US1930143A - Bromide recovery from spent developers - Google Patents
Bromide recovery from spent developers Download PDFInfo
- Publication number
- US1930143A US1930143A US614622A US61462232A US1930143A US 1930143 A US1930143 A US 1930143A US 614622 A US614622 A US 614622A US 61462232 A US61462232 A US 61462232A US 1930143 A US1930143 A US 1930143A
- Authority
- US
- United States
- Prior art keywords
- silver
- electrolysis
- developer
- developers
- bromide
- 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
Links
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 title description 5
- 238000011084 recovery Methods 0.000 title description 5
- 229910052709 silver Inorganic materials 0.000 description 27
- 239000004332 silver Substances 0.000 description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 26
- 238000005868 electrolysis reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 230000003716 rejuvenation Effects 0.000 description 8
- 150000001649 bromium compounds Chemical class 0.000 description 7
- 239000003518 caustics Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- QFTLTYBDMFRHQI-UHFFFAOYSA-M [Br-].[Ag].[Ag+] Chemical compound [Br-].[Ag].[Ag+] QFTLTYBDMFRHQI-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229910052572 stoneware Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/31—Regeneration; Replenishers
Definitions
- the invention relates-to photographic developers and more particularly to the recovery by electrolysis of soluble bromides from spent developers and the subsequent reduction of the silver bromide thusformed to metallic silver.
- Our invention is a simple operation and comprises subjecting the spent developer in neutral or acid solution to electrolysis in which a silver element constitutes the anode and silver, carbon or other suitable metal constitutes the cathode. Silver bromide is thus which remains as pure metallic silver upon the; element which in the second electrolysis consti- This silver element may then tuted the cathode. be reused as the anode in the primary electrolysis of further spent developers.
- soluble bromides and other constitutents although it will be understood that-the particular developer treated is immaterial as photographic developers vary in composition according to the process for which they are employed and our process is directed merely to the recovery of soluble bromidesfrom any of the developers customarily employed in the art.
- a silver anode of suitable size and a cathode preferably constituted of carbon are placed in' the developer a short 80 distance apart and a current density of approximately 4 amperes per square foot is conducted between the, anode and cathode through the developer.
- the process will work with some degree of satisfaction with an alkaline developer, we have found it more satisfactory to make the developer neutral or slightly acid, .prior to the electrolysis, by pass 76 carbon dioxide through the developer or ad a small amount of an'acid, such as sulphuric or acetic.
- the developer may be reused in developing processes byj suitably balancing it to bring it back to its original formula; boiling the developer, removes bicarbonate or it may be neutralized with caustic alkali.
- the 'foregoingelectrolysis has merely removed bromide ions, at the expense of an equivalent or 95 greater amount of sulphite and developing agent, it will be apparent that mores'ulphite and developing agent, may be added to restore the de- X veloper to its original vigor.
- the advantage in this is, however, that those constituents necessary to be added are substantially less than would be needed to compound a fresh developer of the same bulk and strength and hence a considerable saving is effected.
- a sheet 'of silver as the modem theforegoing electrolysis, it is preferable to employ.
- the cathode may,
- the current density may be adjusted for greatest efliciency for each cell, it being understood that the current density may be gradually reduced a fraction of an ampere as the developer passes along through the various cells, for instance from five to ten cells in number, although more or less may be employed as found desirable to the skilled operator.
- silver bromide can now be reduced to substantially pure silver by removing the anode and subjecting it to further electrolysis in the opposite direction by making the silver-silver bromide element the cathode in a caustic soda or potash solution of a strength or from one per cent or less to a concentrated solution.
- an anode such as graphite, a
- the current density employed may be within the range employed in the first electrolysis and after electrolysis has continued for a short period it will be found that the bromine hasbeen split off from the silver, leaving substantially pure silver upon the oathode, sodium or potassium bromide being formed in solution.
- the sodium or potassium bromide thus produced may be concentrated and employed as desired, while the silver cathode may be withdrawn and used as an'anode in further primary electrolysis of spent developers.
- the process of producing silver which comprises subjecting a silver element coated with silver bromide as the cathode, to electrolysis in a caustic solution until substantially all of the silver bromide is reduced to silver.
