CN114622213A - Environment-friendly neutral copper pickling solution - Google Patents
Environment-friendly neutral copper pickling solution Download PDFInfo
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- CN114622213A CN114622213A CN202210267009.3A CN202210267009A CN114622213A CN 114622213 A CN114622213 A CN 114622213A CN 202210267009 A CN202210267009 A CN 202210267009A CN 114622213 A CN114622213 A CN 114622213A
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- pickling solution
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000010949 copper Substances 0.000 title claims abstract description 111
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 110
- 238000005554 pickling Methods 0.000 title claims abstract description 98
- 230000007935 neutral effect Effects 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims abstract description 26
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 26
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 18
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 18
- 229960001484 edetic acid Drugs 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 105
- 239000011259 mixed solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 150000007522 mineralic acids Chemical class 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000013522 chelant Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000005202 decontamination Methods 0.000 description 3
- 230000003588 decontaminative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004432 carbon atom Chemical class C* 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical group COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
Abstract
The invention relates to the field of copper material surface cleaning solution, in particular to an environment-friendly neutral copper material pickling solution, which comprises the following components: hydroxyethylidene diphosphonic acid, ethylene diamine tetraacetic acid, sodium dodecyl benzene sulfonate, a pH value regulator and water; the pH value of the prepared environment-friendly neutral copper pickling solution is 6-7, the concentration of hydroxyethylidene diphosphonic acid in the prepared environment-friendly neutral copper pickling solution is 15.0-20.0 g/L, the concentration of disodium ethylene diamine tetraacetate in the prepared environment-friendly neutral copper pickling solution is 8.0-10.0 g/L, and the concentration of sodium dodecyl benzene sulfonate in the prepared environment-friendly neutral copper pickling solution is 1.0-2.0 g/L. The environment-friendly neutral copper material pickling solution prepared by the invention does not contain heavy metals and other toxic and harmful substances, meets the requirement of environmental protection, can be used under a neutral condition, can be used for washing various oxides and oily substances on the surface of a copper material, and can improve the corrosion resistance of the copper material.
Description
Technical Field
The invention relates to the field of copper material surface cleaning solution, in particular to an environment-friendly neutral copper material pickling solution.
Background
Copper and copper alloy are widely used in many fields such as building materials, automobile parts, home furnishing, toys, war industry, municipal engineering, equipment manufacturing, electronic information, biological pharmacy and the like, and are one of the most important materials in modern society. The copper simple substance is easily oxidized when exposed to air, and in actual use, the surface oxide and various oil stain attachments need to be removed. Based on the advantages of convenient operation, low cost, wide application range, high production efficiency and the like, the chemical method soaking passivation process is one of the most common means for pickling the surface of the copper material, but the traditional pickling solution takes inorganic acid as a main rust removing substance, although the use is convenient, the rust removing performance is excellent, most of the inorganic acid belongs to strong acid, not only can corrode the skin, but also has great pollution and harm to the environment and the human health.
In recent years, with the increasing awareness of environmental protection, researchers at home and abroad turn to develop weak acid or neutral pickling solution to replace inorganic acid so as to solve the problem of environmental pollution caused by the acidity of the inorganic acid. The inorganic acid pickling processes which are published and reported at present are many, and mainly comprise various systems such as hydrochloric acid, sulfuric acid, nitric acid and the like. However, due to the problems of low pickling speed, poor pickling effect, over-corrosion of pickling and the like, no neutral pickling solution product can really replace the traditional inorganic pickling solution to realize large-scale application.
In order to remove various oxides and impurities on the surface of copper materials and ensure that pickling cannot be over-corroded, most of the existing methods are used for washing away the oxides on the copper materials through chemical action by high-concentration hydrogen ions in strong acid. At present, acid pickling processes which are paid attention to and researched by people are basically acid systems, most of the acid pickling processes are optimized by mainly using inorganic strong acid and adding a plurality of corrosion inhibitors, chelating agents and the like, and the acid pickling processes have the defects of large intrinsic acidity, difficulty in treating waste liquid after acid pickling, large harm to the environment and human bodies and the like.
Disclosure of Invention
The invention aims to provide an environment-friendly neutral copper pickling solution aiming at the problems in the background technology.
