AU605302B2 - Process for inhibiting the spontaneous oxidation of low rank coal - Google Patents

Description

1B OR 102 FORM N.44245 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-1973 COMPLETE SPECIFICATION (original) FOR OFFICE USE: Class Int. Class 4

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Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: S- Lt~,d iS L'j. s fl I :Related Art:

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S5 OSO S Name of Applicant(s): Address of Applicant(s): SHELL OIL COMPANY 900 Louisiana Street Houston Texas 77002 USA MARK ALAN SIDDOWAY, NEAL DON STIDHAM and WILLIAM CARL MACHMER Davies Collinson 1 Little Collins Street Melbourne Victoria 3000 Australia Actual Inventor(s): Address for Service: Complete Specification for the invention entitled: "PROCESS FOR INHIBITING THE SPONTANEOUS OXIDATION OF LOW RANK COAL" The following statement is a full description of this invention, including the best method of performing it known to us:- 1 la The present invention relates to a process for inhibiting the spontaneous ignition of low rank coals wherein the coal is dried while being oxidized and cooled in order to increase its stability.

Numerous treatments have been designed for oxidizing coal to reduce its content of sulphur and ash. For example, US-A-3,909,211 describes heating coal at 38 to 260 0

C

(100-500 0 F) with a gas comprising NO 2 US-A- 4,022,588 describes reacting coal with specified metal oxides and then 10 washing or extracting the treated coal. US-A-4,097,244 and US-A-4,105,416 describe treating coal with an aqueous solution containing an iron complexing agent and a metal f oxidant and reacting the so-treated coal with a hydrogen donor. US-A-4,183,730 describes reacting coal with an 0 15 aqueous solution of hydrogen peroxide and sodium chloride and then washing the treated coal. U.S.A. 4,256,464 describes contacting coal with a liquid organic solvent for nitrogen oxides and then reacting it with gas containing oxygen and nitric oxide. US-A-4,328,002 describes treating coal with an aqueous oxidizing agent, washing it, reacting it with oxygen to an extent causing an exothermic temperature peak, then washing and drying the treated coal.

Oxidative processes have also been proposed to reduce the molecular weight of the coal and/or render parts of the coal soluble in organic solvents. US-A-2,242,822 and 2 US-A-2,338,634 relate to oxidizing coal, first with air, then with nitric acid, in order to generate hydroxycarhoxylic acid groups that cause the non-fusain organic materials to become soluble in organic solvents containing heterocyclic oxygen, with ammonium nitrate or other oxides being used as catalysts in the oxidizing step.

There are several known methods for inhibiting spontaneous ignition of low rank coal by oxidizing the coal to lower its oxidative reactivity. Spontaneous ignition may 10 also be inhibited by limiting oxygen contact with the coal particle surfaces, for example by compaction to decrease air penetration into a pile of coal and/or coating the coal with a substance for limiting oxygen access to surfaces of the coal. Several currently used methods of oxidizing coal 0* *15 expose the coal particles to molecular oxygen. For example, US-A-3,723,079 describes treating coal which has been dried to 1 to 10 percent moisture content by means of an air oxidation that provides an oxygen uptake of 0.5 to 8 percent then rehydrating the coal. US-A-4,396,394 and S 20 US-A-4,401,436 describe sequentially drying the coal to near the moisture content desired for the product, oxidizing it by an upflow of hot oxygen-containing gas, then cooling the a treated coal to less than about 38 0 C (100 0 or doing the cooling while adding water i n order to increase the rate ofcooling by water evaporation. The stabilization provided by such methods is based on a decrease in the rate of the oxidation reaction as the coal is oxidized.

k 6 3 The present invention provides a process wherein low rank coal is dried, oxidized and cooled to reduce its tendency toward spontaneous combustion, characterized by spraying particulate coal with an aqueous solution of an oxidant containing combined oxygen to distribute the aqueous solution substantially homogeneously over the surfaces of the coal particles without adding more than 10% by weight of water to the coal, drying the resulting wetted coal by heating the coal particles from ambient temperature to at 10 most 2040C (4000F) to reduce the moisture content to cubstanti allythe moisture content desired for the coal product, and cooling the so-treated coal to a temperature of less than 38°C (100 0

F).

