CN114855221A - System and method for recovering copper-containing nitric acid waste liquid of circuit board - Google Patents
System and method for recovering copper-containing nitric acid waste liquid of circuit board Download PDFInfo
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- CN114855221A CN114855221A CN202210406706.2A CN202210406706A CN114855221A CN 114855221 A CN114855221 A CN 114855221A CN 202210406706 A CN202210406706 A CN 202210406706A CN 114855221 A CN114855221 A CN 114855221A
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- nitric acid
- waste liquid
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- acid waste
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- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 104
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000007788 liquid Substances 0.000 title claims abstract description 102
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 83
- 239000002699 waste material Substances 0.000 title claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000003860 storage Methods 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 238000004064 recycling Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 239000002912 waste gas Substances 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 10
- 239000012459 cleaning agent Substances 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical group O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a system and a method for recovering copper-containing nitric acid waste liquid of a circuit board, wherein the recovery system comprises a nitric acid waste liquid storage device, a filtering storage device, an electrolytic circulating device, a blending and recycling device, a waste gas absorption device and a circulating cooling device which are connected through a pipeline and a valve; the nitric acid waste liquid storage device is connected with the filtering storage device, the filtering storage device is connected with the electrolysis circulating device, and the electrolysis circulating device is respectively connected with the blending and recycling device, the waste gas absorption device and the circulating cooling device. According to the circuit board copper-containing nitric acid waste liquid recovery system and method provided by the invention, the inhibitor is conveniently added into the waste liquid, the generation of nitrogen oxides in the electrolytic process of the nitric acid waste liquid is reduced, the electrolytic copper is protected from being stably deposited on the cathode, the short circuit phenomena such as copper prick and the like are avoided, the copper content in the prepared recycled nitric acid is low, the recycling use can be efficiently realized, the requirements of clean production and recycling economy are met, and the emission of total nitrogen is reduced.
Description
Technical Field
The invention relates to the field of circuit board waste recovery, in particular to a system and a method for recovering a copper-containing nitric acid waste liquid of a circuit board.
Background
In the electronics industry, the production of circuit boards is a fundamental industry, where various chemicals are used and large amounts of chemical waste, such as nitric acid waste, are also produced. The nitric acid waste liquid cannot be directly discharged, the environmental pollution is serious, and meanwhile, the nitric acid waste liquid often contains high-value copper elements, so that valuable components in the nitric acid waste liquid need to be recycled.
The common copper-containing nitric acid waste liquid recovery system and method have the advantages and disadvantages, for example, the patent application No. CN201710979885.8 describes that copper nitrate waste liquid is neutralized with ammonia water and then copper is recovered through electrolysis, and ammonium ions contained in nitric acid recycled by the method are not easy to remove. In the document with the patent application number of CN201010233782, it is stated that an iron rod is used as an insoluble anode for nitric acid recovery, iron in the method can be slowly dissolved to influence the purity of a copper product, and meanwhile, the conductivity of the anode is poor, and energy consumption and heating are easy. The document of patent application No. CN202011225716.3 describes the use of a membrane electrolysis process for the extraction of copper, which process results in an anode membrane which is relatively expensive and which is easily damaged during operation. It can be seen that it is not easy to achieve a balanced recycling of the copper-containing nitric acid waste liquor.
Disclosure of Invention
In view of the above, it is necessary to provide a system and a method for recovering a copper-containing nitric acid waste liquid of a circuit board, which address at least one of the above-mentioned problems.
In a first aspect, the application provides a circuit board copper-containing nitric acid waste liquid recovery system, which comprises a nitric acid waste liquid storage device, a filtering storage device, an electrolysis circulating device, a blending and recycling device, an exhaust gas absorption device and a circulating cooling device, wherein the nitric acid waste liquid storage device, the filtering storage device, the electrolysis circulating device, the blending and recycling device, the exhaust gas absorption device and the circulating cooling device are connected through a pipeline and a valve;
the nitric acid waste liquid storage device is connected with the filtering storage device, the filtering storage device is connected with the electrolysis circulating device, and the electrolysis circulating device is respectively connected with the allocation and reuse device, the waste gas absorption device and the circulating cooling device.
