CN117550768A - Electroplating sludge resource utilization method - Google Patents
Electroplating sludge resource utilization method Download PDFInfo
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- CN117550768A CN117550768A CN202410046633.XA CN202410046633A CN117550768A CN 117550768 A CN117550768 A CN 117550768A CN 202410046633 A CN202410046633 A CN 202410046633A CN 117550768 A CN117550768 A CN 117550768A
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- sludge
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- electroplating
- treating agent
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- 239000010802 sludge Substances 0.000 title claims abstract description 104
- 238000009713 electroplating Methods 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- 239000006228 supernatant Substances 0.000 claims abstract description 50
- 238000005188 flotation Methods 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 39
- 238000004062 sedimentation Methods 0.000 claims abstract description 38
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004064 recycling Methods 0.000 claims abstract description 31
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 230000001105 regulatory effect Effects 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 238000010979 pH adjustment Methods 0.000 claims abstract description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 19
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012991 xanthate Substances 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 5
- 229920001661 Chitosan Polymers 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011553 magnetic fluid Substances 0.000 claims description 17
- 229920002472 Starch Polymers 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 16
- 239000003518 caustics Substances 0.000 claims description 16
- 239000008107 starch Substances 0.000 claims description 16
- 235000019698 starch Nutrition 0.000 claims description 16
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 15
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 15
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 13
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 12
- 229940032147 starch Drugs 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229940080313 sodium starch Drugs 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 239000010865 sewage Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 29
- 238000006722 reduction reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 230000009467 reduction Effects 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 or the like Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000666 effect on cation Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a method for recycling electroplating sludge, and belongs to the field of sewage treatment. The electroplating sludge recycling method comprises the following steps: s1: regulating the pH value of electroplating wastewater; s2: reducing the electroplating wastewater after the pH adjustment, wherein the reducing agent in the reducing treatment is sodium sulfite or sodium bisulfite; s3: adding a first treating agent into the reduced electroplating wastewater for first precipitation treatment, stirring and settling, separating a first supernatant and first sludge, and regulating the pH value of the first supernatant; s4: adding a second treating agent into the first supernatant after the pH adjustment to carry out secondary precipitation treatment, and separating the second supernatant and second sludge after stirring and sedimentation; s5: mixing the first sludge and the second sludge to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, and adding double xanthate and heavy pyridine into the sludge suspension to perform flotation so as to realize heavy metal recovery.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for recycling electroplating sludge.
Background
The electroplating wastewater has high toxicity, large discharge and difficult treatment, and is particularly worth focusing on. According to incomplete statistics, electroplating plants in various scales nationwide have nearly 2 tens of thousands, and the annual electroplating wastewater discharge amount accounts for about 10% of the total industrial wastewater discharge amount.
Electroplating is a process that utilizes chemical methods to decorate, protect, and acquire certain new properties from metallic and non-metallic surfaces. In order to ensure the quality of the electroplated product, the metal coating has a smooth and flat good appearance and is firmly combined with the base member, the plated member must be pretreated before electroplating, and the residual chemical cleaning liquid or electroplating liquid on the surface of the plated member must be cleaned by adopting tap water after electroplating, so that a large amount of waste water is necessarily generated in the electroplating production process. According to the electroplating process, the electroplating wastewater can be roughly divided into cyanide-containing wastewater, heavy metal wastewater such as chromium, nickel, copper and the like, acid wastewater, alkaline wastewater and the like according to the contained pollutants, and when the wastewater of different plating species and pollutants are mixed together, the mixed electroplating wastewater is generally called as mixed electroplating wastewater. Since electroplating wastewater contains various harmful substances such as heavy metal ions, organic compounds, inorganic compounds and the like, the substances enter the environment and have wide and serious harm to the ecological environment and human beings, and therefore, the treatment and recycling of the electroplating wastewater are not negligible problems.
However, at present, the recycling utilization of electroplating wastewater is difficult to efficiently recycle various heavy metals.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a method for recycling electroplating sludge, which aims to solve the problem that the recycling of electroplating wastewater is difficult to efficiently recycle various heavy metals at present.
