EP2173929A1 - Process recycling of electroplating baths - Google Patents
Process recycling of electroplating bathsInfo
- Publication number
- EP2173929A1 EP2173929A1 EP08773942A EP08773942A EP2173929A1 EP 2173929 A1 EP2173929 A1 EP 2173929A1 EP 08773942 A EP08773942 A EP 08773942A EP 08773942 A EP08773942 A EP 08773942A EP 2173929 A1 EP2173929 A1 EP 2173929A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- reactor
- mixture
- heat
- evaporation
- 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.)
- Withdrawn
Links
Classifications
-
- 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
-
- 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
Definitions
- the invention relates to a method for producing a metallic coating on a substrate, in particular on a conductive substrate, comprising the deposition of at least one metal in a galvanic bath from an aqueous, organic additives and at least one electrolyte in dissolved form and at least one rinsing process, in which the coated substrate is freed of electrolyte residues.
- the invention relates to a device for the UV treatment of an aqueous, organic additives and at least one electrolytic solution containing metal in dissolved form, which can be used in such a process.
- the electrolytes used in a galvanic deposition generally contain various organic additives which are said to improve the properties of the electrolytes with regard to the quality of the metal layer to be deposited and with regard to its chemical resistance.
- the additives - due to chemical oxidation and reduction processes - are at least partially converted over time into a large number of organic decomposition products which reduce the efficiency of the electrolyte and possibly lead to coating defects. At regular intervals, therefore, the electrolyte used in a galvanic bath must be replaced.
- metals contained in the electrolyte are lost.
- there is a continuous loss of electrolyte since a residue of electrolyte always adheres to coated substrates, which must subsequently be removed in one or more rinsing operations.
- the spent rinse waters accordingly contain a small amount of the metal to be deposited.
- An immediate return of the rinsing water in a galvanic bath is not possible because the metal concentration in the rinse water is too low.
- the rinse waters can not be easily discarded. Instead, they must be fed to a costly and expensive disposal.
- Such a recycling process is known, for example, from DE 103 25 101, in which a method is described according to which a portion of the electrolyte contained therein is taken from a galvanic bath, an oxidizing agent is added to the removed portion, and the removed electrolyte is UV-coated Light is irradiated and then returned to the galvanic bath after supplementing the destroyed organic additives.
- a method according to the invention is used for producing a metallic layer or coating on a substrate, in particular for producing a metallic coating on a conductive substrate.
- the conductive substrate may be, for example, a metal substrate or a metallized circuit board.
- the method according to the invention comprises at least one rinsing process in which the coated substrate is freed from electrolyte residues.
- the substrate is preferably rinsed with water, in particular with deionized water.
- the organic additives are, in particular, brighteners, levelers, wetting agents and further additives such as polypropylene glycol, benzotriazoles, derivatives of the thiourea, polyamines, etc. Suitable additives are known to the person skilled in the art and need no further explanation in the context of the present description.
- the organic additives in a galvanic deposition by chemical oxidation and reduction processes can be at least partially converted into a variety of organic degradation products, which is why an electrolyte used in a galvanic process must be regularly replaced or recycled. This is also provided according to the invention.
- the electrolyte is removed from the bath for this purpose.
- the withdrawn electrolyte is not processed directly, instead the removed electrolyte is mixed with rinsing water, which is forcibly obtained in the mentioned rinsing processes. This has the at least one metal present in dissolved form, as a rule in low concentrations.
- the mixture of the removed electrolyte and the rinse water is then passed through at least one UV reactor. In this organic compounds contained in the mixture and degradation products of these additives by irradiation with UV light at least partially converted into carbon dioxide, which can then be removed from the mixture.
- the mixture is at least partially evaporated or concentrated by evaporation. This is preferably done in at least one evaporation device, in which the mi can be transferred for this purpose.
- the water vapor formed during evaporation can be removed from the evaporation device.
- the carbon dioxide can be removed together with the resulting water vapor.
- rinsing water obtained is therefore not discarded or disposed of, but it is sent for recycling. It is thus ensured that metals are not discharged undesirably from the galvanic bath and lost. This increases the efficiency of the process and protects the environment. In addition, if necessary, high-quality condensate (from the water vapor) is obtained, which can also be recycled.
