US968499A - Process of coking coals. - Google Patents
Process of coking coals. Download PDFInfo
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- US968499A US968499A US54462510A US1910544625A US968499A US 968499 A US968499 A US 968499A US 54462510 A US54462510 A US 54462510A US 1910544625 A US1910544625 A US 1910544625A US 968499 A US968499 A US 968499A
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- US
- United States
- Prior art keywords
- sulfur
- coking
- coal
- phosphorus
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000000034 method Methods 0.000 title description 24
- 238000004939 coking Methods 0.000 title description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 23
- 229910052717 sulfur Inorganic materials 0.000 description 23
- 239000011593 sulfur Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000003245 coal Substances 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- -1 hydrogen sulfid H 8 Chemical compound 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B19/00—Heating of coke ovens by electrical means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S44/00—Fuel and related compositions
- Y10S44/904—Method involving electric or wave energy
Definitions
- the object of my invention is to provide a process of'coking by means of which coke maybe produced from coals having a comparatively high sulfur or phosphorus content and in particular the object of my invention is to provide a coking process in which the impurities existing in the coals, notably sulfur, phosphorus, iron, and silica,
- the monosulfid is readily decomposedby dilute mineral acids with the evolution of hydrogen sulfidand a salt of the metal, in accordance with the following equations:
- I first treat the carbonaceous material to be coked chemically so that reactions Similar to those above described may be carried out and the sulfur and phos- 55
- an electrolytic shown) tank A of any suitable shape and dimeni sionsxis provided with revolvingelectrodes B and G mounted on the shaft D. and driven in. any desired manner as by the gears E and E and pulley E which in turn are electrical energy through the contact ring F and brush G and the electrode C is .con-
- the electrolytic tank A has a single compartment in which the electrodes of different polarity revolve, but if desired a double compartment may be employed, and the electrodes B and C placed in separate compartments, the prodnets of electrolysis being thus separatedas is well known in the art.
- the coal to be electrolyzed is preferably in a finely subdivided form and is submerged in the electrolyte, so that upon revolving the electrodes B and C a continual agitation of the substance in contact with the products of electrolysis results.
- the electrolyte used may be varied to suit the substances existing in the coal, and may be conveyed into the tank by any suitable means such as a pump P.
- I preferably use an acid or acid-forming electrolyte such as sulfuric acid in water or any soluble sulfate which will have a combined decomposing action on the sulfids of iron, the acids converting the monosulfid into hydrogen sulfid and a soluble sulfate, at the same time that oxygen and water are decomposing the bisulfid.
- an acid or acid-forming electrolyte such as sulfuric acid in water or any soluble sulfate which will have a combined decomposing action on the sulfids of iron, the acids converting the monosulfid into hydrogen sulfid and a soluble sulfate, at the same time that oxygen and water are decomposing the bisulfid.
- the electrolyte is decomposed by the electric current, the acid radical and the oxygen traveling to the ositive pole or anode causes an active and e ective action on the substances in the vicinity of the anode.
- the particles of FeS are oxidized in the electrolyte, the product bein soluble ferrous and ferric sulfate and by rogen sulfid, while the monosulfid of iron is acted upon by the acids.
- the sulfates, being soluble, are, of course, retained in the electrolytic solution, and are removed with said solution.
- the sulfur may be volatiliz'ed and particularly upon intimate contact with large quantities of hydrogen distilled from the coal with which hydrogen, sulfur can readily be caused to unite.
- the sulfur may, therefore, be distilled from the coal as a volatile compound with hydrogen such as hydrogen sulfid H 8, as volatile compound with carbon disulfid CS or as various hydrocarbon compounds such as thiophen.
- the carbonaceous ma erial may be conveyed from the electrolytic tank to the hopper by any suitable means.
- I have illustrated an inclined conveyer floor H down which the material may run from the tank to the hopper.
- Beneath this conveyer floor I have shown a heating device S, which may be of any suitable construction, such as steam pipes, for the purpose of drying the material as it passes to the coking apparatus.
- the carbonaceous material may be conveyed to the floor H by any suitable means.
- 1 have shown the tank as )rovided with a hinged door W, which may e opened to allow the material in the tank to ass therefrom to the floor H, it being unotwithstandingood, of course, that the solution is drained away, or separated from the material in any suitable manner.
- a hinged door W which may e opened to allow the material in the tank to ass therefrom to the floor H, it being unotwithstandingood, of course, that the solution is drained away, or separated from the material in any suitable manner.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
L. L. SUMMERS.
PROCESS OF GOKING'GOALS.
APPLIOATION FILED FEB.18, 1910.
968,499. Patented Aug.23,1910.