In order to achieve the above purpose, the invention provides a method for recycling electroplating sludge, which comprises the following steps: s1: regulating the pH value of electroplating wastewater; s2: reducing the electroplating wastewater after the pH adjustment, wherein the reducing agent in the reducing treatment is sodium sulfite or sodium bisulfite; s3: adding a first treating agent into the reduced electroplating wastewater for first precipitation treatment, stirring and settling, separating a first supernatant and first sludge, and regulating the pH value of the first supernatant; the first treating agent comprises caustic alkali, sodium sulfide, sodium hypochlorite and starch; s4: adding a second treating agent into the first supernatant after the pH adjustment to carry out secondary precipitation treatment, and separating the second supernatant and second sludge after stirring and sedimentation; the second treating agent comprises a component A and a component B: the component A comprises chitosan and a chitosan/acrylamide grafted copolymer, and the component B comprises dodecyl amine, ethanol, trisodium nitrilotriacetate and polyaluminum ferric calcium chloride; s5: mixing the first sludge and the second sludge to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, and adding double xanthate and heavy pyridine into the sludge suspension to perform flotation so as to realize heavy metal recovery.
Optionally, the first treating agent includes, in parts by weight: 65-100 parts of caustic alkali, 30-40 parts of sodium sulfide, 20-30 parts of sodium hypochlorite and 0.5-1 part of starch.
Optionally, the a component of the second treatment agent includes, in parts by weight: 3-6 parts of chitosan, 1-3 parts of chitosan/acrylamide grafted copolymer; the component B of the second treating agent comprises the following components in parts by weight: 20-25 parts of dodecyl amine, 1-5 parts of ethanol, 5-10 parts of trisodium nitrilotriacetate and 1-2 parts of polyaluminum ferric calcium chloride.
Optionally, the double xanthate is 5-10 parts by weight; and/or 5-10 parts by weight of heavy pyridine.
Optionally, the pH value of the electroplating wastewater is adjusted to be 6-8; and/or adjusting the pH value of the first supernatant to be 2-2.5.
Optionally, the "adding a second treating agent to the first supernatant after pH adjustment for the second precipitation treatment" includes: and adding the component A of the second treating agent to treat, and then adding the component B of the second treating agent to treat.
Optionally, the first treating agent comprises 3-5 parts of magnetic fluid, the second treating agent comprises 3-5 parts of magnetic fluid, and the sedimentation comprises: settling is carried out by utilizing a steady-state magnetic field device, and then standing and settling are carried out.
Optionally, the magnetic field strength of the steady state magnetic field device is no more than 2000GS.
Optionally, in step S5, the flotation is performed in a mechanical flotation mixer.
Optionally, in the step S5, the stirring time of the flotation is 10-15 min, and the stirring speed is 1000-1100 r/min.
The invention has the beneficial effects that: according to the electroplating sludge recycling method provided by the invention, the pH value of electroplating wastewater is regulated, then reduction treatment is carried out, then a first treating agent is added, sodium hypochlorite is added to control the valence state of heavy metal ions, caustic alkali and the heavy metal ions generate hydroxide precipitation, starch interacts with the hydroxide precipitation surface through hydroxyl groups to flocculate the hydroxide precipitation, sodium sulfide is used as a precipitating agent to rapidly precipitate the hydroxide, and residual heavy metal ions are vulcanized to finish the first heavy metal ion precipitation. And adjusting the pH value in the separated first supernatant to facilitate the second treating agent to play a role in the activity pH value, adding the second treating agent, adsorbing heavy metal ions, complexing residual metal ions and phosphorus, and completing the sedimentation of the second residual heavy metal ions. The sludge obtained by twice sedimentation is collected to be made into suspension, double xanthate is added to be used as a collecting agent, heavy pyridine is used as a foaming agent, the suspension of the sludge is subjected to flotation, a large amount of heavy metal ions are obtained by trapping in the upper layer of flotation bubbles, tailings are harmless to the environment, and the sludge can be directly buried, so that harmless treatment and recycling of the sludge are realized.
The electroplating sludge recycling method provided by the invention can efficiently collect and recycle heavy metal ions in the sludge, and particularly has high collection strength on chromium, copper, nickel and other ions, and the recycling degree is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a step diagram of a method for recycling electroplating sludge according to an embodiment of the invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below, and it should be understood that the following embodiments are only for explaining the present invention and are not limited thereto.
Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning in the art to which the claimed subject matter belongs.
To facilitate an understanding of embodiments of the present invention, the following terms are explained:
CTS refers to chitosan.
CAM, chitosan/acrylamide graft copolymer, which is a copolymer prepared by graft copolymerization of chitosan (chitosan) and Acrylamide (AM) as monomers.
PAFCC refers to polyaluminum ferric calcium chloride.
ORP, oxidation-Reduction Potential, refers to the Oxidation-reduction potential.
In order to solve the problems, the invention provides a method for recycling electroplating sludge, which comprises the following steps:
s1: regulating the pH value of electroplating wastewater;
s2: reducing the electroplating wastewater after the pH adjustment, wherein the reducing agent in the reducing treatment is sodium sulfite or sodium bisulfite;
s3: adding a first treating agent into the reduced electroplating wastewater for first precipitation treatment, stirring and settling, separating a first supernatant and first sludge, and regulating the pH value of the first supernatant; the first treating agent comprises caustic alkali, sodium sulfide, sodium hypochlorite and starch;
s4: adding a second treating agent into the first supernatant after the pH adjustment to carry out secondary precipitation treatment, and separating the second supernatant and second sludge after stirring and sedimentation; the second treating agent comprises a component A and a component B: the component A comprises chitosan and a chitosan/acrylamide grafted copolymer, and the component B comprises dodecyl amine, ethanol, trisodium nitrilotriacetate and polyaluminum ferric calcium chloride;
s5: mixing the first sludge and the second sludge to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, and adding double xanthate and heavy pyridine into the sludge suspension to perform flotation so as to realize heavy metal recovery.
In the scheme, the pH value of the electroplating wastewater is regulated and then reduced, the valence of heavy metal ions is reduced after the reduction treatment, and the electroplating wastewater after the reduction treatment is acidic. In some embodiments, the reducing agent is sodium sulfite and the ORP of the wastewater in the reduction reaction is controlled to be 200mv to 300mv.
Adding a first treating agent, and taking sodium hypochlorite as an oxidant to control the valence state of heavy metal ions. In some embodiments, the oxidizing agent may also be a mixed oxidizing agent formed by mixing sodium hypochlorite with other hypochlorous acid oxidizing agents.
The caustic alkali may be sodium hydroxide, potassium hydroxide, calcium hydroxide, or the like, and any caustic alkali that can form hydroxide precipitate with heavy metal ions may be used in the electroplating wastewater treatment of the present embodiment.
Each glucose monomer of the starch has 3 hydroxyl groups, polar groups can be combined with water molecules through the action of hydrogen bonds, and can be adsorbed on the hydroxide precipitation surface containing elements with high electronegativity (such as oxygen), so that mineral hydroxide is precipitated, or is adsorbed on the hydroxide precipitation surfaces, interaction is carried out with the hydroxide precipitation surfaces through the modes of hydrogen bond action, electrostatic action, chemical adsorption, acid-base action and the like of the hydroxyl groups, a hydrophilic starch adsorption layer is formed on the hydroxide precipitation surfaces, and hydroxide precipitation is flocculated by virtue of macromolecule bridging.
Sodium sulfide is used as a precipitator to rapidly precipitate hydroxide which is adsorbed and flocculated by starch, and meanwhile, the sodium sulfide can react with residual metal ions which do not form hydroxide precipitate with caustic alkali to generate corresponding metal sulfide which is used as a vulcanizing agent to pave on a hydrophobic surface formed by the precipitate for subsequent flotation.
The first supernatant is further treated, the pH value is adjusted in the separated first supernatant so that the second treating agent can play a role in the activity pH value, and the second treating agent is added, wherein the effect of adsorbing heavy metal ions by the chitosan and the chitosan/acrylamide grafted copolymer is remarkable, and the dodecyl amine, the ethanol, the trisodium nitrilotriacetate and the polyaluminum ferric chloride form hydrogen bonds through weak chemical adsorption, so that the residual metal ions can be effectively complexed to form metal amine and phosphorus complexes, and the sedimentation of the second residual heavy metal ions is completed.
The double xanthate interacts with the surface of heavy metal precipitate to generate xanthate, and the xanthate is arranged on the outer layer, so that the surface of the precipitate is hydrophobic and contacts with bubbles to form mineralized foam to float upwards.
Pyridine is a heterocyclic compound containing nitrogen atoms. Heavy pyridine is the most representative pyridine-based foaming agent. In the acidic electroplating sludge suspension, pyridine attracts hydrogen ions to exist in the form of pyridine hydrogen ions, aromatic hydrocarbon can be inserted into the gas, and polar groups are hydrophilic to generate hydration, so that heavy pyridine is adsorbed at a gas-liquid interface and bubbles are stabilized.
In some embodiments, the method for recycling electroplating sludge is realized by using a device, the device comprises a first regulating tank, a reduction tank, a first sedimentation tank, a second regulating tank, a second sedimentation tank and a flotation tank, the first regulating tank, the reduction tank, the first sedimentation tank, the second regulating tank, the second sedimentation tank and the flotation tank are sequentially connected through pipelines, a switch and a pump are arranged on each pipeline for connection, after each step is finished, the switch and the pump are turned on, and the intermediate step treatment liquid or sludge is pumped into the next device for treatment.
The first regulating tank is used for regulating the pH value of electroplating wastewater;
the reducing tank is used for receiving the electroplating wastewater after the pH adjustment and reducing heavy metal ions in the electroplating wastewater after the pH adjustment, and the reducing agent in the reducing treatment is sodium sulfite or sodium bisulphite;
the first sedimentation tank is used for receiving the reduced electroplating wastewater, adding a first treating agent into the first sedimentation tank, stirring and settling, and separating a first supernatant and a first sludge, wherein the first treating agent comprises caustic alkali, sodium sulfide, sodium hypochlorite and starch;
the second regulating tank is used for receiving the first supernatant and regulating the pH value of the first supernatant;
the second sedimentation tank is used for receiving the first supernatant after the pH adjustment, adding a first treating agent into the second sedimentation tank, stirring and settling, and separating a second supernatant and second sludge, wherein the second treating agent comprises a component A and a component B: the component A comprises chitosan, chitosan/acrylamide grafted copolymer, and the component B comprises dodecyl amine, ethanol, trisodium nitrilotriacetate and polyaluminum ferric calcium chloride;
and the flotation tank is used for floating heavy metal ions in the sludge to obtain selected heavy metal precipitates in the flotation bubble and harmless tailings which can be directly discharged and buried.
In some embodiments, the stirring is achieved by a mechanical stirring device comprising a rod-like structure and an impeller disposed on the rod-like structure, the lower end of the rod-like structure extending into the sedimentation tank, which can create severe turbulence of the flocculated sediment suspension, enhance the contact surface of the reaction, and enhance the separation effect of the supernatant and the sludge. The stirring speed is any integer value of 60-100 r/min, such as 60r/min, 65r/min, 70r/min, 75r/min, 80r/min, 85r/min, 90r/min, 95r/min, 100r/min, and the like.
The electroplating sludge recycling method provided by the invention can efficiently collect and recycle heavy metal ions in the sludge, and particularly has high collection strength on chromium, copper, nickel and other ions, and the recycling degree is high.
Further, the first treating agent comprises, in parts by weight: 65-100 parts of caustic alkali, 30-40 parts of sodium sulfide, 20-30 parts of sodium hypochlorite and 0.5-1 part of starch. Within the above range, caustic alkali, sodium sulfide, sodium hypochlorite and starch are able to form more hydroxide and synergistically flocculate and settle the hydroxide precipitate, thereby making the first supernatant less residual heavy metal ions and not unduly burdening the next pH adjustment step.
In some embodiments, the first treatment agent preferably comprises: 65-85 parts of caustic alkali, 40 parts of sodium sulfide, 25 parts of sodium hypochlorite and 0.5 part of starch.
Further, the a component of the second treatment agent includes, in parts by weight: 3-6 parts of chitosan and 1-3 parts of chitosan/acrylamide grafted copolymer. In some embodiments, the molecular weight of the chitosan is 500kDa to 900kDa.
Further, the B component of the second treatment agent includes, in parts by weight: 20-25 parts of dodecyl amine, 1-5 parts of ethanol, 5-10 parts of trisodium nitrilotriacetate and 1-2 parts of polyaluminum ferric calcium chloride. In the scheme, the dodecyl amine and the trisodium nitrilotriacetate can neutralize excessive acidity in the second precipitation treatment besides complexing heavy metal ions, and the dodecyl amine has a collecting effect on cations and can form a synergistic effect with reagents in flotation. Besides being used as a precipitator, the polyaluminum ferric chloride has a good turbidity removing effect, and meanwhile, the polyaluminum ferric chloride also has a certain removing effect on phosphorus and ammonia nitrogen.
Further, the weight of the double xanthate is 5-10 parts, and the weight of the pyridine is 5-10 parts. In some embodiments, the bisxanthate is 5, 6, 7, 8, 9 or 10 parts; the amount of the bipyridine is 5, 6, 7, 8, 9 or 10 parts, preferably, the amount of the biflava and the bipyridine is 1:2.
further, the pH value of the electroplating wastewater is adjusted to be 6-8; and/or adjusting the pH value of the first supernatant to be 2-2.5. When the pH of the system is within the above range, the degree of activity of the first treatment agent and the second treatment agent is higher. Preferably, the pH value of the electroplating wastewater is adjusted to be 8. Preferably, the pH of the first supernatant is adjusted to a pH of 2.
Further, the "adding a second treating agent to the first supernatant after pH adjustment to perform a second precipitation treatment" includes: and adding the component A of the second treating agent to treat, and then adding the component B of the second treating agent to treat. In other embodiments, the A-component and the B-component may also be added simultaneously from different feed inlets to the apparatus for the second precipitation treatment. The component A is added for treatment, and the component B is added for treatment, so that the second precipitation treatment reaction is more sufficient.
Further, the first treating agent comprises 3-5 parts of magnetic fluid, the second treating agent comprises 3-5 parts of magnetic fluid, and the sedimentation comprises: settling is carried out by utilizing a steady-state magnetic field device, and then standing and settling are carried out.
On one hand, the residual heavy metal ions are acted by the magnetic force, so that the movement track of the ions is complicated, concentration polarization is reduced, the chemical reaction of the first precipitation treatment is promoted, and the treatment effect is improved. On the other hand, the sedimentation is carried out by the steady-state magnetic field device, so that the sedimentation stability is greatly improved, and the first supernatant and the first sludge are fully separated. Meanwhile, the magnetic metal ions can be positioned in the first or second sludge, so that the further recovery of the magnetic metal ions after the sludge flotation is facilitated.
In some embodiments, the magnetic fluid comprises an iron-based magnetic fluid, an iron-cobalt-based magnetic fluid, and the like, the first treatment agent comprises 3 parts of the magnetic fluid, and the second treatment agent comprises 5 parts of the magnetic fluid.
Further, the magnetic field strength of the steady state magnetic field device is not more than 2000GS. The steady-state magnetic field device is sleeved outside the first sedimentation tank and the second sedimentation tank, and can assist in collecting magnetic heavy metals within the magnetic field intensity range. In some embodiments, the magnetic field strength is any integer value from 0 to 2000GS, such as 800GS, 1000GS, 1200GS, 1500GS, 2000GS, etc.
Further, in step S5, the flotation is performed in a mechanical flotation mixer. The mechanical floatation mixer has strong stirring force, can ensure the sediment suspension with larger density and granularity, and can promote the dispersion and emulsification of the biflava and the pyridine.
Further, in the step S5, the stirring time of the flotation is 10-15 min, and the stirring speed is 1000-1100 r/min. It will be appreciated that the agitation of the sludge before it enters the flotation machine is to accelerate the interaction of the electroplating waste with the medicament, and the agitation of the sludge suspension in the flotation machine is to suspend the sediment, disperse the bubbles, and promote the adhesion of the sediment to the bubbles. In some embodiments, the stirring time is 10min, 11min, 12min, 13min, 14min, or 15min. In some embodiments, the agitation rate is 1000r/min, 1050r/min, 1100r/min.
In some embodiments, the flotation cell includes a attemperator. In some embodiments, the temperature in the flotation cell is controlled to be 60 ℃ to 80 ℃. The temperature of the flotation tank can influence the actual flotation performance, bubble formation (size, stability and quantity) and particle hydrophobicity, the flotation temperature is comprehensively considered, the flotation efficiency is improved, and the flotation result is optimized.