- the amount of energy necessary for evaporation can basically be introduced into the mixture via the at least one UV reactor. This is preferably done both by its own heat output and by the reaction heat released by the chemical reaction
- a method according to the invention is characterized in particular by the fact that it is optimized from an energy point of view. More preferably, the thermal energy to be expended is at least partially recovered from the water vapor. As an alternative or in addition to this measure, in a method according to the invention the heat energy to be expended can be provided at least partially by at least one separate heat generating unit. It has been shown that, with regard to the overall energy balance of the method according to the invention, rens is much more advantageous than to introduce the heat energy required for constriction exclusively in the mixture via the UV reactor.
- the mixture of withdrawn electrolyte and rinse water is usually highly diluted, which is why the concentration step described above is usually required when the mixture of withdrawn electrolyte and rinse water after UV treatment and constriction is to be transferred back into the galvanic bath.
- concentration step described above is usually required when the mixture of withdrawn electrolyte and rinse water after UV treatment and constriction is to be transferred back into the galvanic bath.
- the latter is preferred according to the invention.
- the thermal energy required for the narrowing is preferably provided in all embodiments of the method according to the invention at least partially by the at least one UV reactor.
- the mixture of the withdrawn electrolyte and the rinse water is usually already significantly heated during the irradiation with UV light in the reactor, so that only an energy difference amount has to be made available for evaporation. This is done according to the invention in particular by the mentioned recovery of the heat energy from the steam and / or the provision of additional heat energy by the mentioned separate heat generating unit. In preferred embodiments, both measures are used in combination.
- the heat energy is recovered from the water vapor with the aid of at least one heat exchanger.
- a countercurrent heat exchanger is used.
- the water vapor while a cooling medium countered, to which the heat energy contained in the water vapor is partially transmitted.
- a cooling medium for example, air or water are suitable. It is preferred that the recovered heat energy is subsequently returned to the mixture, in particular via at least one heat pump.
- the recovered heat is brought to a sufficiently high temperature level in order to be used for narrowing the mixture of the withdrawn electrolyte and the rinse water can.
- a submersible burner As a separate heat generating unit according to the invention, in particular a submersible burner can be used.
- a submersible burner is a device known to a person skilled in the art for the particularly effective heating or vaporization of liquids with very good utilization of the heat generated by the burner.
- open-flame or flameless fuels can be burned within the vaporizing liquid, so that a very high energy efficiency of almost 100 percent can be achieved.
- all known combustible liquids and gases are suitable as fuels, although natural gas or hydrogen are particularly preferably used.
- the mixture of withdrawn electrolyte and rinse water is transferred back into the galvanic bath after the UV treatment and the constriction. Before the transfer, it is preferable to add fresh organic additives and optionally a proportion of one or more metal salts to the concentrated mixture. Preferably, the organic additives are added in sufficient amount to completely replace the additives removed by the UV treatment.
- the removal of electrolyte from the galvanic bath can be done both at regular intervals and continuously. correspond The same applies to the recycling of the UV-treated and concentrated mixture into the galvanic bath.
- the mixture of withdrawn electrolyte and rinse water is circulated through the at least one UV reactor.
- an oxidizing agent is preferably added to the mixture.
- the oxidizing agent is preferably added in an amount sufficient to effectively minimize the content of organic additives in the electrolyte.
- the oxidizing agent is in particular ozone and / or hydrogen peroxide.
- the latter is preferably used as a 30% strength aqueous solution, for example in an amount of from 3 to 30 ml / l of electrolyte.
- oxygen can be added as an oxidizing agent.
- the electrolyte in the galvanic bath preferably also contains one or more acids and optionally inorganic chlorides. Suitable acids are in particular sulfuric and / or hydrochloric acid in question. Chlorides or sulfates are preferably added in the form of the corresponding metals to be deposited as metal salts (eg, CuSO 4 or NiSO 4 ). Chlorides can also be added in the form of HCl and sulfates as sulfuric acid.
