CN112176368A - Potassium chloride acidic zinc plating electroplating solution and application thereof - Google Patents
Potassium chloride acidic zinc plating electroplating solution and application thereof Download PDFInfo
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- CN112176368A CN112176368A CN202010936235.7A CN202010936235A CN112176368A CN 112176368 A CN112176368 A CN 112176368A CN 202010936235 A CN202010936235 A CN 202010936235A CN 112176368 A CN112176368 A CN 112176368A
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- potassium chloride
- acidic
- zinc plating
- plating
- plating bath
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 134
- 238000007747 plating Methods 0.000 title claims abstract description 86
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 68
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 68
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 38
- 239000011701 zinc Substances 0.000 title claims abstract description 38
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 37
- 238000009713 electroplating Methods 0.000 title abstract description 32
- 238000005246 galvanizing Methods 0.000 claims abstract description 26
- MACMAADVRVVHBD-VMPITWQZSA-N (e)-1-(2,4-dihydroxyphenyl)-3-(2-hydroxyphenyl)prop-2-en-1-one Chemical compound OC1=CC(O)=CC=C1C(=O)\C=C\C1=CC=CC=C1O MACMAADVRVVHBD-VMPITWQZSA-N 0.000 claims abstract description 23
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- QNTYDPGMWBEHDK-UHFFFAOYSA-N n-carbamoylpyridine-3-carboxamide Chemical class NC(=O)NC(=O)C1=CC=CN=C1 QNTYDPGMWBEHDK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 13
- 239000004902 Softening Agent Substances 0.000 claims abstract description 12
- MACMAADVRVVHBD-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-3-(2-hydroxyphenyl)prop-2-en-1-one Natural products OC1=CC(O)=CC=C1C(=O)C=CC1=CC=CC=C1O MACMAADVRVVHBD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims abstract description 11
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 10
- 239000011592 zinc chloride Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005282 brightening Methods 0.000 claims abstract description 9
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 9
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 8
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical class CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 6
- 229920000570 polyether Polymers 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 13
- 239000002671 adjuvant Substances 0.000 claims description 12
- 229920001444 polymaleic acid Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- QDPYDWXGZVHLMJ-UHFFFAOYSA-K potassium;zinc;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[K+].[Zn+2] QDPYDWXGZVHLMJ-UHFFFAOYSA-K 0.000 claims description 3
- 150000001450 anions Chemical group 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 18
- 239000002351 wastewater Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- -1 salt zinc chloride Chemical class 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229930008407 benzylideneacetone Natural products 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- BCKAHPMIUGPVJN-UHFFFAOYSA-M sodium;1-chloropropane-1-sulfonate Chemical compound [Na+].CCC(Cl)S([O-])(=O)=O BCKAHPMIUGPVJN-UHFFFAOYSA-M 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- VTEIFHQUZWABDE-UHFFFAOYSA-N 2-(2,5-dimethoxy-4-methylphenyl)-2-methoxyethanamine Chemical compound COC(CN)C1=CC(OC)=C(C)C=C1OC VTEIFHQUZWABDE-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- ZQUDHVGNIZTEDK-UHFFFAOYSA-M potassium;propane-1-sulfonate Chemical compound [K+].CCCS([O-])(=O)=O ZQUDHVGNIZTEDK-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- LGORLCOUTMVEAC-UHFFFAOYSA-M sodium;2-nonylphenolate Chemical compound [Na+].CCCCCCCCCC1=CC=CC=C1[O-] LGORLCOUTMVEAC-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a potassium chloride acidic galvanizing plating solution containing KCl 120-150 g/L and ZnCl230～40g/L，H3BO325-30 g/L of brightening agent, 0.1-0.5 mL/L of softening agent, 20-30 mL/L of softening agent and 6-12 mL/L of auxiliary agent; in the brightener, the Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate accounts for 20-30 wt%, and the benzalacetone accounts for 10-25 wt%; the softener contains 5-10 wt.% of 2,2 ', 4' -trihydroxychalcone, 10-20 wt.% of beta-naphthol polyether sulfonate, 1-3 wt.% of nicotinoyl urea derivative and 5-10 wt.% of nicotinoyl urea derivative
EN 16-80, 1 wt.% to 3 wt.% sodium benzoate. The potassium chloride acidic zinc plating solution greatly reduces the concentration of main salt and conductive salt in the plating solution, greatly reduces the concentration of chloride ions in wastewater, and can still keep the characteristics of high current efficiency, wide current density range, fine crystallization, excellent dispersion and the like of the traditional potassium salt zinc plating process, and the characteristics are shown in the tableExcellent leveling and walking performance is shown; the invention has the advantages of less consumption of main salt and conductive salt, raw material cost saving, no increase of cell voltage and no additional increase of energy expenditure in the same current electroplating, and is suitable for rack plating and barrel plating.