The amount of water added by spraying with the 15 aqueous solution of oxidant is preferably less than 2% by weight of water based on the weight of the coal. The oxidant-wetted coal is dried by heating it to reduce its water content to substantially that desired for the coal product. The heating temperature is controlled so that the 20 coal particle temperature is at most 204 0 C (4000F), with at most 149 0 C (300°F) being preferred and at most 1210C (250 0 say between 66 and 121 0 C (150 and 250°F), being especially preferred. The coal can be heated at lower temperatures, say from above 38°C to 66 0 C (100 to 150 0

F),

but this is not preferred. The dried coal is then cooled to a temperature of less than 38 0 C (100 0

F).

g *000 0 0*00 0@ 0 @0 0 000 00000 0 0 0 6 0 00 0 4 In preferred embodiments the coal is screened into relatively coarse and relatively fine fractions. The aqueous solution of the oxidizing agent is then separately applied to the coarser and finer fractions or only to the finer fraction. The oxidant-sprayed finer fraction is dried and recombined with the coarser fraction. In a particularly preferred embodiment, the hot, oxidant-sprayed, dried fines are blended with the coarse oxidant-sprayed coarser fraction and the blended fractions are cooled.

10 In the process of the invention the coal is oxidized by contacting it with an aqueous solution of an oxidant in which the oxygen exists in combined form, as opposed to molecular oxygen. In general, the oxidant can be substantially any relatively mild, relatively water-soluble, 15 oxygen-containing oxidant. The oxidant is preferably present in the aqueous solution in a relatively high concentration, preferably a concentration which substantially saturates the solution;- Particularly suitable oxidants include perchlorates, chlorates, peroxides, 20 hypochlorites or nitrates and are suitably used as aqueous solutions in which the cations comprise metal, hydrogen or ammonium ions. Contacting the coal with an aqueous oxidant allows the surfaces of the coal to be substantially uniformly contacted, does not require special equipment such as oxidizing vessels, and avoids any need to increase the moisture content of the contacted coal by more than preferably not more than by weight of the coal.

0000 0 *000 *0 00 *0 0 0 .j A j ~1 5 In a preferred embodiment the oxidant solution is sprayed ont.o the coal at a drop point, or on a belt, and is nearly saturated, to .a.,xtent minimizing the amount of water without causing precipitation of the oxidant. Where desired, the oxidant solution can be heated and can be applied using a conventional spraying or atomizing nozzle.

In the process of the invention the aqueous oxidant contacts the coal before the coal is dried. This enables the water-soluble oxidant to diffuse into water which may be present in and on surfaces of the coal and to penetrate beyond the peripheral surfaces of the coal. This application, prior to the heating and evaporation which occurs in the drier, causes the oxidation reaction to be accelerated at the elevated temperature of the drier and the concentrating of the oxidizing chemical due to the evaporation of water. Where desired, for example when using a relatively low cost and/or relatively unreactive oxidizer, a supplemental addition of the oxidant solution can be made S to the coal after it leaves the drier and before it enters a S 20 cooler.

Laboratory Test (Magnesium Perchlorate) For these experiments a sample of Western sub-bituminous coal was riffled into two 1000 gm homologous aliquots. The coal was from the Southern Powder River Basin in Wyoming. An untreated control sample was created by slurrying one aliquot with 1000 milliliters distilled water.

A treated coal sample was created by slurrying the other 6 homologous aliquot with solution of 10 gms magnesium perchlorate per 1000 milliliters of distilled water to an extent providing 1.4% by weight of magnesium perchlorate based on the weight of the dried coal. The treated and untreated samples were dried in a nitrogen-purged vacuum oven at 105-110 0 C for 48 hours. The dried coal samples were placed in isothermal reactors through which a steady current of air was passed, and the oxygen consumption was measured as a function of time.

