US2827410A - Electrolytic refining of lead - Google Patents
Electrolytic refining of lead Download PDFInfo
- Publication number
- US2827410A US2827410A US658486A US65848657A US2827410A US 2827410 A US2827410 A US 2827410A US 658486 A US658486 A US 658486A US 65848657 A US65848657 A US 65848657A US 2827410 A US2827410 A US 2827410A
- Authority
- US
- United States
- Prior art keywords
- lead
- electrolyte
- chestnut extract
- goulac
- soluble
- 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
- 238000007670 refining Methods 0.000 title description 7
- 239000000284 extract Substances 0.000 claims description 34
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 241001070941 Castanea Species 0.000 description 28
- 235000014036 Castanea Nutrition 0.000 description 28
- 239000002253 acid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002195 soluble material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241001116389 Aloe Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 244000000188 Vaccinium ovalifolium Species 0.000 description 2
- 235000011399 aloe vera Nutrition 0.000 description 2
- AFHJQYHRLPMKHU-WEZNYRQKSA-N aloin B Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1[C@H]1C2=CC(CO)=CC(O)=C2C(=O)C2=C(O)C=CC=C21 AFHJQYHRLPMKHU-WEZNYRQKSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000219428 Fagaceae Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000005031 sulfite paper Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
Definitions
- the present invention relates to electrolytic refining of lead and more particularly it relates to a new and improved method using an aqueous electrolyte that is comprised of lead fluosilicate, fiuosilicic acid, the electrolytesoluble and water-soluble portions of goulac, and the electrolyte-soluble and water-soluble portions of chestnut extract.
- the practice of utilizing addition agents in the electrolyte solutions in the refining of metals has long been recognized as essential in order to improve the structure of the cathode when more or less pure metal is deposited in the electrolytic process.
- the ideal cathode, long sought after is one that is smooth surfaced, dense and uniform in purity of deposited metal.
- the cathodes produced by the electrodeposition process have fallen short of the ideal in that they have often had irregular or porous surfaces and have possessed protuberances in the form of trees, lumps or feathers.
- the pores in the surface of the cathode tends to collect and retain impurities from the electrolyte bath.
- the present invention comprises the use of a mixture of the water-soluble or. electrolyte-soluble portions of goulac and chestnut extract as an addition agent in a lead fiuosilicate electrolyte.
- water-soluble portions and electrolyte-soluble extract portions include respectively all water-soluble material and electrolyte-soluble materials present in the chestnut extract and the goulac. Inasmuch as we have not been able to identify all the materials present in such extracts and solutions and inasmuch as all such extracts and solutions may be used in the electrolytic bath of this invention, these terms are believed to be properly descriptive of the chestnut extract we have found useful.
- Chestnut extract may be made from the dried ground leaves (Castanca dentala) of the chestnut tree called Castanea of the family Fagaceae. These leaves contain to 99.5% water-soluble material.
- the extract is obtained by percolation with a suitable menstruum. The liquid so obtained is evaporated and the solid extract remains after evaporation is complete.
- the chestnut extract so manufactured is practically soluble in water and dissolves readily with very little agitation so that special equipment is not required for its percolation.
- Goulac also used in the electrolytic bath of this invention, is a by-product of the sulfite paper process obtained from the waste sulfite liquor. It consists essentially of lignin sulfates and sulfonates. It is also known as sulfite lignose.
- the electrolytic bath used in the present invention consists of an aqueous solution of lead fluosilicate and fluosilicic acid preferably containing from 4.0 percent to 9.5 percent lead as lead fiuosilicate and from 4.0 percent to 9.5 percent fluosilicic acid. Since both of these compounds partially dissociate in water into their constituent ions, the electrolytic bath contains lead ions, fiuosilicate ions, and hydrogen ions as well as undissociated electrolytes. In accordance with this invention there is then added to this electrolyte, for each ton of lead deposited on the cathodes, from 0.1 to 5.0 pounds of goulac and from 3.0 to 0.1 pounds of chestnut extract.
