GB1564765A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1564765A – Process for removing sulphur from coal
– Google Patents

GB1564765A – Process for removing sulphur from coal
– Google Patents
Process for removing sulphur from coal

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Publication number
GB1564765A

GB1564765A
GB39579/77A
GB3957977A
GB1564765A
GB 1564765 A
GB1564765 A
GB 1564765A
GB 39579/77 A
GB39579/77 A
GB 39579/77A
GB 3957977 A
GB3957977 A
GB 3957977A
GB 1564765 A
GB1564765 A
GB 1564765A
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United Kingdom
Prior art keywords
coal
sulfur
oxidant
complexing agent
oxygen
Prior art date
1976-09-23
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GB39579/77A
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Atlantic Richfield Co

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Atlantic Richfield Co
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1976-09-23
Filing date
1977-09-22
Publication date
1980-04-16

1977-09-22
Application filed by Atlantic Richfield Co
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Atlantic Richfield Co

1980-04-16
Publication of GB1564765A
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patent/GB1564765A/en

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Classifications

C—CHEMISTRY; METALLURGY

C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT

C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS

C10L9/00—Treating solid fuels to improve their combustion

C10L9/02—Treating solid fuels to improve their combustion by chemical means

Description

PATENT SPECIFICATION ( 11)
( 21) Application No 39579/77 ( 22) Filed 22 Sept 1977 ( 31) Convention Application No 726 082 ( 19 ( 32) Filed 23 Sept 1976 in ( 33) United States of America (US) ( 44) Complete Specification published 16 April 1980 ( 51) INT CL 3 Cl OL 9/06 ( 52) Index at acceptance C 5 G 6 B 6 C 6 G 6 L 6 X ( 54) PROCESS FOR REMOVING SULFUR FROM COAL
( 71) We, ATLANTIC RICHFIELD
COMPANY, a corporation organised under the laws of the State of Pennsylvania, United States of America, of ARCO Plaza, 515 Flower Street, Los Angeles, California, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
The field of this invention relates to a process for reducing the sulfur content of coal.
The problem of air pollution due to the emission of sulfur oxides when sulfur-containing fuels are burned has received increasing attention in recent years It is now widely recognized that sulfur oxides can be particularly harmful pollutants since they can combine with moisture to form corrosive acidic compositions which can be harmful and/or toxic to living organisms in very low concentrations.
Coal is an important fuel, and large amounts are burned in thermal generating plants primarily for conversion into electrical energy One of the principal drawbacks in the use of coal as a fuel is that many coals contain amounts of sulfur which generate unacceptable amounts of sulfur oxides on burning.
The sulfur content of coal, nearly all of which is emitted as sulfur oxides during combustion, is present in essentially two forms:
inorganic, primarily metal pyrites, and organic sulfur The inorganic sulfur compounds are mainly iron pyrites, with lesser amounts of other metal pyrites and metal sulfates The organic sulfur may be in the form of thiols, disulfide, sulfides and thiophenes (substituted, terminal and sandwiched forms) chemically associated with the coal structure itself Depending on the particular coal, the sulfur content can be primarily in the form of either inorganic sulfur or organic sulfur Distribution between the two forms varies widely among various coals.
Heretofore, it was recognized that it would be highly desirable to remove (or at least lower) the sulfur content of coal prior to combustion A number of processes, for example, have been suggested for removing the inorganic (pyritic) sulfur from coal.
For example, it is known that at least some pyritic sulfur can be physically removed from coal by grinding the coal, and subjecting the ground coal to froth flotation or washing processes While such processes can desirably remove some pyritic sulfur, these processes are not fully satisfactory because a significant portion of the pyritic sulfur is not removed.
Attempts to increase the portion of pyritic sulfur removed have not been successful because these processes are not sufficiently selective Because the process is not sufficiently selective, a large portion of coal can be discarded along with ash and pyrite.
There have also been suggestions heretofore to chemically remove sulfur from coal For example, U S Patent 3,768,988 to Meyers, issued October 30, 1973, discloses a process for reducing the pyritic sulfur content of coal involving exposing coal particles to a solution of ferric chloride The patent suggests that in this process ferric chloride reacts with pyritic sulfur to provide free sulfur according to the following reaction process:
