CN115926893A - Recyclable cleaning agent and preparation method and application thereof - Google Patents
Recyclable cleaning agent and preparation method and application thereof Download PDFInfo
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- CN115926893A CN115926893A CN202111223155.8A CN202111223155A CN115926893A CN 115926893 A CN115926893 A CN 115926893A CN 202111223155 A CN202111223155 A CN 202111223155A CN 115926893 A CN115926893 A CN 115926893A
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- cleaning
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims description 7
- -1 primary amine compounds Chemical class 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 20
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 133
- 235000019198 oils Nutrition 0.000 claims description 133
- 239000000243 solution Substances 0.000 claims description 116
- 238000004140 cleaning Methods 0.000 claims description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 239000007864 aqueous solution Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 27
- 239000010687 lubricating oil Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 17
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- GBSUVYGVEQDZPG-UHFFFAOYSA-N (2,4-dimethylphenyl)methanamine Chemical compound CC1=CC=C(CN)C(C)=C1 GBSUVYGVEQDZPG-UHFFFAOYSA-N 0.000 claims description 2
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical compound CC1=CC=CC=C1CN CJAAPVQEZPAQNI-UHFFFAOYSA-N 0.000 claims description 2
- PXNRCZQMDSDSHJ-UHFFFAOYSA-N (3,4-dimethylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1C PXNRCZQMDSDSHJ-UHFFFAOYSA-N 0.000 claims description 2
- LESUPVCBJDWKJH-UHFFFAOYSA-N (3-chloro-2-methylphenyl)methanamine Chemical compound CC1=C(Cl)C=CC=C1CN LESUPVCBJDWKJH-UHFFFAOYSA-N 0.000 claims description 2
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 claims description 2
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 claims description 2
- OELBLPCWLAWABI-UHFFFAOYSA-N 1,2,4-tribromo-5-(2,5-dibromophenyl)benzene Chemical compound BrC1=CC=C(Br)C(C=2C(=CC(Br)=C(Br)C=2)Br)=C1 OELBLPCWLAWABI-UHFFFAOYSA-N 0.000 claims description 2
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 150000003939 benzylamines Chemical class 0.000 claims description 2
- 239000002173 cutting fluid Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010721 machine oil Substances 0.000 claims description 2
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 claims description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ADPUQRRLAAPXGT-UHFFFAOYSA-M sodium;2-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=O ADPUQRRLAAPXGT-UHFFFAOYSA-M 0.000 claims description 2
- AFIUOLGCFDPAKN-UHFFFAOYSA-M sodium;3-formylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(C=O)=C1 AFIUOLGCFDPAKN-UHFFFAOYSA-M 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical group C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 claims 3
- 229960001716 benzalkonium Drugs 0.000 claims 2
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 1
- 229960002233 benzalkonium bromide Drugs 0.000 claims 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 230000003993 interaction Effects 0.000 claims 1
- 150000003141 primary amines Chemical class 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 46
- 150000002466 imines Chemical class 0.000 description 37
- 229910001220 stainless steel Inorganic materials 0.000 description 29
- 239000010935 stainless steel Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 26
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 24
- 206010057239 Post laminectomy syndrome Diseases 0.000 description 21
- 238000007667 floating Methods 0.000 description 21
- 229920000742 Cotton Polymers 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 16
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 241000252212 Danio rerio Species 0.000 description 14
- 238000010494 dissociation reaction Methods 0.000 description 12
- 230000005593 dissociations Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 9
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 7
- GOVPDHQFCUYKRI-UHFFFAOYSA-M (4-formylphenyl)methyl-trimethylazanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=C(C=O)C=C1 GOVPDHQFCUYKRI-UHFFFAOYSA-M 0.000 description 6
- URCJRDMSDWTSGZ-UHFFFAOYSA-N benzaldehyde;sodium Chemical compound [Na].O=CC1=CC=CC=C1 URCJRDMSDWTSGZ-UHFFFAOYSA-N 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 3
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 230000001960 triggered effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 231100000820 toxicity test Toxicity 0.000 description 2
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of cleaning agents, and particularly relates to a recyclable cleaning agent, which comprises the following raw materials: primary amine compounds and compounds containing active aldehyde groups; the primary amine compound is selected from one, two or more of hydroxylamine, aliphatic amine, benzylamine, aromatic amine and the like; the compound containing the active aldehyde group is selected from a compound shown in a formula I and/or a compound shown in a formula II, wherein X ‑ Is selected from F ‑ ，Cl ‑ ，Br ‑ ，I ‑ ，SO 3 ‑ ，COO ‑ Or HSO 4 ‑ ，Y + Selected from Na + Or K + . The cleaning agent has high using recyclability and long service life.