In certain implementations of the first aspect, the nitric acid waste liquid storage device includes a liquid inlet pump and a first storage barrel connected by a pipeline and a valve; the filtering and storing device comprises a filtering pump, a filter element filter and a second storage barrel which are connected through a pipeline and a valve; the electrolytic circulating device comprises a circulating barrel, a circulating pump, a rotational flow electrolyzer, a liquid discharge pump, an inhibitor dosing pump, an electrolytic copper cleaning tank and a relay pump which are connected through a pipeline and a valve; the blending and recycling device comprises a blending barrel, a blending pump, a blending circulating tank, a concentrated nitric acid pump, a concentrated nitric acid barrel, a circulating pump of the circulating tank, a liquid discharge pump and a liquid recovery barrel which are connected through a pipeline and a valve; the waste gas absorption device comprises a reducing alkali liquor waste gas washing tower in series connection with three sections.
Optionally, with reference to the first aspect embodiment and the foregoing implementation manners, in some implementation manners of the first aspect embodiment, a ratio of an outer diameter of an anode of the spiral-flow electrolyzer to an inner diameter of a cathode of the spiral-flow electrolyzer to a height of the spiral-flow electrolyzer is 1:2 to 3:10 to 15.
With reference to the first aspect and the foregoing implementation manners, in certain implementation manners of the first aspect, the anode of the swirl electrolyzer is a copper rod coated with a titanium alloy and a metal oxide layer, and the metal oxide layer is an iridium oxide or ruthenium oxide coating.
With reference to the first aspect and the foregoing implementation manners, in certain implementation manners of the first aspect, the thickness of the titanium alloy is greater than or equal to 1mm, and the thickness of the oxidized metal layer is greater than or equal to 0.02 mm.
With reference to the first aspect and the foregoing implementation manners, in some implementation manners of the first aspect, an anode of the swirl electrolyzer is clamped into a spacer ring at the bottom of the swirl electrolyzer, and a circular fixing snap ring having an inner diameter consistent with that of the anode is disposed at the top of the anode.
In a second aspect, the present application provides a method for recovering a copper-containing nitric acid waste liquid of a circuit board, which employs the circuit board copper-containing nitric acid waste liquid recovery system described in any one of the first aspects of the present application, and performs the following steps:
starting the waste gas absorption device and the nitric acid waste liquid storage device, and pumping the copper-containing nitric acid waste liquid into the nitric acid waste liquid storage device for precipitation for 24 hours;
starting the filtering and storing device to pump the copper-containing nitric acid waste liquid into the electrolytic circulating device for standing for 5min, then adding an inhibitor into the copper-containing nitric acid waste liquid after standing, starting the electrolytic circulating device and the circulating cooling device, and circulating the copper-containing nitric acid waste liquid in the electrolytic circulating device and the circulating cooling device for 24 hours in a steady flow mode to contact with air;
and discharging the treated waste liquid to the blending and recycling device, recycling and cleaning the obtained electrolytic copper by using an organic cleaning agent, adding concentrated nitric acid into the residual liquid medicine of the blending and recycling device, and circularly treating for 30 minutes to obtain recycled nitric acid.
In certain implementations of the second aspect, the inhibitor includes PEG and hydrazine hydrate, the PEG has a molecular weight of 100 to 1000, and the PEG is 1 to 10% and the hydrazine hydrate is 40 to 80% by mass.
With reference to the second aspect and the foregoing implementation manners, in some implementation manners of the second aspect, the organic cleaning agent includes citric acid, and the citric acid is 5% to 20% by mass.
With reference to the second aspect and implementations described above, in certain implementations of the second aspect, the cooling circulation coil in the circulation cooling device is grade 316L or greater stainless steel.