The technical scheme provided by the invention is that the copper material environment-friendly neutral pickling solution comprises the following components: hydroxyethylidene diphosphonic acid, ethylene diamine tetraacetic acid, sodium dodecyl benzene sulfonate, a pH value regulator and water;
the pH value of the prepared environment-friendly neutral copper pickling solution is 6-7, the concentration of hydroxyethylidene diphosphonic acid in the prepared environment-friendly neutral copper pickling solution is 15.0-20.0 g/L, the concentration of disodium ethylene diamine tetraacetate in the prepared environment-friendly neutral copper pickling solution is 8.0-10.0 g/L, and the concentration of sodium dodecyl benzene sulfonate in the prepared environment-friendly neutral copper pickling solution is 1.0-2.0 g/L.
Preferably, the pH regulator is NaOH solution, KOH solution, Na2CO3Solution, Na3PO3Solution, Na2SiO3One or more of a solution and ammonia.
The preparation method of the environment-friendly neutral copper pickling solution comprises the following specific steps:
s1, determining the amount of the environment-friendly neutral copper pickling solution required to be prepared;
s2, weighing water with the volume of 50-70% of that of the environment-friendly neutral copper pickling solution in S1;
s3, adding the weighed hydroxyethylidene diphosphonic acid, disodium ethylene diamine tetraacetate and sodium dodecyl benzene sulfonate into water, uniformly mixing to obtain a mixed solution, adding a pH value regulator and water into the mixed solution, and fixing the volume to the required volume of the environment-friendly neutral copper pickling solution, wherein the pH value of the environment-friendly neutral copper pickling solution is 6-7; the concentration of the hydroxyethylidene diphosphonic acid in the prepared copper environment-friendly neutral pickling solution is 15.0-20.0 g/L, the concentration of the disodium ethylene diamine tetraacetate in the prepared copper environment-friendly neutral pickling solution is 8.0-10.0 g/L, and the concentration of the sodium dodecyl benzene sulfonate in the prepared copper environment-friendly neutral pickling solution is 1.0-2.0 g/L.
The technical scheme of the invention has the following beneficial technical effects:
the environment-friendly neutral copper pickling solution prepared by the invention does not contain heavy metals and other toxic and harmful substances, is more environment-friendly and harmless to human bodies; when the environment-friendly neutral copper pickling solution prepared by the invention is used under the neutral or weak acid condition, H is provided by acidic substances+Since the copper surface oxide is mainly CuO, it can be in H+With O in copper oxide2-Reaction to form H2O, no other pollutants are generated, and the product belongs to a real green environment-friendly product;
the environment-friendly neutral copper pickling solution prepared by the invention contains hydroxyethylidene diphosphonic acid; the hydroxyethylidene diphosphonic acid belongs to an organic phosphonic acid scale and corrosion inhibitor, prevents copper from over-corroding under an acidic condition, and plays the roles of a stabilizer and a corrosion inhibitor in the pickling process; can form a six-ring chelate with metal ions, particularly copper ions, thereby having better scale inhibition effect and obvious solution limit effect, and showing ideal synergistic effect when being used in combination with other treating agents; the environment-friendly neutral copper pickling solution prepared by the invention contains disodium ethylene diamine tetraacetate; disodium edetate is a hexadentate ligand that can chelate a variety of metal ions. 4 acid parts and 2 amine parts of the copper complex can be used as teeth of a ligand, and form a chelate with other metal ions on the surface of copper so as to be dissolved in pickling solution, so that the copper complex has better stability and environmental protection property than an inorganic acid system; the environment-friendly neutral copper pickling solution prepared by the invention contains sodium dodecyl benzene sulfonate; the sodium dodecyl benzene sulfonate is neutral, is sensitive to water hardness, is not easy to oxidize, has strong foaming power and high detergency, is easy to be compounded with various auxiliaries, has obvious detergency effect on granular dirt, protein dirt and oily dirt, and is an excellent anionic surfactant; under the synergistic effect of the three components, the dissolution of various dirt and oxides on the surface of copper can be accelerated, and the pickling effect equivalent to or even superior to that of inorganic acid is achieved;
in addition, the copper material environment-friendly neutral pickling solution provided by the invention has the advantages of simple preparation process, stable pickling solution and good decontamination performance, and the time for oxide to appear on the surface of copper under the salt spray condition exceeds 120 hours.
