent points ~F. as measured by the procedures of ASTM-D1160-77, pre-viously described or ASTM D86 entitled "Standard Method for Distillation of Petroleum Products", published in the 1978 Annual Book of ASTM Standards, Part 23. ASTM D86 is for products which decompose when distilled at atmospheric pressure.
A difference of a few tenths in characterization factor may seem small, but this ~actor is readily determined to an accuracy of 0.1 and it can be used and interpreted with considerable confidence and reliability. This factor is useful in identifying hydrocarbons. For example, materials wih a characterization factor of 9.5 are pure polynuclear aromatics called PNS which are highly carcinogenic substances. On the other end of the scale, - materials with a characterization factor of 13 are pure paraffins like innocuous vaseline. The characterization factor correlates well with many other physical properties of an oil, such as molecular weight, viscosity, therma] expansion, specific heat, critical properties, heat of combustion, and the like.
Accordingly, in the use of the special oil, sometime after the dried coal particles are removed from dryer 24, the coal particles are contacted with the special deactivating oil composition previously described. The special oil composition may be used in any suitable quantity; but between 0.5 to 4.0 gallons of special oil per 2000 pounds of dried coal will usually be adequate. Additional quantities of the special oil may be used if required for dust control.

The intimate mixing of the dried coal and deactivating oil is readily accomplished in a vessel such as shown in Figures 4 and 5.
Other suitable materials for use as deactivating fluids are water-base dispersions or emulsions of latex paint type solids.
After the dried coal particles are removed from dryer 24, the coal particles are contacted with the deactivating fluid.
The deactivating fluid may be sprayed on the particles before, during or after the hot coal solids are cooled. This deactivating fluid is an elastic film forming water-base dispersion comprised of finely divided or milled latex paint type solids dispersed or emulsified with water. This includes emulsion polyrnerization.
Surfactants, proteckive colloids and similar paint additives may be added to help spread and stabilize the solids and to increase the adherence of the solids. It appears that dispersions with concentrations as low as 0.25% by weight of latex paint type solids will be successful. The rnaximum concentration will depend on costs; but it is believed that the maximum concentration will not exceed 60~ by weight of latex paint type solids. The disper-sion may be used in any suitable quantity, but tests indicate that quantities between 0.5 to 2.0 gallons of dispersion per 2000 pounds of dried coal will usually be adequate. Suitable solids are vinyl acetate, polyvinyl chloride, vinyl acetate/acrylic copolymers, styrene-butadiene, acrylic latex or resins, natural gums or resins, tall oil, neoprene, rubber and polyesters. If the quantity of solids in relation to the coal is significant, halogen containing solids wiIl not be used, but for the most part, the arnount of solids is practically negligible in comparison to the weight of the dried coal.

The latex paint type solids form an elastic film on the dried coal particles and thereby reduce its tendency to sponta-neously ignite. The dispersion or emulsion is easy to apply at ordinary temperatures, and is relatively nonflammable and non-toxic, and has very little unpleasant odox. The dispersion is readily formed on site from dry or concentrated chemicals, thereby reducing shipping, storing and handling costs.
The intimate mixing of the dried coal and deactivating fluid is readily accomplished in vessels such as shown in Figures 4 and 5.
In the practice of the method of the present invention as shown in Figures l and 2, it may be desirable in some instances that an oxidation step be used, whereas with other coal feed stocks, such a step may not be necessary. In general, it is believed that it will be necessary to cool all low rank coals to produce a desirable dried coal fuel which is not undesirably susceptible to spontaneous ignition. In many instances, it may be necessary to do no more than dry the coal and cool the re-sulting dried coal to produce a stable fuel. In other instances, it may be necessary to use a deactivating fluid with the dried coal. In still other instances with more reactive coal, it may be necessary to use drying in combination with oxidation, cooling and/or a deactivating fluid. The selection of the particular process will be dependent to a large extent upon the particular coal feed stock used. Another variable which may affect the choice of the process for a particular low rank coal is the risk involved upon spontaneous ignitionO For instance, it may be desirable to over-treat dried coal products which are to be shipped by sea or the like in view of the substantially greater risk of damage upon spontaneous ignition than would be the case for coals which are to be stacked near a coal~consuming facility.

lZC~

A multitude of considerations will affect the particular process chosen; however, it is believed that the particular combination of steps set forth will be found effective in the treatment of substantially any low rank coal to produce a dried fuel product which has a reduced tendency toward spontaneous ignition.
Having thus described the present invention by reference to certain of its preferred embodiments, it is respectfully pointed out that the embodiments discussed are illustrative rather than limiting in nature, and that many variations and modifications O are possible within the scope of the present invention. Many such variations and modifications may be considered obvious and desirable based upon a review of the foregoing description of preferred embodimentsO
Having thus described the invention, we claim:

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. An apparatus for partially oxidizing a dried par-ticulate low rank coal to reduce the tendency of said dried particulate low rank coal to spontaneously ignite, said apparatus comprising:
a. an oxidizer vessel, having an upper and a lower end;
b. a particulate coal inlet in said upper end of said oxidizer vessel;
c. a distributor means positioned in said vessel to distribute said particulate coal from said particulate coal inlet uniformly in said vessel;
d. a grate means positioned in said lower end of said vessel for supporting said particulate coal in said vessel;
and removing controlled quantities of oxidized particulate coal from said lower end of said vessel so that said particulate coal moves relatively uniformly downwardly through said oxidizer vessel;
f. an air inlet means positioned in said lower end of said vessel for the injection of air into said particulate coal; and, g. an air outlet means positioned in said upper end of said vessel.

2. The apparatus of Claim 1 wherein said air inlet means comprises a plurality of tubular members having a plurality of air discharge openings, positioned to discharge air into said lower end of said oxidizer vessel.

3. The apparatus of Claim 2 wherein said tubular members are positioned beneath shield members to protect said tubular members from contact with said particulate coal.

4. The apparatus of Claim 3 wherein the spacing be-tween said shield members is at least three times the average diameter of the largest coal particles to be charged to said vessel.

5. A method for partially oxidizing a particulate low rank coal selected from the group consisting of sub-bituminous, lignite and brown coals to reduce the tendency of said particulate low rank coal to spontaneously ignite, said method consisting essentially of:
a. drying said particulate low rank coal to a water content from about 1 to about 5 weight percent greater than the water content desired" in the dried oxidized low rank coal to produce a partially dried coal;
b. charging said partially dried coal to a coal oxidation zone;
c. contacting said partially dried coal with a free-oxygen contaning gas in said coal oxidation zone at a temperature from about 80 to about 107°C. for a time sufficient to result in the reaction of from about 6 to about 25 lbs. of oxygen per ton of partially dried coal with said partially dried coal to produce 2 dried, oxidized coal; and, d. recovering said dried oxidized coal.

6. The method of Claim 5 wherein from about 6 to about 15 lbs. of oxygen per ton of partially dried coal are reacted with said partially dried coal.