Description
Technical Field
The invention belongs to the field of cleaning agents, and particularly relates to a recyclable cleaning agent, and a preparation method and application thereof.
Background
The industrial cleaning belongs to the technical field of multidisciplinary fusion, and effective industrial cleaning can not only remove industrial dirt and improve the appearance quality of industrial products, but also keep the high-efficiency performance of the industrial products and ensure the safety and reliability of the industrial products, so that the industrial cleaning plays a vital role in a wide range of industrial fields, such as automobiles, trains, ships, aviation, household appliances, optics, electronics, hardware, electroplating and the like. Industrial cleaning essentially requires the use of industrial cleaning agents, which play an important role in cleaning performance. The current industrial cleaning agent is gradually changed from an organic solvent cleaning agent and a semi-organic solvent cleaning agent to a complete water-based cleaning agent. The water-based cleaning agent is mainly prepared by using water as a solvent, using a surfactant as a main component and adding a defoaming agent, an antirust agent or other additives. The water-based cleaning agent has a series of advantages of water replacing oil, energy saving, environmental friendliness, safe use, low cost and the like, and thus the water-based cleaning agent is concerned.
The surfactant is the most main component of the water-based cleaning agent, and the currently commonly used surfactants comprise Sodium Dodecyl Benzene Sulfonate (SDBS), dodecyl Trimethyl Ammonium Bromide (DTAB), fatty alcohol polyoxyethylene ether (JFC, AEO and peregal series), alkylphenol polyoxyethylene ether (TX-10), coconut oil diethanolamide (6501, 6502 and 6503) and the like. By regulating the compounding ratio of the surfactants, a plurality of high-efficiency water-based cleaning agent formulas can be obtained, and the high-efficiency water-based cleaning agent formulas have the function of cleaning dirt on various metal solid surfaces. Although the cleaning effect of water-based cleaning agents is continuously improved, industrial cleaning also faces a great problem, namely the problem of recycling of the cleaning agent, which is not solved so far. The existing cleaning agent is difficult to recycle, generally only once, and when the cleaning agent is used again, the cleaning efficiency is greatly reduced or no cleaning effect is generated, so that the cleaning agent needs to be continuously supplemented to maintain high-efficiency cleaning. This leads on the one hand to a large consumption of cleaning agent and therefore to a high cost; on the other hand, industrial wastewater generated by repeatedly using a large amount of cleaning agent pollutes the environment and is unfavorable for the ecological environment and the life health. The emulsion formed by the cleaning agent and the oil stain is relatively stable, the purification treatment of the wastewater is very difficult, and the cost required for reaching the wastewater treatment discharge standard is extremely high.
Therefore, the development of a high-efficiency recyclable cleaning agent is urgently needed, the service life of the cleaning agent is prolonged, the wastewater treatment cost is reduced, and the damage to the ecological environment is reduced.
Disclosure of Invention
In order to solve the above-mentioned problems, it is an object of the present invention to provide a cleaning agent, a method for producing the same, and use thereof, which has high recyclability and long service life.