2 Fe C 13 +Fe S, -X 3 Fe CI,+S While this process is of interest, a disadvantage of this process is that the liberated sulfur solids must then be separated from the coal solids Processes involving froth flotation, vaporization and solvent extraction are proposed to separate the sulfur solids All of these proposals, however, inherently represent a second discrete process step with its attendant problems and cost which must be employed to remove the sulfur from coal.
In another approach, U S Patent 3,824,084 to Dillon issued July 16, 1974, discloses a process involving grinding coal containing pyritic sulfur in the presence of water to form a slurry, and then heating the slurry under pressure in the presence of oxygen The patent 1564765 1,564,765 discloses that under these conditions the pyritic sulfur (for example, Fe S,) can react to form ferrous sulfate and sulfuric acid which can further react to form ferric sulfate The patent discloses that typical reaction equations for the process at the conditions specified are as follows:
Fe 52 H 20 + 7/20, Fe SOQ+H 25 O, 2 Fe SO,+H 2 SO 4 + 1/202 -) Fe,(S Oj I),+H 20 These reaction equations indicate that in this particular process the pyritic sulfur content continues to be associated with the iron as sulfate While it apparently does not always occur, a disadvantage of this is that insoluble material, basic ferric sulfate, can be formed.
When this occurs, a discrete separate separation procedure must be employed to remove this solid material from the coal solids to adequately reduce sulfur content Several other factors detract from the desirability of this process The oxidation of sulfur in the process does not proceed at a rapid rate, thereby limiting output for a given processing capacity.
In addition, the oxidation process is not highly selective such that considerable amounts of coal itself can be oxidized This is undesirable, of course, since the amount of coal recovered from the process is decreased.
Numerous other methods have been proposed for reducing the sulfur content of coal.
For example, U S Patent 3,938,966, to Kindig et al issued February 17, 1976, discloses treating coal with iron carbonyl to enhance the magnetic susceptibility of iron pyrites to permit removal with magnets In summary, while the problem of reducing the sulfur-content of coal has received much attention, there still exists a present need for a practical method to more effectively reduce the sulfur content of coal.
This invention provides a practical method for more effectively reducing the sulfur content of coal In summary, this invention involves a process for reducing the pyritic sulfur content of coal comprising:
1) contacting coal particles with an aqueous solution of iron complexing agent and an oxidant; and 2) recovering coal particles of reduced sulfur content.
Contacting coal containing pyritic sulfur with an aqueous solution containing an iron complexing agent and an oxidant provides faster reaction rates (reducing processing time), more selective oxidation of sulfur compounds, and with some coals, some organic sulfur removal These desirable attributes are important, and are made available in the process of this invention.
The novel process of this invention is especially effective for reducing the pyritic sulfur content of coal An advantage of the process is that it can also provide a reduction in the organic sulfur content of some coals.
A further advantage of the process is that the ash content of the coal is reduced.
Suitable coals which can be employed in the process of this invention include brown coal, lignite, subbituminous, bituminous (high volatile, medium volatile, and low volatile), semi-anthracite, and anthracite Regardless of the rank of the feed coal, excellent pyrite removal can be achieved by the process of this invention Metallurgical coals, and coals which can be processed to metallurgical coals, containing sulfur in too high a content can be particularly benefited by the process of this invention.
The coal particles employed in this invention can be provided by a variety of known processes, for example, grinding.
The particle size of the coal can vary over wide ranges and in general the particles need only be sufficiently small to enhance contacting with the aqueous medium For instance, the coal may have an average particle size of one-fourth inch in diameter or larger in some instances, and as small as minus 200 mesh (Tyler Screen) or smaller The most practical particle size is often minus 5 mesh, preferably minus 18 mesh, as less energy is required for grinding and yet the particles are sufficiently small to achieve the optimum rate of pyrite removal.