The technical scheme provided by the embodiment of the invention has the following beneficial technical effects:
according to the circuit board copper-containing nitric acid waste liquid recovery system and method provided by the invention, the inhibitor is conveniently added into the waste liquid, the generation of nitrogen oxides in the electrolytic process of the nitric acid waste liquid is reduced, the electrolytic copper is protected from being stably deposited on the cathode, short-circuit phenomena such as copper spurs and the like are avoided, the electrolytic copper is protected by the organic cleaning agent after being taken out, the biting corrosion of residual nitric acid on the electrolytic copper is avoided, the product purity is improved, the electrolytic circulating device in the recovery system adopts the circulating cooling system to improve the operation stability of equipment, the purity of a copper product can be ensured under the condition of low energy consumption through the recovery system, the copper content in the prepared and recycled nitric acid is low, the copper can be efficiently recycled, the requirements of clean production and circular economy are met, and the emission of total nitrogen is reduced.
Additional aspects and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic diagram of a connection structure of a circuit board copper-containing nitric acid waste liquid recovery system in one embodiment of the present invention;
FIG. 2 is a schematic diagram of the internal structure of a cyclone electrolyzer in an embodiment of the present invention.
Description of reference numerals:
100-nitric acid waste liquid storage device, 200-filtering storage device, 300-electrolysis circulating device, 400-blending and recycling device, 500-waste gas absorption device and 600-circulating cooling device;
101-liquid inlet pump, 102-first storage barrel;
201-a filter pump, 202-a cartridge filter, 203-a second storage tank;
301-circulating barrel, 302-circulating pump, 303-cyclone electrolyzer, 304-liquid discharge pump, 305-inhibitor dosing pump, 306-electrolytic copper cleaning tank, 307-relay pump;
401-preparing barrel, 402-preparing pump, 403-preparing circulating tank, 404-concentrated nitric acid pump, 405-concentrated nitric acid barrel, 406-circulating tank circulating pump, 407-liquid discharge pump and 408-recovering liquid barrel.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Possible embodiments of the invention are given in the figures. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein by the accompanying drawings. The embodiments described by way of reference to the drawings are illustrative for the purpose of providing a more thorough understanding of the present disclosure and are not to be construed as limiting the present invention. In addition, if a detailed description of known technologies is not necessary for the features of the present invention shown, such technical details may be omitted.
It will be understood by those skilled in the relevant art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It is to be understood that the term "and/or" as used herein is intended to include all or any and all combinations of one or more of the associated listed items.
The technical solution of the present invention and how to solve the above technical problems will be described in detail with specific examples.
The embodiment of the first aspect of the present application provides a circuit board copper-containing nitric acid waste liquid recovery system, as shown in fig. 1, which includes a nitric acid waste liquid storage device 100, a filtering storage device 200, an electrolysis circulation device 300, a blending and recycling device 400, an exhaust gas absorption device 500, and a circulation cooling device 600, which are connected through a pipeline and a valve. Specifically, the nitric acid waste liquid storage device 100 is connected with the filtering storage device 200, the filtering storage device 200 is connected with the electrolysis circulation device 300, the electrolysis circulation device 300 is respectively connected with the blending and recycling device 400, the exhaust gas absorption device 500 and the circulation cooling device 600, other specific connection structures are shown in fig. 1, and in fig. 1, the devices arranged above the first storage barrel 102, the second storage barrel 203, the circulation barrel 301, the blending barrel 401 and the like are exhaust gas extraction hoods which can be used for collecting exhaust gas coming out of the devices.