Example 1
S1: adjusting the pH value of the electroplating wastewater to 8 in a first adjusting tank;
s2: pumping the electroplating wastewater with the pH value adjusted into a reduction tank, adding sodium sulfite into the reduction tank, and controlling the ORP of the wastewater in the reduction reaction to be 300mv;
s3: pumping the reduced electroplating wastewater into a first sedimentation tank, adding 75 parts of caustic alkali, 30 parts of sodium sulfide, 25 parts of sodium hypochlorite, 1 part of starch and 3 parts of iron-based magnetic fluid into the first sedimentation tank, performing first sedimentation treatment, setting the stirring speed of a mechanical stirring device to be 80r/min, setting the temperature to be 60 ℃ by using a temperature regulating device, stirring for 2-5 h, settling for 30min under a magnetic field of 800GS, standing and settling for 1h, and separating a first supernatant and first sludge;
s4: adjusting the pH of the first supernatant to 2.5;
s5: pumping the first supernatant after pH adjustment into a second sedimentation tank, adding 5 parts of chitosan and 2 parts of chitosan/acrylamide graft copolymer into the first supernatant after pH adjustment, setting the stirring speed of a mechanical stirring device to be 60r/min, setting the temperature to be 60 ℃ by using a temperature adjusting device, stirring for 1h, and then adding 25 parts of dodecyl amine, 1 part of ethanol, 5 parts of trisodium nitrilotriacetate, 3 parts of iron-based magnetic fluid and 2 parts of polyaluminum ferric calcium chloride; setting the stirring speed of a mechanical stirring device to be 60r/min, setting the temperature to be 60 ℃ by using a temperature regulating device, stirring for 1h, settling for 30min under a magnetic field of 1500GS, standing and settling for 1h, and separating a second supernatant and second sludge;
s6: mixing the first sludge and the second sludge in a flotation tank to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, adding 5 parts of double xanthate and 10 parts of pyridine into the sludge suspension for flotation, stirring the flotation at 70 ℃ for 10min at a speed of 1100r/min, and collecting upper-layer bubbles to realize heavy metal recovery.
Example 2:
s1: adjusting the pH value of the electroplating wastewater to 7 in a first adjusting tank;
s2: pumping the electroplating wastewater with the pH value adjusted into a reduction tank, adding sodium sulfite into the reduction tank, and controlling the ORP of the wastewater in the reduction reaction to be 300mv;
s3: pumping the reduced electroplating wastewater into a first sedimentation tank, adding 70 parts of caustic alkali, 30 parts of sodium sulfide, 25 parts of sodium hypochlorite, 1 part of starch and 5 parts of iron-based magnetic fluid into the first sedimentation tank, performing first sedimentation treatment, setting the stirring speed of a mechanical stirring device to be 80r/min, setting the temperature to be 65 ℃ by using a temperature regulating device, stirring for 2-5 h, settling for 30min under a 1200GS magnetic field, standing and settling for 1h, and separating a first supernatant and first sludge;
s4: adjusting the pH value of the first supernatant to 2;
s5: pumping the first supernatant after pH adjustment into a second sedimentation tank, adding 6 parts of chitosan and 3 parts of chitosan/acrylamide graft copolymer into the first supernatant after pH adjustment, setting the stirring speed of a mechanical stirring device to be 60r/min, setting the temperature to be 60 ℃ by using a temperature adjusting device, stirring for 1h, and then adding 20 parts of dodecyl amine, 5 parts of ethanol, 10 parts of trisodium nitrilotriacetate, 3 parts of iron-based magnetic fluid and 2 parts of polyaluminum ferric chloride calcium; setting the stirring speed of a mechanical stirring device to be 60r/min, setting the temperature to be 65 ℃ by using a temperature regulating device, stirring for 1h, settling for 30min under a magnetic field of 800GS, standing and settling for 1h, and separating a second supernatant and second sludge;
s6: mixing the first sludge and the second sludge in a flotation tank to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, adding 6 parts of double xanthate and 8 parts of heavy pyridine into the sludge suspension for flotation, stirring the flotation at the temperature of 60 ℃ for 12min at the speed of 1000r/min, and collecting upper-layer bubbles to realize heavy metal recovery.
