GB1574990A - Control of alkali metal concentration in halogen electrotinning baths - Google Patents
Control of alkali metal concentration in halogen electrotinning baths Download PDFInfo
- Publication number
- GB1574990A GB1574990A GB1816579A GB1816579A GB1574990A GB 1574990 A GB1574990 A GB 1574990A GB 1816579 A GB1816579 A GB 1816579A GB 1816579 A GB1816579 A GB 1816579A GB 1574990 A GB1574990 A GB 1574990A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compartment
- tin
- alkali metal
- bath
- plating bath
- 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
Links
- 229910052736 halogen Inorganic materials 0.000 title claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 title claims description 7
- 150000001340 alkali metals Chemical class 0.000 title claims description 7
- 150000002367 halogens Chemical class 0.000 title description 7
- 238000007747 plating Methods 0.000 claims description 33
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 11
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000000909 electrodialysis Methods 0.000 claims description 5
- -1 tin halogen Chemical class 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
PATENT SPECIFICATION
( 11) 1 574 990 Application No 18165/79 ( 22) Filed 15 Aug 1977 Divided Out of No 1 574 988 Convention Application No.
716 225 ( 32) Filed 20 Aug 1976,in United States of America (US) Complete Specification published 17 Sept 1980
INT CL 3 C 25 D 21/22 3/30 Index at acceptance C 7 B 102 106 120 265 267 552 737 KC Inventor RICHARD E HORN ( 54) CONTROL OF ALKALI METAL CONCENTRATION IN HALOGEN ELECTROTINNING BATHS ( 71) We, PITT METALS AND CHEMICALS, INC, a corporation organised and existing under the laws of the Commonwealth of Pennsylvania, having its principal place of business at 4314 Main Street, Pittsburgh, Pennsylvania 15224, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: -
This invention relates to the control of the alkali metal concentration in halogen electrotinning baths.
A typical halogen electrotinning bath is disclosed in United States Patent 3,907,653.
The bath contains a tin fluoride complex with a fluostannite ion The fluoride complex in the bath is stable and does not precipitate the basic tin salts when the p H of the bath is within the range of 2 5 and 4.0.
During the tin-plating of strip steel, the strip very rapidly moves through the bath and air is introduced into the bath by the rapid movement of the strip steel and agitation from other sources The air introduced into the bath oxidizes a portion of the tin fluoride complex The oxidized tin is in the form of a stable anionic complex and has the formulation Na Sn F 6.
The oxidized tin compound does not have any adverse effects on the bath but, because of its low solubility, precipitates and settles to the bottom of the bath in a crystalline mass Sodium ferrocyanide is also added to the bath and reacts with the iron drawn in with the rapidly moving strip of sheet ' steel to form an iron ferrocyanide compound.
The oxidation process results in 'a loss of tin and fluoride compounds and increases the 'p H of the bath due 'to the formation 'of sodium hydroxide The loss of tin due to oxidation does not change the fluoride to tin mol ratio 'which is desirable to maintain at about 6 and 7 to 1 The increase in p H however, requires the addition of sodium bifluoride (Na F HF) 50 or hydrochloric acid to maintain the p H at the desired level of between about 2 5 and 4 0.
There has been a tendency in plating operations to install countercurrent rinsing 55 after the plating bath with the solution from the last stage of the countercurrent rinsing being returned to the plating bath proper The net result is that there is a general increase of total dissolved solids 60 in the plating bath Such an increase in dissolved solids creates a need for a means of reducing the p H in the halogen tinplating bath without increasing the total dissolved solids If the formation or amount 65 of sodium hydroxide or alkali metal hydroxide in the bath is controlled the p H will also 'be controlled and can be maintained at the desired level.
Broadly speaking, in accordance with the 70 present invention the alkali metal content of such baths, i e containing a tin-halogen complex e g a fluostannite or fluostannate, is controlled by electrodialysis either of the plating bath itself, or the rinse water, or 75 both.
More specifically, the process of the present invention comprises a tin-plating process which comprises electrodepositing tin on a workpiece from an aqueous tin-' 80 plating bath containing in solution a tinhaolgen complex and alkali metal ions, wherein the alkali metal content of the bath is controlled by periodically or continuously withdrawing a quantity of the 85 tin-plating bath, and/or rinse water from' rinsing step, passing said quantity of tinplating bath and/or said rinse water to an electrodialysis cell, said cell comprising an anode compartment containing an aqueous -90 ' o ( 21) Co ( 62) Ch ( 31) It ( 33) ( 44) ( 51) ( 52) ( 72) 1 574 990 anolyte, a cathode compartment containing an aqueous catholyte and a central compartment into which is fed said quantity of plating bath and/or said rinse water, and central compartment being separated from said anode and cathode compartments by cation permselective membranes, electrodialysing the plating bath and/or said rinse water whilst in said cell, thereby to effect migration of alkali metal ions through the permselective membrane into the cathode compartment from the central compartment and hydrogen ions from the anode compartment into the central compartment, and thereafter recycling the electrodialysed liquid from the central compartment to the plating bath.
