CN118109826A - Environment-friendly steel rust removing liquid and application thereof - Google Patents
Environment-friendly steel rust removing liquid and application thereof Download PDFInfo
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- CN118109826A CN118109826A CN202410062354.2A CN202410062354A CN118109826A CN 118109826 A CN118109826 A CN 118109826A CN 202410062354 A CN202410062354 A CN 202410062354A CN 118109826 A CN118109826 A CN 118109826A
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 84
- 239000010959 steel Substances 0.000 title claims abstract description 84
- 239000007788 liquid Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001413 amino acids Chemical class 0.000 claims abstract description 30
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 26
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 21
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 18
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 41
- 229960003067 cystine Drugs 0.000 claims description 35
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 32
- 235000001014 amino acid Nutrition 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- -1 imidazole anions Chemical class 0.000 claims description 15
- 235000018417 cysteine Nutrition 0.000 claims description 11
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 11
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 9
- 229930182817 methionine Natural products 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 125000005594 diketone group Chemical group 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 6
- 230000036541 health Effects 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 65
- 229910052751 metal Inorganic materials 0.000 description 36
- 239000002184 metal Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 238000005260 corrosion Methods 0.000 description 27
- 230000007797 corrosion Effects 0.000 description 26
- 239000000758 substrate Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 21
- 229910000805 Pig iron Inorganic materials 0.000 description 16
- 238000002791 soaking Methods 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 229910001447 ferric ion Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 238000002531 positive electrospray ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 125000005616 oxoacid group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical group [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004879 molecular function Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses an environment-friendly steel rust removing liquid and application thereof, wherein the environment-friendly steel rust removing liquid comprises the following components: an ionic compound, an amino acid complexing agent and water; wherein the chemical structural formula of the ionic compound is shown as formula I. R 1～R5 are each independently selected from saturated alkane groups containing oxy acid groups, and any 1-3 of R 1～R5 are selected from saturated alkane groups containing both oxy acid groups and mercapto groups; the oxo acid radical has a negative charge; AA is selected from amino acids containing sulfhydryl groups, methylthio groups and disulfide bonds; the value of m is determined by the cationic charge n; the amino acid complexing agent is selected from any one or more than two of amino acids containing sulfhydryl, methylthio and disulfide bonds and derivatives thereof. The steel rust remover disclosed by the invention does not contain harmful substances, does not cause harm to the environment and human health, and meanwhile, the novel rust remover can rapidly and thoroughly remove rust on the surface of steel in the rust removing effect, so that the original luster and strength of the steel rust remover are recovered.
Description
Technical Field
The invention relates to a steel rust removing liquid, in particular to an environment-friendly steel rust removing liquid and application thereof.
Background
Steel is an important structural material and is widely used in various industries. However, over time, steel products are often subjected to oxygen, moisture, and other environmental factors, creating a rust phenomenon. Rust on steel not only affects the aesthetic appearance, but also reduces the strength and durability of the material, thereby affecting the service life thereof. Therefore, the rust removal work is important for maintaining and prolonging the service life of the iron and steel products.
Conventional steel rust removal methods typically employ chemical rust removers, including acid washing, acid leaching, strong reducing agent treatments, and the like, which are indeed effective in removing rust, but are also accompanied by a series of environmental and safety concerns. Firstly, the chemical rust remover often contains strong acid components, which causes pollution to the environment and is unfavorable for sustainable development; second, the use of these chemicals tends to cause operator health problems, increasing the risk of work; in addition, the chemical rust remover is complex in use and treatment process, high in cost and not economical. For example, in patent CN 102071416B, 4 to 10% by mass of oxalic acid and 3 to 10% by mass of phosphoric acid are used, in patent CN 106757095B, 2 to 4% by mass of hydroxyethylidene triphosphate is used, and in patent CN103046036B, 10 to 40% by mass of phosphoric acid is a medium strong acid having a pKa value of about 1 to 2.
In addition, some physical methods, such as sand blasting, polishing and the like, can remove the rust on the surface, but easily generate a large amount of waste, and do not meet the environmental protection requirements. And the workpiece with a complex structure cannot be completely derusted.
In summary, the problems of the prior art are: the traditional chemical method generates a large amount of waste acid polluting the environment, cannot give consideration to cost, environmental protection and effect, and is not suitable for environmental protection and economic requirements of industrial production in new era. The physical method has the problems of more solid wastes, small applicable workpiece range for rust removal and the like. Therefore, a new and environmentally friendly rust remover for steel is urgently needed.
Disclosure of Invention
The invention aims to provide an environment-friendly steel rust removing liquid and application thereof, which solve the problem of environmental pollution caused by the existing rust remover, the steel rust removing liquid does not contain harmful substances and does not cause harm to the environment and human health, and meanwhile, the novel rust remover can quickly and thoroughly remove rust on the surface of steel in the rust removing effect, so that the original luster and strength of the steel rust remover are recovered.
In order to achieve the above purpose, the invention provides an environment-friendly steel rust removing liquid, which is characterized by comprising the following components in parts by weight: 2-10% of ionic compound, 0.2-2% of amino acid complexing agent and the balance of water.
Wherein the chemical structural formula of the ionic compound is as follows:
In the formula I, R 1～R5 is independently selected from saturated alkane groups containing oxo acid groups, and 1-3 of R 1～R5 are selected from saturated alkane groups containing oxo acid groups and mercapto groups at the same time, and the rotation of the side chain containing the mercapto group is the key for completing rust removal of a weak acid system; the oxyacid radical has a negative charge.
In the formula I, AA is selected from amino acid containing sulfhydryl, methylthio and disulfide bond; the value of m is determined by the cationic charge n. Specifically, m is a value ranging from 2 to 4 depending on the type of amino acid selected.