- the amounts of goulac and chestnut extract are complementary, in that the use of an increased amount of one calls for the use of a decreased amount of the other.
- goulac and chestnut extract addition agents may be varied within the relatively wide ranges indicated above, under normal conditions the best results are obtained within the somewhat narrower ranges of 1.0 to 2.0 lbs. of goulac and 0.9 to 0.3 lb. of chestnut extract.
- exceptional conditions due to a number of causes such as a change in current density, a shortage or change in the cost of one of the addition agents and numerous other conditions can make it necessary to change the rate of addition of goulac or chestnut extract toward or to one or the other of the extreme limits heretofore stated.
- the rule of complementary amounts which has been previously mentioned, is not a rigid one inasmuch as operating conditions have an effect on the amounts of addition agents that must be used.
- a suitable composition of the electrolytic bath for best economy of operation and production of satisfactory cathodes comprises an aqueous solution containing: lead (as lead fluosilicate) 85 grams per liter, fluosilicic acid 85 grams per liter. To this is added for each ton of lead pound, goulac 1.5 pounds. Under these conditions a current density of 14 amperes per square foot of anode surface and an electrolyte temperature of approximately 115 F. is satisfactory.
- the step which comprises the addition to the electrolyte for each ton'of lead deposited of from 0. 1 to 5.0 pounds of goulac and from 3.0 to 01 pound of material selected from the group consisting of water-soluble portions of chestnut extract and electrolyte-soluble portions of chestnut extract.
- the step which comprises the addition to the electrolyte for each ton of lead deposited of from 1.0 to 2.0 pounds of goulac and from 0.9 to 0.3 pound of material selected from the group consisting of Water-soluble portions of chestnut extract and electrolyte-soluble portions of chestnut extract.
- An electrolyte for depositing lead electrolytically consisting of water-soluble portions of chestnut extract and electrolyte-soluble portions of chestnut extract.
- An electrolyte for depositing lead electrolytically comprising an aqueous solution of lead fluosilicate and fluosilicic acid and containing for each ton of lead 'to be deposited approximately 1.5 pounds'goulac and 0.5 pound of material selected from the group consisting of water-soluble portions of chestnut extract and electrolytesoluble portions of chestnut extract.
- An electrolyte for depositing lead electrolytically comprising an aqueous solution of from 4.0% to 9.5 leadas lead fluosilicate, from 4.0% to 9.5 fiuosilicic acid and containing, for each ton of lead to be deposited from 0.1 to 5.0 pounds of goulac and from 3.0 to 0.! pounds of material selected from the group consisting of Water-soluble portions of chestnut extract and electrolytesoluble portions of chestnut extract.
- An electrolyte for depositiing lead electrolytically comprising an aqueous solution of from 4.0% to 9.5% lead as lead fluosilicate, from 4.0% to 9.5% llnosilicic acid and containing, for each ton of'lead to be deposited from 1.0 to. 2.0 pounds of goulac and from 0.9 to 0.3 pound of material selected from the group consisting of 3 water-soluble portions of chestnut extract and electrolytesoluble portions of chestnut extract.
- An electrolyte for depositing leadelectrolytically comprising an aqueous solution of from 4.0% to 9. 5% lead as lead fluosilicate, from 4.0% to 9.5% fluosilicic acid and containing, for each ton of lead to be deposited approximately 1.5 pounds goulac and 0.5 pound of material selected from the group consisting of Water-soluble portions of chestnut extract, and electrolyte-soluble p0rtions of chestnut extract.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Description
United States Patent TO ELECTROLYTIC surname or LEAD Frank C. Smyers, Munster, Ind, Grover B. Lantz, Corona Del Mar, Calif., and Frank C. Mathers, Bloonnington, Ind., assignors to United States Smeiting Refining and Mining Company, Boston, Mass, a corporation of Maine No Drawin Application May 13, 1957 Serial No. 658,486
8 Claims. (Cl. 204-114) The present invention relates to electrolytic refining of lead and more particularly it relates to a new and improved method using an aqueous electrolyte that is comprised of lead fluosilicate, fiuosilicic acid, the electrolytesoluble and water-soluble portions of goulac, and the electrolyte-soluble and water-soluble portions of chestnut extract.