The invention provides a cleaning agent, which comprises the following raw materials: primary amine compounds and compounds containing active aldehyde groups;
the primary amine compound is selected from one, two or more of hydroxylamine, aliphatic amine, benzylamine, aromatic amine and the like;
the compound containing the active aldehyde group is selected from a compound shown in a formula I and/or a compound shown in a formula II,
wherein, X - Is selected from F - ，Cl - ，Br - ，I - ，SO 3 - ，COO - Or HSO 4 - ，Y + Selected from Na + Or K + 。
According to an embodiment of the invention, the aromatic amine may be selected from substituted or unsubstituted anilines, such as p-methoxyaniline, p-nitroaniline, p-chloroaniline.
According to an embodiment of the invention, the benzylamine may be selected from substituted or unsubstituted benzylamines, such as o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, benzylamine, 3,4-dimethylbenzylamine, 2,4-dimethylbenzylamine, 2-methyl-3-chlorobenzylamine, N-methylbenzylamine, or α -methylbenzylamine.
According to an embodiment of the invention, the hydroxylamine is selected from 2-hydroxyethylamine polyoxyethylene ether, 3-hydroxypropylamine polyoxyethylene ether, or 4-hydroxybutylamine polyoxyethylene ether.
According to an embodiment of the present invention, the aliphatic amine may be selected from C3-20 linear or branched aliphatic amines, preferably C3-20 linear aliphatic amines, and preferably the aliphatic amine includes one, two or more selected from C6-18 linear aliphatic amines, such as hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine.
According to an embodiment of the invention, the compound of formula I may be one, two or three of sodium 2-formylbenzenesulfonate, sodium 3-formylbenzenesulfonate and sodium 4-formylbenzenesulfonate.
According to an embodiment of the invention, the compound of formula II may be
For example, one, two or three kinds of 4-formyl N, N, N-trimethyl benzyl ammonium bromide, 4-formyl N, N, N-trimethyl benzyl ammonium iodide, 4-formyl N, N, N-trimethyl benzyl ammonium fluoride and the like.
According to the embodiment of the invention, the cleaning agent contains a compound with imine bond-C = N-, and the compound with imine bond-C = N-is formed by the action of dynamic covalent bonds of the primary amine compound and a compound containing active aldehyde groups.
According to an embodiment of the invention, the molar ratio of the primary amine compound to the compound containing an active aldehyde group is 1:3 to 3:1, preferably the molar ratio of the primary amine compound to the compound containing an active aldehyde group is 1:1 to 2:1, for example 1:1.
According to an embodiment of the present invention, the feedstock further comprises water, a lower alcohol, preferably at least one of methanol, ethanol, propanol, butanol, and a halide salt, which is NaBr, KCl or NaCl, e.g. the feedstock further comprises water, ethanol and NaBr.
According to the embodiment of the invention, the cleaning agent is prepared from the raw materials.
According to an embodiment of the invention, the cleaning agent has recyclable properties.
When the cleaning agent is alkaline, the cleaning agent has a pH of 7.5 to 14, preferably a pH of 8 to 11 or 9 to 10, exemplary 7.5, 9.45, 9.5, 10.3, 10.6, 11, 11.3, 11.5, and a compound having an imine bond-C = N-is contained in the cleaning agent, and the cleaning agent has an ability to clean oil stains. At this time, the cleaning agent was milky white. Preferably, the mass fraction of the cleaning agent is 0.3 to 1.0%, for example 0.4 to 0.8%, exemplarily 0.5%.
When the cleaning agent is non-alkaline, for example, the pH of the cleaning agent is 2 to 7, preferably the pH of the cleaning agent is 3 to 6, more preferably the pH of the cleaning agent is 4 to 5, illustratively 2, 2.5.
When the cleaning agent is non-alkaline, the imine bond of the compound with the imine bond-C = N-in the cleaning agent is dissociated to obtain a primary amine compound and a compound containing active aldehyde group, so that oil stain can be quickly released, and oil-water separation is realized.
