US4083944A
Expired / Lapsed
US
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Regenerative process for flue gas desulfurization
Assignee: Arthur G McKee and Co
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Filing: 1976-12-17
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Granted: 1978-04-11
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Expires: 1996-12-17
Abstract
Abstract A continuous process is disclosed for removing sulfur dioxide from stack gases or other gaseous effluents without prior gas cleaning or dust removal and for converting the sulfur values to industrially useable elemental sulfur. The uncleaned gaseous effluent is scrubbed using a buffered absorbent to absorb the SO 2 and remove particulate material, and the undissolved particulate material is removed from the scrubbing liquor as by filtration. The scrubbing liquor is then contacted with sulfide ion to form elemental sulfur while regenerating the absorbent in the liquor. Most of the liquor is separated from the precipitated sulfur and solid impurities, and the remaining material is heated to permit gravity separation of molten sulfur, scrubbing liquor and impurities. The separated scrubbing liquor is recycled for the scrubbing steps. The process is particularly advantageous when employing a sulfide ion source, such as sodium bisulfide or the like, to precipitate elemental sulfur. The NaHS solution is regenerated, for example by treating a portion of the scrubber effluent with calcium sulfide.
Inventors
- 👤 Franklin S. Chalmers
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 10:09
CPC Classifications
C; C01; C01B; C01B17/00; C01B17/02; C01B17/04; C01B17/05; B; B01; B01D; B01D53/00; B01D53/34; B01D53/46; B01D53/48; B01D53/50; B01D53/501
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
199 words
A method for removing sulfur dioxide from sulfur dioxide-containing gaseous emission having entrained solid contaminants therein, which method comprises: absorbing said sulfur dioxide and undissolved entrained solid contaminants in an acidic aqueous buffered absorbent from said gaseous emission in an absorption zone; separating undissolved entrained solid contaminants from said sulfur dioxide-containing buffered absorbent, passing to a sulfur precipitation and absorbent regeneration zone at least a portion of the sulfur dioxide-containing buffered absorbent from which undissolved entrained solid contaminants have been separated, introducing into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone sulfide ion in an amount sufficient to precipitate sulfur as elemental sulfur from said sulfur dioxide-containing buffered absorbent, heating said precipitated elemental sulfur along with said buffered absorbent and entrained precipitated solid impurities under conditions that melt said elemental sulfur while substantially suppressing vaporization of said buffered absorbent, maintaining said heating and said conditions to cause said elemental sulfur to remain molten for a sufficient period of time to allow phase separation by gravity of molten sulfur from buffered absorbent, of solid impurities from buffered absorbent, and solid impurities from molten sulfur, and recovering essentially pure elemental sulfur from a lower separated phase.
Claim 2
Independent Claim
199 words
A method for removing sulfur dioxide from sulfur dioxide-containing gaseous emission having entrained solid contaminants therein, which method comprises: absorbing said sulfur dioxide and undissolved entrained solid contaminants in an acidic aqueous buffered absorbent from said gaseous emission in an absorption zone; separating undissolved entrained solid contaminants from said sulfur dioxide-containing buffered absorbent, passing to a sulfur precipitation and absorbent regeneration zone at least a portion of the sulfur dioxide-containing buffered absorbent from which undissolved entrained solid contaminants have been separated, introducing into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone sulfide ion in an amount sufficient to precipitate sulfur as elemental sulfur from said sulfur dioxide-containing buffered absorbent, heating said precipitated elemental sulfur along with said buffered absorbent and entrained precipitated solid impurities under conditions that melt said elemental sulfur while substantially suppressing vaporization of said buffered absorbent, maintaining said heating and said conditions to cause said elemental sulfur to remain molten for a sufficient period of time to allow phase separation by gravity of molten sulfur from buffered absorbent, of solid impurities from buffered absorbent, and solid impurities from molten sulfur, and recovering essentially pure elemental sulfur from a lower separated phase.