Description
I Patented Oct. 1933 BROMIDE RECOVERY FROM SPENT DEVELOPERS Kenneth C. D. Hickman and Walter J. Weyerts, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New York No Drawing. Application May 31, 1932 Serial No. 614,622
6 Claims.
The invention relates-to photographic developers and more particularly to the recovery by electrolysis of soluble bromides from spent developers and the subsequent reduction of the silver bromide thusformed to metallic silver.
In photographic developing processes; soluble bromides accumulate in the developer, as it is continuously employed for the development of photographic negatives, to a point where the developer ceases to function satisfactorily, It has heretofore been usual to discard this developer, thus sustaining the loss of the more or less expensive constituents of the developer.
'We have found that thebromides may be recovered from spent developer by subjecting it to electrolysis and this in spite of the fact that sulphite and hydroquinoneor other developing agent residues are present in the developer which frequently are thought to impede or at least complicate electrolysis. Our invention is a simple operation and comprises subjecting the spent developer in neutral or acid solution to electrolysis in which a silver element constitutes the anode and silver, carbon or other suitable metal constitutes the cathode. Silver bromide is thus which remains as pure metallic silver upon the; element which in the second electrolysis consti- This silver element may then tuted the cathode. be reused as the anode in the primary electrolysis of further spent developers.
It is therefore an object of our invention to pro- 40 vide a process for the rejuvenation of spent developers which process may include the reduction of the silver bromide formed to substantially, pure silver. Other objects will appear from a perusal of the. following specification. In its simplest form, the process'constituting our invention may be carried out in a non-corrosible container such as glass or stoneware. Into this is placed a quantity of spent developer containing, for instance, sodium sulphite endearbonate, hydroquinonepr other developing agent,
soluble bromides and other constitutents, although it will be understood that-the particular developer treated is immaterial as photographic developers vary in composition according to the process for which they are employed and our process is directed merely to the recovery of soluble bromidesfrom any of the developers customarily employed in the art. A silver anode of suitable size and a cathode preferably constituted of carbon are placed in' the developer a short 80 distance apart and a current density of approximately 4 amperes per square foot is conducted between the, anode and cathode through the developer. While 4 amperes is approximately that preferred for an average spent developer, we may employ from one to twelve amperes per square foot, depending upon the progress of the recovery operation, it being understood that as the developer becomes more and more rejuvenated (and the bromine removed) the current density may be decreased somewhat. Although the process will work with some degree of satisfaction with an alkaline developer, we have found it more satisfactory to make the developer neutral or slightly acid, .prior to the electrolysis, by pass 76 carbon dioxide through the developer or ad a small amount of an'acid, such as sulphuric or acetic. After the electrolysis has continued for a short time it will be found that substantially all of the bromide in the developer has beende posited upon and combined with the silver anode to form silver bromide and the developer substantially rejuvenated. It is preferable to perform this electrolysis at a temperaturenear the freezing point of water, although considerable variation from this temperature'is permissible; the process, in fact, being operable even at room temperature. o
Following this rejuvenation the developer may be reused in developing processes byj suitably balancing it to bring it back to its original formula; boiling the developer, removes bicarbonate or it may be neutralized with caustic alkali. As the 'foregoingelectrolysis has merely removed bromide ions, at the expense of an equivalent or 95 greater amount of sulphite and developing agent, it will be apparent that mores'ulphite and developing agent, may be added to restore the de- X veloper to its original vigor. The advantage in this is, however, that those constituents necessary to be added are substantially less than would be needed to compound a fresh developer of the same bulk and strength and hence a considerable saving is effected. While we may employ a sheet 'of silver as the modem theforegoing electrolysis, it is preferable to employ. a porous composite of wires and :inert cage material'similanto the elements employed in anlidison battery. The cathode may,
be a relatively small carbon ormetal rod as no 'one, the developer being subjected to only a short treatment in each cell. Thus, the current density may be adjusted for greatest efliciency for each cell, it being understood that the current density may be gradually reduced a fraction of an ampere as the developer passes along through the various cells, for instance from five to ten cells in number, although more or less may be employed as found desirable to the skilled operator.