Iron complexing agents which promote selective oxidation and removal of pyritic sulfur, and do not have an adverse effect on the coal, are used in the process of this invention.
The most suitable amount of iron complexing agent employed depends upon the pyrite and ash content of the coal, and the complexing agent employed A mole ratio of complexing agent to pyrite of from 005 to 10, and preferably 1 0 to 6 0, can be suitably 105 employed It is generally convenient to employ aqueous solutions of iron complexing agent which are fed from 0 05 to 1 0 molar, preferably 0 05 to O 3 molar with respect to iron complexing agent 110 Suitable iron complexing agents for use in this invention are compounds which can complex ferrous and/or ferric ions Preferred complexing agents are compounds which can form ferrous complexes or ferric complexes 115 having a stability constant of -log 1,K-greater than 1, and preferably greater than 2 0.
Convenient compilations providing stability constants of many complexing agents for iron are Martell and Calvin, «Chemistry of the 120 Metal Chelate Compounds», U S copyright 1952, and «Stability Constants of Metal-Ion Complexes, Supplement No 1, Special Publication No 25, published by The Chemical Society, U S copyright 197 i 125 1,6,6 Examples of suitable iron complexing agents include the following: carboxylic acids and carboxylic acid salts, for example, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, lactic acid, gluconic acid, salicylic acid, and salts thereof; diols and polyols, for example, glycol, glycerol, butane-1,3 diol, mannitol, sorbitol, glucose, lactose, fructose and sucrose; amines, for example, ethylenediamine, diethylenetriamine and triethylenetetramine; amino acids, for example glycine and asparagine, and salts thereof; amino polycarboxylic acids and amino polycarboxylic acid salts, for example, N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid, N,Ndi ( 2-hydroxyethyl) glycine and N,N,N’,N’ethylene diaminetetraacetic acid and salts thereof; phosphonic acids and phosphonic acid salts, for example, ethane 1 hydroxy 1,1diphosphonic acid; and condensed phosphates, for example trimetaphosphoric acid and tripolyphosphoric acid, and salts thereof Mixtures of complexing compounds can be very desirably employed.
As will be recognized by those skilled in the art, the stability of the ferrous and ferric complexes formed will often be affected by the p H of the aqueous medium In such cases, it is contemplated that the p H will be such that a stability constant -log 10 K greater than 1 is maintained and more preferably, the optimum p H for the particular complexing agent will be maintained The particular p H employed can also affect the salt form of the complexing agent employed, and such salts are complexing agents within the scope of this invention.
Many of the complexing agents useful in the process of this invention can be very desirably formed in situ prior to or in the course of the process For example, cellulosic materials can be oxidized to form a complex mixture of polyols, hydroxy carboxylic acids, carboxylic acids and corresponding acid salts which can provide a complexing solution meeting the requirements of this invention.
(Any aqueous solution of complexing agents which complexes the iron in coal satisfies the requirements of this invention).
Oxalic acid salts, for example, sodium, potassium and ammonium oxalate are preferred complexing agents for use in the process of the invention in that they are effective complexing agents which are readily available and inexpensive.
Suitable oxidants for use in this invention are those oxidants which preferentially oxidize the sulfur contained in the coal rather than the carbon portion of the coal By this is meant that the oxidation of sulfur atoms occurs without substantial oxidation of carbon atoms to form, for example, ketones, carboxyl acids or other carbonyl-containing compounds, carbon monoxide and carbon dioxide This preferential oxidation, or selectivity is important in maintaining the heat content of the coal.
Included among the oxidants which are useful herein are organic oxidants and inorganic oxidants 70 The organic oxidants include by way of example hydrocarbon peroxides, hydrocarbon hydroperoxides and hydrocarbon peracids wherein the hydrocarbon radicals in general contain from 1 to 30 carbon atoms per active 75 oxygen atom With respect to the hydrocarbon peroxides and hydrocarbon hydroperoxides, it is particularly preferred that such hydrocarbon radical contain from 4 to 18 carbon atoms per active oxygen atom, i e, per peroxide 80 linkage, and more particularly from 4 to 16 carbon atoms per peroxide linkage With respect to the hydrocarbon peracids, the hydrocarbon radical is defined as that radical which is attached to the carbonyl carbon and it is 85 preferred that such hydrocarbon radical contain from 1 to 12 carbon atoms, more preferably from 1 to 8 carbon atoms, per active oxygen atom It is intended that the term organic peracid include, by way of definition, 90 performic acid It is contemplated within the scope of this invention that the organic oxidants can be prepared in situ.