Optionally, in certain implementations of embodiments of the first aspect of the present application, as shown in fig. 1, the nitric acid waste liquid storage apparatus 100 includes a liquid inlet pump 101 and a first storage barrel 102 connected by a pipe and a valve. The filtering storage device 200 includes a filtering pump 201, a filter 202 and a second storage tank 203 connected by pipes and valves. The second storage barrel 203 is used for temporarily storing the filtered waste liquid. The electrolytic circulating device 300 comprises a circulating barrel 301, a circulating pump 302, a cyclone electrolyzer 303, a drain pump 304, an inhibitor dosing pump 305, an electrolytic copper cleaning tank 306 and a relay pump 307 which are connected through pipelines and valves. The blending and recycling device 400 comprises a blending barrel, a blending pump, a blending circulating tank, a concentrated nitric acid pump, a concentrated nitric acid barrel, a circulating tank circulating pump 302, a liquid discharge pump 304 and a liquid recovery barrel which are connected through a pipeline and a valve. The waste gas absorption device 500 comprises a series three-section type reducing alkali liquor waste gas washing tower. The connection mode of the components in each device and the connection mode of the devices with each other are specifically referred to the connection structure shown in fig. 1.
Optionally, with reference to the first aspect embodiment and the foregoing implementation manners, in some implementation manners of the first aspect embodiment, a ratio of an outer diameter of an anode of the spiral-flow electrolyzer 303, an inner diameter of a cathode of the spiral-flow electrolyzer 303, and a height of the spiral-flow electrolyzer 303 is 1:2 to 3:10 to 15. When the ratio of the outer diameter of the anode to the inner diameter of the cathode is more than 2, short circuit is easily formed in the electrolysis process, and when the ratio of the outer diameter of the anode to the inner diameter of the cathode is less than 2, the current density of the anode is overlarge, the anode rod is easy to generate heat, and the energy consumption is large. When the ratio of the inner diameter of the cathode to the height of the cyclone electrolyzer is more than 3: when 10 hours, the retention time of the waste liquid in the equipment is short, and the electrolysis efficiency is reduced. When the ratio of the inner diameter of the cathode to the height of the cyclone electrolyzer is less than 2: 15 hours, because the current density at the bottom of the cathode is low, copper bonding is uneven, the thickness is thin, the bottom of a copper product is easy to break into fragments and sink to the bottom, and the whole copper product is not easy to take out. The proportion is obtained by long-term test and consideration of factors such as current efficiency, operation safety, copper product quality and the like.
Optionally, in some embodiments of the foregoing implementation, the anode of the spiral-flow electrolyzer 303 is a copper rod coated with a titanium alloy and a metal oxide layer, and the metal oxide layer is an iridium oxide or ruthenium oxide coating. The intermediate layer is a titanium layer and is resistant to nitric acid corrosion, and the outermost layer is iridium oxide or ruthenium oxide to protect the anode and reduce the attack of nitric acid on the titanium alloy. Optionally, the thickness of the titanium alloy is greater than or equal to 1mm, and the thickness of the oxidized metal layer is greater than or equal to 0.02 mm. The titanium alloy coating is too thin, is easy to fall off and is not easy to protect the copper layer, so that a titanium alloy layer with larger thickness is adopted. The oxidized metal layer is a noble metal layer, and the nitric acid cannot penetrate through gaps among atoms to corrode the titanium alloy layer and the internal copper layer until the thickness reaches a certain thickness, so that the nitric acid is unnecessarily thick, and the cost is increased.
Optionally, with reference to the embodiment of the first aspect and the foregoing implementation manners, in some implementation manners of the embodiment of the first aspect, as shown in fig. 2, an anode of the cyclone electrolyzer 303 is clamped into a spacer ring at the bottom of the cyclone electrolyzer 303, and a circular fixing snap ring having an inner diameter consistent with the size of the anode is disposed at the top of the anode. In order to prevent the waste liquid from driving the anode bar to shake to generate copper thorn short circuit in the circulating electrolysis process, the anode bar serving as an anode is clamped into the isolating ring at the bottom of the cyclone electrolyzer 303, and the top of the anode bar is provided with a circular annular fixing snap ring with the inner diameter consistent with the size of the anode bar. In order to ensure the balance of the anode installation, a special double-hand balance weight is used for installation. The balance weight is a hollow pipe type, the outer diameter is slightly smaller than the inner diameter of the cathode of the cyclone electrolyzer 303 by 1cm, and the inner diameter is larger than the outer diameter of the anode. The upper end of the balance weight is provided with a double-hand handle.
