DE1118566B - Process for the regeneration of used sulfuric acid or phosphoric acid pickling solutions containing iron salts - Google Patents
Process for the regeneration of used sulfuric acid or phosphoric acid pickling solutions containing iron saltsInfo
- Publication number
- DE1118566B DE1118566B DEC17029A DEC0017029A DE1118566B DE 1118566 B DE1118566 B DE 1118566B DE C17029 A DEC17029 A DE C17029A DE C0017029 A DEC0017029 A DE C0017029A DE 1118566 B DE1118566 B DE 1118566B
- Authority
- DE
- Germany
- Prior art keywords
- iron
- ions
- pickling
- solution
- acid
- 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.)
- Pending
Links
- 238000005554 pickling Methods 0.000 title claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims description 5
- 159000000014 iron salts Chemical class 0.000 title claims description 5
- 230000008929 regeneration Effects 0.000 title description 4
- 238000011069 regeneration method Methods 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 13
- -1 iron ions Chemical class 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000003014 ion exchange membrane Substances 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 1
- 235000013980 iron oxide Nutrition 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000005374 membrane filtration Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 150000007513 acids Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Description
INTERNAT. KL. C 23 gINTERNAT. KL. C 23 g
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
C 17029 VIb/48dC 17029 VIb / 48d
BEKANNTMACHUNG DER ANMELDUNG UNDAUSGABEDERNOTICE THE REGISTRATION ANDOUTPUTE
In der Eisenbeizerei fallen sehr große Mengen von verbrauchten — sogenannten stumpfen — Beizsäufen an, die neben der Schwefelsäure so viel Eisensalze enthalten, daß sie nicht mehr zum Beizen verwendet werden können. Man beseitigt sie im allgemeinen so, daß man sie mit Kalk neutralisiert, in großen Absitzbecken klärt. Die überstehende, klare Flüssigkeit kann dann in den Vorfluter abgelassen werden. In gewissen Zeiträumen muß der Kalk-Eisen-Schlamm ausgegraben und auf Halde gebracht werden. Außer anderen Mängeln, die diesem Verfahren anhaften, benötigt es vor allen Dingen sehr viel Platz für die Absitzbecken und Arbeitskraft, wenn der Schlamm auf Halde gelegt werden muß; dabei geht die gesamte Schwefelsäure verloren. Außerdem bringt diese Art der Beseitigung von Beizsäuren eine große Belastung des Wasserhaushaltes mit sich. Es hat deshalb nicht an Versuchen gefehlt, das Abwasserproblem dadurch zu lösen, daß man die Beizsäuren regeneriert. Zum Beispiel ist die Abscheidung von Eisensulfat-mooo- bzw. -heptahydrat je nach dam angewandten Verfahren gebräuchlich, doch kann solches Eisensulfat nur in sehr hegrenzter Menge wirtschaftlich wiederverwendet werden. Die direkte elektrolytische Regeneration der Beizsäuren scheiterte an deren niedrigen pjj-Werten, bei denen eine Abscheidung des Eisens nicht möglich ist.In the iron pickling shop, very large quantities of used - so-called blunt - pickling drinks fall that contain so much iron salts in addition to sulfuric acid that they are no longer used for pickling can be. They are generally eliminated by neutralizing them with lime, in large settling basin clarifies. The supernatant, clear liquid can then be drained into the receiving water will. In certain periods of time the lime-iron sludge has to be dug up and dumped will. Besides other shortcomings inherent in this process, above all it is very much needed plenty of space for the settling basins and manpower when the sludge has to be dumped; all the sulfuric acid is lost in the process. Also, this brings out the elimination of Pickling acids have a major impact on the water balance. It therefore has no attempts there is no solution to the waste water problem by regenerating the pickling acids. For example that is Separation of iron sulfate mooo- or heptahydrate Commonly used depending on the process used, but such iron sulfate can only be used to a very great extent can be reused economically in a limited amount. The direct electrolytic regeneration of the Pickling acids failed because of their low pjj values, where a separation of the iron is not possible.