Detailed Description
Example 1
The invention provides an environment-friendly neutral copper pickling solution, which comprises the following components: hydroxyethylidene diphosphonic acid, ethylene diamine tetraacetic acid, sodium dodecyl benzene sulfonate, a pH value regulator and water;
wherein the pH value of the prepared environment-friendly neutral copper pickling solution is 6-7;
the concentration of the hydroxyethylidene diphosphonic acid in the prepared copper material environment-friendly neutral pickling solution is 15.0-20.0 g/L;
the concentration of the ethylene diamine tetraacetic acid in the prepared environment-friendly neutral copper pickling solution is 8.0-10.0 g/L;
the concentration of the sodium dodecyl benzene sulfonate in the prepared environment-friendly neutral copper pickling solution is 1.0-2.0 g/L;
the pH regulator comprises NaOH solution, KOH solution, and Na2CO3Solution, Na3PO3Solution, Na2SiO3One or more of a solution and ammonia; NaOH solution and KOH solution are strong alkali solution, Na2CO3Solution, Na3PO3Solution and Na2SiO3The solution is strong base weak acid salt solution, and the ammonia water is alkaline and selects ammonia water with the mass fraction of 25%;
the water may be deionized water or distilled water, or tap water or mineral water for direct drinking.
Example 2
The invention provides a preparation method of an environment-friendly neutral copper pickling solution, which comprises the following specific steps:
s1, determining the amount of the environment-friendly neutral copper pickling solution required to be prepared;
s2, weighing water with the volume of 50-70% of that of the environment-friendly neutral copper pickling solution in S1;
s3, adding the weighed hydroxyethylidene diphosphonic acid, disodium ethylene diamine tetraacetate and sodium dodecyl benzene sulfonate into water, uniformly mixing to obtain a mixed solution, adding a pH value regulator and water into the mixed solution, and fixing the volume to the copper material environment-friendly neutral pickling solution with the required volume; the adding sequence of the hydroxyethylidene diphosphonic acid, the disodium ethylene diamine tetraacetate and the sodium dodecyl benzene sulfonate is not required, and the three components are immediately stirred uniformly after being added;
at the moment, the pH value of the environment-friendly neutral copper pickling solution is 6-7;
the concentration of the hydroxyethylidene diphosphonic acid in the prepared copper material environment-friendly neutral pickling solution is 15.0-20.0 g/L;
the concentration of the ethylene diamine tetraacetic acid in the prepared environment-friendly neutral copper pickling solution is 8.0-10.0 g/L;
the concentration of the sodium dodecyl benzene sulfonate in the prepared environment-friendly neutral copper pickling solution is 1.0-2.0 g/L.
Example 1
The preparation method of the environment-friendly neutral copper pickling solution comprises the following specific steps:
s1, determining the amount of the environment-friendly neutral copper pickling solution to be prepared to be 1L;
s2, adding 500ml of water into a container;
s3, adding 15.0g of hydroxyethylidene diphosphonic acid into the container in the S2, and stirring until the hydroxyethylidene diphosphonic acid is completely dissolved to obtain a mixed solution A;
s4, adding 8.0g of disodium ethylene diamine tetraacetate into the mixed solution A, and stirring until the disodium ethylene diamine tetraacetate is completely dissolved to obtain mixed solution B;
s5, adding 1.0g of sodium dodecyl benzene sulfonate into the mixed solution B, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution C;
s6, adding a pH value regulator and water into the mixed solution C until the volume of the solution in the container is 1L according to the pH value of the copper material environment-friendly neutral pickling solution to be prepared as 6 to obtain the copper material environment-friendly neutral pickling solution; wherein, the PH value regulator is sodium hydroxide.