In addition, in a certain implementation manner of the first aspect of the present application, the circulation cooling device 600 includes a cooling circulation coil therein, the cooling circulation coil is made of stainless steel grade over 316L, and a teflon coating is disposed on the outer layer. Stainless steel with grade over 316L is adopted, and the Teflon coating is arranged on the outer layer of the cooling coil, so that the cooling coil has good heat conductivity in nitric acid waste liquid, and nitric acid cannot bite and damage the ice water main machine for cooling easily.
In a second aspect, the present application provides a method for recovering a copper-containing nitric acid waste liquid of a circuit board, which employs the circuit board copper-containing nitric acid waste liquid recovery system described in any one of the first aspects of the present application, and performs the following steps:
s100: and starting the waste gas absorption device 500 and the nitric acid waste liquid storage device 100, and pumping the copper-containing nitric acid waste liquid into the nitric acid waste liquid storage device 100 for precipitation for 24 hours.
S200: starting the filtering and storing device 200 to pump the copper-containing nitric acid waste liquid into the electrolytic circulating device 300 for standing for 5min, then adding an inhibitor into the copper-containing nitric acid waste liquid after standing, starting the electrolytic circulating device 300 and the circulating cooling device 600, circulating the copper-containing nitric acid waste liquid in the electrolytic circulating device 300 and the circulating cooling device 600 for 24 hours in a steady flow mode, and then contacting air.
S300: and discharging the treated waste liquid to a blending and recycling device 400, recycling and cleaning the obtained electrolytic copper by using an organic cleaning agent, adding concentrated nitric acid into the residual liquid medicine of the blending and recycling device 400, and circularly treating for 30 minutes to obtain recycled nitric acid.
Specifically, the waste gas absorption device 500 is started, the liquid inlet pump 101 is started to pump the copper-containing nitric acid waste liquid into the first storage barrel 102, and the waste liquid is left to stand and settle for 24 hours. The filter pump 201 is started, the copper-containing nitric acid waste liquid is pumped into the electrolytic circulation barrel 301 through the filter element filter 202 by the relay pump 307, and then the electrolytic circulation barrel is kept still for 5 min. Inhibitor is added to the circulation tank 301 with an inhibitor addition pump 305. The electrolytic circulation pump 302 is started, the rectifier power supply is started, and a current stabilization mode is adopted. Setting the current to be 150A, and after the operation is carried out for 1.5 hours, starting the circulating cooling device 600 to control the temperature of the solution in the circulating barrel 301 to be 30-38 ℃. The operating current is adjusted according to the concentration of copper ions in the waste liquid, the concentration of the copper ions is 50-5 g/L, the electrolytic current runs at 300-480A, the power supply of a rectifier is closed after the cyclone electrolyzer 303 normally runs for 24 hours, the circulating pump 302 is closed, and all the electrode column covers (the covers on the cyclone electrolyzer) are opened until air enters.
The drain pump 304 in the blending and recycling device 400 is started to drain the waste liquid to the blending barrel. The electrolytic copper is lifted out by using a manipulator and placed in a copper washing tank, organic cleaning agents are placed in the copper washing tank, after the electrolytic copper is completely lifted out, a cathode titanium plate is inserted into the cyclone electrolyzer 303, it is ensured that each initial anode rod is well assembled and in place, (the lower initial anode rod is completely inserted into the isolation ring, and the upper initial anode rod is positioned on the scale mark and is regarded as being in place), all covers are closed and locked, and the machine is started for next batch of production after normal inspection is finished. The whole electrolytic process is batch cycle electrolysis. For safety, the rectifier is turned off when electrolysis is completed for one batch, and is turned on when electrolysis is performed for the next batch.