Example 3:
s1: adjusting the pH value of the electroplating wastewater to 6 in a first adjusting tank;
s2: pumping the electroplating wastewater with the pH value adjusted into a reduction tank, adding sodium sulfite into the reduction tank, and controlling the ORP of the wastewater in the reduction reaction to be 300mv;
s3: pumping the reduced electroplating wastewater into a first sedimentation tank, adding 70 parts of caustic alkali, 40 parts of sodium sulfide, 25 parts of sodium hypochlorite, 1 part of starch and 5 parts of iron-based magnetic fluid into the first sedimentation tank, performing first sedimentation treatment, setting the stirring speed of a mechanical stirring device to be 80r/min, setting the temperature to be 65 ℃ by using a temperature regulating device, stirring for 2-5 h, settling for 30min under a magnetic field of 800GS, standing and settling for 1h, and separating a first supernatant and first sludge;
s4: adjusting the pH of the first supernatant to 2.5;
s5: pumping the first supernatant after pH adjustment into a second sedimentation tank, adding 6 parts of chitosan and 3 parts of chitosan/acrylamide graft copolymer into the first supernatant after pH adjustment, setting the stirring speed of a mechanical stirring device to be 60r/min, setting the temperature to be 60 ℃ by using a temperature adjusting device, stirring for 1h, and then adding 25 parts of dodecyl amine, 5 parts of ethanol, 10 parts of trisodium nitrilotriacetate, 3 parts of iron-based magnetic fluid and 2 parts of polyaluminum ferric chloride calcium; setting the stirring speed of a mechanical stirring device to be 60r/min, setting the temperature to be 65 ℃ by using a temperature regulating device, stirring for 1h, settling for 30min under a magnetic field of 800GS, standing and settling for 1h, and separating a second supernatant and second sludge;
s6: mixing the first sludge and the second sludge in a flotation tank to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, adding 6 parts of double xanthate and 8 parts of heavy pyridine into the sludge suspension for flotation, stirring the flotation at the temperature of 60 ℃ for 12min at the speed of 1000r/min, and collecting upper-layer bubbles to realize heavy metal recovery.
Comparative example 1:
the difference from example 1 is that the flotation agent is 10 parts xanthate and 10 parts sodium oleate.
Further, the recovery rate of heavy metals in the sludge obtained in examples 1 to 3 and comparative example 1 was tested, and the results were recorded as the following table 1:
table 1.
Referring to the table above, it is proved that the electroplating sludge recycling method of the embodiment of the invention adjusts the pH value of electroplating wastewater, then carries out reduction treatment, and then adds the first treating agent to realize the first heavy metal ion sedimentation. And adjusting the pH value in the separated first supernatant to facilitate the second treating agent to play a role in the activity pH value, adding the second treating agent, adsorbing heavy metal ions, complexing residual metal ions and phosphorus, and completing the sedimentation of the second residual heavy metal ions. The sludge obtained by twice sedimentation is collected to be made into suspension, a proper amount of double xanthate is added to be used as a collector, the heavy pyridine is used as a foaming agent, the suspension of the sludge is subjected to flotation, a large amount of heavy metal ions are collected in the upper layer of flotation bubble, tailings are harmless to the environment, and the sludge can be directly buried, so that harmless treatment and recycling of the sludge are realized.
The electroplating sludge recycling method provided by the invention can efficiently collect and recycle heavy metal ions in the sludge, and particularly has high collection strength on chromium, copper, nickel and other ions, and the recycling degree is high.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The electroplating sludge recycling method is characterized by comprising the following steps of:
s1: regulating the pH value of electroplating wastewater;
s2: reducing the electroplating wastewater after the pH adjustment, wherein the reducing agent in the reducing treatment is sodium sulfite or sodium bisulfite;
s3: adding a first treating agent into the reduced electroplating wastewater for first precipitation treatment, stirring and settling, separating a first supernatant and first sludge, and regulating the pH value of the first supernatant; the first treating agent comprises caustic alkali, sodium sulfide, sodium hypochlorite and starch;
s4: adding a second treating agent into the first supernatant after the pH adjustment to carry out secondary precipitation treatment, and separating the second supernatant and second sludge after stirring and sedimentation; the second treating agent comprises a component A and a component B: the component A comprises chitosan and a chitosan/acrylamide grafted copolymer, and the component B comprises dodecyl amine, ethanol, trisodium nitrilotriacetate and polyaluminum ferric calcium chloride;
s5: mixing the first sludge and the second sludge to obtain mixed sludge, adding water into the sludge to obtain a sludge suspension, and adding double xanthate and heavy pyridine into the sludge suspension to perform flotation so as to realize heavy metal recovery.