The practice of utilizing addition agents in the electrolyte solutions in the refining of metals has long been recognized as essential in order to improve the structure of the cathode when more or less pure metal is deposited in the electrolytic process. In the electrolytic refining of lead, the ideal cathode, long sought after, is one that is smooth surfaced, dense and uniform in purity of deposited metal. However, in many instances the cathodes produced by the electrodeposition process have fallen short of the ideal in that they have often had irregular or porous surfaces and have possessed protuberances in the form of trees, lumps or feathers. The pores in the surface of the cathode tends to collect and retain impurities from the electrolyte bath. These impurities consist of valuable amounts of gold, silver and bismuth which can be recovered from the slimes if not entrapped Within the surface of the cathode. The protuberances are particularly objectionable in that they grow to such an extent that they cause short-circuits in the bath.
There have been a great number of materials used as addition agents, in different electrolyte baths, for the refining of different metals, to attempt to overcome these difficulties and to produce, as nearly as possible, the ideal cathode. While experiments have been conducted on a wide range of different materials, in varying types of baths, as yet there is no theory or satisfactory explanation that would predict how a material successfully utilized in one electrolytic system will aifect another system. In the refinement of lead by electrodeposition, the most commonly satisfactory addition agents have been glue and goulac in an aqueous electrolyte that is comprised of lead fiuosilicate and fluosilicic. acid (H SiF After long experimentation it was found that a mixture of aloes or aloin residue with goulac gives more satisfactory results (Mathers and Lantz Patent No. 2,664,393). An objection to the use of aloes or aloin residue has been its high cost.
Another serious objection to known addition agents has been their tendency to form gummy residues which plug the electrolyte circulation system. The plugging of the electrolyte circulation system results in poor distribution of the electrolyte. Some cells receive too much, causing them to overflow, while others receive too little, causing stratification of ions in the cells. In such an instance lead ions, being the heavier, tend to settle causing their concentration to be lowest in the upper part and highest in the lower part of the bath and the distribution of other ions and of undissociated electrolytes becomes unbalanced. This results in higher cell voltage, poor cathode deposits, uneven corrosion of the anode and increased percentages of impurities in the cathode,
ice
all of which cause poor current efiiciency and result in increased power and operating costs.
It is the principal object of the present invention to provide baths for electrolytic refining and electrodeposition of lead which are less expensive than those heretofore used, and further to provide a bath which is substantially free of gummy and resinous materials.
With this object in view, with others that willhereinafter appear, the present invention comprises the use of a mixture of the water-soluble or. electrolyte-soluble portions of goulac and chestnut extract as an addition agent in a lead fiuosilicate electrolyte.
The terms water-soluble portions and electrolyte-soluble extract portions include respectively all water-soluble material and electrolyte-soluble materials present in the chestnut extract and the goulac. Inasmuch as we have not been able to identify all the materials present in such extracts and solutions and inasmuch as all such extracts and solutions may be used in the electrolytic bath of this invention, these terms are believed to be properly descriptive of the chestnut extract we have found useful.
Chestnut extract may be made from the dried ground leaves (Castanca dentala) of the chestnut tree called Castanea of the family Fagaceae. These leaves contain to 99.5% water-soluble material. The extract is obtained by percolation with a suitable menstruum. The liquid so obtained is evaporated and the solid extract remains after evaporation is complete. The chestnut extract so manufactured is practically soluble in water and dissolves readily with very little agitation so that special equipment is not required for its percolation.
Goulac, also used in the electrolytic bath of this invention, is a by-product of the sulfite paper process obtained from the waste sulfite liquor. It consists essentially of lignin sulfates and sulfonates. It is also known as sulfite lignose.