The invention will be further described with reference to the accompanying drawings in which the single figure is a flow diagram illustrating a tin-plating tank, a reclaim rinse tank and a three compartment electrodialytic cell The circulation of the solution from either the plating tank or rinse tank to the centre compartment of the cell and the recycle of the tin compounds to the plating tank is diagrammatically illustrated.
Referring to the drawing, there is illustrated diagrammaticaly, a tin-plating process in which the material to be plated is electrochemically plated in the aqueous plating bath in a plating tank 150 The material after plating is transported to a first rinse tank 152 where the plated material is rinsed with water Subsequent to the first rinse, the material is transported to a second rinse tank 154 where the material is again rinsed with water.
The transfer of the material from the plating tank 150 to the first rinse tank 152 is indicated by the line 156 and the transfer of the material from the first rinse tank 152 to the second rinse tank 154 is indiciated by the line 158 Where strip steel is being plated it passes at high velocity from the plating bath 150 to the rinse tanks, and a substantial amount of the tin units are lost by drag out and where a halogen plating bath is used, the halogen tin complex is oxidized and precipitates in the bath and rinse water.
As previously explained this oxidation process results in a loss of tin and fluoride compounds and increases the p H of the bath due to the formation of sodium hydroxide.
In the process of the present invention as illustrated by the drawing the p H of the bath is controlled by withdrawing the plating solution through conduit 160, or the rinse water through conduit 162, and introducing the solution from conduit 160 or the rinse water from conduit 162 into a filter 164 Valves 166 and 168 are provided to control the flow to the filter 164 from either the plating bath in tank 150 or the rinse water tank 152 After the solution has been filtered in filter 164 it may be further treated to remove organic im 70 purities by suitable means and is thereafter introduced through conduit 170 to an electrodialytic cell 172 that has a centre compartment 174 and an anode compartment 176 and cathode compartment 178 75 The centre compartment 174 is separated from the anode compartment 176 by a cation permselective membrane 180 and the centre compartment is separated from the cathode compartment by a similar cation 80 permselective membrane 182 The cathode compartment contains an aqueous solution of an alkali metal hydroxide and a conventional cathode 184 The anode compartment contains an acid and an in 85 soluble anode 186 Conduit 188 is provided to supply make-up acid to the anode compartment 176.
When a current is impressed across the cell the alkali metal ions in the solution in 90 the centre compartment 174 migrate through the permselective membrane 182 to the cathode compartment 178 and hydrogen ions are passed from the anode compartment 176 and the solution withdrawn 95 from the centre compartment 174 through conduit 190 has a reduced concentration of alkali metal ions The solution withdrawn from the centre compartment 174 is fed through conduit 190 into the plating tank 100 150.
In this manner, excess alkali metal ions in the plating bath is removed The tin in solution which is in the form of either a fluostannite ion (Sn F 4)-2 or the fluostannate 105 ion (Sn F 6)-2 does not pass through either membrane 180 or 182 and is returned to the plating bath In addition, the three cell compartment prevents the tin from being oxidized as it is necessary to retain as much 110 tin as possible in the stannous (fluostannite) condition The process described herein is similar in certain respects to the process disclosed in our copending Application No.
34222/77 (Serial No 1574988) In that pro 115 cess, however, the tin is in the stannic (stannate) form and can be passed across the anode whereas in the process of this invention the tin is in the stannous condition and must be kept away from the 120 anode The permselective membrane 180 and 182 are conventional cation permselective membranes, a typical example being that manufactured by lonac Chemical Company and designated MC 3470 125 Although the embodiment illustrated in the drawing discloses a three compartment cell it should be understood that cells having a greater number of compartments may be employed as long as there is a 130 1 574 990 neutral' compartment between the anode and cathode compartments.
In conclusion, attention is drawn to our related and copending applications 34221/ 77 (Serial No 1574987) and 7918164 (Serial No 1574989).