Typical examples of organic oxidants are hydroxyheptyl peroxide, cyclohexanone per 95 oxide, t-butyl peracetate, di-t-butyl diper phthalate, t-butyl-perbenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, pinane hydroperoxide, 2,5 dimethylhexane 2,5 di 100 hydroperoxide, tetrahydronaphthalene hydroperoxide and cumene hydroperoxide as well as organic peracids, such as performic acid, peracetic acid, trichloroperacetic acid, perbenzoic acid and perphthalic acid 105 Inorganic oxidants include by way of example, oxygen, singlet oxygen, ozone, peroxides and superoxides Typical examples of inorganic peroxides are H 202, K Mn O 4, K 202, Na,O, and Rb 202; typical examples of inor 110 ganic superoxides are KO 2, Rb O 2, Cs O 2, Na 2 SO, and Na 2,S O 2.
Oxygen is a preferred oxidant.
In general, the mole ratio of oxidant to.
pyritic sulfur is from 0 5 to 10 atoms of active 115 (i.e, reducable) oxygen per atom of sulfur.
More or less oxidant could be employed, however The most effective oxidation will generally occur when the mole ratio oxidant to pyritic sulfur is greater than 4; for example, 120 when 5 to 10 atoms of active oxygen per atom of sulfur are present.
The preferred oxidant, oxygen, can be present as pure oxygen gas or it can be mixed with other inert gases For example, air or air 125 enriched with oxygen can be suitably employed as a source of gaseous oxygen Preferably, the gaseous oxygen is above atmospheric pressure, for example, pressures of from 5 to 500 psig, preferably 25 to 400 psig, and 130 1,564,765 R 4 1 6 6 4 more preferably from 50 to 300 psig If the oxygen is mixed with other gases, the partial pressure of oxygen is most suitably within the pressure ranges mentioned hereinbefore.
Elevated temperatures can be desirably employed to accelerate the process For example, temperatures of from 150 to 500 ‘F, preferably from 150 to 400 ‘F, and more preferably from 175 to 350 ‘F, can be suitably employed Under these reaction conditions, the pyritic sulfur can be preferentially oxidized without significant adverse oxidation of the coal substrate.
Under these conditions, pyritic sulfur is readily removed from the coal It is believed that removal involves oxidation of the pyritic sulfur to sulfate, thionate and thiosulfate forms.
As the reaction proceeds, oxidant is consumed.
Additional oxidant can be added to the system if necessary.
The coal should be held under these conditions for a period of time sufficient to effect a significant reduction in the pyritic sulfur content, i e, a reduction of at least 25 %, and more preferably, a reduction of from 70 % to % or more, by weight, of pyritic sulfur.
Generally, a time period in the range of from minutes to 5 hours, or more, can be satisfactorily employed Preferably, a time period of from 10 minutes to 2 hours is employed.
During this time, it can be desirable to agitate the coal slurry Known mechanical mixers, for example, can be employed to agitate the slurry.
It has been found that the presence of iron complexing agent provides faster reaction rates, i.e, faster removal of pyritic sulfur, and more selective oxidation Depending upon the complexing agent employed, these desirable results can be optimized by adjusting the p H to an optimum sulfur removal range For example, a p H of from 4 0 to 7 0 is preferred, when the complexing agent is oxalic acid, and its corresponding salts, for example, sodium, potassium and ammonium salts.
When the pyritic sulfur in coal is oxidized in the process of this invention, sulfur acids, for example, sulfuric acid, can be formed If the pyritic sulfur content of the coal is high and/or the amount of aqueous solution in the coal slurry low, it can often be necessary to add a basic material to maintain a desired p H On the other hand, depending on the complexing agent, the character and content of ash in the coal, it may be necessary to add an acidic material to maintain a desired p H.
It will be recognized by those skilled in the art that there are many ways to maintain the p H of the aqueous slurry within the desired range For example, the p H of the slurry can be continuously monitored using commercially available p H meters, and a suitable quantity of basic or acidic material can be metered to the slurry as needed to maintain the desired p H Another suitable method to obtain a p H in the desired range involves adding an appropriate amount of basic or acidic material to the aqueous slurry of coal and water prior to subjecting the slurry to the reaction conditions involving increased temperature and pressure 70 Examples of suitable basic materials include alkali and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and their corresponding oxides Other suitable basic 75 materials include ammonia and alkali and alkaline earth carbonates such as sodium carbonate, sodium bicarbonate and potassium bicarbonate, ammonium bicarbonate and ammonium carbonate Among these basic 80 materials, sodium hydroxide, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate are preferred.