Wherein the amino acid complexing agent is selected from any one or more than two of amino acids containing sulfhydryl, methylthio and disulfide bonds and derivatives thereof. The AA is selected from the group consisting of mercapto, methylthio and disulfide bonds, has high binding capacity for transition metal/ion, and facilitates the transition metal ion with mechanical molecule mercapto to enter solution phase.
The rust layer on the surface of steel is a complex substance composed of loose and porous iron oxide hydroxide and hydrate, so that weak acid substances can penetrate through the thin compact oxide layer on the surface of metal to expose a certain area of the surface of metal. The conventional rust remover is highly dependent on the dissolution/reaction of a strong acidic reagent and a strong reducing reagent on rust, has strong corrosiveness on a metal substrate, and designs and synthesizes a class of mechanical molecular salt (namely the ionic compound) which takes heterocycle as a parent body and has a sidechain with electrophilic negative electricity, a flexible sidechain with difunctional electrophilic/ferric ions and a weak acid/complexing anion. The salt is a weak acid molecule as a whole, the acidity is less than 1/10 of that of acetic acid, and the pKa=4.23-5.96. In a rust-removing aqueous solution environment, a hydrated ferrous ion layer with a thickness of more than ten atoms is generated on the interface between two phases of iron and aqueous solution, and the layer is wholly electropositive. The mechanical molecules form a dynamic ionic network in aqueous solution, where the anionic components of the mechanical molecules approach the positive charge layer due to electrostatic interactions, thereby approaching the metal surface. Meanwhile, due to the existence of thermal motion, the anionic components close to the metal surface can further contact the metal surface and bond with transition metals such as iron atoms on the metal surface through negative groups on the negative and iron-philic side chains of the anionic components, so that firm surface adhesion is realized, a firm netlike ion network coating is formed on the exposed metal surface, and further corrosion of the metal substrate by the weak acid aqueous solution is prevented. While the above process occurs, the flexible side chain of the difunctional electrophilic/ferric ion is combined with the transition metal ion in the rust layer through the mercapto group of the electrophilic ion, and a series of processes are performed through the combined action of the mercapto group and the carboxyl group on the amino acid cation in the solution system.
Specifically, the following process occurs at the mechanical molecules and rust layer:
(1) The acidic hydrogen on the carboxyl is combined with hydroxide radical and oxygen anion in the rust layer to generate water;
(2) Mercapto on flexible side chain of bi-functional iron/iron ion in anion structure in mechanical molecule can coordinate with iron ion; since the binding of the electron rich groups, such as phosphate groups, on the side chains to the metal substrate is a thermodynamically favourable process as a whole, the flexible side chains of the bi-functional electrophilic/ferric ions begin to flip through the flexible alkyl chains, the phosphate groups thereon bond to the metal substrate, the thiol-coordinated ferric ions leave the interface layer opposite the phosphate groups as a result of the side chain thiol groups and enter the solution phase, a large number of amino acid cations/amino acids in the solution compete for coordination with the side chain thiol groups, the amino acid cations/amino acid coordinated ferric ions enter the solution phase, rust is dissolved, and the newly exposed metal substrate is protected.
Transition metal cations such as ferric iron, ferrous iron and the like caused by rust removal of the system enter the solution to form a complex, and needle-shaped crystals are separated out after the complex reaches a certain concentration, and the complex can be used as a chemical raw material after filtration. The rust removing liquid can be continuously used by only adding mechanical molecules in proportion, so that no acid waste liquid is generated in the using process of the rust removing liquid.
Preferably, the saturated alkane group has 1 to 4 carbon atoms. The excessively long number of carbon chains of the saturated alkane groups can cause excessively high side chain flexibility, excessive disordered thermal swing and failure to achieve mechanical molecular functions. And too long chain length can make the ion network too sparse, influence the surface protection effect.
Preferably, the oxyacid radical is selected from any one or more than two of carboxyl, phosphate, sulfate and sulfite. Unlike the four acid groups selected in the present invention, the nitric acid and alkyl chain forming nitro compound or nitrate does not have negative charge, has very weak affinity to metal/metal ion, and the synthesis of partial nitro compound or nitrate has a rather high safety risk.
Preferably, the AA is one or more than two selected from methionine, cystine and cysteine; the amino acid complexing agent is selected from any one or more than two of methionine, cystine, cysteine and derivatives thereof.
Preferably, the amino acid complexing agent is selected from any one or more than two of amino acids containing sulfhydryl groups, methylthio groups and disulfide bonds, and esters and salts thereof.
Preferably, the ionic compound is selected from any one of the following combinations of multi-side imidazole anions with AA cations:
In the formulas II and III, X 1～X5 is independently selected from oxo acid radicals;
In the formulas II and III, Y is selected from O or C;
In the formulas II and III, n 1～n5 is independently selected from 1 to 3.
Preferably, the ionic compound is selected from any one of the following combinations of multi-side imidazole anions with AA cations:
Preferably, when the ionic compound is [ SP 5C2Im]4- and AA cations, the environment-friendly steel rust removing liquid comprises the following components in parts by weight: 2% of ionic compound, 0.2% of amino acid complexing agent and the balance of water; when the ionic compound is [ SS 5C2Im]4- and AA cations are combined, the environment-friendly steel rust removal liquid comprises the following components in parts by weight: 4% of ionic compound, 0.5% of amino acid complexing agent and the balance of water; when the ionic compound is the combination of [ SSC 5C2Im]4- and AA cations, the environment-friendly steel rust removal liquid comprises the following components in parts by weight: 6% of ionic compound, 0.25% of amino acid complexing agent and the balance of water; when the ionic compound is [ SC 5C1Im]4- and AA cations, the environment-friendly steel rust removal liquid comprises the following components in parts by weight: 10% of ionic compound, 1.0-2.0% of amino acid complexing agent and the balance of water.