Claims (6)
1 A tin-plating process, which comprises electrodepositing tin on a workpiece from an aqueous tin-plating bath containing in solution a tin halogen complex and alkali metal ions, wherein the alkali metal content of the bath is controlled by electrodialysis to remove excess alkali metal ions accumulating therein, said electrodialysis being performed in a divided electrodialytic cell comprising at least one anode compartment and at least one cathode compartment with a central compartment positioned therebetween and separated therefrom by cation permselective membranes.
2, A process according to claim 1, wherein the alkali metal content of the bath is controlled by periodically or continuously withdrawing a quantity of the tin-plating bath, and/or rinse water from rinsing step, passing said quantity of tinplating bath and/or said rinse water to an electrodialysis cell, said cell comprising an anode compartment containing an aqueous anolyte, a cathode compartment containing an aqeous catholyte and a central compartment into which is fed said quantity of plating bath and/or said rinse water, said 35 central compartment being separated from said anode and cathode compartments by cation permselective membranes, electrodialysing the plating bath and/or said rinse water whilst in said cell, thereby to effect 40 migration of alkali metal ions through the perselective membrane into the cathode compartment from the central compartment and hydrogen ions from the anode compartment into the central compartment, 45 and thereafter recycling the electrodialysed liquid from the central compartment to the plating bath.
3 A process according to claim 2, wherein said anolyte is an aqueous acid solution 50
4 A process according to claim 2 or 3, wherein said catholyte is an aqueous alkali metal hydroxide solution.
A process according to claim 1, 2 or 3, wherein the tin-halogen complex is a 55 fluostannate or stannite.
6 A process according to claim 1, substantially as hereinbefore described with reference to the accompanying drawings.
For the Applicants, D YOUNG & CO, Chartered Patent Agents, 9 & 10 Staple Inn, London, WC 1 V 7RD.
Printed for Her Majesty's Stationery Office by The Tweeddale Press Ltd, Berwick-upon-Tweed, 1980.
Published at the Patent Office, 25 Southampton Buildings, London, W$C 2 A l AY, from which copies may be obtained.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/716,225 US4111772A (en) | 1975-05-22 | 1976-08-20 | Process for electrodialytically controlling the alkali metal ions in a metal plating process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1574990A true GB1574990A (en) | 1980-09-17 |
Family
ID=24877233
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1816479A Expired GB1574989A (en) | 1976-08-20 | 1977-08-15 | Metal plating process |
| GB3422277A Expired GB1574988A (en) | 1976-08-20 | 1977-08-15 | Process for the control of the alkali metal hydroxide in metal plating baths |
| GB1816579A Expired GB1574990A (en) | 1976-08-20 | 1977-08-15 | Control of alkali metal concentration in halogen electrotinning baths |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1816479A Expired GB1574989A (en) | 1976-08-20 | 1977-08-15 | Metal plating process |
| GB3422277A Expired GB1574988A (en) | 1976-08-20 | 1977-08-15 | Process for the control of the alkali metal hydroxide in metal plating baths |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5326237A (en) |
| CA (1) | CA1133418A (en) |
| GB (3) | GB1574989A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2645292A1 (en) * | 1989-03-30 | 1990-10-05 | Morgane | Method and installation for regulating the pH of a medium which is reactional by electrodialysis |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439293A (en) * | 1981-03-09 | 1984-03-27 | Vaughan Daniel J | Electrodialytic purification process |
| CN112321047B (en) * | 2020-10-12 | 2025-05-23 | 光大绿色环保管理（深圳）有限公司 | A device and method for recycling nitric acid type tin stripping waste liquid |
| CN113003658B (en) * | 2021-01-21 | 2022-12-20 | 新疆新鑫矿业股份有限公司阜康冶炼厂 | Treatment process of nickel insoluble anode electrolyte |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5030354A (en) * | 1973-07-20 | 1975-03-26 |
-
1977
- 1977-08-15 GB GB1816479A patent/GB1574989A/en not_active Expired
- 1977-08-15 GB GB3422277A patent/GB1574988A/en not_active Expired
- 1977-08-15 GB GB1816579A patent/GB1574990A/en not_active Expired
- 1977-08-16 JP JP9860077A patent/JPS5326237A/en active Pending
- 1977-08-19 CA CA285,045A patent/CA1133418A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2645292A1 (en) * | 1989-03-30 | 1990-10-05 | Morgane | Method and installation for regulating the pH of a medium which is reactional by electrodialysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1133418A (en) | 1982-10-12 |
| GB1574988A (en) | 1980-09-17 |
| GB1574989A (en) | 1980-09-17 |
| JPS5326237A (en) | 1978-03-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |