US3770630A - Treatment of electroless process and stripping solutions - Google Patents
Treatment of electroless process and stripping solutions Download PDFInfo
- Publication number
- US3770630A US3770630A US00177421A US3770630DA US3770630A US 3770630 A US3770630 A US 3770630A US 00177421 A US00177421 A US 00177421A US 3770630D A US3770630D A US 3770630DA US 3770630 A US3770630 A US 3770630A
- Authority
- US
- United States
- Prior art keywords
- solution
- metal
- waste
- workpiece
- treatment
- 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
- 238000011282 treatment Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 title description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 48
- 239000002184 metal Substances 0.000 abstract description 48
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 abstract description 13
- 239000002699 waste material Substances 0.000 abstract description 11
- 238000007772 electroless plating Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010892 non-toxic waste Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000001143 conditioned effect Effects 0.000 abstract description 2
- 239000010814 metallic waste Substances 0.000 abstract description 2
- 239000000615 nonconductor Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 229910052759 nickel Inorganic materials 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- -1 citric Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- the solution is then allowed to settle and is decanted with less than one mg./l. of dissolved metal content, and with precipitated solid metal waste being thus removed. Subsequently, the thus treated solution may be recirculated and if necessary, further conditioned for its particular use and then employed in an applicable rinsing operation. On the other hand, if desired, it can be discharged as a substantially non-toxic waste solution.
- This invention relates to an integrated or batch treatment of a used electroless process solution for substantially eliminating its dissolved metal content and particularly, to a treatment which will enable such a solution to be either discarded as non-toxic waste to the environment or to be recirculated and used in accomplishing workpiece washing or rinsing.
- Copper, nickel, cobalt are typical electroless plating metals that have been used as a base coating or layer on a workpiece to provide corrosion resistance. They represent the basis for a smooth and bright deposit, such as for a thin final chromium plated deposit, that may serve principally to protect the workpiece against surface oxidation and tarnish.
- the practice has been in electroplating to reduce the applicable metal on a workpiece employed as a cathode by providing the metal in ionic form, such as is easily available from an acid solution of the metal, or from its cyanide complex. In accordance with this procedure, the anion is reduced by hydrogen to yield the desired metal ion and deposit it on the cathode surface.
- a recent trend in the technology has as its aim the deposition of such a representative metal from a neutral or slightly acid solution on a workpiece of a specially prepared plastic or glass or other non-conducting base material. This necessitates at least applying the initial metallic deposit by means of a non-electrolytic process for rendering the surface conductive to make a subsequent electro depositing operation possible.
- a reducing agent such as formaldehyde, boron hydride, hypophosphite, etc., is used to reduce the metal 'ice from its salt or salts, as dissolved in the deposition solution, to a metallic form.
- Such a process generically has been termed making use of an electroless plating solution.
- the basic make-up of the two is somewhat similar. That is, disregarding the respective use of reducing or oxidizing agents and other additives to enhance the particular characteristics and performance of each type of solution, the basic makeup of both types of solutions employs solubilizing agents (chelating agents) for metal salts, such as of copper, nickel, cobalt. Chelating agents are used where the metal salts in an alkaline or slightly acidic solution would otherwise precipitate as insoluble hydroxides, carbonates or oxides of the particular metals.
- Solubilizing or chelating agents capable of such use are varied and extend from the simplest form as represented by ammonia and phosphates, to an array of organic amine complexes, such as aryl-, alkyl-amines, polyphosphates, organo-phosphate compounds; organic acids such as citric, acetic, boric and tartaric; a variety of hydroxyacetic and hydroxycarboxylic acids and their salts; and finally, a combination of organic acids with the amines.
- organic acids such as citric, acetic, boric and tartaric
- organic acids such as citric, acetic, boric and tartaric
- a variety of hydroxyacetic and hydroxycarboxylic acids and their salts and finally, a combination of organic acids with the amines.
- complexing agents such as ethylene diamine tetra acetic acid (EDTA), and nitrilo tetra acetic acid (NTA) or their salts.
- the usual requirement is to in some manner reduce the nickel or copper content of the waste solution to a one mg./1. level or less. This clearly was not obtained and could not be obtained by the above approaches.
- Another object has been to develop a process for after conditioning or treating electroless plating and metal stripping solutions to organically effect a separating-out of substantially the full dissolved metal content, in order that the solution can be reused for rinsing or discarded without adverse results.
- a further object of the invention has been to devise chemical means and operating conditions for effectively removing objectionable soluble metal content in a previously used aqueous solution formulated for electroless plating or metal stripping of a workpiece.
- the process has also been found to be well suited for the treatment of a discarded electroless treating solution that has outlived its usefulness, and that may contain a soluble metal concentration within a range of about 3 to 8 g./l. It was found to be equally suitable for treating a discarded metal stripping solution containing metals in a concentration of up to about 50 to 60 g./l. In the latter case, the treatment procedure is effected by firstwaterdiluting the waste until its soluble metal content is reduced to a range of about 3 to g./l.