And in the nitric acid back-distribution process, the liquid medicine in the preparation barrel is pumped into the preparation circulating tank by using a preparation pump, the concentration of the nitric acid is analyzed, and after a circulating pump of the circulating tank is started for 10 minutes, the amount of 68% concentrated nitric acid required for preparing the nitric acid with the concentration of 40% +/-1% is calculated. And (3) starting a concentrated nitric acid pump to pump concentrated nitric acid in the concentrated nitric acid barrel into the blending circulation tank, starting a circulation pump 302 of the circulation tank for half an hour, analyzing to determine that the concentration of the nitric acid meets the requirement, and closing the circulation pump 302 of the circulation tank. And starting a liquid discharge pump 304, and pumping the recycled nitric acid into a recycling liquid barrel.
In certain implementation manners of the second aspect, the inhibitor comprises PEG and hydrazine hydrate, wherein the molecular weight of PEG is 100-1000, the PEG accounts for 1-10% by mass, and the hydrazine hydrate accounts for 40-80%. In the reaction process of the application, hydrazine hydrate can be decomposed in the electrolytic process to be basically decomposed into nitrogen and water, and no pollution or residue exists.
With reference to the second aspect and the foregoing implementation manners, in some implementation manners of the second aspect, the organic cleaning agent includes citric acid, and the citric acid is 5% to 20% by mass.
According to the circuit board copper-containing nitric acid waste liquid recovery system and method provided by the invention, the inhibitor is conveniently added into the waste liquid, the generation of nitrogen oxides in the electrolytic process of the nitric acid waste liquid is reduced, the electrolytic copper is protected from being stably deposited on the cathode, short-circuit phenomena such as copper spurs and the like are avoided, the electrolytic copper is protected by the organic cleaning agent after being taken out, the biting corrosion of residual nitric acid on the electrolytic copper is avoided, the product purity is improved, the electrolytic circulating device in the recovery system adopts the circulating cooling system to improve the operation stability of equipment, the purity of a copper product can be ensured under the condition of low energy consumption through the recovery system, the copper content in the prepared and recycled nitric acid is low, the copper can be efficiently recycled, the requirements of clean production and circular economy are met, and the emission of total nitrogen is reduced.
Those of skill in the art will appreciate that the various operations, methods, steps in the processes, acts, or solutions discussed in this application can be interchanged, modified, combined, or eliminated. Further, other steps, measures, or schemes in various operations, methods, or flows that have been discussed in this application can be alternated, altered, rearranged, broken down, combined, or deleted. Further, steps, measures, schemes in the prior art having various operations, methods, procedures disclosed in the present application may also be alternated, modified, rearranged, decomposed, combined, or deleted.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless otherwise specified.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in this application will be understood to be a specific case for those of ordinary skill in the art.
In the description herein, particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
It should be understood that, although the steps in the flowcharts of the figures are shown in order as indicated by the arrows, the steps are not necessarily performed in order as indicated by the arrows. The steps are not performed in the exact order shown and may be performed in other orders unless explicitly stated herein. Moreover, at least a portion of the steps in the flow chart of the figure may include multiple sub-steps or multiple stages, which are not necessarily performed at the same time, but may be performed at different times, which are not necessarily performed in sequence, but may be performed alternately or alternately with other steps or at least a portion of the sub-steps or stages of other steps.
The foregoing is only a partial embodiment of the present application, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the principle of the present application, and these modifications and decorations should also be regarded as the protection scope of the present application.
Claims (10)
1. A circuit board copper-containing nitric acid waste liquid recovery system is characterized by comprising a nitric acid waste liquid storage device, a filtering storage device, an electrolytic circulating device, a blending and recycling device, a waste gas absorption device and a circulating cooling device which are connected through a pipeline and a valve;
the nitric acid waste liquid storage device is connected with the filtering storage device, the filtering storage device is connected with the electrolysis circulating device, and the electrolysis circulating device is respectively connected with the allocation and reuse device, the waste gas absorption device and the circulating cooling device.