Description
Technical Field
The invention belongs to the field of metal corrosion protection and surface treatment, and particularly relates to a potassium chloride acidic zinc plating electroplating solution and application thereof.
Background
Along with the rapid increase of water resource demand, the water pollution situation becomes more and more serious, people pay more and more attention to the water pollution treatment technology, and the technology for removing pollutants such as COD, BOD, nitrogen, phosphorus, heavy metals and the like is greatly developed; however, in practical production, the content of chloride ions in electroplating wastewater, especially chloride galvanizing wastewater, is the most difficult problem to solve, and the removal technology of chloride ions in electroplating wastewater is relatively less because the chloride ions are not utilized by microorganisms, so that a large amount of chloride enters the environment and can cause serious harm to the environment and organisms.
The chloride galvanizing technology has been developed greatly, and accounts for about 40 percent of the total galvanizing amount at present. Because high-concentration chloride in water can corrode metal pipelines and structures and influence water quality (particularly in water-deficient areas such as the north), the rapid development of the chloride galvanizing technology is accompanied by the rapid increase of the wastewater treatment capacity, and particularly after small electroplating plants are integrated into a park in succession, the treatment of electroplating wastewater becomes a key bottleneck restricting the development of the park. In the potassium chloride acidic galvanizing process, although potassium chloride has weak complexation effect on zinc ions, the potassium chloride mainly has the functions of conducting and activating an anode, and the optimal concentration of the potassium chloride is 185-210 g/L. When the concentration of potassium chloride is high, the quality of the coating in the low current region can be improved, the dispersing capacity of the plating solution can be improved, and the anode passivation can be prevented. When the content of potassium chloride is too low, the dispersing ability of the plating solution is obviously reduced, the current efficiency is low, the conductivity is poor, the plating layer is dark, and the low region is blackened. Zinc chloride is a main salt, generally speaking, the optimal concentration range of the zinc chloride is 45-75 g/L, when the concentration is low, the concentration polarization is large, the current of electroplating is not large, the bright area is narrowed, and the scorching phenomenon is easy to occur in the high current area. However, if the content of chloride ions in the potassium chloride galvanizing wastewater is to be reduced, the content of chloride ions in the electroplating solution, i.e., the total chlorine of potassium chloride and zinc chloride, must be reduced, but the reduction of the concentration of chloride ions will cause the dispersing ability of the electroplating solution to be obviously reduced, and will cause the faults of low current efficiency, poor conductivity, dark plating layer, blackened low region, etc., and will cause the problems of voltage rise, energy consumption increase, etc. under the same electroplating current, thereby reducing the consumption of chloride, but increasing the expenditure of electric energy, and not paying for the expense.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a potassium chloride acidic zinc plating electroplating solution which can reduce the discharge of chloride ions and the production cost and has the advantages of the traditional potassium chloride zinc plating and application thereof.
The technical scheme provided by the invention is as follows:
the invention provides a potassium chloride acidic zinc plating electroplating solution, which comprises:
wherein:
in the brightener, the Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate accounts for 20-30 wt%, the benzylidene acetone accounts for 10-25 wt%, and the balance is water;
the softener contains 5-10 wt.% of 2,2 ', 4' -trihydroxychalcone, 10-20 wt.% of beta-naphthol polyether sulfonate, 1-3 wt.% of nicotinoyl urea derivative and 5-10 wt.% of nicotinoyl urea derivative
EN 16-80, 1 wt.% to 3 wt.% of sodium benzoate, and the balance of water.