- a process solu 4 tion can be made up containing an alkalinity and maintained within a pH range of about 5 to 9, with a sodium hydrosulfite concentration of about 50 to 500 mg./l. Higher concentrations of the sodium hydrosulfite were not found to be harmful.
- the above thus-prepared process solution can be used as an integrated treatment wash or rinse following an electroless plating or metal stripping process for the removal of the toxic metal containing chemical film carried-over on the workpiece.
- the wash solution is then taken-off for treatment from the washing bath or tank (see the tank C of the in-line operation represented by Lancy U.S. Pat. No. 2,725,314).
- the precipitation treatment of the takenoff solution can then be effected in a separate tank or reservoir (see the reservoir E of the reference patent) and the precipitate removed before the solution is rechan neled and reused, or is discarded by running it into a sewer, for example.
- wash solution taken-off from the reservoir is to be recirculated for reuse, it is provided with the desired alkalinity by adding alkaline metal hydroxide (hydride) or carbonate, and by adding the sodium hydrosulfite in proportion to the consumption thereof that is involved. It is important to maintain an excess quantity (above about 50 mg./l.) of sodium hydrosulfite and thus, the effectiveness of the reducing condition.
- a typical treatment system may employ a batch dumping of the process solution from either an electroless plating solution or metal workpiece stripping treatment. This involves first acidfying the solution to preferably a pH of about 5 and if highly alkaline in nature, to at least reduce the pH to about 8 or 9. Secondly, the batch waste solution should be diluted so that its metal content concentration is not more than 5 g./l. Thirdly, the solution should be heated to at least and preferably or as an optimum to about or higher.
- alkalinity is added along with an excess (above a stoichiometric amount) of sodium hydrosulfite so as to provide the solution with an excess of the latter of at least about 50 mg./l., but as an optimum higher, and up to about 500 mg./l.
- the solution is then allowed to settle and the treated liquid is decanted, resulting in a content of less than one mg./l. of dissolved metal.
- the solid waste is removed and discarded which, of course, is insoluble and thus suitable for solid waste disposal.
- the same process may be used for a chemical treatment rinse or for an integrated and recirculated treatment wash solution, with the described chemical conditions being maintained by either adding alkalinity to provide the desired higher pH after an acidic treating process or for an acidic solution.
- An alkali metal salt such as calcium chloride will tend to precipitate and thereby reduce the pH; it can be used while maintaining the reducing conditions through continuous or intermediate hydrosulfite additions to maintain in the necessary excess.
- a waste rinsing, electroless process or a metal stripping solution containing metals dissolved therein of the class consisting of copper, nickel and cobalt that are in the form of stable complexes due to the presence of a solubilizing complexing agent in the nature of a chelating agent and thus are difficult to precipitate out the steps of first providing the solution wtih a slightly acid to slightly alkaline pH within a maximum of about 9, adding water to the solution as may be required to assure a dilute soluble metal content concentration of not more than a maximum of about 5 g./l.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Chemically Coating (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17742171A | 1971-09-02 | 1971-09-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3770630A true US3770630A (en) | 1973-11-06 |
Family
ID=22648533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00177421A Expired - Lifetime US3770630A (en) | 1971-09-02 | 1971-09-02 | Treatment of electroless process and stripping solutions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3770630A (OSRAM) |
| JP (1) | JPS517949B2 (OSRAM) |
| CA (1) | CA952657A (OSRAM) |
| CH (1) | CH594059A5 (OSRAM) |
| DE (1) | DE2242473A1 (OSRAM) |
| GB (1) | GB1344787A (OSRAM) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4083915A (en) * | 1975-11-20 | 1978-04-11 | Kennecott Copper Corporation | Cobalt stripping process |