The invention also aims to provide the application of the environment-friendly steel rust removing liquid in rust removing of steel surfaces.
Preferably, the environment-friendly steel rust removing liquid is used for soaking steel for 1-25 min at 20-90 ℃ to remove rust on the surface of the steel.
Preferably, after the soaking is finished, the steel is lifted out of the liquid surface, and the surface liquid is blown off by compressed air.
Another object of the present invention is to provide an ionic compound for a rust removing liquid for steel, the ionic compound having a chemical structural formula:
In the formula I, R 1～R5 is independently selected from saturated alkane groups containing oxo acid radicals, and any 1-3 of R 1～R5 are selected from saturated alkane groups containing oxo acid radicals and mercapto radicals simultaneously; the oxo acid radical has a negative charge; in the formula I, AA is selected from amino acid containing sulfhydryl, methylthio and disulfide bond; the value of m is determined by the cationic charge n.
Preferably, the saturated alkane group has 1 to 4 carbon atoms.
Preferably, the oxyacid radical is selected from any one or more than two of carboxyl, phosphate, sulfate and sulfite.
Preferably, the AA is one or more selected from methionine, cystine and cysteine.
Another object of the present invention is to provide a method for preparing the ionic compound, which comprises:
(1) The diketone shown in the formula A, the amine shown in the formula B1 and the formula B2 and the aldehyde shown in the formula C are heated and stirred to react, and after the reaction is finished, the diketone, the amine shown in the formula B1 and the formula B2 are concentrated and cooled at low temperature to separate out a product shown in the formula D;
Wherein R 6～R9 is selected from saturated alkane groups containing OH, and 1-3 of R 6～R9 are selected from saturated alkane groups containing OH and mercapto simultaneously;
(2) Grinding the product shown in the formula D and the fixed oxide corresponding to the oxo acid radical under heating for solid phase synthesis, extracting the product after the reaction is finished, and removing the solvent to obtain the product shown in the formula E;
or, reacting the product shown in the formula D with a gas oxide corresponding to the oxo acid radical at room temperature to obtain a product shown in the formula E;
(3) Stirring and reacting a product shown in a formula E and amino acid AA in water at room temperature, and removing water after the reaction is finished to obtain an ionic compound;
The environment-friendly steel rust removing liquid and the application thereof solve the problem of environmental pollution caused by the existing rust remover and have the following advantages:
Compared with the prior art, the environment-friendly steel rust removing liquid is weak acid rust removing, strong acid waste liquid with great harm is not generated, the rust removing material generates an ion network coating on the surface of steel in situ, the over-corrosion of a substrate and the corrosion after rust removal are prevented, meanwhile, the effect of the rust removing liquid can be maintained by regularly filtering crystalline sediment and properly supplementing mechanical molecules and complexing agents, so that the service life of the rust removing material is long, the service life of the rust removing material can be prolonged by adding the mechanical molecules, the rust removing efficiency is high, and good economic and environmental benefits are achieved.
The environment-friendly steel rust removing liquid can realize efficient rust layer removal on the premise of damaging a metal substrate to the minimum extent through the formation of the water phase/interface biphase ion network.
The environment-friendly steel rust removing liquid is environment-friendly, has wide application prospect in industrial production, can be used for rust removing treatment of various steel products, including building structures, transportation tools, equipment parts and the like, can remarkably improve the efficiency of rust removing operation due to the high-efficiency, safe and economic characteristics, reduces the production cost, and meets the requirements of environmental protection regulations.
Drawings
Fig. 1 is a flowchart of the rust removal of the steel surface by using the rust removal material of the present invention.
Fig. 2 is an SEM image of the workpiece before and after Q195 is treated with the environment-friendly steel surface rust removing material of example 3 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 2% [ Cys ] 4[SP5C2 Im ] (pka=5.73), 0.2% cystine, balance water.
Wherein, [ Cys ] 4[SP5C2 Im ] is prepared as follows:
(1) The two raw materials of aldehyde and P 2O5 are mixed according to a mol ratio of 1:1, grinding the solid phase synthesis at 80 ℃, extracting the product with acetone after 24 hours of reaction, and removing the solvent to obtain the product with 96 percent of yield.
(2) Diketones, amines and aldehydes in a molar ratio of 1:2:1 are added into water in turn, stirred and reacted for 24 hours at 65 ℃, the temperature is controlled during the reaction, overhigh is avoided, and the product is concentrated and cooled at low temperature after the reaction is finished, and the yield is 83 percent.
(3) Preparation the two raw materials are mixed according to a mole ratio of 4:1, grinding the solid phase synthesis at 60 ℃, extracting the product with acetone after 24 hours of reaction, and removing the solvent to obtain the SP 5C2 Im with the yield of 94%.
(4) SP 5C2 Im was mixed with cysteine in a molar ratio of 1:4 is dissolved in water, stirred for 0.5h at room temperature and then dehydrated to obtain [ Cys ] 4[SP5C2 Im ], and the yield is 99%.