2. The circuit board copper-containing nitric acid waste liquid recovery system of claim 1, wherein the nitric acid waste liquid storage device comprises a liquid inlet pump and a first storage barrel which are connected through a pipeline and a valve; the filtering and storing device comprises a filtering pump, a filter element filter and a second storage barrel which are connected through a pipeline and a valve; the electrolytic circulating device comprises a circulating barrel, a circulating pump, a rotational flow electrolyzer, a liquid discharge pump, an inhibitor dosing pump, an electrolytic copper cleaning tank and a relay pump which are connected through a pipeline and a valve; the blending and recycling device comprises a blending barrel, a blending pump, a blending circulating tank, a concentrated nitric acid pump, a concentrated nitric acid barrel, a circulating pump of the circulating tank, a liquid discharge pump and a liquid recovery barrel which are connected through a pipeline and a valve; the waste gas absorption device comprises a reducing alkali liquor waste gas washing tower in series connection with three sections.
3. The circuit board copper-containing nitric acid waste liquid recovery system of claim 2, wherein the ratio of the outer diameter of the anode to the inner diameter of the cathode of the cyclone electrolyzer to the height of the cyclone electrolyzer is 1: 2-3: 10-15.
4. The circuit board copper-containing nitric acid waste liquid recovery system of claim 2, wherein the anode of the cyclone electrolyzer is a copper bar coated with titanium alloy and a metal oxide layer, and the metal oxide layer is an iridium oxide or ruthenium oxide coating.
5. The circuit board copper-containing nitric acid waste liquid recovery system of claim 4, wherein the thickness of the titanium alloy is greater than or equal to 1mm, and the thickness of the oxidized metal layer is greater than or equal to 0.02 mm.
6. The circuit board copper-containing nitric acid waste liquid recovery system according to claim 2, wherein an anode of the cyclone electrolyzer is clamped in an isolation ring at the bottom of the cyclone electrolyzer, and a circular fixing snap ring with the inner diameter consistent with the size of the anode is arranged at the top of the anode.
7. A method for recovering a copper-containing nitric acid waste liquid of a circuit board, which is characterized by adopting the system for recovering the copper-containing nitric acid waste liquid of the circuit board as defined in any one of claims 1 to 6, and performing the following steps:
starting the waste gas absorption device and the nitric acid waste liquid storage device, and pumping the copper-containing nitric acid waste liquid into the nitric acid waste liquid storage device for precipitation for 24 hours;
starting the filtering and storing device to pump the copper-containing nitric acid waste liquid into the electrolytic circulating device for standing for 5min, then adding an inhibitor into the copper-containing nitric acid waste liquid after standing, starting the electrolytic circulating device and the circulating cooling device, and circulating the copper-containing nitric acid waste liquid in the electrolytic circulating device and the circulating cooling device for 24 hours in a steady flow mode to contact with air;
and discharging the treated waste liquid to the blending and recycling device, recycling and cleaning the obtained electrolytic copper by using an organic cleaning agent, adding concentrated nitric acid into the residual liquid medicine of the blending and recycling device, and circularly treating for 30 minutes to obtain recycled nitric acid.
8. The method for recovering the copper-containing nitric acid waste liquid of the circuit board according to claim 7, wherein the inhibitor comprises PEG and hydrazine hydrate, the molecular weight of the PEG is 100-1000, and the PEG accounts for 1-10% and the hydrazine hydrate accounts for 40-80% by mass.
9. The method for recovering the copper-containing nitric acid waste liquid of the circuit board according to claim 7, wherein the organic cleaning agent comprises citric acid, and the citric acid accounts for 5-20% by mass.
10. The method for recovering the copper-containing nitric acid waste liquid of the circuit board according to claim 7, wherein a cooling circulation coil in the circulation cooling device is stainless steel of grade over 316L.
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Address after: 435000 No.88 Daqi Avenue, Wangren Town, Huangshi economic and Technological Development Zone, Hubei Province Applicant after: Chaoying Electronic Circuit Co.,Ltd. Address before: 435000 No.88 Daqi Avenue, Wangren Town, Huangshi economic and Technological Development Zone, Hubei Province Applicant before: DYNAMIC ELECTRONICS (HUANGSHI) Co.,Ltd. |
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