The invention also provides a preparation method of the cleaning agent, which comprises the following steps: and mixing the primary amine compound, the compound containing active aldehyde group, water, lower alcohol and halide salt, and adjusting the pH value of the system to obtain the cleaning agent.
According to an embodiment of the invention, the preparation method comprises the steps of:
1) Preparing a primary amine compound aqueous solution;
2) Preparing an aqueous solution containing an active aldehyde compound;
3) Mixing the primary amine compound aqueous solution and the active aldehyde compound aqueous solution, and then adding lower alcohol and halide salt to obtain a dynamic imine bond surfactant solution;
4) And adjusting the pH value of the dynamic imine bond surfactant solution to 7.5-14 to obtain the cleaning agent.
According to an embodiment of the present invention, the concentration of the aqueous solution of the primary amine compound in step 1) is 0.1 to 1mol/L, preferably the concentration of the aqueous solution of the primary amine compound is 0.2 to 0.8mol/L, more preferably the concentration of the aqueous solution of the primary amine compound is 0.3 to 0.6mol/L, and even more preferably the concentration of the aqueous solution of the primary amine compound is 0.4 to 0.5mol/L.
Preferably, the primary amine compound aqueous solution is a colorless transparent liquid.
According to an embodiment of the present invention, the concentration of the aqueous solution containing an active aldehyde group compound in step 2) is 1 to 5mol/L, and preferably, the concentration of the aqueous solution containing an active aldehyde group compound is 2 to 4mol/L.
Preferably, the aqueous solution of the active aldehyde-based compound is a colorless transparent liquid.
According to an embodiment of the present invention, the concentration of the primary amine compound aqueous solution after mixing and dilution in step 3) is 5 to 60mM, and the concentration of the active aldehyde group-containing compound aqueous solution after mixing and dilution is 5 to 60mM.
According to an embodiment of the present invention, the concentration of the lower alcohol in step 3) is 0.5 to 10%, preferably the concentration of the lower alcohol is 1 to 8%, more preferably the concentration of the lower alcohol is 2 to 6%, further preferably the concentration of the lower alcohol is 3 to 5%, such as 2%, 3%, 5%, 6%, 7%, 8%.
According to an embodiment of the invention, the concentration of the halide salt in step 3) is 1 to 5%, preferably the concentration of the halide salt is 2 to 4%, for example 1.5%, 2%, 3.5%.
According to an embodiment of the present invention, the temperature at the time of mixing in step 3) is 0 to 40 ℃, for example 10 to 30 ℃, more preferably 20 to 25 ℃, for example 10 ℃, 20 ℃, 25 ℃, 30 ℃.
Preferably, the step 4) is followed by a step of adjusting the temperature of the system to 0 to 40 ℃.
The invention also provides an application of the cleaning agent in removing oil stains, such as treating oily sewage.
According to an embodiment of the invention, the oil contamination comprises cutting fluid, machine oil, lubricating oil, rust preventive oil, stretching oil, peanut oil and/or soybean oil.
The invention also provides a method for removing oil stains by using the cleaning agent, which comprises the following steps: the cleaning agent is contacted with oil stains on the workpiece, or the cleaning agent is mixed with the oily sewage.
According to an embodiment of the invention, the cleaning agent has a pH value of 7.5-14 and a temperature of 0-40 ℃ when in use.
According to an embodiment of the present invention, the contacting includes contacting by ultrasound, soaking, spraying, and the like.
According to an embodiment of the invention, the workpiece comprises a plastic, rubber, metal, glass, silicon wafer, cotton cloth and/or circuit board piece.
The invention also provides a method for recycling the cleaning agent, which comprises the following steps: adjusting the pH value of the cleaning agent system after degreasing to 2-7, separating oil from water, adjusting the pH value of the water phase to 7.5-14, and recovering the cleaning function.
The oil and water phases can be separated by means of suction drainage and/or oil absorption by the oil absorbent cotton. For example, the time for oil-water separation may be 1 to 10 minutes.