Structural characterization data of [ Cys ] 4[SP5C2 Im ] are as follows:
1H NMR(130MHz,25℃,TMS):δ＝5.3-5.4(m,4H),4.6-4.7(m,1H),4.3-4.4(m,4H),4.2-4.3(m,4H),3.2-3.3(m,8H),2.8-2.9(m,2H),2.1-2.2(m,2H)ppm,2.3(t,4H)ppm;
13C NMR(100MHz,25℃,TMS):δ＝172,154,134,77,62,58,57,48,32,27,26ppm；
IR(ATR,25℃):ν＝3050-3200,2840-2990,2922,2853,2550,2082,1700,1570,1425,1394,1380,1348,1300-1250,1239,1087,1055,900-600,538cm-1;
TOF MS ES+:m/z＝103.01,TOF MS ES–:m/z＝175.48。
the preparation of the rust removing material comprises the following steps: sequentially dissolving [ Cys ] 4[SP5C2 Im and cystine in water, and forming a dynamic ion network after 10min at room temperature to obtain the environment-friendly steel rust removing liquid.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
Referring to fig. 2, the method for removing rust on the surface of steel by using the rust removing material takes the brand FC350 pig iron (the main component is iron and the rest is C: 2.11-4.3 percent) as an example, and comprises the following steps:
(1) Introducing an environment-friendly steel rust removing liquid into a rust removing groove, and adjusting the temperature of the groove to 90 ℃ for standby;
(2) Directly putting 500g brand pig iron into 1L environment-friendly steel rust removing liquid to be soaked for 1min, then taking the steel out of the liquid surface, blowing off the surface liquid by compressed air, and transferring to complete the rust removing step.
The results show that the method of the embodiment has a surface rust removal rate of 99%, and the corrosion resistance time of the metal substrate is measured at a temperature of 25 ℃ and a relative humidity of 35% at a corrosion mass ratio of 0.6/10000: about 100 hours.
Example 2
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 2% [ Cystine ] 2[SP5C2 Im ] (pka=5.26), 0.2% Cystine, balance water.
Wherein the preparation of [ Cystine ] 2[SP5C2 Im ] is similar to the preparation of [ Cys ] 4[SP5C2 Im ] of example 1, with Cys being replaced with Cystine.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
Referring to fig. 2, the method for removing rust on the surface of steel by adopting the rust removing material takes the mark QT400 pig iron (main component is iron and the rest is C: 2.11-4.3 percent) as an example, and comprises the following steps:
(1) Introducing an environment-friendly steel rust removing liquid into a rust removing groove, and adjusting the temperature of the groove to 90 ℃ for standby;
(2) Directly putting 500g brand pig iron into 1L environment-friendly steel rust removing liquid to be soaked for 1min, then taking the steel out of the liquid surface, blowing off the surface liquid by compressed air, and transferring to finish the rust removing step. The rust-removing liquid can be recovered, concentrated and fed back to the rust-removing tank, and the stability of the components of the rust-removing liquid can be maintained according to the detection result of the tank liquid.
Taking 6 points as contour heights on warps and wefts of the points through a three-dimensional surface profiler, taking the thickness of the rust layer exposed through manual polishing as a reference, integrating the contour heights to obtain uniform thickness, and dividing the reference thickness to obtain the surface rust removal rate.
The results show that the method of the embodiment has a surface rust removal rate of 99%, a metal substrate corrosion mass ratio (the ratio of the mass of the lost elemental metal to the mass of the elemental metal before treatment) of 0.6/10000, and a rust resistance time measured at a temperature of 25 ℃ and a relative humidity of 35%: about 100 hours.
Example 3
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 4% [ Cys ] 4[SS5C2 Im ] (pka=4.43), 0.5% cysteine, balance water.
Wherein the preparation of [ Cys ] 4[SS5C2 Im ] is similar to the preparation of [ Cys ] 4[SP5C2 Im ] of example 1, and is specifically as follows:
(1) The two raw materials are mixed according to a mole ratio of 1:1.02 at room temperature, wherein SO 3 is diluted to 8% by air, and the reaction system is purged by air after 1h of reaction to obtain the product with 99% yield.
(2) Diketones, amines and aldehydes in a molar ratio of 1:2:1 are added into water in turn, stirred and reacted for 24 hours at 60 ℃, the temperature is controlled during the reaction, overhigh is avoided, and the product is concentrated and cooled at low temperature after the reaction is finished, so that the yield is 84%.
(3) SS 5C2 Im preparation of two starting materials in a molar ratio of 1:4.08 at room temperature, wherein SO 3 is diluted to 8% by air, the reaction system is purged by air after 1h of reaction to obtain the product with the yield of 99%
(4) Preparation SS 5C2 Im was mixed with cysteine in a molar ratio of 1:4 is dissolved in water, mixed and stirred for 0.5h at room temperature, and [ Cys ] 4[SS5C2 Im is obtained after water removal, and the yield is 99%.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
Structural characterization data of [ Cys ] 4[SS5C2 Im ] are as follows:
1H NMR(130MHz,25℃,TMS):δ＝5.4-5.5(m,4H),4.6-4.7(m,1H),4.3-4.4(m,4H),4.2-4.3(m,4H),3.2-3.3(m,8H),2.8-2.9(m,2H),2.1-2.2(m,2H)ppm,2.3(t,4H)ppm;
13C NMR(100MHz,25℃,TMS):δ＝172,154,134,79,64,60,58,49,32,27,26ppm；
IR(ATR,25℃):ν＝3052-3203,2846-2996,2921,2850,2547,2089,1708,1576,1428,1397,1383,1240,1239,900-600,830,538cm-1;
TOF MS ES+:m/z＝103.01,TOF MS ES–:m/z＝198.46。
The method for removing rust on the surface of steel by adopting the rust removing material takes the brand Q195 steel (the main component is iron, the rest C is less than or equal to 0.7 percent, S is more than 0.25 percent and P is more than or equal to 0.40 percent) as an example, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
in the step (1), the temperature of the tank is regulated to 85 ℃;
In the step (2), soaking for 3min.