The electrolytic bath used in the present invention consists of an aqueous solution of lead fluosilicate and fluosilicic acid preferably containing from 4.0 percent to 9.5 percent lead as lead fiuosilicate and from 4.0 percent to 9.5 percent fluosilicic acid. Since both of these compounds partially dissociate in water into their constituent ions, the electrolytic bath contains lead ions, fiuosilicate ions, and hydrogen ions as well as undissociated electrolytes. In accordance with this invention there is then added to this electrolyte, for each ton of lead deposited on the cathodes, from 0.1 to 5.0 pounds of goulac and from 3.0 to 0.1 pounds of chestnut extract. The amounts of goulac and chestnut extract are complementary, in that the use of an increased amount of one calls for the use of a decreased amount of the other.
Although the goulac and chestnut extract addition agents may be varied within the relatively wide ranges indicated above, under normal conditions the best results are obtained within the somewhat narrower ranges of 1.0 to 2.0 lbs. of goulac and 0.9 to 0.3 lb. of chestnut extract. However, exceptional conditions due to a number of causes such as a change in current density, a shortage or change in the cost of one of the addition agents and numerous other conditions can make it necessary to change the rate of addition of goulac or chestnut extract toward or to one or the other of the extreme limits heretofore stated. It will be understood that the rule of complementary amounts, which has been previously mentioned, is not a rigid one inasmuch as operating conditions have an effect on the amounts of addition agents that must be used.
A suitable composition of the electrolytic bath for best economy of operation and production of satisfactory cathodes comprises an aqueous solution containing: lead (as lead fluosilicate) 85 grams per liter, fluosilicic acid 85 grams per liter. To this is added for each ton of lead pound, goulac 1.5 pounds. Under these conditions a current density of 14 amperes per square foot of anode surface and an electrolyte temperature of approximately 115 F. is satisfactory. i Y
In'summary, it may be noted that one of the principal advantages of the invention lies in the solubility of chestnut extract. It may be added to the electrolyte as a solution or directly in the form of lumps or powder. (The weights given are for the extract in solid form.) The cathodes are equal or superior in quality to those obtained 'With'the hitherto preferred aloes-goulac agent.
Having thus described the invention, we claim: 7
1. In the electrolytic process of depositing lead in an aqueous electrolyte containing lead fiuosilicate, the step which comprises the addition to the electrolyte for each ton'of lead deposited of from 0. 1 to 5.0 pounds of goulac and from 3.0 to 01 pound of material selected from the group consisting of water-soluble portions of chestnut extract and electrolyte-soluble portions of chestnut extract.
2. In the electrolytic process of. depositing lead in an aqueous electrolyte containing lead fiuosilicate, the step which comprises the addition to the electrolyte for each ton of lead deposited of from 1.0 to 2.0 pounds of goulac and from 0.9 to 0.3 pound of material selected from the group consisting of Water-soluble portions of chestnut extract and electrolyte-soluble portions of chestnut extract.
3. An electrolyte for depositing lead electrolytically consisting of water-soluble portions of chestnut extract and electrolyte-soluble portions of chestnut extract.
5. An electrolyte for depositing lead electrolytically comprising an aqueous solution of lead fluosilicate and fluosilicic acid and containing for each ton of lead 'to be deposited approximately 1.5 pounds'goulac and 0.5 pound of material selected from the group consisting of water-soluble portions of chestnut extract and electrolytesoluble portions of chestnut extract.
6. An electrolyte for depositing lead electrolytically comprising an aqueous solution of from 4.0% to 9.5 leadas lead fluosilicate, from 4.0% to 9.5 fiuosilicic acid and containing, for each ton of lead to be deposited from 0.1 to 5.0 pounds of goulac and from 3.0 to 0.! pounds of material selected from the group consisting of Water-soluble portions of chestnut extract and electrolytesoluble portions of chestnut extract.