Further, the pH value of the potassium chloride acidic zinc plating solution is 4.8-6.2.
Further, the potassium chloride acidic zinc plating solution contains KCl 150g/L, ZnCl2 35g/L，H3BO330g/L, 0.2mL/L of brightening agent, 25mL/L of softening agent and 10mL/L of auxiliary agent.
Further, the anionic structural formula of the Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate is as follows:
wherein p is 1 to 10, q is 1 to 10, n is 5 to 20, and X is F, Cl or Br.
Further, the preparation method of the brightener comprises the following steps: adding 20-30% of Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate by mass into a stirring kettle, heating to 40 ℃, adding 10-25% of solid benzalacetone by mass into the stirring kettle in batches, keeping the temperature and stirring until the benzalacetone is melted and is completely and uniformly dispersed to form a transparent uniform solution, adding 45-70% of water by mass into the kettle while keeping stirring, uniformly stirring, and cooling to room temperature to obtain a light yellow transparent solution, namely the brightener.
Further, in the softening agent, 5-10 wt% of 2,2 ', 4' -trihydroxychalcone, 10-20 wt% of beta-naphthol polyether sulfonate, 1-3 wt% of nicotinoyl urea derivative,
EN 16-80 accounts for 5-10 wt.%, sodium benzoate accounts for 1-3 wt.%, and the balance is water.
Further, the preparation method of the softening agent comprises the following steps: firstly, 10 to 20 mass percent of beta-naphthol polyether sulfonate and 5 to 10 mass percent of beta-naphthol polyether sulfonate are added into a stirring kettle
EN 16-80, stirring and mixing uniformly, adding 5-10% of 2,2 ', 4' -trihydroxychalcone and 1-3% of sodium benzoate in percentage by mass into a kettle, heating to 55 ℃, keeping the temperature and stirring for 1h, cooling to room temperature, adding 1-3% of nicotinoyl urea derivatives and half of a specified amount of water in percentage by mass, stirring until the materials are completely dissolved, finally adding the balance of water into the kettle, wherein the percentage by mass of all the water is 50-80%, and stirring uniformly to obtain a yellow to brown yellow transparent viscous solution, thus obtaining the softener.
Further, the structural formula of 2,2 ', 4' -trihydroxychalcone is as follows:
the structural formula of the nicotinoyl urea derivative is as follows:
the auxiliary agent is selected from polymaleic acid,
LF-Na50 and water, wherein the polymaleic acid accounts for 5-15 wt%,
LF-Na50 accounts for 5 wt.% to 15 wt.%, and the balance is water.
Further, the preparation method of the adjuvant comprises the following steps: the mass percentage is 5 wt.% to 15 wt%
Adding LF-Na50 and polymaleic acid with the mass percentage of 5 wt.% to 15 wt.% into a stirring kettle, introducing cooling water into a coil of the stirring kettle, controlling the temperature in the kettle to be not more than 35 ℃, uniformly stirring, adding water with the mass percentage of 70 wt.% to 90 wt.% into the kettle, and uniformly stirring to obtain the auxiliary agent.
The invention also provides a method for galvanizing by using the potassium chloride acidic galvanizing plating solution, and the galvanizing conditions are controlled as follows: the pH value is approximately equal to 6, and the current density is 0.5-5A/dm2The rack plating voltage is 3-8V, the barrel plating voltage is 6-12V, and the operation temperature is 33 ℃.
Further, additives were added in the following amounts: brightening agent: 80-150mL/KAH, softening agent: 80-150mL/KAH, adjuvant: 20-30 mL/KAH.
Of the above raw materials, the inventors of the present invention developed the compound of the formula, and other raw materials were commercially availableAll have sales on the surface, wherein
EN 16-80 is a product of RASCHIG, Germany,
LF-Na50 is a product of Lesi chemical company, and polymaleic acid is a product with the relative molecular mass of 450-600 and the solid content of more than or equal to 50 wt.%.