The results show that the rust removal rate of the surface of the method in the embodiment is 100%, the corrosion mass ratio of the metal substrate is 0.9/10000, and the rust resistance time is measured at the temperature of 25 ℃ and the relative humidity RH of 35%: 120h.
Example 4
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 6% [ Met ] 4[SSC5C2 Im ] (pka=4.23), 0.25% methionine, balance water.
Wherein the preparation of [ Met ] 4[SSC5C2 Im ] is similar to the preparation of [ Cys ] 4[SP5C2 Im ] of example 1, and is specifically as follows:
(1) Aldehyde and hydrogen sulfide starting materials were reacted in a 1: mixing under the reaction condition with the molar ratio of 1.01, wherein the catalyst is 1% of aluminum chloride by mole, keeping the temperature after 3 hours of reaction, introducing nitrogen, absorbing tail gas by sodium hydroxide solution to obtain the product with the yield of 97%
(2) Diketones, amines and aldehydes in a molar ratio of 1:2:1 are added into water in turn, stirred and reacted for 24 hours at 60 ℃, the temperature is controlled during the reaction, overhigh is avoided, and the product is concentrated and cooled at low temperature after the reaction is finished, and the yield is 86%.
(3) Preparation of SSC 5C2 Im to methionine in a molar ratio of 1:4 is dissolved in water, mixed and stirred for 0.5h at room temperature, and [ Met ] 4[SSC5C2 Im is obtained after water removal, and the yield is 99%.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
Structural characterization data for [ Met ] 4[SSC5C2 Im ] are as follows:
1H NMR(130MHz,25℃,TMS):δ＝4.3-4.5(m,4H),3.7-3.8(m,4H),3.4-3.5(m,4H),3.2-3.3(m,4H),3.1(d,2H),3.0(m,1H),2.9-3.0(m,4H),2.5-2.6(m,8H),2.2-2.3(m,4H)ppm,2.1-2.2(m,8H),2.0(t,14H)ppm;
13C NMR(100MHz,25℃,TMS):δ＝175,154,130,63,61,57,56,55,54,52,49,32,31,26,15ppm；
IR(ATR,25℃):ν＝3052-3203,2846-2996,2921,2850,2547,2089,1708,1576,1428,1397,1383,1239,900-600,538cm-1;
TOF MS ES+:m/z＝149.21,TOF MS ES–:m/z＝173.01。
The method for removing rust on the surface of steel by adopting the rust removing material takes SPHT1 steel (C is less than or equal to 0.10%, si is less than or equal to 0.35%, mn is less than or equal to 0.50%, P is less than or equal to 0.035% and S is less than or equal to 0.035%) as an example, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
in the step (1), the temperature of the tank is regulated to 70 ℃;
In the step (2), soaking for 4min.
The results show that the rust removal rate of the surface of the method in the embodiment is 99%, the corrosion mass ratio of the metal substrate is 0.2/10000, and the rust resistance time is measured at the temperature of 25 ℃ and the relative humidity RH of 35%: 120h.
Example 5
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 6% [ Met ] 4[SSC5C2 Im ] (pka=4.32), 0.15% methionine, 0.1% cysteine, balance water.
Wherein [ Met ] 4[SSC5C2 Im ] was prepared similarly to [ Cys ] 4[SSC5C2 Im ] of example 4, cys was replaced with Met.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
The method for removing rust on the surface of steel by adopting the rust removing material takes 60Si2Mn steel (main component is iron, the rest is C is 0.56-0.64%, si is 1.50-2.00%, mn is 0.60-0.90%) as an example, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
in the step (1), the temperature of the tank is regulated to 40 ℃;
In the step (2), soaking for 6min.
The results show that the rust removal rate of the surface of the method in the embodiment is 99%, the corrosion mass ratio of the metal substrate is 0.5/10000, and the rust resistance time is measured at the temperature of 25 ℃ and the relative humidity RH of 35%: about 105h.
Example 6
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 10% [ cysteine ] 2[SC5C1 Im ] (pka=5.96), 0.25% methionine, 0.75% cysteine, balance water.
Wherein the preparation of [ Cystine ] 2[SC5C1 Im ] is similar to the preparation of [ Cystine ] 2[SP5C2 Im ] of example 1, and specifically as follows:
(1) Aldehyde and hydrogen sulfide starting materials were reacted in a 1: mixing under the reaction condition with the molar ratio of 1.01, wherein the catalyst is 1% of aluminum chloride by mole, keeping the temperature after 3 hours of reaction, introducing nitrogen, absorbing tail gas by sodium hydroxide solution to obtain the product with the yield of 96%
(2) The diketone, amine and aldehyde are added into water in sequence, stirred and reacted for 36 hours at 60 ℃, the temperature is controlled during the stirring, overhigh temperature is avoided, the reaction is finished, the concentration is carried out at low temperature, and the product is separated out, and the yield is 82%.
(3) Preparation of SC 5C1 Im with cystine in a molar ratio of 1:2 is dissolved in water, mixed and stirred for 0.5h at room temperature, and the [ Cystine ] 2[SC5C1 Im is obtained after water removal, and the yield is 99%.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
Structural characterization data of [ Cystine ] 2[SC5C1 Im ] were as follows:
1H NMR(130MHz,25℃,TMS):δ＝4.5(s,4H),4.2-4.3(t,4H),3.8-3.9(m,4H),3.4-3.5(d,8H),3.3-3.4(d,2H),3.2-3.3(m,1H),2.6(d,1H)ppm;
13C NMR(100MHz,25℃,TMS):δ＝175,154,130,63,61,57,56,55,54,52,49,32,31,26,15ppm;178,176,172,154,152,130,55,50,46,39,35,31
IR(ATR,25℃):ν＝3072-3200,2830-2980,2912,2833,2540,2072,1750,1700,1670,1570,1425,1394,1380,1348,1300-1250,1239,900-600,cm-1;
TOF MS ES+:m/z＝121.01,TOF MS ES–:m/z＝103.51。
the method for rust removal of steel surface by adopting the rust removal material takes HT350 cast iron (main component is iron, the rest is C: 2.8-3.4, si: 1.8-2.3) as an example, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
In the step (1), the temperature of the tank is regulated to 20 ℃;
In the step (2), soaking for 7min.