7. An electrolyte for depositiing lead electrolytically comprising an aqueous solution of from 4.0% to 9.5% lead as lead fluosilicate, from 4.0% to 9.5% llnosilicic acid and containing, for each ton of'lead to be deposited from 1.0 to. 2.0 pounds of goulac and from 0.9 to 0.3 pound of material selected from the group consisting of 3 water-soluble portions of chestnut extract and electrolytesoluble portions of chestnut extract.
8. An electrolyte for depositing leadelectrolytically comprising an aqueous solution of from 4.0% to 9. 5% lead as lead fluosilicate, from 4.0% to 9.5% fluosilicic acid and containing, for each ton of lead to be deposited approximately 1.5 pounds goulac and 0.5 pound of material selected from the group consisting of Water-soluble portions of chestnut extract, and electrolyte-soluble p0rtions of chestnut extract.
Transactions of the Electrochemical Society, volt 26' (1914), pp. 99-116 by Mathers.
Claims (1)
1. IN THE ELECTROLYTIC PROCESS OF DEPOSITING LEAD IN AN AQUEOUS ELECTROLYTE CONTAINING LEAD FLUOSILICATE, THE STEP WHICH COMPRISES THE ADDITION TO THE ELECTROLYTE FOR EACH TON OF LEAD DEPOSITED OF FROM 0.1 TO 5.0 POUNDS OF GOULAC AND FROM 3.0 TO 0.1 POUND OF MATERIAL SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE PORTIONS OF CHESTNUT EXTRACT AND ELECTORLYTE-SOLUBLE PORTIONS OF CHESTNUT EXTRACT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US658486A US2827410A (en) | 1957-05-13 | 1957-05-13 | Electrolytic refining of lead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US658486A US2827410A (en) | 1957-05-13 | 1957-05-13 | Electrolytic refining of lead |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2827410A true US2827410A (en) | 1958-03-18 |
Family
ID=24641437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US658486A Expired - Lifetime US2827410A (en) | 1957-05-13 | 1957-05-13 | Electrolytic refining of lead |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2827410A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2877165A (en) * | 1956-04-10 | 1959-03-10 | Cons Mining & Smelting Co | Process for the electrolytic refining of lead |
| US3002982A (en) * | 1959-04-08 | 1961-10-03 | Nepera Chemical Co Inc | Method of preparing 2-hydroxyethyl p-sulfamylcarbanilate |
| DE1180140B (en) * | 1962-07-20 | 1964-10-22 | Dehydag Gmbh | Process for the separation of fine-grained deposits in the refining and reduction electrolysis of nickel, zinc, silver, tin, lead and especially copper |
| US4124461A (en) * | 1978-03-03 | 1978-11-07 | Uop Inc. | Production of metallic lead |
| US4177117A (en) * | 1978-04-06 | 1979-12-04 | Cominco Ltd. | Bipolar refining of lead |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2664393A (en) * | 1951-05-16 | 1953-12-29 | Us Smelting Refining And Minin | Electrolytic refining of lead |
-
1957
- 1957-05-13 US US658486A patent/US2827410A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2664393A (en) * | 1951-05-16 | 1953-12-29 | Us Smelting Refining And Minin | Electrolytic refining of lead |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2877165A (en) * | 1956-04-10 | 1959-03-10 | Cons Mining & Smelting Co | Process for the electrolytic refining of lead |
| US3002982A (en) * | 1959-04-08 | 1961-10-03 | Nepera Chemical Co Inc | Method of preparing 2-hydroxyethyl p-sulfamylcarbanilate |
| DE1180140B (en) * | 1962-07-20 | 1964-10-22 | Dehydag Gmbh | Process for the separation of fine-grained deposits in the refining and reduction electrolysis of nickel, zinc, silver, tin, lead and especially copper |
| US4124461A (en) * | 1978-03-03 | 1978-11-07 | Uop Inc. | Production of metallic lead |
| US4177117A (en) * | 1978-04-06 | 1979-12-04 | Cominco Ltd. | Bipolar refining of lead |
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