Patent US4400360A successfully refreshed from Google Patents.
US4400360A
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Recovery of gadolinium and gallium oxides
Assignee: Honeywell International Inc
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Filing: 1982-12-01
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Granted: 1983-08-23
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Expires: 2002-12-01
Abstract
Abstract A process is described whereby the by-products derived from the fabrication of Gd 3 Ga 5 O 12 (GGG) wafers sliced from boules grown from Gd 2 O 3 and Ga 2 O 3 can be reprocessed in sufficient purity to be re-used in the process of growing GGG boules, thereby improving the economics of GGG wafer production. Gadolinium and gallium oxides are recovered and separated from transition metal impurities introduced during fabrication of GGG wafers. The "saw kerf" produced from slicing the crystal boule is dissolved in HCl and filtered to remove residual solids. Gasolinium oxalate is precipitated from the acidic solution by the addition of oxalic acid. Calcination at 850° C. resulted in the isolation of Gd 2 O 3 of >99.99 purity. The pH of the filtrate is adjusted to about 11 with alkali metal hydroxide followed by the addition of sulfide ion. The precipitated transition metal sulfides are removed by filtration. Excess sulfide is removed by treatment with 30% H 2 O 2 . The pH is adjusted to 8.5 and the gallium hydroxide, which precipitated, removed by filtration. Calcination at about 850° C. resulted in the recovery of Ga 2 O 3 in yields of the order of 95% and of 99.99% purity.
Inventors
- 👤 David Nalewajek
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 03:51
CPC Classifications
C; C01; C01G; C01G15/00; C01F; C01F17/00; C01F17/20; C01F17/206; C01F17/224; C01P; C01P2004/00; C01P2004/60; C01P2004/61; C01P2006/00; C01P2006/80
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
163 words
A method for recovering gadolinium and gallium oxides from by-product material which contains these oxides, transition metals and various other impurities comprising the steps of: (a) dissolving the by-product material which contains the gadolinium and gallium oxide in an acid medium, (b) isolating the filtrate, (c) precipitating gadolinium values from said filtrate by forming gadolinium oxalate, (d) separating, washing and drying the precipitated gadolinium oxalate, (e) converting the gadolinium oxalate salt from step (d) to gadolinium oxide by pyrolysis, (f) basifying the filtrate of step (b), (g) adding sulfide ion to the filtrate of step (f) to precipitate therefrom the transition metal sulfides from the aqueous solution and filtering the solids, (h) acidifying the filtrate from step (g) and oxidizing residual sulfide ion from said filtrate by the addition of an oxidant, and adjusting the pH of the filtrate to a base condition to precipitate gallium hydroxide, and (i) isolating, drying and calcining the gallium hydroxide from step (h) to yield gallium oxide.
Claim 2
Independent Claim
163 words
A method for recovering gadolinium and gallium oxides from by-product material which contains these oxides, transition metals and various other impurities comprising the steps of: (a) dissolving the by-product material which contains the gadolinium and gallium oxide in an acid medium, (b) isolating the filtrate, (c) precipitating gadolinium values from said filtrate by forming gadolinium oxalate, (d) separating, washing and drying the precipitated gadolinium oxalate, (e) converting the gadolinium oxalate salt from step (d) to gadolinium oxide by pyrolysis, (f) basifying the filtrate of step (b), (g) adding sulfide ion to the filtrate of step (f) to precipitate therefrom the transition metal sulfides from the aqueous solution and filtering the solids, (h) acidifying the filtrate from step (g) and oxidizing residual sulfide ion from said filtrate by the addition of an oxidant, and adjusting the pH of the filtrate to a base condition to precipitate gallium hydroxide, and (i) isolating, drying and calcining the gallium hydroxide from step (h) to yield gallium oxide.
Claim 3
Dependent Claim
22 words
The method of claim 1 wherein gadolinium and gallium oxide dissolved in step (a) is pretreated by pyrolyzing to remove organic impurities.
Claim 4
Dependent Claim
17 words
The method of claim 1 wherein the by-product material in step (a) is dissolved in hydrochloric acid.
Claim 5
Dependent Claim
23 words
The method of claim 1 wherein the gadolinium oxalate salt from step (e) is pyrolyzed at a temperature in excess of 800° C.
Claim 6
Dependent Claim
23 words
The method of claim 1 wherein the basifying of the filtrate in step (f) is adjusted to a pH in excess of 9.
Claim 7
Dependent Claim
18 words
The method of claim 1 wherein the pH in step (h) is adjusted to between 8 and 9.