According to an embodiment of the present invention, the time for restoring the washing function may be 1 to 5 minutes.
Definition of terms:
benzylamine has the structure:
by aromatic amine is meant an amine having one aromatic substituent, i.e. -NH 2 -NH or a nitrogen-containing group is attached to an aromatic hydrocarbon; the aromatic hydrocarbon generally has one or more benzene rings in the structure, i.e. the nitrogen atom is directly connected with the carbon atom of the benzene ring through a chemical bond.
Advantageous effects
The cleaning agent comprises a primary amine compound and a compound with active aldehyde groups, wherein the primary amine compound and the compound with active aldehyde groups form a compound with imine bonds (R-C = N-R') in an aqueous solution through the action of dynamic covalent bonds, the compound with imine bonds can form an aggregate structure under the condition that the pH value is 7.5-14, oil stains are wrapped, the oil stains on the surface of an object are transferred into a cleaning system, the aggregate releases the wrapped oil stains and forms an oil-water separation system under the condition that the pH value is 2-7, the oil stains are separated and then regenerated into the cleaning system, the cleaning capacity of the regenerated cleaning system is still strong, the regeneration time is short, the operation difficulty is low, the cleaning system can be recycled for more than 10 times, the service life of the cleaning agent is effectively prolonged, the cleaning cost is reduced, the difficulty of a wastewater treatment process is low, and the damage of emissions to the ecological environment can be reduced.
Drawings
FIG. 1 is an appearance diagram of FBSS-7C solution of example 2 of the present invention and comparative examples 1-4;
FIG. 2 is a microscopic view under a microscope of a FBSS-7C solution in example 2 of the present invention;
FIG. 3 is a graph showing the regeneration solution and cleaning effect of FBSS-7C solution in test example 1 for 10 cycles of cleaning stainless steel sheets;
FIG. 4 is a graph showing the cleaning effect and the emulsion treatment before and after the control groups 1 to 4 in test example 1 of the present invention;
FIG. 5 is a graph showing a comparison of dynamic surface tensions of the solutions of the experimental group 1FBSS-7C and the control groups 1 to 4 in the test example 2 of the present invention;
FIG. 6 is a graph showing a comparison of the oil-water interfacial tensions of the experimental FBSS-7C solution and the control 1-4 solutions in test example 3;
FIG. 7 is a graph showing the results of a toxicity test on zebra fish in which the solutions of FBSS-7C of the test group and the solutions of FBSS-7C of the control groups 1 to 4 were diluted 100 times;
FIG. 8 is an appearance view and a microscopic view under a microscope of an FBAI-6C solution in example 6;
FIG. 9 is a graph showing the regenerating solution and the cleaning effect of the FBAI-6C cleaning solution of the experimental group in test example 1 for 10 cycles of cleaning the stainless steel sheet;
FIG. 10 is a graph of the oil-water interfacial tension of the experimental FBAI-6C cleaning solution;
FIG. 11 is a graph showing the results of the toxicity test on zebra fish of 100-fold dilution of the wastewater discharged from experimental group FBAI-6C in test example 4.
Detailed Description
The cleaning agent of the present invention, its preparation method and its application will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Preparing a 10mM hexylamine solution and a 10mM 2-formyl benzene sodium sulfonate aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:3 at room temperature, adding 5% ethanol and 3% NaBr, adjusting the pH value to 10.6, and stirring at a low speed for 10min to obtain a dynamic imine type cleaning agent solution FBSS-6C (hereinafter referred to as a cleaning solution).
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.5, and dissociation of the dynamic imine cleaning agent can be initiated, so that oil stain is released quickly, and oil-water separation is realized in a short time. And (3) sucking the floating oil stain on the water surface, using an oil absorption cotton to absorb the oil when the oil stain is less, and adjusting the pH to 10.6 after the oil stain is removed to ensure that the dynamic imine cleaning agent is formed again and the cleaning function is recovered.