The initial oxygen consumption rate of the treated

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sample was only about 50 percent of that of the untreated sample. The change in the natural logarithm of the oxidation rate with cumulative oxidation (or the integral of the amount of prior oxidation) indicates that the oxidizer has an effect which is roughly similar to molecular oxygen in that the initial rate of oxidation is diminished; which indicates that the utilization of an oxidant which contains combined oxygen, rather than molecular oxygen, causes a preoxidation of the coal which prevents, or at least delays, subsequent spontaneous ignition and does this in a way that is more easily accomplished than it could be done with molecular oxygen. In addition, since a solution of water-soluble oxidizer is sprayed onto the surface of the coal the oxidizer is free to migrate through the coal's original moisture into contact with the coal's surface in and around fine interstices and fine pores.

7 The effectiveness of the water-soluble oxidizer dissolved in a slurry of the coal means that the process of the invention can be used to treat coal in a coal/water slurry being pipelined, and thus mitigate storing and handling problems at the receiving end of the pipeline.

Laboratory Test (Ammonium Nitrate)

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Treated coal was prepared by slurrying about 1000 gms of wet, as-received sub-bituminous coal in solutions of ammonium nitrate in 1000 milliliters distilled water. An 10 untreated control sample was prepared by slurrying about 1000 gms of homologous wet coal in 1000 milliliters pure distilled water. The samples were then dried in nitrogen-purged vacuum ovens at 100-105 0 C for 48 hours. The isothermal uptake of oxygen with time was monitored for the 15 samples. The ammonium nitrate decreased the rate at which the dried coal absorbed oxygen. Significant decreases were observed when concentrations of the ammonium nitrate were 0.7 and 1.4% by weight based on the weight of the dried coal.

A preferred procedure for processing low rank coal where all of the coal is to be dried is one in which run-of-mine wet coal is sprayed with an aqueous solution of oxidant, the wet coal is passed to a dryer in which it is dried with a heating drying gas, the exhaust gas from the dryer is passed to a dust collector, the dry hot coal from the dryer is passed to a cooler in which it is cooled using, for example, ambient air, the exhaust from the cpoler is "e 5

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1 r 8passed to a dust collector, and the cool, dry treated coal is stockpiled. The functioning of the spraying procedure is substantially analogous to the slurrying procedures of the laboratory tests described above.

Another particularly preferred procedure is one wherein run-of-the-mill coal is screened to relatively coarse and fine fractions, each fraction is separately •co *sprayed with an aqueous oxidant solution, the treated fines fraction is dried, the treated fractions are recombined, the 10 blend is passed to a cooler, and the cooled blend is Ie stockpiled.

A variation on this procedure was tested at a mine site in the Powder River Basin. The procedure used in the ee Powder River test differed from that described in that the treated fines fraction was cooled before it was mixed with the treated coarse fraction. In the Powder River field test, run-of-the-mine 5cm x 0 (2 inch x 0) coal was fed onto a 1.9cm inch) mesh screen. The fines fraction which passed through the screen was dried but the coarse fraction which flowed over the screen was not dried. An ammonium nitrate solution containing 25-33% by weight of ammonium nitrate in water was sprayed on after the screening to both the coarse and fine fraction. In the Powder River test, the dried fines and the wet coarse fraction were blended after cooling the dried fines. The fine coal particles were heated from ambient temperature to 66 to 121 0 C (150-250°F) It 9 in 2 to 10 minutes and the cooler reduced the temperature of the fine dried coal particles by 28 to 56 0 C (50-100 0

F).

The amounts of the oxidant solution applied to the fines and coarse fractions were kept the same for both fractions. 5 x 104 kg (50t) of coal were treated with less than 0.2% by weight ammonium nitrate and 5 x 10 kg (50t) of the coal was treated with less than 0.5% by weight ammonium nitrate. The treated samples were stockpiled next to each other in a specially prepared berm area to make a 105kg 10 (100t) stockpile. The stockpile began smoldering after 33 days. A control untreated pile which was dried by means of the same process and conditions, except for not being sprayed with the ammonium nitrate solution, began smoldering after being stockpiled for only 8 days.

