Patent US4060586A successfully refreshed from Google Patents.
US4060586A
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Recovery of fluorides from gypsum
Assignee: Pennzoil Quaker State Co
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Filing: 1976-06-15
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Granted: 1977-11-29
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Expires: 1996-06-15
Abstract
Abstract In a process for the reaction of phosphate rock and sulfuric acid in the presence of potassium ion to form a mixture of phosphoric acid and a precipitated gypsum wherein the presence of the potassium ion causes precipitation of fluorides from the phosphate rock as potassium silicofluoride as a coprecipitate with the gypsum, and the phosphoric acid is separated from the gypsum slurry, the potassium silicofluoride is separated from the gypsum by extraction with phosphoric acid which may contain from 0-25 weight percent of sulfuric acid based on the amount of gypsum to be extracted or such phosphoric acid which may contain some fluorine. This extraction procedure provides a substantially fluoride-free gypsum product and an extraction solution containing recoverable potassium silicofluoride.
Inventors
- 👤 John B. Sardisco
- 👤 Erhart Karl Drechsel
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 05:47
CPC Classifications
C; C01; C01F; C01F11/00; C01F11/46; C01B; C01B25/00; C01B25/16; C01B25/18; C01B25/22; C01B33/00; C01B33/08; C01B33/10; C01B33/103
Claims Analysis
Total Claims: 10
Claim 1
Independent Claim
232 words
A method for conducting an acidulation reaction for the production of phosphoric acid, gypsum and alkali metal silicofluoride which comprises reacting phosphate rock, sulfuric acid, and potassium ion provided by addition of a member selected from the group consisting of KH 2 PO 4 , KHSO 4 , K 2 SO 4 , KOH and mixtures thereof, in sufficient amounts to acidulate the phosphate rock to form phosphoric acid and to cause precipitation of fluorides as potassium silicofluoride, containing the acidulation reaction to obtain reaction products comprising: a. a phosphoric acid solution; and b. a gypsum solids precipitate containing potassium silicofluoride; separating the gypsum precipitate from the phosphoric acid solution, removing the gypsum solids precipitate to an extractor maintained at a temperature of about 60°-100° C., contacting the gypsum in the extractor with an extractant solution selected from the group consisting of, (a) 5-30 weight percent phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum solids to be extracted, and (b) a fluorine-containing phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum being extracted, said extraction being carried out by contacting the gypsum mixture with a ratio of 3-10 parts of phosphoric acid solution per part of the gypsum mixture at a temperature of about 60°-100° C., separating and recovering the gypsum solids and a phosphoric acid extractant solution containing potassium silicofluoride.
Claim 2
Independent Claim
232 words
A method for conducting an acidulation reaction for the production of phosphoric acid, gypsum and alkali metal silicofluoride which comprises reacting phosphate rock, sulfuric acid, and potassium ion provided by addition of a member selected from the group consisting of KH 2 PO 4 , KHSO 4 , K 2 SO 4 , KOH and mixtures thereof, in sufficient amounts to acidulate the phosphate rock to form phosphoric acid and to cause precipitation of fluorides as potassium silicofluoride, containing the acidulation reaction to obtain reaction products comprising: a. a phosphoric acid solution; and b. a gypsum solids precipitate containing potassium silicofluoride; separating the gypsum precipitate from the phosphoric acid solution, removing the gypsum solids precipitate to an extractor maintained at a temperature of about 60°-100° C., contacting the gypsum in the extractor with an extractant solution selected from the group consisting of, (a) 5-30 weight percent phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum solids to be extracted, and (b) a fluorine-containing phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum being extracted, said extraction being carried out by contacting the gypsum mixture with a ratio of 3-10 parts of phosphoric acid solution per part of the gypsum mixture at a temperature of about 60°-100° C., separating and recovering the gypsum solids and a phosphoric acid extractant solution containing potassium silicofluoride.
Claim 3
Dependent Claim
36 words
A method according to claim 1 wherein the gypsum solids mixture is extracted with a phosphoric acid extracting solution containing up to about 0.3 parts of sulfuric acid per part of gypsum mixture to be extracted.
Claim 4
Dependent Claim
31 words
A method according to claim 1 wherein the gypsum solids mixture is extracted with a phosphoric acid extracting solution containing fluorine and about 5-25 weight percent P 2 O 5 .