Claim 8
Dependent Claim
19 words
The method of claim 1 wherein the gallium hydroxide in step (i) is pyrolyzed to at least 800° C.
Claim 9
Independent Claim
169 words
A method for recovering gadolinium and gallium oxides from by-product material which contains these oxides and various impurities comprising the steps of: (a) dissolving the gadolinium and gallium oxide in an acid medium, (b) isolating the filtrate, (c) precipitating gadolinium values from said filtrate by forming gadolinium oxalate, (d) separating, washing and drying the precipitated gadolinium oxalate, (e) converting the gadolinium oxalate salt from step (d) to gadolinium oxide by pyrolyzing at a temperature in excess of 800° C., (f) basifying the filtrate from step (b) to a pH in excess of about pH 9, (g) adding sulfide ion to the filtrate of step (f) and precipitating the transition metal sulfides from the aqueous solution and filtering the solids, (h) acidifying the filtrate from step (g) and removing remaining traces of sulfide ion from said filtrate by oxidizing same through the addition of hydrogen peroxide and thereafter adjusting the pH to about 8.5 to precipitate gallium hydroxide, and (i) isolating, drying and calcining the gallium hydroxide from step (h).
Claim 10
Independent Claim
169 words
A method for recovering gadolinium and gallium oxides from by-product material which contains these oxides and various impurities comprising the steps of: (a) dissolving the gadolinium and gallium oxide in an acid medium, (b) isolating the filtrate, (c) precipitating gadolinium values from said filtrate by forming gadolinium oxalate, (d) separating, washing and drying the precipitated gadolinium oxalate, (e) converting the gadolinium oxalate salt from step (d) to gadolinium oxide by pyrolyzing at a temperature in excess of 800° C., (f) basifying the filtrate from step (b) to a pH in excess of about pH 9, (g) adding sulfide ion to the filtrate of step (f) and precipitating the transition metal sulfides from the aqueous solution and filtering the solids, (h) acidifying the filtrate from step (g) and removing remaining traces of sulfide ion from said filtrate by oxidizing same through the addition of hydrogen peroxide and thereafter adjusting the pH to about 8.5 to precipitate gallium hydroxide, and (i) isolating, drying and calcining the gallium hydroxide from step (h).
Claim 11
Independent Claim
146 words
The method for recovering gadolinium and gallium oxides from by-product material which contains these oxides, transition metals and various other impurities comprising the steps of: (a) dissolving the by-product material which contains the gadolinium and gallium oxide in an acid medium, (b) isolating the filtrate, (c) precipitating gadolinium values from said filtrate by forming gadolinium oxalate, (d) separating, washing and drying the precipitated gadolinium oxalate, (e) converting the gadolinium oxalate salt from step (d) to gadolinium oxide by pyrolysis, (f) basifying the filtrate of step (b), (g) adding sulfide ion to the filtrate of step (f) to precipitate therefrom the transition metal sulfides from the aqueous solution and filtering the solids, (h) adding ammonium oxalate to the filtrate of step (g) to yield ammonium gallium oxalate as a precipitate, and (i) isolating, drying and calcining the ammonium gallium oxalate from step (h) to yield gallium oxide.
Claim 12
Independent Claim
146 words
The method for recovering gadolinium and gallium oxides from by-product material which contains these oxides, transition metals and various other impurities comprising the steps of: (a) dissolving the by-product material which contains the gadolinium and gallium oxide in an acid medium, (b) isolating the filtrate, (c) precipitating gadolinium values from said filtrate by forming gadolinium oxalate, (d) separating, washing and drying the precipitated gadolinium oxalate, (e) converting the gadolinium oxalate salt from step (d) to gadolinium oxide by pyrolysis, (f) basifying the filtrate of step (b), (g) adding sulfide ion to the filtrate of step (f) to precipitate therefrom the transition metal sulfides from the aqueous solution and filtering the solids, (h) adding ammonium oxalate to the filtrate of step (g) to yield ammonium gallium oxalate as a precipitate, and (i) isolating, drying and calcining the ammonium gallium oxalate from step (h) to yield gallium oxide.
Claim 13
Dependent Claim
27 words
The method of claim 9 wherein the by-product material from which gadolinium and gallium oxides are to be recovered is pretreated by pyrolyzing to remove organic material.
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) | 1986-08-22 | 1987-02-21 | 1987-08-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-22 | 1991-02-21 | 1991-08-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-22 | 1995-02-21 | 1995-08-23 | $7700.00 | Window Closed / Lapsed |