Claim 3
Independent Claim
237 words
A method for removing sulfur dioxide from sulfur dioxide-containing gaseous emission having entrained solid contaminants therein, which method comprises, absorbing said sulfur dioxide and undissolved entrained solid contaminants in an acidic aqueous buffered absorbent from said gaseous emission in an absorption zone, separating undissolved entrained solid contaminants from said sulfur dioxide-containing buffered absorbent, passing to a sulfur precipitation and absorbent regeneration zone at least a portion of the sulfur dioxide-containing buffered absorbent from which undissolved entrained solid contaminants have been separated, introducing into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone sulfide ion in an amount sufficient to precipitate sulfur as elemental sulfur from said sulfur dioxide-containing buffered absorbent, heating said precipitated elemental sulfur along with said buffered absorbent and entrained precipitated solid impurities under conditions that melt said elemental sulfur while substantially suppressing vaporization of said buffered absorbent, maintaining said heating and said conditions to cause said elemental sulfur to remain molten for a sufficient period of time to allow phase separation by gravity of molten sulfur from buffered absorbent, of solid impurities from buffered absorbent, and solid impurities from molten sulfur, recovering essentially pure elemental sulfur from a lower separated phase, separating solid impurities from buffered absorbent in a separated phase, comprising buffered absorbent and solid impurities, above said lower separated phase of molten sulfur, and using said buffered absorbent from which solids have been removed in said absorption zone.
Claim 4
Independent Claim
237 words
A method for removing sulfur dioxide from sulfur dioxide-containing gaseous emission having entrained solid contaminants therein, which method comprises, absorbing said sulfur dioxide and undissolved entrained solid contaminants in an acidic aqueous buffered absorbent from said gaseous emission in an absorption zone, separating undissolved entrained solid contaminants from said sulfur dioxide-containing buffered absorbent, passing to a sulfur precipitation and absorbent regeneration zone at least a portion of the sulfur dioxide-containing buffered absorbent from which undissolved entrained solid contaminants have been separated, introducing into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone sulfide ion in an amount sufficient to precipitate sulfur as elemental sulfur from said sulfur dioxide-containing buffered absorbent, heating said precipitated elemental sulfur along with said buffered absorbent and entrained precipitated solid impurities under conditions that melt said elemental sulfur while substantially suppressing vaporization of said buffered absorbent, maintaining said heating and said conditions to cause said elemental sulfur to remain molten for a sufficient period of time to allow phase separation by gravity of molten sulfur from buffered absorbent, of solid impurities from buffered absorbent, and solid impurities from molten sulfur, recovering essentially pure elemental sulfur from a lower separated phase, separating solid impurities from buffered absorbent in a separated phase, comprising buffered absorbent and solid impurities, above said lower separated phase of molten sulfur, and using said buffered absorbent from which solids have been removed in said absorption zone.
Claim 5
Dependent Claim
26 words
The method of claim 1 in which vaporization of said buffered absorbent is prevented while said precipitated sulfur buffered absorbent and entrained solid impurities are heated.
Claim 6
Dependent Claim
28 words
The method of claim 2 including separating solid impurities from a separated phase of a mixture of sulfur and solid impurities and thereby recovering essentially pure elemental sulfur.
Claim 7
Dependent Claim
34 words
The method of claim 1 in which said elemental sulfur being heated is in an aqueous liquid and said sulfur and liquid are heated to a temperature of about 121° C. to 145° C.
Claim 8
Dependent Claim
34 words
The method of claim 2 in which said elemental sulfur being heated is in an aqueous liquid and said sulfur and liquid are heated to a temperature of about 121° C. to 145° C.
Claim 9
Dependent Claim
30 words
The method of claim 1 in which the buffered absorbent is an aqueous citrate solution, and sulfide ion is selected from the group consisting of hydrogen sulfide and sodium bisulfide.
Claim 10
Dependent Claim
30 words
The method of claim 2 in which the buffered absorbent is an aqueous citrate solution and sulfide ion is selected from the group consisting of hydrogen sulfide and sodium bisulfide.
Claim 11
Dependent Claim
34 words
The method of claim 1 in which the sulfide ion is selected from the group consisting of hydrogen sulfide, alkali metal sulfide and a source of hydrogen ion, alkali metal bisulfides, and ammonium bisulfide.
Claim 12
Dependent Claim
33 words
The method of claim 2 in which sulfide ion is selected from the group consisting of hydrogen sulfide, alkali metal sulfide and a source of hydrogen ion, alkali metal bisulfides, and ammonium bisulfide.