2. The method for recycling electroplating sludge according to claim 1, wherein the first treating agent comprises, in parts by weight: 65-100 parts of caustic alkali, 30-40 parts of sodium sulfide, 20-30 parts of sodium hypochlorite and 0.5-1 part of starch.
3. The method for recycling electroplating sludge according to claim 1, wherein the a component of the second treating agent comprises, in parts by weight: 3-6 parts of chitosan, 1-3 parts of chitosan/acrylamide grafted copolymer;
and/or, the B component of the second treatment agent comprises, in parts by weight: 20-25 parts of dodecyl amine, 1-5 parts of ethanol, 5-10 parts of trisodium nitrilotriacetate and 1-2 parts of polyaluminum ferric calcium chloride.
4. The electroplating sludge recycling method according to claim 1, wherein the double xanthate is 5-10 parts by weight;
and/or 5-10 parts by weight of heavy pyridine.
5. The method for recycling electroplating sludge according to claim 1, wherein the pH value of the electroplating wastewater is adjusted to be 6-8;
and/or adjusting the pH value of the first supernatant to be 2-2.5.
6. The method for recycling electroplating sludge according to claim 1, wherein adding a second treating agent to the first supernatant after the pH adjustment to perform a second precipitation treatment comprises: and adding the component A of the second treating agent to treat, and then adding the component B of the second treating agent to treat.
7. The method for recycling electroplating sludge according to claim 1, wherein the first treating agent comprises 3-5 parts of magnetic fluid, the second treating agent comprises 3-5 parts of magnetic fluid, and the sedimentation comprises: settling is carried out by utilizing a steady-state magnetic field device, and then standing and settling are carried out.
8. The method for recycling electroplating sludge according to claim 7, wherein the magnetic field strength of the steady state magnetic field device is not more than 2000GS.
9. The electroplating sludge recycling process of claim 1, wherein in step S5, the flotation is performed in a mechanical flotation mixer.
10. The electroplating sludge recycling method according to claim 1, wherein in the step S5, the stirring time of the flotation is 10-15 min, and the stirring speed is 1000-1100 r/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6254782B1 (en) * | 1995-05-19 | 2001-07-03 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| US20030082084A1 (en) * | 2001-05-30 | 2003-05-01 | Cort Steven L. | Methods for removing heavy metals from water using chemical precipitation and field separation methods |
| US20050258103A1 (en) * | 2001-05-30 | 2005-11-24 | Cort Steven L | Methods for removing heavy metals from water using chemical precipitation and field separation methods |
| CN109482355A (en) * | 2018-11-16 | 2019-03-19 | 西北矿冶研究院 | Low-grade fine-grained copper ore flotation collector |
| CN112028338A (en) * | 2020-09-24 | 2020-12-04 | 广东省科学院资源综合利用研究所 | Wastewater treatment method for recovering copper from electroplating wastewater containing cyanogen and copper |
| CN116441058A (en) * | 2023-05-15 | 2023-07-18 | 河南富龙新材料科技有限公司 | Method for reducing magnesium oxide content of concentrate in copper-nickel sulfide ore floatation |
-
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- 2024-01-12 CN CN202410046633.XA patent/CN117550768B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6254782B1 (en) * | 1995-05-19 | 2001-07-03 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| US20030082084A1 (en) * | 2001-05-30 | 2003-05-01 | Cort Steven L. | Methods for removing heavy metals from water using chemical precipitation and field separation methods |
| US20050258103A1 (en) * | 2001-05-30 | 2005-11-24 | Cort Steven L | Methods for removing heavy metals from water using chemical precipitation and field separation methods |
| CN109482355A (en) * | 2018-11-16 | 2019-03-19 | 西北矿冶研究院 | Low-grade fine-grained copper ore flotation collector |
| CN112028338A (en) * | 2020-09-24 | 2020-12-04 | 广东省科学院资源综合利用研究所 | Wastewater treatment method for recovering copper from electroplating wastewater containing cyanogen and copper |
| CN116441058A (en) * | 2023-05-15 | 2023-07-18 | 河南富龙新材料科技有限公司 | Method for reducing magnesium oxide content of concentrate in copper-nickel sulfide ore floatation |
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