| US4200526A (en) * | 1978-03-06 | 1980-04-29 | Gerber Products Company | Process for treating waste water |
| US4260493A (en) * | 1979-05-21 | 1981-04-07 | Shipley Company, Inc. | Solution waste treatment |
| US4420401A (en) * | 1979-05-21 | 1983-12-13 | Shipley Company Inc. | Solution waste treatment |
| US4670244A (en) * | 1984-10-15 | 1987-06-02 | Hoechst Aktiengesellschaft | Process for reducing metal ions in aqueous solutions |
| US4789484A (en) * | 1988-02-22 | 1988-12-06 | Occidental Chemical Corporation | Treatment of electroless nickel plating baths |
| US5006262A (en) * | 1989-11-21 | 1991-04-09 | Met. Rev. Inc. | Process for recovering copper from copper ion containing aqueous solutions |
| US5122279A (en) * | 1991-04-08 | 1992-06-16 | Romar Technologies Inc. | Ferrous dithionite process and compositions for removing dissolved heavy metals from water |
| US5354458A (en) * | 1990-07-11 | 1994-10-11 | International Environmental Systems, Inc., Usa | Sequencing batch liquid treatment |
| US5462670A (en) * | 1991-04-08 | 1995-10-31 | Romar Technologies, Inc. | Process for removing oils and greases from aqueous solution |
| US5976383A (en) * | 1991-04-08 | 1999-11-02 | Romar Technologies, Inc. | Recycle process for removing dissolved heavy metals from water with aluminum particles |
| USH1852H (en) * | 1997-12-05 | 2000-06-06 | Morton International Inc. | Waste treatment of metal plating solutions |
| WO2001030693A1 (en) * | 1999-10-28 | 2001-05-03 | Aron Vecht | Preparation of sulphides |
| US20030085177A1 (en) * | 2001-11-06 | 2003-05-08 | Dubin Valery M. | Method of treating an electroless plating waste |
| US20080083623A1 (en) * | 2006-10-04 | 2008-04-10 | Golden Josh H | Method and apparatus for treatment of plating solutions |
| US20080083673A1 (en) * | 2006-10-04 | 2008-04-10 | Golden Josh H | Method and apparatus for treatment of plating solutions |
| CN113526731A (zh) * | 2021-07-26 | 2021-10-22 | 哈尔滨工业大学 | 一种六价铬-乙酸盐复合体系中六价铬的强化去除方法 |
| CN113526747A (zh) * | 2021-08-30 | 2021-10-22 | 江苏理工学院 | 一种pta残渣高浓度含溴废水高值化利用的方法 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50103471A (OSRAM) * | 1974-01-18 | 1975-08-15 | ||
| JPS5480242U (OSRAM) * | 1977-11-17 | 1979-06-07 | ||
| SE446562B (sv) * | 1982-03-04 | 1986-09-22 | Malte Skoog | Plattvermevexlare med turbulensalstrande asar innefattande ett forsta slag av plattor der asarna bildar viss vinkel med plattans langsida och ett andra slag med en viss annan vinkel |
| JP2843887B2 (ja) * | 1989-03-28 | 1999-01-06 | 株式会社日阪製作所 | ３液プレート式熱交換器 |
| DE4013974C1 (OSRAM) * | 1990-04-30 | 1991-09-19 | Guenter Dipl.-Ing. 5100 Aachen De Straten | |
| DE4136939A1 (de) * | 1990-11-22 | 1992-05-27 | Sandoz Ag | Verfahren zur reinigung von kupfer-enthaltenden industrieabwassern |
| JPH0646216U (ja) * | 1992-11-30 | 1994-06-24 | 新日軽株式会社 | 壁内設置型空調機の排水装置 |
| CN109609988B (zh) * | 2019-01-04 | 2020-07-07 | 武汉船用机械有限责任公司 | 一种管件镀前清洗方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3537896A (en) * | 1968-09-23 | 1970-11-03 | Lancy Lab | Beneficial after-treatment of workpieces |
-
1971
- 1971-09-02 US US00177421A patent/US3770630A/en not_active Expired - Lifetime
-
1972
- 1972-08-22 CA CA150,275A patent/CA952657A/en not_active Expired
- 1972-08-29 DE DE2242473A patent/DE2242473A1/de active Pending
- 1972-08-31 CH CH1282972A patent/CH594059A5/xx not_active IP Right Cessation
- 1972-09-01 GB GB4072672A patent/GB1344787A/en not_active Expired
- 1972-09-01 JP JP7287216A patent/JPS517949B2/ja not_active Expired
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4083915A (en) * | 1975-11-20 | 1978-04-11 | Kennecott Copper Corporation | Cobalt stripping process |
| US4200526A (en) * | 1978-03-06 | 1980-04-29 | Gerber Products Company | Process for treating waste water |
| US4260493A (en) * | 1979-05-21 | 1981-04-07 | Shipley Company, Inc. | Solution waste treatment |
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| CN113526731A (zh) * | 2021-07-26 | 2021-10-22 | 哈尔滨工业大学 | 一种六价铬-乙酸盐复合体系中六价铬的强化去除方法 |
| CN113526731B (zh) * | 2021-07-26 | 2022-07-01 | 哈尔滨工业大学 | 一种六价铬-乙酸盐复合体系中六价铬的强化去除方法 |
| CN113526747A (zh) * | 2021-08-30 | 2021-10-22 | 江苏理工学院 | 一种pta残渣高浓度含溴废水高值化利用的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1344787A (en) | 1974-01-23 |
| JPS517949B2 (OSRAM) | 1976-03-12 |
| CA952657A (en) | 1974-08-13 |
| DE2242473A1 (de) | 1973-10-18 |
| JPS4833663A (OSRAM) | 1973-05-11 |
| CH594059A5 (OSRAM) | 1977-12-30 |
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