- Sulfuric acid copper baths preferably have the following concentrations:
- the at least one metal present in dissolved form is, in particular, copper and / or a noble metal.
- the working range in the electrodeposition is preferably between 5 and 60 g of metal per liter of electrolyte.
- the at least one metal is present in the electrolyte in ionized and / or complexed form. It is admitted to the electrolyte in particular as a metal salt, for example as copper sulfate or copper sulfate pentahydrate.
- the pH of the mixture Before introducing the mixture of withdrawn electrolyte and rinsing water into the at least one UV reactor, it is preferable to set the pH of the mixture in a targeted manner, in particular to a substantially neutral value. This can be done, for example, by adding sodium hydroxide and / or lithium hydroxide.
- a device according to the invention is used in particular for the UV treatment of aqueous, organic additives and at least one electrolytic solution containing metal in dissolved form. It is excellent for use in a process as already described above. In particular, it is suitable for treating a mixture of withdrawn electrolyte and rinse water, as described above.
- a device comprises at least one UV reactor, at least one evaporation device, in which the electrolyte solutions can be at least partially concentrated, and at least one heat exchanger.
- the at least one heat exchanger serves to recover heat from the steam generated in the evaporator.
- the device according to the invention may have at least one separate heat-generating unit.
- a device according to the invention preferably has one or more storage containers, into or into which the electrolyte solution to be treated can be transferred, for example, from one or more galvanic baths.
- a device according to the invention it is furthermore possible in particular to provide at least one pump, if appropriate at least one storage container for at least one oxidizing agent and at least one storage container for a liquor and / or an acid.
- the device according to the invention has at least one heat pump.
- the at least one heat pump serves to bring the heat recovered with the aid of the at least one heat pump to a sufficiently high temperature level in order to be used for constricting the electrolyte solutions.
- the at least one UV reactor serves for the above-described at least partial conversion of the organic additives of the electrolyte solution and / or of their degradation products into carbon dioxide.
- the at least one UV reactor is in preferred embodiments at least one UV reactor with medium pressure Spotlights.
- the device according to the invention can also have one or more UV reactors with low-pressure radiators.
- a device according to the invention as a UV reactor has at least one UV reactor with doped low-pressure radiators.
- a device according to the invention particularly preferably has at least one high-temperature UV reactor marketed by the Applicant under the trade name Enviolet®.
- the device according to the invention in preferred embodiments comprises at least one column.
- the column is led to evaporate the electrolyte solution of this an air stream, which can saturate with water vapor.
- the at least one column comprises at least one packed column.
- a device according to the invention can have as evaporation device a spraying device in which the electrolyte solution can be sprayed into an air stream for evaporation.
- the device according to the invention can also comprise, as vaporization device, a gassing device in which air is bubbled into the electrolyte solution.
- a device according to the invention may e.g. have one or more vapor compressors.
- the at least one UV reactor is part of a first circulatory system in which the electrolyte can circulate. It is further preferred that the at least one evaporation device is part of a second circulation system in which the electrolyte can circulate.
- the first and the second circuit are coupled.
- at least one intermediate memory is provided. This is connected in particularly preferred embodiments with one or more of the aforementioned reservoir.
- An introduction of electrolyte solution to be treated into the first circuit and / or into the second circuit preferably takes place via the at least one temporary store.
- the device according to the invention comprises at least one dosing agent, via which the addition of oxidizing agent can be regulated.
- the device according to the invention comprises at least one dosing agent, via which the addition of the at least one liquor and / or the at least one acid can be regulated.
- the at least one heat exchanger is coupled to the at least one evaporation device so that heat can be recovered from water vapor generated in the evaporation device.
- the recovered heat energy can, as described above, be used in a method according to the invention for concentrating the electrolyte solution.
- the at least one heat exchanger is preferably coupled to the at least one heat pump. About the at least one heat pump, the recovered heat energy of the electrolyte solution can be supplied again.
- the device according to the invention can, as already mentioned, have a separate heat-generating unit.
- it has at least one immersion burner as heat generating unit, as has already been described.
- Energy can be introduced into the electrolyte solution in a particularly effective manner via the immersion burner, so that it can be concentrated efficiently in the at least one evaporation device.