Example 2
The preparation method of the environment-friendly neutral copper pickling solution comprises the following specific steps:
s1, determining the amount of the environment-friendly neutral copper pickling solution to be prepared to be 1L;
s2, adding 600ml of water into a container;
s3, adding 17.0g of hydroxyethylidene diphosphonic acid into the container in the S2, and stirring until the hydroxyethylidene diphosphonic acid is completely dissolved to obtain mixed liquid A;
s4, adding 9.0g of disodium ethylene diamine tetraacetate into the mixed solution A, and stirring until the disodium ethylene diamine tetraacetate is completely dissolved to obtain mixed solution B;
s5, adding 1.5g of sodium dodecyl benzene sulfonate into the mixed solution B, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution C;
s6, adding a pH value regulator and water into the mixed solution C until the volume of the solution in the container is 1L to obtain the environment-friendly neutral copper pickling solution, wherein the pH value of the environment-friendly neutral copper pickling solution prepared as required is 6.5; wherein the pH regulator is sodium silicate.
Example 3
The preparation method of the environment-friendly neutral copper pickling solution comprises the following specific steps:
s1, determining the amount of the environment-friendly neutral copper pickling solution to be prepared to be 1L;
s2, adding 700ml of water into a container;
s3, adding 20.0g of hydroxyethylidene diphosphonic acid into the container in the S2, and stirring until the hydroxyethylidene diphosphonic acid is completely dissolved to obtain a mixed solution A;
s4, adding 10.0g of disodium ethylene diamine tetraacetate into the mixed solution A, and stirring until the disodium ethylene diamine tetraacetate is completely dissolved to obtain mixed solution B;
s5, adding 2.0g of sodium dodecyl benzene sulfonate into the mixed solution B, and stirring until the sodium dodecyl benzene sulfonate is completely dissolved to obtain a mixed solution C;
s6, adding a pH value regulator and water into the mixed solution C until the volume of the solution in the container is 1L to obtain the environment-friendly neutral copper pickling solution, wherein the pH value of the environment-friendly neutral copper pickling solution prepared as required is 7; wherein the PH value regulator adopts sodium carbonate and ammonia water with the mass fraction of 25%, and the mass volume ratio of the sodium carbonate to the ammonia water is 1: 2.
In order to verify the pickling effect of the prepared copper material environment-friendly neutral pickling solution, weighing the copper material environment-friendly neutral pickling solution in specific examples 1-3 with the same volume, and selecting a copper material sample treated under the same environment;
the environment-friendly neutral copper pickling solution prepared in each specific example is divided into three parts, so that nine experimental groups are obtained;
three copper material samples are respectively put into three groups of environment-friendly neutral copper material pickling solutions prepared according to the specific example 1 to be soaked for 20s, then the copper material samples are taken out to be naturally dried, at the moment, the appearances of the copper material samples are uniformly bright purple red, the three groups of dried copper material samples are treated under the condition of salt mist, and the time of oxide appearing on the surfaces of the copper material samples exceeds 120 hours;
three copper material samples are respectively put into three groups of environment-friendly neutral copper material pickling solutions prepared according to specific example 2 to be soaked for 20s, then the copper material samples are taken out and naturally dried, at the moment, the appearances of the copper material samples are uniformly bright purple red, the three groups of dried copper material samples are treated under the condition of salt mist, and the time of oxide appearing on the surfaces of the copper material samples exceeds 145 hours;
three copper material samples are respectively put into three groups of environment-friendly neutral copper material pickling solutions prepared according to the specific example 3 to be soaked for 20s, then the copper material samples are taken out to be naturally dried, at the moment, the appearances of the copper material samples are uniformly bright purple red, the three groups of dried copper material samples are treated under the condition of salt mist, and the time of oxide appearing on the surfaces of the copper material samples exceeds 150 hours;
in conclusion, the environment-friendly neutral copper pickling solution prepared by the invention has good decontamination effect on the surface of the copper material;