WITNESSES:
' IN VENTOR Mm 'Wwa:
A T TORNE Y To all whom it may concern:
" providin a method UNITED STATES PATENT OFFICE.
LELAND L. SUMMERS, OF CHICAGO,
COMPANY, A; CORPORATION or MAINE.
PROCESS OF COKING GOALS.
Specification of Letters Patent. Patented Aug, 23, 1910, Application filed February 18, 1910. Serial No. 544,625.
Be it known that I, LELAND L. SUMMERS, a citizen of the United States, residin at Ghica o, county of Cook, and State of dllinois, gave invented certain new and useful Improvements in the Process. of Coking Goals, of which the following is a specification.
The object of my invention is to provide a process of'coking by means of which coke maybe produced from coals having a comparatively high sulfur or phosphorus content and in particular the object of my invention is to provide a coking process in which the impurities existing in the coals, notably sulfur, phosphorus, iron, and silica,
. and similar impurities may be removed during the coking process, thus producing coke of suitable character for use as a. fuel for metallurgical purposes.
As is well known, sulfur and phosphorus existing in certain coals together with iron, and similar impurities are in such state or combination as to be detrimental to the coking process as carried on in the oven, because owing to the state or combination in which these naturally exist they are not readily volatilized as hereinafter explained. In general terms my process consists in by which such impurities are rst acted upon chemicallyso that their condition is changed and they are removed in part and in part become capable of being volatilized, and then the coals are subjected to the ordinary coking process durin which these volatile products are cause to pass off so that they are not precipitated as chemical compounds in the coke. The general characteristics of phosphorus resemble those of sulfur in formin phosphides and phosphates and also in orming various volatile compounds. Hence, the treatment for the sulfur will ordinarily re sult in the removal of phosphorus and in this specification the details covering the one will in general apply to theother, particularly as sulfur exists in much greater quantities than phosphorus in coal.
The following explanation in connection with the removal and treatment ofsulfur will in general be applicable to the removal and treatment of the phosphorus.
I will describe my invention in connection with an apparatus suitable for the practice ofsuch invention or method, yet it is to be understood that my invention is not limited in respect to the particular method of-partially removing and transforming sulfur and the like into volatile products, nor to any character of apparatus which may be used for. this purpose, but that my method may be practiced in other ways."
A portion ofthe sulfur in the coal ordinarily exists in the form of iron pyrites or bisulfid of iron -FeS Another'portion of the sulfur exists as the monosulfid of iron FeS and still another-portion exists as sesquisulfidFe s The monosulfid is readily decomposedby dilute mineral acids with the evolution of hydrogen sulfidand a salt of the metal, in accordance with the following equations:
.into the other form by oxidation and dilute acids. The action of oxygen and water on the bisulfid is expressed by the following. equation: n
ILLINOIS, AssIerioR T0 con'rmuousrnocnss COKE In the carrying out of my improved cok- 90.
ing process, I first treat the carbonaceous material to be coked chemically so that reactions Similar to those above described may be carried out and the sulfur and phos- 55 Referring to the drawings, an electrolytic shown) tank A of any suitable shape and dimeni sionsxis provided with revolvingelectrodes B and G mounted on the shaft D. and driven in. any desired manner as by the gears E and E and pulley E which in turn are electrical energy through the contact ring F and brush G and the electrode C is .con-
nected with the negativelead from the same source of electrical energy through contact ring F and brush G. The electrolytic tank A has a single compartment in which the electrodes of different polarity revolve, but if desired a double compartment may be employed, and the electrodes B and C placed in separate compartments, the prodnets of electrolysis being thus separatedas is well known in the art.
The. method so far described is based essentially upon the well known fact that upon the passage of an electric current in a suitable electrolyte,electrolytic decomposition will result.
According to my method as practiced, the coal to be electrolyzed is preferably in a finely subdivided form and is submerged in the electrolyte, so that upon revolving the electrodes B and C a continual agitation of the substance in contact with the products of electrolysis results. The electrolyte used may be varied to suit the substances existing in the coal, and may be conveyed into the tank by any suitable means such as a pump P.
. In this method of extracting the sulfur, I preferably use an acid or acid-forming electrolyte such as sulfuric acid in water or any soluble sulfate which will have a combined decomposing action on the sulfids of iron, the acids converting the monosulfid into hydrogen sulfid and a soluble sulfate, at the same time that oxygen and water are decomposing the bisulfid. As the electrolyte is decomposed by the electric current, the acid radical and the oxygen traveling to the ositive pole or anode causes an active and e ective action on the substances in the vicinity of the anode. Thus, the particles of FeS are oxidized in the electrolyte, the product bein soluble ferrous and ferric sulfate and by rogen sulfid, while the monosulfid of iron is acted upon by the acids. The sulfates, being soluble, are, of course, retained in the electrolytic solution, and are removed with said solution.