When only the nonionic surfactant is added into the potassium chloride galvanizing solution, the gray coating with uniform grain size and consistent shape is obtained by electroplating; when organic matter with ketene conjugated structure is added, a coating with fine crystals and bright mirror surface can be obtained, which shows that the surfactant has the function of inhibiting the transfer reaction of electrons, increasing the polarization of metal electrodeposition process and playing a key role in the deep plating and dispersion capability of the additive; the synergistic effect of the organic compound with the ketene conjugated structure and the surfactant acts on the growth process of the metal crystal nucleus, inhibits the crystal growth, promotes the crystal nucleus generation, influences the nucleation mechanism, and finally obtains a bright and fine plating layer with excellent dispersion and deep plating performance; after the concentration of chloride ions is reduced, the electrolyte concentration in the plating solution is reduced, the conductivity of the plating solution is reduced, the current density distribution acting on the surface of the cathode is uneven, the concentration polarization in the plating solution is increased, the cell voltage is increased, and the high-region crystal is rough and even scorch appears.
After the use amounts of main salt zinc chloride and conductive salt potassium chloride are reduced, the potassium chloride acidic zinc plating solution provided by the invention adopts a Guerbet alcohol polyoxyethylene ether with a branched chain and an anion modified product of naphthol polyoxyethylene ether with deep plating performance as a carrier brightener, so that the problem of poor permeability and dispersion performance of the potassium chloride acidic zinc plating solution caused by the reduction of the concentration of chloride ions is solved, the pyridine ionic liquid compound has the characteristic of conductivity, and the concentration polarization in the potassium chloride acidic zinc plating solution is reduced by adding the nicotinoyl urea derivative; the invention also utilizes the synergistic effect of various organic compounds to ensure that the anode is normally dissolved and the high area of the plating layer is not burnt, and the dispersion performance, the covering capability and the deposition speed of the electroplating solution are hardly influenced.
Compared with the traditional potassium chloride galvanizing plating solution, the invention has the following advantages and beneficial effects:
the main salt zinc chloride and the conductive salt potassium chloride in the potassium chloride acidic zinc plating solution provided by the invention are used in a reduced amount, so that the raw material cost expenditure of enterprises is reduced, and the chloride ion concentration in wastewater is reduced.
Drawings
FIG. 1 is a schematic illustration of plated sheets prepared with different electrolytes under the plating conditions of Table 1; wherein, 1 adopts electroplating solution base liquid, 2 adopts potassium chloride acidic zinc plating solution V, 3 adopts potassium chloride acidic zinc plating solution VI, and 4 adopts potassium chloride acidic zinc plating solution IV.
FIG. 2 is a graph showing the trend of potassium chloride content (g/L) in waste water before and after improvement in a galvanizing line in an industrial park over time.
FIG. 3 is a graph showing the time-dependent trend of the total chlorine content (ppm) in the wastewater of a certain industrial park galvanizing line after potassium chloride acid galvanizing plating solution I is used.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Adopted in the invention
NAPE 14-90 is beta-naphthol polyoxypropylene polyoxyethylene ether potassium propanesulfonate, a product of RASCHIG company in Germany; the beta-naphthol polyoxyethylene (12) ether is a product of Germany BASF company, and has the code of BNO-12; the 2,2 ', 4' -trihydroxychalcone adopted by the invention has a CAS number of No.26962-50-5 and a structure as follows:
the nicotinoyl urea derivative adopted by the invention has the structure of CAS No.3298-38-2 as follows:
example 1: preparation of electroplating solution base liquid
Adding 40L of water into an electroplating bath, then slowly adding 3.5kg of zinc chloride and 1.5kg of potassium chloride under the condition of strong stirring, and stirring until the solid is completely dissolved; heating another 20L of deionized water to 90 ℃, slowly pouring 3kg of boric acid into the deionized water while stirring, and stirring until the solid is completely dissolved to obtain a boric acid solution; then pouring the boric acid solution into an electroplating bath, and uniformly mixing; and then adding water into the electroplating bath to 90% of the specified volume, detecting the pH value, adjusting the electroplating bath to the proper pH value by using 10 wt.% hydrochloric acid or 10 wt.% potassium hydroxide to obtain an electroplating bath base solution, and performing small-current electrolysis to obtain the plating test.