Claim 5
Dependent Claim
23 words
A method according to claim 1 wherein the phosphoric acid extractant solution is obtained by washing the extracted gypsum precipitate with hot water.
Claim 6
Independent Claim
262 words
A method for conducting an acidulation reaction for the production of phosphoric acid, gypsum and potassium silicofluoride which comprises reacting phosphate rock, sulfuric acid, and potassium ion provided by addition of a member selected from the group consisting of KH 2 PO 4 , KHSO 4 , K 2 SO 4 , KOH, and mixtures thereof, in sufficient amounts to acidulate the phosphate rock to form phosphoric acid and to cause precipitation of fluorides as potassium silicofluoride, continuing the acidulation reaction to obtain reaction products comprising: a. a phosphoric acid solution; and b. a gypsum solids precipitate containing potassium silicofluoride; separating the gypsum precipitate from the phosphoric acid solution, removing the gypsum solids precipitate to an extractor maintained at a temperature of about 60°-100° C., contacting the gypsum in the extractor with an extractant solution selected from the group consisting of, (a) 5-30 weight percent phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum solids to be extracted, and (b) a fluorine-containing phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum being extracted, said extraction being carried out by contacting the gypsum mixture with a ratio of 3-10 parts of the phosphoric acid extractant solution per part of the gypsum mixture at a temperature of about 60°-100° C., separating and recovering the gypsum solids and a phosphoric acid extractant solution containing potassium silicofluoride, cooling the phosphoric acid extractant solution and precipitating the potassium silicofluoride from the solution, recovering the solid potassium silicofluoride, and recycling the extractant phosphoric acid to the extraction step.
Claim 7
Independent Claim
262 words
A method for conducting an acidulation reaction for the production of phosphoric acid, gypsum and potassium silicofluoride which comprises reacting phosphate rock, sulfuric acid, and potassium ion provided by addition of a member selected from the group consisting of KH 2 PO 4 , KHSO 4 , K 2 SO 4 , KOH, and mixtures thereof, in sufficient amounts to acidulate the phosphate rock to form phosphoric acid and to cause precipitation of fluorides as potassium silicofluoride, continuing the acidulation reaction to obtain reaction products comprising: a. a phosphoric acid solution; and b. a gypsum solids precipitate containing potassium silicofluoride; separating the gypsum precipitate from the phosphoric acid solution, removing the gypsum solids precipitate to an extractor maintained at a temperature of about 60°-100° C., contacting the gypsum in the extractor with an extractant solution selected from the group consisting of, (a) 5-30 weight percent phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum solids to be extracted, and (b) a fluorine-containing phosphoric acid containing up to 0.3 parts of sulfuric acid per part of gypsum being extracted, said extraction being carried out by contacting the gypsum mixture with a ratio of 3-10 parts of the phosphoric acid extractant solution per part of the gypsum mixture at a temperature of about 60°-100° C., separating and recovering the gypsum solids and a phosphoric acid extractant solution containing potassium silicofluoride, cooling the phosphoric acid extractant solution and precipitating the potassium silicofluoride from the solution, recovering the solid potassium silicofluoride, and recycling the extractant phosphoric acid to the extraction step.
Claim 8
Dependent Claim
61 words
A method according to claim 5 wherein the extraction of the gypsum solids containing the potassium silicofluoride is conducted with weak phosphoric acid containing fluorine, which weak phosphoric acid is obtained by washing of the gypsum solids obtained by the extraction step with sufficient water to form a weak phosphoric acid solution containing 5-25 weight percent P 2 O 5 .
Claim 9
Dependent Claim
36 words
A method according to claim 5 wherein the gypsum solids mixture is extracted with a phosphoric acid extracting solution containing up to about 0.3 parts of sulfuric acid per part of gypsum mixture to be extracted.
Claim 10
Dependent Claim
31 words
A method according to claim 5 wherein the gypsum solids mixture is extracted with a phosphoric acid extracting solution containing fluorine and about 5-25 weight percent P 2 O 5 .
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-11-28 | 1981-05-30 | 1981-11-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-11-28 | 1985-05-30 | 1985-11-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-11-28 | 1989-05-30 | 1989-11-29 | $7700.00 | Window Closed / Lapsed |