The hydro en sulfid formed by the above reactions is ecomposed by the oxygen, in accordance with the following equation:
The result of the action of this electrolyte u on the sulfide of iron has thus been to p ace the iron in solution and precipitate sulfur overthat contained in untreated coal. It is apparent, however,rthat the sulfur existing in the coal has been changed in its mode. of occurrence, so that itno longer is united to iron for which it has #a very pronounced chemical aflinityor heat of combination. It is also apparent that as the metallic particles have been entirely removed from the coal with which the sulfur will readily combine, the sulfur is free to combine with other. substances and upon char ing the coal into a coke oven and highIy heating the coal,the sulfur may be volatiliz'ed and particularly upon intimate contact with large quantities of hydrogen distilled from the coal with which hydrogen, sulfur can readily be caused to unite. The sulfur may, therefore, be distilled from the coal as a volatile compound with hydrogen such as hydrogen sulfid H 8, as volatile compound with carbon disulfid CS or as various hydrocarbon compounds such as thiophen.
In the foregoing description of the electrolytic treatment of the coal I have described one specific chemical treatment for the coal but it is to be understood that I do not intend thereby to limit my process to any special chemical treatment as any suitable method of causing .the necessary reactions may be employed.
A suitable oven for heating the carbonaceous material to drive off the volatilizable substances and complete the coking operation is described in my Patent No. 943,610 granted on the 14th day of December, 1909, to which reference is made for a more complete description. This patent shows an apparatus suitable for a continuous coking process in which the carbonaceous material to be coked is fedinto the retort and conveyed therethrough while the coking operation is going on. In the drawings, I have illustrated diagrammatically such a coking apparatus, I being the hopper into which the carbonaceous material is conveyed from the electrolytic tank to K, the coking retort. I have not here illustrated the feeding and conveying devices as these are fully shown and described in my patent above referred to.
The carbonaceous ma erial may be conveyed from the electrolytic tank to the hopper by any suitable means. In the drawing, I have illustrated an inclined conveyer floor H down which the material may run from the tank to the hopper. Beneath this conveyer floor I have shown a heating device S, which may be of any suitable construction, such as steam pipes, for the purpose of drying the material as it passes to the coking apparatus. i
The carbonaceous material may be conveyed to the floor H by any suitable means. In the drawing, 1 have shown the tank as )rovided with a hinged door W, which may e opened to allow the material in the tank to ass therefrom to the floor H, it being un erstood, of course, that the solution is drained away, or separated from the material in any suitable manner. As the particular means for accomplishing these results form no part of my present invention. I do not deem it necessary to describe them more fully.
It will be understood that while I have illustrated only one way in which my improved. process may be carried out, the process itself is not rcstricted to the particular form of a )paratus herein described andt-hatit may carried out in widely different formsof apparatus without departing from the spirit of my invention.
I claim:'
1. The process of coking carbonaceous material containing compounds of sulfur, phosphorus, or the like, which consists in first treating the carbonaceous material to transform the sulfur, phosphorus, or the like in said compounds into \"olatilizable condition and then subjecting the carbonaceous material to a coking temperature in a closed retort.
2. The process of coking carbonaceous material containing compounds of sulfur, phosphorus, or the like which consists in first chemically treating the carbonaceous material to transform the sulfur, phosphorus, or the like in said compounds into volatilizable condition, and then heating the said material in a closed retort.
3. The process of coking carbonaceous materiahwhich consists in chemically treatin said material to transform its content of su furcompounds and the like into volatilizable condition, then feeding said material to a heated coking retort and conveying the material through said retort.
material, thereby placing the sulfur, phosphorus, or thelike in said compounds in volatilizable condition, and then subjecting the carbonaceous material to a coking temperature in a closed retortwhereby the volatilizable substances are driven oil.
LELAND L. SUMMERS.
\Vitnesses M. E. Srnu'rnuuuon, IV. J. RYAN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54462510A US968499A (en) | 1910-02-18 | 1910-02-18 | Process of coking coals. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54462510A US968499A (en) | 1910-02-18 | 1910-02-18 | Process of coking coals. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US968499A true US968499A (en) | 1910-08-23 |
Family
ID=3036890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US54462510A Expired - Lifetime US968499A (en) | 1910-02-18 | 1910-02-18 | Process of coking coals. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US968499A (en) |
-
1910
- 1910-02-18 US US54462510A patent/US968499A/en not_active Expired - Lifetime
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