Example 2: preparation of brightener I
Adding 30kg of Guerbet cetyl polyoxyethylene ether (21) sodium chloropropane sulfonate into a stirring kettle, heating to 40 ℃, starting stirring, then adding 15kg of benzalacetone, gradually melting and dissolving the benzalacetone in the heating and stirring process, continuously stirring until the materials are uniformly mixed, then adding 55kg of deionized water into the stirring kettle, continuously keeping the temperature and stirring until a uniform solution is formed, cooling to room temperature, and discharging to obtain 100kg of brightener I.
Example 3: preparation of brightener II
The preparation method is the same as example 2, except that the feed amount of each component is as follows: 25kg Guerbet ceteth (15) sodium chloropropanesulfonate, 15kg benzylidene acetone and 60kg deionized water, 100kg brightener II is obtained.
Example 4: preparation of brightener III
The preparation method is the same as example 2, except that the feed amount of each component is as follows: 30kg Guerbet ceteth (10) sodium chloropropanesulfonate, 18kg benzylidene acetone and 52kg deionized water, 100kg brightener III was obtained.
Example 5: preparation of softener I
20kg of a solvent was added to the stirred tank
NAPE 14-90 and 10kg
EN 16-80, starting mechanical stirring to uniformly stir and mix the materials, slowly heating to about 55 ℃, adding 8kg of 2,2 ', 4' -trihydroxychalcone and 3kg of sodium benzoate into a stirring kettle, stirring for 1 hour under heat preservation, cooling to room temperature, adding 2kg of N-carbamyl nicotinamide-1-propane sulfonate and 27kg of deionized water into the kettle, stirring until the materials are dissolved, continuing stirring for 30 minutes under heat preservation, then adding 30kg of deionized water, uniformly mixing, cooling to room temperature, and discharging to obtain the softener I.
Example 6: preparation of softener II
The preparation method is the same as example 5, except that the feed amount of each component is as follows: 18kg of sodium beta-naphthol polyoxyethylene (12) ether succinate sulfonate (prepared from BNO-12 with maleic anhydride and sodium bisulfite), 10kg of
EN 16-80, 6kg of 2,2 ', 4' -trihydroxychalcone, 3kg of sodium benzoate, 3kg of N-carbamoylnicotinamide-1-propane sulfonate and 60kg of deionized water to obtain the softener II.
Example 7: preparation of softener III
The preparation method is the same as example 5, except that the componentsThe feeding amount is as follows: 20kg of beta-naphthol polyoxyethylene (12) ether ammonium sulfonate (prepared by synthesizing BNO-12 and sulfamic acid) and 10kg of
EN 16-80, 10kg of 2,2 ', 4' -trihydroxychalcone, 2.5kg of sodium benzoate, 2.5kg of N-carbamoylnicotinamide-1-propanesulfonate and 55kg of deionized water to obtain the softener III.
Example 8: preparation of adjuvant I
Adding 15kg of polymaleic acid and 15kg of polymaleic acid into a stirring kettle
LF-Na50 and 70kg deionized water, introducing cooling water into a coil pipe of the stirring kettle, controlling the temperature in the kettle to be not more than 35 ℃, uniformly stirring and mixing, and discharging to obtain an auxiliary agent I.
Example 9: preparation of adjuvant II
The preparation method is the same as example 8, except that the feeding amount of each component is as follows: 15kg of polymaleic acid, 10kg of
LF-Na50 and 75kg of deionized water to give adjuvant II.
Example 10: preparation of adjuvant III
The preparation method is the same as example 8, and the feeding amount of each component is as follows: 13kg of polymaleic acid, 15kg of
LF-Na50 and 72kg of deionized water to give adjuvant III.
Example 11: preparation of potassium chloride acidic zinc plating electroplating solution
The plating bath base solution prepared in example 1, the brighteners prepared in examples 2 to 4, the softeners prepared in examples 5 to 7, and the adjuvants prepared in examples 8 to 10 were prepared into potassium chloride acid zinc plating baths in the amounts added and under the process conditions shown in Table 1: the potassium chloride acid zinc plating electroplating solution I consists of electroplating solution base liquid, a brightening agent I, a softening agent I and an auxiliary agent I, the potassium chloride acid zinc plating electroplating solution II consists of electroplating solution base liquid, a brightening agent II, a softening agent II and an auxiliary agent II, the potassium chloride acid zinc plating electroplating solution III consists of electroplating solution base liquid, a brightening agent III, a softening agent III and an auxiliary agent III, and the potassium chloride acid zinc plating electroplating solution IV consists of electroplating solution base liquid, a brightening agent I, a softening agent II and an auxiliary agent III.