Assuming now that we have a silver anode upon which a quantity of silver bromide has been produced by the combination of the electrolyzed bromine with the silver, this: silver bromide can now be reduced to substantially pure silver by removing the anode and subjecting it to further electrolysis in the opposite direction by making the silver-silver bromide element the cathode in a caustic soda or potash solution of a strength or from one per cent or less to a concentrated solution. In this second or secondary electrolysis we may employ an anode such as graphite, a
noble metal or the like. The current density employed may be within the range employed in the first electrolysis and after electrolysis has continued for a short period it will be found that the bromine hasbeen split off from the silver, leaving substantially pure silver upon the oathode, sodium or potassium bromide being formed in solution. The sodium or potassium bromide thus produced may be concentrated and employed as desired, while the silver cathode may be withdrawn and used as an'anode in further primary electrolysis of spent developers.
It will be apparent that considerable variation from the details above given may be employed by those skilled in the art, but that such equivalents are intended to come within the scope of the claims appended hereto and forming a part hereof.
What we claim as our invention and desire to be secured by Letters Patent in the United States is:
1. The process of rejuvenating spent photographic developers containing soluble bromides in solution which comprises subjecting such developers to electrolysis in which a silver anode is employed until substantially all of the bromine has been deposited upon the anode of the electrolytic system.
2. The process of rejuvenating spent photographic developers containing soluble bromides in solution which comprises subjecting such developers to electrolysis in which a silver anode is employed until substantially all of the bromine has been deposited upon the anode of the electrolytic system and the bromine has combined with silver of the anode to form silver bromide.
3. The process of rejuvenating spent photographic developers containing soluble bromides in solution which comprises subjecting such developers to electrolysis with a silver anode until bromine is deposited upon and combined with silver of the anode and then subjecting such silver bromide-coated element as the cathode to electrolysis in the presence of a caustic solution.
4. The process of rejuvenating spent photographic developers containing soluble bromides in solution which comprises subjecting such developers to electrolysis with a silver anode until substantially all of the bromine isdeposited upon and combined with silver of the anode and then subjecting such silver bromide-coated element as the cathode to electrolysis in the presence of a caustic solution until substantially all of the silver bromide has been reduced to metallic silver.
5. The process of producing silver which comprises subject bromide, as t caustic solution.
6. The process of producing silver which comprises subjecting a silver element coated with silver bromide as the cathode, to electrolysis in a caustic solution until substantially all of the silver bromide is reduced to silver.
KENNETH C. D. HICKMAN. WALTER J. WEYERTS.
cathode, to electrolysis in a an element coated with silver
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US614622A US1930143A (en) | 1932-05-31 | 1932-05-31 | Bromide recovery from spent developers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US614622A US1930143A (en) | 1932-05-31 | 1932-05-31 | Bromide recovery from spent developers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1930143A true US1930143A (en) | 1933-10-10 |
Family
ID=24462052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US614622A Expired - Lifetime US1930143A (en) | 1932-05-31 | 1932-05-31 | Bromide recovery from spent developers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1930143A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3998710A (en) * | 1975-03-11 | 1976-12-21 | The Japan Carlit Co., Ltd. | Process for electrolytically purifying a photographic waste solution |
| US4046655A (en) * | 1974-02-21 | 1977-09-06 | The Japan Carlit Company, Ltd. | Process for electrolytically purifying a photographic developer waste solution |
| US4162206A (en) * | 1978-11-16 | 1979-07-24 | The United States Of America As Represented By The United States Department Of Energy | Separation of iodine from mercury containing scrubbing solutions |
-
1932
- 1932-05-31 US US614622A patent/US1930143A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046655A (en) * | 1974-02-21 | 1977-09-06 | The Japan Carlit Company, Ltd. | Process for electrolytically purifying a photographic developer waste solution |
| US3998710A (en) * | 1975-03-11 | 1976-12-21 | The Japan Carlit Co., Ltd. | Process for electrolytically purifying a photographic waste solution |
| US4162206A (en) * | 1978-11-16 | 1979-07-24 | The United States Of America As Represented By The United States Department Of Energy | Separation of iodine from mercury containing scrubbing solutions |
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