An especially suitable acidic material is carbon dioxide Other known acidic materials, 85 of course, can be employed.
Materials which are buffering agents can be a very useful aid in maintaining the desired p H An example of a suitable buffering agent is sodium acetate As oxidation of the pyritic 90 sulfur proceeds to generate sulfuric acid, part of the sodium acetate is converted to acetic acid to yield a buffer mixture, sodium acetate and acetic acid, in situ in the reactor Control of p H within a very narrow range can be 95 achieved using such a buffering agent Other buffering agents for maintaining a desired p H are known to those skilled in the art.
It will be recognized by those skilled in the art that many complexing agents suitable 100 for use in the process of this invention are also buffering agents For example, many carboxylic acid salts and aminocarboxylic acid salts can ‘find use as both complexing agents and buffering agents in the process (As will 105 also be recognized by those skilled in the art, depending upon the p H such complexing/ buffering agents will be present as a mixture of acid and salt forms) Oxalic acid salts, for example sodium, potassium and ammonium 110 oxalate, are illustrative of preferred complexing/buffering agents employed in the process of this invention.
The most suitable basic materials for maintaining the p H of the aqueous solution in the 115 process are those having cations which form soluble salts with sulfur-oxygen anions such as thiosulfate, sulfate and thionate The most suitable basic materials have cations comprising sodium, ammonium and/or potassium 120 since such materials are readily available and form water soluble materials with sulfate.
Preferably the coal particles are contacted with the aqueous solution of iron complexing agent by forming a slurry of the solution and 125 coal particles The slurry can be formed, for example, by grinding coal in the presence of of water and adding a suitable amount of iron complexing agent and oxidant or an aqueous solution of iron complexing agent and 130 1,564,765 1,564,765 5 oxidant can be added to coal particles of a suitable size Preferably, the slurry contains from 5 to 50 %, by weight of the slurry, coal particles and more preferably from 10 to 30 %, by weight of the slurry, coal particles.
From 0 01 to 1 %, by weight of coal, of a wetting agent can be a useful addition to the slurry Suitable wetting agents include anionic, nonionic and am Dhoteric surfactants.
When coal particles are contacted with the aqueous solution of iron complexing agent and oxidant in accordance with this process, most of the pyritic sulfur and some organic sulfur can be oxidized to form water separable sulfur compounds, for example water soluble sulfate salts.
This water, containing dissolved sulfur compounds, is separated from the coal particles.
Such a liquids-solids separation is relatively simple, and can be effected in a variety of ways Filtering with bar sieves or screens, or centrifuging, for example, can be employed to separate the coal and water.
The resulting coal product has a substantially reduced pyritic sulfur content and can exhibit a diminished organic sulfur content.
Preferably, the coal is dried prior to use or storage.
The water separated from the coal, containing dissolved sulfur compounds, can be discarded or, more preferably, is treated to remove the sulfur content The sulfur content can be removed, for example, by treating the water with compounds which form insoluble compounds with the oxidized sulfur compound Preferably, the sulfur content is concentrated prior to such treatment, for example, by evaporating a portion of the water For example, barium chloride added to concentrated water solutions of sulfate compound will form insoluble barium sulfate which will precipitate from the water solution The precipitate and water can be separated by conventional methods, such that the resulting water is substantially free of sulfate content.
The following specific embodiments are provided to more specifically illustrate the invention described herein.
EXAMPLE I.
West Virginia Peerless Seam coal was ground and screened to provide a quantity of coal having a particle size of less than 100 mesh (Tyler Screen) The feed coal had the following analysis:
Percent by Weight Wet Basis Dry Basis Sulfate sulfur 0 01 0 01 Pyritic sulfur 1 82 1 84 Organic sulfur 1 35 1 37 Total Sulfur 3 18 3 22 Ash 8 11 8 20 Water 1 12 The coal was treated in the following manner to reduce its sulfur content Thirty grams (wet basis) of this coal and 200 ml.