The plating piece for performance test is prepared, and the pretreatment process comprises the following steps: alkaline degreasing → hot water rinsing → tap water rinsing → acid pickling activation → tap water rinsing → acid galvanizing → tap water rinsing → blow drying.
TABLE 1 Potassium chloride acidic galvanizing plating bath Components and Process conditions for preparing galvanized sheets
| Composition of | Concentration of |
| KCl(g/L) | 150 |
| ZnCl2(g/L) | 35 |
| H3BO3(g/L) | 30 |
| Brightener (mL/L) | 0.2 |
| Softening agent (mL/L) | 25 |
| Adjuvant (mL/L) | 10 |
| pH value | 6.0 |
| Current Density (A/dm)2) | 0.5～5 |
| Hanging plating voltage (V) | 3～8 |
| Barrel plating voltage (V) | 6～12 |
| Operating temperature (. degree.C.) | 33 |
| Plating time (min) | 5 |
Comparative example 1
As shown in Table 2, a potassium chloride acidic zinc plating bath V was prepared by adding the LAN-918 brightener and the LAN-919 softener to the plating bath base solution prepared in example 1; as shown in Table 3, an acid potassium chloride zinc plating bath VI was prepared by adding the LAN-918 brightener and the LAN-919 softener to the bath base liquid prepared in example 1. FIG. 1 shows plated pieces prepared with different electrolytes under the plating conditions of Table 1.
TABLE 2 composition of potassium chloride acidic galvanizing bath V
| LAN-918 brightener (mL/L) | 2 |
| LAN-919 softener (mL/L) | 20 |
| Adjuvant III (mL/L) | 0 |
| pH value | 6.0 |
TABLE 3 composition of acidic potassium chloride galvanising bath VI
| LAN-918 brightener (mL/L) | 2 |
| LAN-919 softener (mL/L) | 20 |
| Adjuvant III (mL/L) | 10 |
| pH value | 6.0 |
The LAN-918 brightener and the LAN-919 softener are common potassium chloride galvanizing additives produced by Wuhanaobang surface technology limited company, wherein the LAN-918 brightener comprises the following components in percentage by weight: 45 wt.% sodium nonylphenol polyoxyethylene ether (15) sulfate, 15 wt.% o-chlorobenzaldehyde and the balance of water; the LAN-919 softener consists of the following components: 40 wt.% of isomeric alcohol polyoxyethylene ether (2) sodium sulfonate, 15 wt.% of benzylidene acetone, 10 wt.% of OP-10, 10 wt.% of dispersing agent M, 3 wt.% of sodium benzoate and the balance of water.
Example 12
The dispersibility test was carried out by the near-far cathode method of the dispersibility test according to the test method of JBT 7704.4-1995 plating solution, the test conditions are shown in Table 4, the test results of the potassium chloride acid zinc plating solutions I-V are shown in Table 5, and the calculation formula is:
TABLE 4 Experimental Process parameters
| Temperature of plating | 25℃ |
| Area of cathode | 60mm×80mm×2 |
| Plating current | 0.98A |
| Current density | 1A/dm2 |
| Time of plating | 25min |
| Value of |
3 |
TABLE 5 dispersing ability test results
Experiments show that the dispersing ability T of the potassium chloride acidic zinc plating solution I-III is more than or equal to 59 percent, and the dispersing property of the potassium chloride acidic zinc plating solution I-III is obviously improved compared with that of the potassium chloride acidic zinc plating solution V before improvement.
Example 13
The potassium chloride acid zinc plating solution V is used in a zinc plating production line of an industrial park before improvement, the potassium chloride acid zinc plating solution I is used after improvement, the content of chloride ions in the potassium chloride acid zinc plating solution is reduced by means of natural bringing on the basis of not supplementing potassium chloride, the tracking data of the potassium chloride content in the potassium chloride acid zinc plating solution, the production line tank pressure and current and the total chlorine content in wastewater discharge are shown in the table 4 and the figure 2, and the change trend of the total chlorine content (ppm) in wastewater after the potassium chloride acid zinc plating solution I is used in the zinc plating production line of the industrial park along with time is shown in the figure 3.