Es ist bekannt, .die -elektrolytische Regeneration von verbrauchten Beizsäuren unter Verwendung einer Anionenaustauschexmembian vorzunehmen, einer Membran also, die nur für Anionen durchlässig, für Kationen dagegen unpassierbar ist. Man arbeitet dabei so, daß die zu regenerierende Beizsäure in den Kathodenraum und verdünnte Schwefelsäure in den Anodenraum einer Elektrolysezelle gebracht werden. Während des Stromdurchganges wandern nun die SO4-Ionen aus der im Kathodenraum stehenden verbrauchten Beizsäure durch die Membran in den Anodenraum und bilden mit den dort entstehenden Wasserstoffionen Schwefelsäure. An der Kathode scheidet sich zunächst Wasserstoff ab; erst wenn der pjj-Wert auf etwa 2 angestiegen ist, scheidet sich Eisen an der Kathode ab. Da mit Verarmung der Kathodenflüssigkeit an Elektrolyten der Widerstand der Zelle ansteigt, ist es nicht möglich, eine vollständige Entsalzung des Katholyten zu erreichen. Man führt deshalb die teilweise vom Eisen befreite Beizsäure vom Kathoden- in den Anodenraum, um dort den Schwefelsäuregehalt zu erhöhen.It is known to carry out the electrolytic regeneration of spent pickling acids using an anion exchange exmembian, i.e. a membrane that is only permeable to anions but impassable to cations. One works in such a way that the pickling acid to be regenerated is brought into the cathode compartment and dilute sulfuric acid is brought into the anode compartment of an electrolysis cell. During the passage of the current, the SO 4 ions migrate from the used pickling acid in the cathode compartment through the membrane into the anode compartment and form sulfuric acid with the hydrogen ions produced there. Hydrogen is initially deposited on the cathode; only when the pjj value has risen to about 2 does iron deposit on the cathode. Since the resistance of the cell increases with the depletion of electrolytes in the catholyte, it is not possible to achieve complete desalination of the catholyte. The pickling acid, which has been partially freed of iron, is therefore led from the cathode to the anode compartment in order to increase the sulfuric acid content there.
Da bei diesem Verfahren an der Kathode zunächst Wasserstoff abgeschieden wird, entstehen relativ Verfahren zum Regenerieren verbrauchter, Eisensalze enthaltender Schwefelsäureoder PhosphorsäurebeizenSince hydrogen is initially deposited on the cathode in this process, relatively Process for regenerating spent sulfuric acid containing iron salts or Phosphoric acid pickling
Anmelder:Applicant:
Chemische Fabrik Budenheim Rudolf A. OetkerK.G., Budenheim, Rheinstr. 6Chemical factory Budenheim Rudolf A. OetkerK.G., Budenheim, Rheinstr. 6th
Dr. Harry Quitmann, Eltville, und Karl Götzmann, Budenheim, sind als Erfinder genannt wordenDr. Harry Quitmann, Eltville, and Karl Götzmann, Budenheim, have been named as inventors
große Stromverluste, die nur in einigen Fällen die Anwendung des Verfahrens .erlauben.large power losses, which only allow the use of the method in some cases.
Es wurde nun überraschenderweise gefunden, daß bessere Ergebnisse erzielt werden, wenn man die zu regenerierende Beizsäure in den Anodenraum der Elektrolysezelle bringt, während im Kathodenraum eine möglichst konzentrierte Eisensalzlösung vorgelegt wird. Vorzugsweise benutzt man hierzu eine solche Eisenlösung, wie sie z. B. zur Elektroplatüerung von Gegenständen bekannt ist, d.h. mit allen die Abscheidung des Eisens begünstigenden Zusätzen. Erfindungsgemäß werden die beiden Elektrodenräume durch eine Kationenaustauschermembran getrennt, d. h. eine Membran, die nur Kationen passieren läßt, Anionen dagegen zurückhält. Während der Elektrolyse wird nun das Eisen aus dem Anoden- in den Kathodenraum übergeführt und dort an der Elektrode abgeschieden. Die Lösung im Anodenraum verarmt an Eisen, d. h., die Säure wird regeneriert und wieder als Beize einsatzfähig gemacht. Wegen der relativ hohen Konzentration an Eisensalz und des höheren pjj-Wertes im Kathodenraum wird von Beginn der Elektrolyse an schon Eisen an der Kathode abgeschieden. Da es weiterhin für die Regenerierung der Beizsäure nicht erforderlich ist, das Eisen sehr weitgehend zu entfernen, sondern es ausreicht, die Konzentration der Eisenionen auf einem bestimmten, für die Beize günstigen Stand zu halten, ist es nicht nötig, das Eisen aus der Anodenflüssigkeit weitgehend zu entfernen. SomitIt has now surprisingly been found that better results are achieved if the pickling acid to be regenerated is brought into the anode compartment of the electrolysis cell while an iron salt solution which is as concentrated as possible is placed in the cathode compartment. For this purpose, such an iron solution is preferably used as it is, for. B. is known for Elektroplatüerung of objects, ie with all the additives favoring the deposition of iron. According to the invention, the two electrode spaces are separated by a cation exchange membrane, ie a membrane which only allows cations to pass through, while retaining anions. During the electrolysis, the iron is now transferred from the anode to the cathode compartment and deposited there on the electrode. The solution in the anode compartment is depleted in iron, ie the acid is regenerated and made usable again as a pickle. Because of the relatively high concentration of iron salt and the higher pjj value in the cathode compartment, iron is deposited on the cathode right from the start of the electrolysis. Since it is furthermore not necessary to remove the iron to a large extent for the regeneration of the pickling acid, but it is sufficient to keep the concentration of the iron ions at a certain level that is favorable for the pickling process, it is not necessary to largely remove the iron from the anolyte to remove. Consequently