Claim 13
Independent Claim
231 words
A method of removing sulfur dioxide from sulfur dioxide-containing gaseous emission, which method comprises: absorbing sulfur dioxide in an acidic aqueous buffered absorbent from said gaseous emission, passing a portion of the sulfur dioxide-containing buffered absorbent to a sulfur precipitation and absorbent regeneration zone, introducing into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone, sulfide ion in the form of an aqueous solution of bisulfide, selected from the group consisting of alkali metal bisulfides, alkali metal sulfide and a source of hydrogen ion, and ammonium bisulfide, in an amount sufficient to precipitate sulfur in said sulfur dioxide-containing aqueous buffered absorbent as elemental sulfur, separating the elemental sulfur from the buffered absorbent and recycling said buffered absorbent to said absorption zone, passing a remaining portion of the sulfur dioxide-containing buffered absorbent from the first step set forth above to a sulfide generation zone, contacting said sulfur dioxide-containing buffered absorbent in said sulfide generation zone with sufficient quantities of a concentrated solution of alkaline earth metal sulfide to generate sulfide ion in the form of an aqueous solution of bisulfide selected from the group consisting of alkali metal bisulfides and ammonium bisulfide, and to precipitate alkaline earth metal sulfite, and separating said precipitated alkaline earth metal sulfite from said aqueous solution of bisulfide and passing said aqueous solution of bisulfide to said sulfur precipitation and absorbent regeneration zone.
Claim 14
Independent Claim
231 words
A method of removing sulfur dioxide from sulfur dioxide-containing gaseous emission, which method comprises: absorbing sulfur dioxide in an acidic aqueous buffered absorbent from said gaseous emission, passing a portion of the sulfur dioxide-containing buffered absorbent to a sulfur precipitation and absorbent regeneration zone, introducing into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone, sulfide ion in the form of an aqueous solution of bisulfide, selected from the group consisting of alkali metal bisulfides, alkali metal sulfide and a source of hydrogen ion, and ammonium bisulfide, in an amount sufficient to precipitate sulfur in said sulfur dioxide-containing aqueous buffered absorbent as elemental sulfur, separating the elemental sulfur from the buffered absorbent and recycling said buffered absorbent to said absorption zone, passing a remaining portion of the sulfur dioxide-containing buffered absorbent from the first step set forth above to a sulfide generation zone, contacting said sulfur dioxide-containing buffered absorbent in said sulfide generation zone with sufficient quantities of a concentrated solution of alkaline earth metal sulfide to generate sulfide ion in the form of an aqueous solution of bisulfide selected from the group consisting of alkali metal bisulfides and ammonium bisulfide, and to precipitate alkaline earth metal sulfite, and separating said precipitated alkaline earth metal sulfite from said aqueous solution of bisulfide and passing said aqueous solution of bisulfide to said sulfur precipitation and absorbent regeneration zone.
Claim 15
Independent Claim
199 words
The method for removing sulfur dioxide from sulfur dioxide-containing gaseous emission which method comprises absorbing sulfur dioxide in an acidic aqueous buffered absorbent from said gaseous emission, passing approximately one-third of the sulfur dioxide-containing buffered absorbent to a sulfur precipitation and absorbent regeneration zone, introducint into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone sulfide ion in the form of an aqueous solution of sodium bisulfide in an amount sufficient to precipitate the sulfur dioxide in said sulfur dioxide containing buffered absorbent as elemental sulfur, separating the elemental sulfur from the buffered absorbent and recycling said buffered absorbent to said absorption zone, passing the remaining approximately two-thirds of the sulfur dioxide-containing buffered absorbent from the first step set forth above to a sulfide generation zone, contacting said sulfur dioxide-containing buffered absorbent in said sulfide generation zone with sufficient quantities of a concentrated solution of calcium sulfide to generate sulfide ion in the form of an aqueous solution of sodium bisulfide and to precipitate calcium sulfite, and separating said precipitated calcium sulfite from said aqueous solution of sodium bisulfide and passing said aqueous solution of sodium bisulfide to said sulfur precipitation and absorbent regeneration zone.