of an aqueous solution of iron complexing agent ( 0 1 M sodium oxalate) were charged to an autoclave forming a slurry The autoclave was sealed and then heated to 2500 F; oxygen was then introduced to the autoclave and maintained at a pressure of 300 psig 02.
The coal was held under these conditions for one hour, and then filtered to separate the coal and the aqueous solution The coal was then dried In the course of the reaction the p H of the slurry fell from 7 6 to 4 50.
The weight of the coal product recovered was 27 7 grams ( 93 % recovery) This high recovery is indicative of the high selectivity of the process.
The recovered coal product had the following analysis:
Percent by weight Dry Basis Sulfate sulfur 0 028 Pyritic sulfur 0 18 Organic sulfur 1 19 Total sulfur 1 40 Ash 6 51 Water The sulfur content of the coal was significantly reduced: 90 % of the pyritic sulfur was removed, and 13 % of the organic sulfur was removed (As used herein, organic sulfur includes any elemental sulfur present) A further advantage of the process of this invention is that the ash content of the coal was reduced.
The recovered coal product is highly improved in that it has a lower sulfur and ash content.
EXAMPLE II.
When, in the process of Example I the following coals were employed, the aqueous 100 solution of iron complexing agent was 0 16 M sodium oxalate, the p H was maintained at 4 5 -5.0, the tempertaure was 250 F, the oxygen pressure was 300-350 psig 02 and the time was 1 to 1-1/2 hours, the following resuilts 105 presented in Table I were obtained:
1,564,765 or TABLE I
Percent Sulfur in Coal Percent Removal of Sulfur Total Sulfate Pyrite Organic Total Pyrite Organic Percent Ash in Coal West Va Upper Freeport Upper Freeport Somerset County, Pa.
Pittsburgh Coal Bed Belmont County, Ohio Feed Treated 5.13 1.42 36 3 41 1.36 12 15 1 15 72.3 95.6 15.5 28.3 24.3 Feed 4 44 14 3 13 1 17 17 4 Treated 70 05 09 56 84 2 97 1 52 14 4 Feed 6 65 12 4 17 2 36 14 2 Treated 2 03 01 17 1 86 69 94 21 8 73 Pocahontas #4 Seam Gary, W Va.
Feed Treated 1.17 01 03 78 48 Dry Ash Free Basis.
EXAMPLE III.
When in Example I one of the following complexing agents were employed instead of sodium oxalate, the same or similar results were obtained in that the sulfur content of the coal was reduced: potassium oxalate, ammonium oxalate, sodium malonate, sodium glycinate, or sodium tripolyphosphate.
EXAMPLE IV.
When in Example I the aqueous solution contained 0 2 M of an oxidant selected from the group consisting of peracetic acid, hydrogen peroxide or potassium superoxide instead of oxygen, the same or similar results were obtained in that sulfur content of the coal was reduced.
EXAMPLES V-IX.
In the following Examples V to IX coal was ground and screened to provide a quantity of coal having a particle mesh size of 100 X 325 (Tyler Screen) Thirty grams of the coal employed and 200 ml of an aqueous solution Coal a% &% 92.2 10.8 9.42 of iron complexing agent (and where indicated, base material) were charged to an autoclave forming a slurry The autoclave was sealed and heated to the indicated temperature; oxygen was then introduced and maintained at the indicated pressure for the indicated time The slurry was then filtered to separate the coal and the aqueous solution.
The various coals, complexing agents, process condition and results obtained are presented in Table 2 In that table, the abbreviation T S.
means total sulfur; S S means sulfate sulfur; P.S means pyritic sulfur; O S means organic sulfur; P Hi means initial p H and P Hf means final p H.
Complexing Agent and Amount TABLE I I
Process Conditions Percent Sulfur in Coal T.S S S P S O S.
Percent Removal T.S P S O S Ash V Iowa, Mahaska County ( 46 g) VI Iowa, Mahaska County ( 46 g) VII Pennsylvania, Pittsburgh Coal Bed ( 40 g) VIII Upper Freeport Seam, Grantsville, Md ( 30 g) EDTA’ ( 36 g) Salicylic Acid ( 18 g) Dextrose ( 8.0 g) Versene 2 ( 12 g) IX Upper Freeport Seam, Phthalic Acid Grantsville, Md ( 25 Ig) ( 12 g) 260 F; 300 psig.
02; 1 Hr; Base:
None p Hi-p Hf ( 9.0 7 0) 260 F; 300 psig.
02; 1 Hr; Base:
KOH p Hi-p Hf ( 6.2 5 1) 260 F; 320 psig.
02; 1 Hr; Base:
KOH p Hi-p Hf ( 8.0 3 4) 260 F; 320 psig.
02; 1 Hr; Base:
None p Hi-p Hf ( 10 6 7 4) 260 F; 300 psig.
02; 1 Hr; Base:
ROH p Hi-p Hf ( 11 5 5 9) Feed 8.43 0 01 3 96 4 38 Treated 4 97 0 21 1 38 3 38 42 65 23 Feed 8 43 0 09 3 96 4 38 Treated 6 9 0 22 2 48 3 39 28 37 23 27 Feed 2 98 0 14 1 68 1 16 Treated 2 17 0 01 0 84 1 32 27 50 -14 7 Feed 2 59 0 04 1 75 0 80 _ Treated 0 88 0 01 0 19 0 68 66 89 15 6 Feed 2 59 0 04 1 75 0 80 Treated 1 71 0 01 1 04 0 68 34 41 15 7 Dry Ash Free Basis.
Sodium ethylenediamine tetraacetic acid.
2 Sodium N,N-di ( 2-hydroxyethyl) glycine.
«Versene» is a Registered Trade Mark.Example
Coal Source and Amount 0 ‘, -,4 0 % ktl 1,564,765