109 747/527109 747/527
Claims (1)
Menge an Eisenionen anpaßt, die unter den gewählten Bedingungen die Austauschermembran leicht pas- 15 1. Verfahren zum Regenerieren verbrauchter, sieren kann. Man verhindert hierdurch ein Abfallen Eisensalze enthaltender Schwefelsäure- oder des pH-Wertes in der Kathodenflüssigkeit und behält Phosphorsäurebeizen durch Elektrolyse unter so dort die günstigsten Bedingungen für die Abschei- Verwendung von Ionenaustauschermembranen, dung des Eisens bei. Um die geringe Menge an Was- dadurch gekennzeichnet, daß die verbrauchte serstoffionen, die durch die Kationenaustauscher- 20 Beizsäure in den Anodenraum gebracht, im Kamembran übergeführt werden, zu beseitigen, kann thodenraum eine konzentrierte Eisensalzlösung man die Kathodenflüssigkeit z. B. über Eisenspäne, vorgelegt wird und die beiden Elektrodenräume Eisenoxyde usw. laufen lassen und so eine Stärkung durch eine Kationenaustauschermembran getrennt des pH-Wertes auf unerwünscht niedrige Werte ver- werden,
hindern. 25 2. Verfahren nach Anspruch 1, dadurch ge-if the current strength in the electrolysis vessel of the PATENT CLAIMS
Adjusts the amount of iron ions that can easily pass through the exchange membrane under the selected conditions. This prevents sulfuric acid containing iron salts or the pH value in the catholyte from falling, and phosphoric acid pickling is retained by electrolysis under the most favorable conditions for the separation of iron using ion exchange membranes. In order to eliminate the small amount of water, characterized in that the consumed hydrogen ions, which are brought into the anode compartment by the cation exchange 20 pickling acid, are transferred in the cam membrane, a concentrated iron salt solution can be added to the cathode liquid z. B. over iron filings, is introduced and run the two electrode chambers iron oxides, etc., and as a strengthening of the p H -value be locked to undesirably low values separated by a cation,
prevent. 25 2. The method according to claim 1, characterized in that
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU37321D LU37321A1 (en) | 1958-06-19 | ||
| DEC17029A DE1118566B (en) | 1958-06-19 | 1958-06-19 | Process for the regeneration of used sulfuric acid or phosphoric acid pickling solutions containing iron salts |
| BE579788A BE579788A (en) | 1958-06-19 | 1959-06-17 | Process for regenerating pickling and products obtained. |
| FR39540A FR1227199A (en) | 1958-06-19 | 1959-06-19 | Process for regenerating pickling acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC17029A DE1118566B (en) | 1958-06-19 | 1958-06-19 | Process for the regeneration of used sulfuric acid or phosphoric acid pickling solutions containing iron salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1118566B true DE1118566B (en) | 1961-11-30 |
Family
ID=7016162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC17029A Pending DE1118566B (en) | 1958-06-19 | 1958-06-19 | Process for the regeneration of used sulfuric acid or phosphoric acid pickling solutions containing iron salts |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE1118566B (en) |
| FR (1) | FR1227199A (en) |
| LU (1) | LU37321A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4326854A1 (en) * | 1993-08-11 | 1995-02-16 | Heraeus Elektrochemie | Process for the regeneration of an aqueous solution containing metal ions and sulfuric acid, and device |
| DE59504691D1 (en) * | 1994-03-07 | 1999-02-11 | Mib Metallurg Und Oberflaechen | ELECTROLYSIS METHOD FOR REGENERATING AN IRON III CHLORIDE OR IRON III SULFATE SOLUTION, ESPECIALLY FOR SPRAYING STEEL |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2636851A (en) * | 1949-07-09 | 1953-04-28 | Ionics | Ion-exchange materials and method of making and using the same |
| GB794368A (en) * | 1954-11-09 | 1958-04-30 | Rohm & Haas | Electrolytic treatment of waste sulfate pickle liquor |
-
0
- LU LU37321D patent/LU37321A1/xx unknown
-
1958
- 1958-06-19 DE DEC17029A patent/DE1118566B/en active Pending
-
1959
- 1959-06-19 FR FR39540A patent/FR1227199A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2636851A (en) * | 1949-07-09 | 1953-04-28 | Ionics | Ion-exchange materials and method of making and using the same |
| GB794368A (en) * | 1954-11-09 | 1958-04-30 | Rohm & Haas | Electrolytic treatment of waste sulfate pickle liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1227199A (en) | 1960-08-19 |
| LU37321A1 (en) |
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