The results show that the rust removal rate of the surface of the method in the embodiment is 99%, the corrosion mass ratio of the metal substrate is 0.1/10000, and the rust resistance time is measured at the temperature of 25 ℃ and the relative humidity RH of 35%: 120h.
Example 7
An environment-friendly steel surface rust removal material comprises the following components in percentage by weight: 10% [ Met ] 4[SC5C1 Im ] (pka=5.92), 2% methyl cystine, balance water.
Wherein [ Met ] 4[SC5C1 Im ] was prepared similarly to [ Cystine ] 2[SC5C1 Im ] of example 6, substituting Cystine with Met.
The procedure for the preparation of the rust removing material described above was the same as in example 1, except that the starting materials were different.
The method for removing rust on the surface of steel by adopting the rust removing material takes 06Cr19Ni10 steel (the main component is iron-chromium-nickel alloy, wherein Cr is more than or equal to 18 percent and Ni is more than or equal to 8 percent) as an example, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
In the step (1), the temperature of the tank is regulated to 20 ℃;
In the step (2), soaking for 25min.
The results show that the rust removal rate of the surface of the method in the embodiment is 100%, the corrosion mass ratio of the metal substrate is 0.1/10000, and the rust resistance time is measured at the temperature of 25 ℃ and the relative humidity RH of 35%: 120h.
Comparative example 1
The steel surface rust removing material has the same composition as in example 1 except that: the [ Na ] 4[SP5C2 Im ] is used to replace [ Cystine ] 2[SP5C2 Im ].
Wherein the preparation of [ Na 4[SP5C2 Im ] is similar to that of [ Cystine ] 2[SP5C2 Im ] of example 1, only differing in one step of proton exchange: 1 equivalent of SP 5C2 Im and four equivalents of sodium hydroxide are respectively dissolved in deionized water, and then the mixture is mixed and stirred for 0.5 hour, and then the water is removed.
The preparation operation of the rust removing material comprises the following steps: the [ Na ] 4[SP5C2 Im ]2% and cystine 0.2% are dissolved in water in order, and a dynamic ion network cannot be formed.
The method for removing rust on the surface of steel by adopting the rust removing material is used for treating pig iron with the same brand as that of the embodiment 1, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
In the step (2), soaking for 10min.
The results show that the comparative example 1 has a surface rust removal rate of 3%, and the metal substrate has a corrosion mass ratio of 0/10000, and cannot resist rust at a temperature of 25 ℃ and a relative humidity of RH of 35%. The Na 4[SP5C2 Im content in the steel surface rust removing material is increased to 20%, and the rust removing rate is still about 4%.
Comparative example 2
The steel surface rust removing material has the same composition as in example 1 except that: the [ Cystine ] [ SO 4 ] is used to replace [ Cystine ] 2[SP5C2 Im ].
The preparation operation of the rust removing material comprises the following steps: [ Cystine ] [ SO 4 ]2%, and Cystine 0.2% were dissolved in water in this order.
The method for removing rust on the surface of steel by adopting the rust removing material is used for treating pig iron with the same brand as that of the embodiment 1, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
In the step (2), soaking for 10min.
The results show that comparative example 2 has an average surface rust removal rate of 0%, and the metal substrate corrosion mass ratio of 0/10000, and the rust cannot be prevented at a temperature of 25 ℃ and a relative humidity of RH 35%. The [ Cystine ] [ SO 4 ] content in the steel surface rust removal material is increased to 20%, and the rust removal rate is still 0%.
Comparative example 3
The method adopts 40 percent (concentration) phosphoric acid as a rust removing material, and is soaked for 10 to 30 minutes at the temperature of T=25 to 40 ℃ to remove rust, and the pig iron with the same brand as that of the example 1 is treated, and the specific operation steps are basically the same as that of the example 1, wherein the difference is that:
in the step (1), the temperature of the tank is regulated to 40 ℃;
In the step (2), soaking is carried out for 30min.
The results show that the average surface rust removal rate of comparative example 3 is 95%, the corrosion mass ratio of the metal substrate is 0.6/10000, and the rust resistance time is 35% at the temperature of 25 ℃ and the relative humidity of RH: 10h, the phosphoric acid is used as a rust removing material to remove rust weakly and easily returning rust.
Comparative example 4
12 Percent hydrochloric acid and 12 percent FeCl 2 are adopted as rust removing materials, the materials are soaked for 1min at the temperature of T=25-40 ℃ to remove rust, pig iron with the same brand as that of the example 1 is treated, and the specific operation steps are basically the same as that of the example 1, wherein the difference is that:
in the step (1), 12% hydrochloric acid and 2% FeCl are led into a rust removing groove, and the temperature of the groove is regulated to 40 ℃;
In the step (2), soaking for 1min.
The results show that the average surface rust removal rate of comparative example 4 is 99%, the corrosion mass ratio of the metal substrate is 1.5/10000, and the rust resistance time is 35% at the temperature of 25 ℃ and the relative humidity RH: 1min, the adoption of hydrochloric acid and FeCl 2 as rust removing materials is strong in corrosion and easy to return rust.