Example 2
Preparing 10mM of heptamine solution and 10mM of 2-formyl benzene sodium sulfonate aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1: 2 at room temperature, adding 5% of ethanol and 3% of NaBr, adjusting the pH value to 7.5, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBSS-7C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.0 to initiate dissociation of the dynamic imine cleaning agent, so that oil stain is quickly released, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 7.5, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 3
Preparing 10mM octylamine solution and 10mM 2-formyl benzene sodium sulfonate aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 5% ethanol and 3% NaBr, adjusting the pH value to 7.5, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBSS-8C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.5, and dissociation of the dynamic imine cleaning agent can be initiated, so that oil stain is released quickly, and oil-water separation is realized in a short time. And (3) sucking floating oil stains on the water surface, and when the oil stains are less, using oil-absorbing cotton to absorb the oil. After the oil stain is removed, the pH value is adjusted to 7.5, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 4
Preparing 1.5mM decylamine solution and 1.5mM 2-formyl benzene sodium sulfonate aqueous solution, mixing the two aqueous solutions according to the volume ratio of 3:1 at room temperature, adding 5% ethanol and 3% NaBr, adjusting the pH value to 11.3, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBSS-10C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 1.5, and dissociation of the dynamic imine cleaning agent can be triggered, so that oil stains are released quickly, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 11.3, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 5
Preparing 1.5mM dodecylamine solution and 1.5mM 2-formyl benzene sodium sulfonate aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 5% ethanol and 3% NaBr, adjusting the pH value to 11, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBSS-12C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.5, and dissociation of the dynamic imine cleaning agent can be initiated, so that oil stain is released quickly, and oil-water separation is realized in a short time. And (3) sucking floating oil stains on the water surface, and when the oil stains are less, using oil-absorbing cotton to absorb the oil. After the oil stain is removed, the pH value is adjusted to 11, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 6
Preparing 10mM hexylamine solution and 10mM 4-formyl N, N, N-trimethyl benzyl ammonium iodide aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 8% ethanol and 2% NaBr, adjusting the pH value to 10.6, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBAI-6C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.0 to initiate dissociation of the dynamic imine cleaning agent, so that oil stain is quickly released, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 10.6, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 7
Preparing 10mM of heptamine solution and 10mM of 4-formyl N, N, N-trimethyl benzyl ammonium iodide aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 8% of ethanol and 2% of NaBr, adjusting the pH value to 11.5, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBAI-7C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.0 to initiate dissociation of the dynamic imine cleaning agent, so that oil stain is quickly released, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 11.5, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 8
Preparing 10mM octylamine solution and 10mM 4-formyl N, N, N-trimethyl benzyl ammonium iodide aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 8% ethanol and 2% NaBr, adjusting the pH value to 9.5, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBAI-8C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.5, and dissociation of the dynamic imine cleaning agent can be initiated, so that oil stain is released quickly, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 9.5, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 9
Preparing a 2mM decylamine solution and a 2mM 4-formyl N, N, N-trimethyl benzyl ammonium iodide aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 8% ethanol and 2% NaBr, adjusting the pH value to 10.3, and stirring at a low speed for 10min to obtain a dynamic imine type cleaning agent solution FBAI-10C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2, so that dissociation of the dynamic imine cleaning agent can be initiated, oil stains are released quickly, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 10.3, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Example 10
Preparing 0.5mM dodecylamine solution and 0.5mM 4-formyl N, N, N-trimethyl benzyl ammonium iodide aqueous solution, mixing the two aqueous solutions according to the volume ratio of 1:1 at room temperature, adding 8% ethanol and 2% NaBr, adjusting the pH value to 9.45, and stirring at low speed for 10min to obtain the dynamic imine type cleaning agent solution FBAI-12C.