15 Smolders were manifest by ash layers on the surface of the pile and smoke. The temperatures of each of the piles were monitored with 20 thermocouples per pile. After 3 days of storage the maximum measured temperature reached °.oo in the control pile was 88°C (190 0 After 25 days' storage the maximum measured temperature reached in the pile treated with ammonium nitrate was about 71 0 C (160 0

F).

It is apparent that the ammonium nitrate treatment has been 6 :shown in the laboratory and field tests to significantly inhibit the spontaneous ignition tendency of dried low rank coal. As known in the art, ammonium nitrate is an inexpensive, non-toxic, and readily available chemical.

10 The processing scheme in which an oxidant wetted coarse fraction of coal is blended with the oxidant wetted and dried fines fraction of coal prior to the cooling of the mixture, is especially preferred. With about the same amount of treating time and expense, the process wherein the coal fractions are blended prior to being cooled will tend to produce a cooler product. A product which is stockpiled 0000 •o at a lower temperature will have a lower spontaneous ignition tendency than one which is initially hotter.

0O 0.10 In general, the water used to form the aqueous S solution of oxidant can be substantially any which is a good oeeoo solvent for, is miscible with the particular oxidizer to be used and is substantially inert to the coal oxidation S reaction. Particularly suitable waters have a total 15 dissolved solids content of no more th.n 10 grams per liter and contents of major cations those present in more than trace amounts) of no more than about 150 muq. per liter.

In general, the process of the invention can be effected using any of the devices, such as coal transfer devices, screens, driers and coolers, which are currently available and suitable for their intended functions.

Claims (13)

1. A process wherein low rank coal is dried, oxidized and cooled to reduce its tendency toward spontaneous combustion, which comprises spraying particulate coal with an aqueous solution of an oxidant containing combined oxygen to distribute the aqueous solution ub tantiall y homogeneously over the surfaces of the coal particles without adding more than 10% by weight of water to the coal, drying the resulting- wetted coal by heating the coal particles from ambient temperature to at most 2040C (4000F) to reduce the moisture content to subs-+ant4 ly the moisture content desired for the coal product, and cooling the so-treated coal to a temperature of less than 38 0 C (100"F).

2. A process according to Claim 1 wherein the coal is separated into coarse and fine fractions, the aqueous solution of oxidant is applied to both fractions, the oxidant-containing fines fraction is dried, and the so-treated fractions are mixed.

3. A process according to Claim 2 wherein the oxidant-containing coarse fraction is mixed with the oxidant-containing dried fines fraction before the so-treated fractions are cooled.

4. A process according to Claim 1 wherein the coal is separated into coarse and fine fractions, the aqueous solution of oxidant is applied only to the fine 12 fraction, the oxidant-containing fines fraction is dried, and the fractions are mixed.

A process according to any one of the preceding claims wherein the oxidant is a perchlorate, chlorate, peroxide, hypochlorite or nitrate.

6. A process according to Claim 5 wherein the exidieab is ammonium perchlorate or ammonium nitrate.

7. A process according to any one of the preceding claims wherein the coal is heated from ambient 0 temperature to at most 149 0 C (300 0 F).

8. A process according to Claim 7 wherein the coal is heated from ambient temperature to between 66 and 121 0 C (150 and 250 0 F).

9. A process according to Claim 7 wherein the 15 coal is heated from ambient temperature to above 38 to 66 0 C o0 (100 to 150 0 F).

10. A process according to any one of the preceding claims wherein the water added by the aqueous j 6.csec^ cn-Vhe. L^&XtI- o t-e. coo solution of oxidant is not more than 2% by weight. 20

11. A process according to Claim 1 substantially as hereinbefore described.

12. Coal when treated in accordance with a process as claimed in any one of the preceding Claims.

-13. The steps--r-f-ea-t-ures-d-i-s ol G d heroin or any- cmbination thereof.- DATED this 30th day of May, 1988 SHELL OIL COMPANY By its Patent Attorneys S DAVIES COLLISON m 1- _11