Comparative example 5
150-200 G/L of industrial sulfuric acid (1.84 g/mL), 3g/L of hexamethylenetetramine, 2g/L of triethanolamine, 200-300 g/L of industrial hydrochloric acid (30%), 200-300 g/L of salt and 10g/L of sodium dodecyl sulfate are adopted as rust removing materials, and the mixed water solution is soaked for 2-5 min at 15-25 ℃ to remove rust, so that pig iron with the same brand as in example 1 is treated, and the specific operation steps are basically the same as in example 1, wherein:
in the step (1), the temperature of the tank is regulated to 25 ℃;
In the step (2), soaking for 1min.
The results show that the average surface rust removal rate of comparative example 5 is 99%, the corrosion mass ratio of the metal substrate is 1.4/10000, and the rust resistance time is 35% at the temperature of 25 ℃ and the relative humidity RH: 30min, the rust removing material adopted in comparative example 5 has strong corrosion and is easy to return rust.
Comparative example 6
The rust removing material comprises the following components in parts by weight: 9% of oxalic acid, 3% of phosphoric acid, 0.05% of sodium dodecyl benzene sulfonate, 0.8% of ethylenediamine tetraacetic acid, 0.6% of triethanolamine, 0.3% of thiourea, 0.5% of hexamethylenetetramine, 0.2% of zinc dihydrogen phosphate and the balance of water, and the specific preparation is prepared by referring to Chinese patent CN 102071416B.
The method for removing rust on the surface of steel by adopting the rust removing material is used for treating pig iron with the same brand as that of the embodiment 1, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
in the step (1), the temperature of the tank is regulated to 45 ℃;
in the step (2), soaking for 20min.
The results show that the average surface rust removal rate of comparative example 6 is 86%, the corrosion mass ratio of the metal substrate is 0.9/10000, and the rust resistance time is 35% at the temperature of 25 ℃ and the relative humidity RH: 45min, the rust removing material adopted in the comparative example 6 is weak in rust removing and easy to return rust.
Comparative example 7
The rust removing material comprises the following components in parts by weight: 2.4% of hydroxyethylidene triphosphate, 2.2% of tartaric acid, 5.5% of citric acid, 3.5% of malic acid, 16% of trisodium phosphate, 0.35% of sodium gluconate, 2% of fatty alcohol polyoxyethylene ether and 67.95% of deionized water, and the specific preparation is prepared by referring to Chinese patent CN 106757095B.
The method for removing rust on the surface of steel by adopting the rust removing material is used for treating pig iron with the same brand as that of the embodiment 1, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
in the step (1), the temperature of the tank is regulated to 32 ℃;
In the step (2), soaking is carried out for 35min.
The results show that the average surface rust removal rate of comparative example 7 is 88%, the corrosion mass ratio of the metal substrate is 0.6/10000, and the rust resistance time is 35% at the temperature of 25 ℃ and the relative humidity RH: 5h, the rust removing material adopted in the comparative example 7 has weak rust removing and is easy to return rust, and flocculent precipitate is generated in the system to influence the appearance of the workpiece.
Comparative example 8
The rust removing material comprises the following components in parts by weight: 18% of phosphoric acid, 0.5% of zinc oxide, 0.5% of aluminum hydroxide, 6% of sodium tripolyphosphate, 5% of fatty alcohol polyoxyethylene ether with a polymerization degree of 9, 0.5% of carboxymethyl cellulose, 3% of acetic acid and 66.5% of deionized water, and the specific preparation is prepared by referring to Chinese patent CN 103046036B.
The method for removing rust on the surface of steel by adopting the rust removing material is used for treating pig iron with the same brand as that of the embodiment 1, and the operation steps are basically the same as those of the embodiment 1, and the difference is that:
in the step (1), the temperature of the tank is regulated to 25 ℃;
In the step (2), soaking for 10min.
The results show that the average surface rust removal rate of comparative example 8 is 82%, the corrosion mass ratio of the metal substrate is 0.5/10000, and the rust resistance time is 35% at the temperature of 25 ℃ and the relative humidity of RH: 11h, the rust removal material adopted in the comparative example 8 is weak in rust removal, and flocculent precipitate is generated in the system, so that the attractiveness of the workpiece is affected.
Comparative example 9
A rust removing material substantially the same as in example 2 except that: the weight percentage of [ Cystine ] 2[SP5C2 Im ] adopted is 1.8%.
The preparation of the rust removing material was substantially the same as that of example 2, except that the weight percentage of [ Cystine ] 2[SP5C2 Im ] was different.
Taking pig iron (main component is iron, and the rest is C2.11-4.3%) with the brand QT400 as an example, the rust removing material is used for removing rust in the same way as in the embodiment 2.
The results show that the surface rust removal rate of the method of the comparative example 9 is 56%, the corrosion mass ratio of the metal substrate is 0.9/10000, and the rust resistance time is as follows at the temperature of 25 ℃ and the relative humidity RH of 35%: about 1h.
Comparative example 10
A rust removing material substantially the same as in example 2 except that: the weight percentage of [ Cystine ] 2[SP5C2 Im ] adopted is 2.2%.
The preparation of the rust removing material was substantially the same as that of example 2, except that the weight percentage of [ Cystine ] 2[SP5C2 Im ] was different.
Taking pig iron (main component is iron, and the rest is C2.11-4.3%) with the brand QT400 as an example, the rust removing material is used for removing rust in the same way as in the embodiment 2.