TABLE 4 sampling table for tank voltage and current of workshop
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A potassium chloride acidic zinc plating bath characterized by comprising:
the brightener contains 20-30 wt.% of Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate, 10-25 wt.% of benzalacetone and the balance of water;
the softener comprises 5-10 wt.% of 2,2 ', 4' -trihydroxychalcone, 10-20 wt.% of beta-naphthol polyether sulfonate, 1-3 wt.% of nicotinoyl urea derivative and 5-10 wt.% of nicotinoyl urea derivative
EN 16-80, 1 wt.% to 3 wt.% of sodium benzoate, and the balance of water.
2. The acidic potassium chloride galvanizing plating bath according to claim 1, characterized in that: the pH value of the potassium chloride acidic zinc plating solution is 4.8-6.2.
3. The acidic potassium chloride galvanizing plating bath according to claim 1, characterized in that: the potassium chloride acidic galvanizing plating solution contains KCl 150g/L and ZnCl2 35g/L，H3BO330g/L, 0.2mL/L of brightening agent, 25mL/L of softening agent and 10mL/L of auxiliary agent.
4. The acidic potassium chloride galvanizing plating bath according to claim 1, characterized in that: the anion structure of the Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate is as follows:
wherein p is 1 to 10, q is 1 to 10, n is 5 to 20, and X is F, Cl or Br.
5. The acidic potassium chloride galvanizing plating bath according to claim 1, characterized in that: the preparation method of the brightener comprises the following steps: heating Guerbet alcohol polyoxyethylene ether halogenated propane sulfonate to 40 ℃, adding solid benzalacetone in batches, keeping the temperature and stirring until the two forms a transparent uniform solution, then adding water and stirring uniformly, and cooling to room temperature to obtain the brightener.
6. The acidic potassium chloride zinc plating bath solution as set forth in claim 1, wherein the structural formula of 2,2 ', 4' -trihydroxychalcone is as follows:
the structural formula of the nicotinoyl urea derivative is as follows:
7. the acidic potassium chloride galvanizing plating bath according to claim 1, characterized in that: the auxiliary agent is prepared from polymaleic acid,
LF-Na50 and water, wherein the polymaleic acid accounts for 5-15 wt%,
LF-Na50 accounts for 5 wt.% to 15 wt.%, and the balance is water.
8. The potassium chloride acidic zinc plating bath as set forth in claim 7, wherein: the relative molecular mass of the polymaleic acid is 450-600, and the solid content is more than or equal to 50 wt.%.
9. A method of zinc plating using the potassium chloride acidic zinc plating bath according to any one of claims 1 to 8, wherein the plating conditions are controlled to: the pH value is approximately equal to 6, and the current density is 0.5-5A/dm2The rack plating voltage is 3-8V, the barrel plating voltage is 6-12V,the operating temperature was 33 ℃.
10. The method of claim 9, wherein: the following additives were added in the following amounts: brightening agent: 80-150mL/KAH, softener: 80-150mL/KAH, adjuvant: 20-30 mL/KAH.
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| CN106521569A (en) * | 2016-12-14 | 2017-03-22 | 宁波翔博机械有限公司 | Electroplating liquid for production of galvanized steel sheet and electroplating method |
| CN110777402A (en) * | 2019-11-21 | 2020-02-11 | 武汉奥邦表面技术有限公司 | Acidic galvanizing carrier and preparation method thereof |
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| US4512856A (en) * | 1979-11-19 | 1985-04-23 | Enthone, Incorporated | Zinc plating solutions and method utilizing ethoxylated/propoxylated polyhydric alcohols |
| JPH08283982A (en) * | 1995-04-17 | 1996-10-29 | Yuken Kogyo Kk | Chloride bath electrogalvanizing method |
| KR20000040954A (en) * | 1998-12-21 | 2000-07-15 | 이구택 | Method for zncl2 plating crude liquid from zn plating waste liquid |
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