the environment-friendly neutral copper pickling solution prepared by the invention contains hydroxyethylidene diphosphonic acid; the hydroxyethylidene diphosphonic acid is an organic phosphonic acid scale and corrosion inhibitor, can form a stable complex with copper metal ions, and can dissolve oxides on the metal surface. It is stable under high pH, not easy to hydrolyze, not easy to decompose under general photo-thermal condition, and can still play a good role in corrosion and scale inhibition at 250 ℃. The acid and alkali resistance and the chlorine oxidation resistance are better than other organic phosphonic acids. Can form a six-ring chelate with metal ions in water, thereby having better scale inhibition effect and obvious solution limit effect, and when the scale inhibitor is used in combination with other water treatment agents, the scale inhibitor shows ideal synergistic effect;
the environment-friendly neutral copper pickling solution prepared by the invention contains disodium ethylene diamine tetraacetate; disodium edetate is a powerful chelating agent, a preservative and an antioxidant, can generate a stable complex with most metal ions except alkali metals due to high stability constant, has wide coordination performance and can form a stable chelate with almost all metal ions. Eliminating metal ions or harmful reactions caused by the metal ions;
the environment-friendly neutral copper pickling solution prepared by the invention contains sodium dodecyl benzene sulfonate; sodium dodecylbenzenesulfonate is less alkyl-substituted carbon atoms, and the shorter the alkyl chain, the less hydrophobic it is, and the more easily it is dissolved in water at room temperature. Conversely, the more carbon atoms, the longer the alkyl chain, the stronger the hydrophobicity and the more difficult the dissolution. According to the dissolving curve chart of the linear alkyl benzene sodium sulfonate, the critical micelle concentration of the surfactant is in a descending trend along with the increase of an alkyl chain from the linear ten-carbon to the linear hexadecyl, so that the surface tension of the linear alkyl benzene sodium sulfonate is low, the wetting power is good, and the linear alkyl benzene sodium sulfonate has excellent foaming performance and decontamination performance;
under the synergistic action of sodium dodecyl benzene sulfonate, disodium ethylenediamine tetraacetate and hydroxyethylidene diphosphonic acid, the dissolution of various dirt and oxides on the surface of copper can be accelerated, and the pickling effect equivalent to or even superior to that of inorganic acid can be achieved.
While the embodiments of the invention have been described in detail, the invention is not limited thereto, and various changes can be made without departing from the spirit of the invention within the knowledge of those skilled in the art.
Claims (3)
1. The environment-friendly neutral copper pickling solution is characterized by comprising the following components: hydroxyethylidene diphosphonic acid, ethylene diamine tetraacetic acid, sodium dodecyl benzene sulfonate, a pH value regulator and water; the pH value of the prepared environment-friendly neutral copper pickling solution is 6-7, the concentration of hydroxyethylidene diphosphonic acid in the prepared environment-friendly neutral copper pickling solution is 15.0-20.0 g/L, the concentration of disodium ethylenediaminetetraacetate in the prepared environment-friendly neutral copper pickling solution is 8.0-10.0 g/L, and the concentration of sodium dodecyl benzene sulfonate in the prepared environment-friendly neutral copper pickling solution is 1.0-2.0 g/L.
2. The environment-friendly neutral copper pickling solution as claimed in claim 1, wherein the pH regulator is NaOH solution, KOH solution or Na solution2CO3Solution, Na3PO3Solution, Na2SiO3One or more of a solution and ammonia.
3. The preparation method of the environment-friendly neutral copper pickling solution is characterized by comprising the following specific steps of:
s1, determining the amount of the copper material environment-friendly neutral pickling solution required to be prepared;
s2, weighing water with the volume of 50-70% of that of the environment-friendly neutral copper pickling solution in S1;
s3, adding the weighed hydroxyethylidene diphosphonic acid, disodium ethylene diamine tetraacetate and sodium dodecyl benzene sulfonate into water, uniformly mixing to obtain a mixed solution, adding a pH value regulator and water into the mixed solution, and fixing the volume to the required volume of the environment-friendly neutral copper pickling solution, wherein the pH value of the environment-friendly neutral copper pickling solution is 6-7; the concentration of the hydroxyethylidene diphosphonic acid in the prepared copper environment-friendly neutral pickling solution is 15.0-20.0 g/L, the concentration of the disodium ethylene diamine tetraacetate in the prepared copper environment-friendly neutral pickling solution is 8.0-10.0 g/L, and the concentration of the sodium dodecyl benzene sulfonate in the prepared copper environment-friendly neutral pickling solution is 1.0-2.0 g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115449440A (en) * | 2022-08-24 | 2022-12-09 | 翱途能源科技(无锡)有限公司 | Cleaning agent and preparation process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449440A (en) * | 2022-08-24 | 2022-12-09 | 翱途能源科技(无锡)有限公司 | Cleaning agent and preparation process thereof |
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