- Fig. 1 shows a flow diagram of an embodiment of a device according to the invention.
- untreated electrolyte solution can be transferred via the feed line 3 into the intermediate store 5.
- Treated electrolyte solution can be transferred from the buffer 7 via the line 4 in the storage container 2.
- the buffer 5 acts as an interface between two circulatory systems, in which can circulate.
- the first circulatory system comprises as stations the buffer 5 and the UV reactor 6.
- the second circulatory system comprises as stations the buffer 5 and the evaporation device 7.
- the UV reactor 6 upstream of the feed nodes 8 and 9 in the flow direction.
- oxidizing agent from the storage container 10 can be added to the circulating electrolyte solution.
- a liquor from the storage tank 11 are metered.
- the UV-treated electrolyte solution is introduced again into the buffer 5.
- it can be supplied to the evaporation device 7 via the supply line 13.
- Steam generated in the evaporator is removed from the system via drain 14.
- non-evaporated electrolyte solution is returned to the buffer 7.
- heat can be recovered from the water vapor and fed back to the electrolyte solution to be evaporated.
- the recovered heat is brought by means of the heat pump 18 to a sufficiently high level in order to be used for the narrowing of the electrolyte mixture can.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200710036651 DE102007036651A1 (en) | 2007-07-25 | 2007-07-25 | Process recycling of galvanic baths |
PCT/EP2008/005616 WO2009012891A1 (en) | 2007-07-25 | 2008-07-10 | Process recycling of electroplating baths |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2173929A1 true EP2173929A1 (en) | 2010-04-14 |
Family
ID=39790246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08773942A Withdrawn EP2173929A1 (en) | 2007-07-25 | 2008-07-10 | Process recycling of electroplating baths |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2173929A1 (en) |
CN (1) | CN101809208B (en) |
DE (1) | DE102007036651A1 (en) |
WO (1) | WO2009012891A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009049565A1 (en) * | 2009-10-09 | 2011-04-14 | Gebr. Schmid Gmbh & Co. | Process and plant for the metallization of silicon wafers |
DE102011081007A1 (en) * | 2011-08-16 | 2013-02-21 | Siemens Aktiengesellschaft | Process for reprocessing a waste water and water treatment device |
DE102011081015A1 (en) * | 2011-08-16 | 2013-02-21 | Siemens Aktiengesellschaft | Process for reprocessing a waste water and water treatment device |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3640331A (en) * | 1966-10-18 | 1972-02-08 | Aisaburo Yagishita | Heating and concentrating tower for plating waste recovery unit |
US3661732A (en) * | 1970-06-01 | 1972-05-09 | Production Machinery Corp | Method and apparatus for electroplating |
AU6477699A (en) * | 1998-10-21 | 2000-05-08 | Nicasio Paulino Mora Vallejo | Installation for the collection of liquid residues applicable to the treatment of parts by electrolytic bath |
US6391209B1 (en) * | 1999-08-04 | 2002-05-21 | Mykrolis Corporation | Regeneration of plating baths |
CA2362244A1 (en) * | 2001-11-14 | 2003-05-14 | Peter Forth | Method of treating an electroplating bath |
DE10325101A1 (en) * | 2003-06-03 | 2004-12-30 | Atotech Deutschland Gmbh | Method for filling µ-blind vias (µ-BVs) |
-
2007
- 2007-07-25 DE DE200710036651 patent/DE102007036651A1/en not_active Withdrawn
-
2008
- 2008-07-10 CN CN2008801085404A patent/CN101809208B/en active Active
- 2008-07-10 WO PCT/EP2008/005616 patent/WO2009012891A1/en active Application Filing
- 2008-07-10 EP EP08773942A patent/EP2173929A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2009012891A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102007036651A1 (en) | 2009-01-29 |
WO2009012891A1 (en) | 2009-01-29 |
CN101809208B (en) | 2012-06-20 |
CN101809208A (en) | 2010-08-18 |
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Legal Events
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AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: SOERENSEN, MARTIN Inventor name: WECKENMANN, JUERGEN |
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DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20131129 |
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Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20160202 |