Claims (22)

WHAT WE CLAIM IS:- 1 A process for reducing the pyritic sulfur content of coal comprising:

1) contacting coal particles with an aqueous solution of iron complexing agent, and an oxidant; 2) recovering coal particles of reduced sulfur content.

2 The process of claim 1 wherein the aqueous solution is maintained at elevated temperature.

3 The process of claim 2 wherein the temperature is from 150 F to 400 F.

4 The process of claim 3 wherein the temperature is from 175 F to 350 F.

The process of any one of claims 1 to 4 wherein the iron complexing agent is present in a mole ratio of iron complexing agent to pyrite of 0 05 to 10.

6 The process of any one of claims 1 to 5 wherein the iron complexing agent is a compound which forms ferrous or ferric complexes having a stability constant-logo K of more than 1.

7 The process of claim 6 wherein the stability constant-loglo K is greater than 2.

8 The process of any one of claims 1 to 7 wherein the complexing agent is selected from carboxylic acids and carboxylic acid salts, diols and polyols, amines, amino acids and amino acid salts, amino polycarboxylic acids and amino polycarboxylic acid salts, phosphonic acids and phosphonic acid salts, condensed phosphates, and salts of condensed phosphates.

9 The process of claim 8 wherein the salts are selected from alkali metal and ammonium salts.

The process of claim 9 wherein the complexing agent is selected from sodium oxalate, potassium oxalate and ammonium oxalate.

11 The process of any one of claims 1 to 10 wherein the oxidant is oxygen.

12 The process of claim 11 wherein the oxygen is maintained at a pressure of from to 500 psig.

13 The process of claim 12 wherein the pressure of oxygen is from about 25 to 400 psig.

14 The process of claim 13 wherein the pressure of oxygen is from about 50 to 300 psig.

The process of any one of claims 1 to wherein the oxidant is selected from ozone and singlet oxygen.

16 The process of any one of claims 1 to 10 wherein the oxidant is an organic oxidant selected from hydrocarbon peroxides, hydrocarbon hydroperoxides and hydrocarbon peracids.

17 The process of any one of claims 1 to 10 wherein the oxidant is an inorganic oxidant selected from peroxides and superoxides.

18 The process of claim 17 wherein the oxidant is hydrogen peroxide.

19 The process of any one of claims 1 to 18 wherein the recovered coal is metallurgical coal.

A process as claimed in claim 1, substantially as hereinbefore described with particular reference to the Examples.

21 A process as claimed in claim 1, substantially as illustrated in any one of the Examples.

22 Coal particles when obtained by the process of any one of the preceding claims.
MATHYS & SQUIRE, Chartered Patent Agents, Fleet Street, London, EC 4 Y l AY.
Agents for the Applicants.
Printed for Her Majesty’s Stationery Office by the Courier Press, Leamington Spa, 1980.
Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
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Process for removing sulphur from coal

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1981-06-15
1987-07-21
Byrne Larry D
Method for agglomerating powdered coal by compaction

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CA
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AU
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patent/AU507811B2/en
not_active
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1977-09-22
GB
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patent/GB1564765A/en
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patent/DE2742766A1/en
not_active
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US
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patent/US4158548A/en
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(en)

1981-06-15
1987-07-21
Byrne Larry D
Method for agglomerating powdered coal by compaction

Also Published As

Publication number
Publication date

CA1094481A
(en)

1981-01-27

AU2776477A
(en)

1979-05-31

AU507811B2
(en)

1980-02-28

US4158548A
(en)

1979-06-19

DE2742766A1
(en)

1978-03-30

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