The results show that the surface rust removal rate of the method of the comparative example 10 is 43%, the corrosion mass ratio of the metal substrate is 0.3/10000, and the rust resistance time is as follows at the temperature of 25 ℃ and the relative humidity RH of 35%: about 80h.
It can be seen from the combination of example 1, comparative examples 9 and 10 that the amount of the mechanical molecules used is critical to the rust removal efficiency and the corrosion resistance after rust removal.
Comparative example 11
A rust removing material substantially the same as in example 2 except that: the weight percentage of cystine used is 0.1%.
The preparation of the above rust removing material was substantially the same as that of example 2, except that the weight percentage of cystine was different.
Taking pig iron (main component is iron, and the rest is C2.11-4.3%) with the brand QT400 as an example, the rust removing material is used for removing rust in the same way as in the embodiment 2.
The results show that the method of the embodiment has the surface rust removal rate of 99%, the corrosion mass ratio of the metal substrate of 6.2/10000, and the rust resistance time at the temperature of 25 ℃ and the relative humidity of RH of 35 percent: about 23h, in addition, the metal surface was pitted.
Comparative example 12
A rust removing material substantially the same as in example 2 except that: the weight percentage of cystine used was 2.2%.
The preparation of the above rust removing material was substantially the same as that of example 2, except that the weight percentage of cystine was different.
Taking pig iron (main component is iron, and the rest is C2.11-4.3%) with the brand QT400 as an example, the rust removing material is used for removing rust in the same way as in the embodiment 2.
The results show that the method of the embodiment has a surface rust removal rate of 23%, the corrosion mass ratio of the metal substrate of 0.3/10000, and the rust resistance time at the temperature of 25 ℃ and the relative humidity of RH of 35 percent: about 20h.
It can be seen from the combination of example 1, comparative examples 11 and 12 that the amino acid complexing agent is critical to the rust removal surface condition and has a close relationship with the mechanical molecules, thereby affecting the rust removal effect and the post-rust corrosion resistance time.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. The environment-friendly steel rust removing liquid is characterized by comprising the following components in parts by weight: 2-10% of ionic compound, 0.2-2% of amino acid complexing agent and the balance of water;
Wherein the chemical structural formula of the ionic compound is as follows:
In the formula I, R 1～R5 is independently selected from saturated alkane groups containing oxo acid radicals, and any 1-3 of R 1～R5 are selected from saturated alkane groups containing oxo acid radicals and mercapto radicals simultaneously; the oxo acid radical has a negative charge;
In the formula I, AA is selected from amino acid containing sulfhydryl, methylthio and disulfide bond; the value of m is determined by the cationic charge n;
Wherein the amino acid complexing agent is selected from any one or more than two of amino acids containing sulfhydryl, methylthio and disulfide bonds and derivatives thereof.
2. The environment-friendly steel rust remover according to claim 1, wherein the saturated alkane group has 1-4 carbon atoms.
3. The environment-friendly steel rust remover according to claim 1, wherein the oxo acid radical is any one or more of carboxyl, phosphate radical, sulfate radical and sulfite radical.
4. The environmentally friendly steel rust remover according to any one of claims 1-3, wherein AA is one or more selected from methionine, cystine, and cysteine; the amino acid complexing agent is selected from any one or more than two of methionine, cystine, cysteine and derivatives thereof.
5. The environment-friendly steel rust remover according to claim 1, wherein the amino acid complexing agent is one or more selected from the group consisting of thiol-, methylthio-and disulfide-bond-containing amino acids, and esters and salts thereof.
6. The environment-friendly steel rust remover according to claim 1, wherein the ionic compound is selected from the group consisting of any one of the following multi-side imidazole anions in combination with AA cations:
In the formulas II and III, X 1～X5 is independently selected from oxo acid radicals;
In the formulas II and III, Y is selected from O or C;
In the formulas II and III, n 1～n5 is independently selected from 1 to 3.
7. The environment-friendly steel rust remover according to claim 1, wherein the ionic compound is selected from the group consisting of any one of the following multi-side imidazole anions in combination with AA cations:
8. Use of the environment-friendly steel rust removing liquid according to any one of claims 1 to 7 for rust removing of steel surfaces.
9. The ionic compound for the steel rust removing liquid is characterized by comprising the following chemical structural formula:
In the formula I, R 1～R5 is independently selected from saturated alkane groups containing oxo acid radicals, and any 1-3 of R 1～R5 are selected from saturated alkane groups containing oxo acid radicals and mercapto radicals simultaneously; the oxo acid radical has a negative charge;
In the formula I, AA is selected from amino acid containing sulfhydryl, methylthio and disulfide bond; the value of m is determined by the cationic charge n.
10. A process for the preparation of an ionic compound as claimed in claim 9, comprising:
(1) The diketone shown in the formula A, the amine shown in the formula B1 and the formula B2 and the aldehyde shown in the formula C are heated and stirred to react, and after the reaction is finished, the diketone, the amine shown in the formula B1 and the formula B2 are concentrated and cooled at low temperature to separate out a product shown in the formula D;
Wherein R 6～R9 is selected from saturated alkane groups containing OH, and 1-3 of R 6～R9 are selected from saturated alkane groups containing OH and mercapto simultaneously;
(2) Grinding the product shown in the formula D and the fixed oxide corresponding to the oxo acid radical under heating for solid phase synthesis, extracting the product after the reaction is finished, and removing the solvent to obtain the product shown in the formula E;
or, reacting the product shown in the formula D with a gas oxide corresponding to the oxo acid radical at room temperature to obtain a product shown in the formula E;
(3) Stirring and reacting a product shown in a formula E and amino acid AA in water at room temperature, and removing water after the reaction is finished to obtain an ionic compound;
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