Claim 16
Independent Claim
199 words
The method for removing sulfur dioxide from sulfur dioxide-containing gaseous emission which method comprises absorbing sulfur dioxide in an acidic aqueous buffered absorbent from said gaseous emission, passing approximately one-third of the sulfur dioxide-containing buffered absorbent to a sulfur precipitation and absorbent regeneration zone, introducint into said sulfur dioxide-containing buffered absorbent in said sulfur precipitation and absorbent regeneration zone sulfide ion in the form of an aqueous solution of sodium bisulfide in an amount sufficient to precipitate the sulfur dioxide in said sulfur dioxide containing buffered absorbent as elemental sulfur, separating the elemental sulfur from the buffered absorbent and recycling said buffered absorbent to said absorption zone, passing the remaining approximately two-thirds of the sulfur dioxide-containing buffered absorbent from the first step set forth above to a sulfide generation zone, contacting said sulfur dioxide-containing buffered absorbent in said sulfide generation zone with sufficient quantities of a concentrated solution of calcium sulfide to generate sulfide ion in the form of an aqueous solution of sodium bisulfide and to precipitate calcium sulfite, and separating said precipitated calcium sulfite from said aqueous solution of sodium bisulfide and passing said aqueous solution of sodium bisulfide to said sulfur precipitation and absorbent regeneration zone.
Claim 17
Dependent Claim
15 words
The method of claim 10 in which the buffered absorbent is an aqueous citrate solution.
Claim 18
Dependent Claim
15 words
The method of claim 11 in which the buffered absorbent is an aqueous citrate solution.
Claim 19
Dependent Claim
47 words
The method of claim 11 in which alkaline earth metal sulfate is precipitated with said alkaline earth metal sulfite, and in which said sulfate and sulfite are separated from said aqueous solution of bisulfide before said bisulfide is passed to said sulfur precipitation and absorbent regeneration zone.
Claim 20
Dependent Claim
48 words
The method of claim 12 in which calcium sulfate is precipitated with said calcium sulfite, and in which said calcium sulfate and calcium sulfite are separated from said aqueous solution of sodium bisulfide before said aqueous solution of sodium bisulfide to said sulfur precipitation and absorbent regeneration zone.
Claim 21
Dependent Claim
18 words
The method of claim 11 comprising reducing said separated alkaline earth metal sulfite to alkaline earth metal sulfide.
Claim 22
Dependent Claim
14 words
The method of claim 12 comprising reducing said separated calcium sulfite to calcium sulfide.
Claim 23
Dependent Claim
37 words
The method of claim 17 comprising leaching said alkaline earth metal sulfide with water to form a solution of alkaline earth metal sulfide that is passed to the sulfide generation zone, and removing solids separated by leaching.
Claim 24
Dependent Claim
31 words
The method of claim 18 comprising leaching said calcium sulfide to form a solution of calcium sulfide that is passed to the sulfide generation zone, and removing solids separated by leaching.
Claim 25
Dependent Claim
66 words
The method of claim 11 in which the hydrogen ion balance of the aqueous buffered absorbent is adjusted as required toward increasing acidity by partially carbonating said solution of alkaline metal earth metal sulfide prior to its contacting the sulfur dioxide-containing buffered absorbent, to increase acidity by converting alkaline earth metal sulfide to alkaline earth metal bisulfide with precipitation, followed by separation, of alkaline earth carbonate.
Claim 26
Dependent Claim
58 words
The method of claim 12 in which the hydrogen ion balance of the aqueous buffered absorbent is adjusted toward increasing acidity by partially carbonating the aqueous solution of calcium sulfide, prior to its contacting the sulfur dioxide-containing buffered absorbent, to increase the acidity by converting calcium sulfide to calcium bisulfide with precipitation, followed by separation, of calcium carbonate.
Claim 27
Dependent Claim
37 words
The method of claim 19 in which the hydrogen ion balance of the aqueous buffered absorbent is adjusted toward decreasing the acidity by adding alkaline earth carbonate to the precipitated alkaline earth sulfite prior to its reduction.
Claim 28
Dependent Claim
35 words
The method of claim 20 in which the hydrogen ion balance of said aqueous buffered absorbent is adjusted to decrease acidity by adding calcium earth carbonate to the precipitated calcium sulfite prior to its reduction.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-04-10 | 1981-10-10 | 1982-04-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-04-10 | 1985-10-10 | 1986-04-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-04-10 | 1989-10-10 | 1990-04-11 | $7700.00 | Window Closed / Lapsed |