Placing the cleaning agent solution in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature at 25 ℃, and performing ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2, so that dissociation of the dynamic imine cleaning agent can be triggered, oil stains are released quickly, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 9.45, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered.
Comparative example 1: preparing tertiary water with pH of 12, placing the tertiary water in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and ultrasonically cleaning for 10min.
Comparative example 2: preparing 0.5% isooctanol polyoxyethylene ether solution (JFC-E), placing in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature at 25 ℃, and performing ultrasonic cleaning for 10min.
Comparative example 3: preparing 0.5% Sodium Dodecyl Benzene Sulfonate (SDBS), placing in an ultrasonic cleaning pool, placing into a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting temperature to 25 deg.C, and ultrasonic cleaning for 10min.
Comparative example 4: preparing 0.5% dodecyl trimethyl ammonium bromide solution (DTAB), placing in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting temperature at 25 deg.C, and ultrasonic cleaning for 10min.
As shown in FIG. 1, which is a physical representation of the FBSS-7C solution of example 2 and the solutions prepared in comparative examples 1-4, the FBSS-7C solution of example 2 is milky white indicating the formation of larger aggregates, and the solutions of comparative examples 1-4 are colorless transparent liquids indicating no or small aggregate size.
As can be seen from fig. 2 and 8, the solution of example 2 and example 6 forms spherical aggregates with larger size, and the solution is rich in liquid phase, so that the solution is turbid and milky, wherein the size of the spherical aggregates is 1-10 microns.
Test example 1: efficient recyclable cleaning agent cleaning effect and oil-water separation effect test
Experimental group 1: example 2 provides a dynamic imine-based cleaner solution FBSS-7C.
Placing FBSS-7C solution in ultrasonic cleaning pool, placing stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting temperature to 25 deg.C, and ultrasonic cleaning for 10min. After cleaning, the pH value of the cleaning solution is adjusted to 2.0, and dissociation of the dynamic imine cleaning agent can be triggered, so that oil stains are released quickly, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 7.5, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered. The cleaning effect and the oil-water separation effect in 10 circulation processes were tested.
Experimental group 2: the dynamic imine-based detergent solution provided in example 6 was FBAI-6C.
Putting the cleaning solution into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and carrying out ultrasonic cleaning for 10min.
After cleaning, the pH value of the cleaning solution is adjusted to 2.0 to initiate dissociation of the dynamic imine cleaning agent, so that oil stain is quickly released, and oil-water separation is realized in a short time. And (4) sucking the floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH value is adjusted to 10.6, so that the dynamic imine cleaning agent can be formed again, and the cleaning function is recovered. The cleaning effect and the oil-water separation effect in 10 circulation processes were tested.
Control group 1: the tertiary water of pH12 prepared in comparative example 1 was placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricant was placed, the ultrasonic power was adjusted to 100W, the temperature was set to 25 ℃, and ultrasonic cleaning was performed for 10min. Adjusting the pH of the solution after cleaning to 2, floating up if oil stains exist, removing the oil stains, adjusting the pH to the pH before cleaning, repeating the cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
Control group 2: the 0.5% isooctanol polyoxyethylene ether solution (JFC-E) prepared in comparative example 2 was placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricant was placed, the ultrasonic power was adjusted to 100W, the temperature was set to 25 ℃, and ultrasonic cleaning was carried out for 10min. Adjusting the pH of the solution after cleaning to 2, floating up if oil stains exist, removing the oil stains, adjusting the pH to the pH before cleaning, repeating the cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
Control group 3: the 0.5% sodium dodecylbenzenesulfonate solution (SDBS) prepared in comparative example 3 was placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricant was placed, the ultrasonic power was adjusted to 100W, the temperature was set to 25 ℃, and ultrasonic cleaning was carried out for 10min. Adjusting the pH of the solution after cleaning to 2, floating up if oil stains exist, removing the oil stains, adjusting the pH to the pH before cleaning, repeating the cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
Control group 4: a0.5% dodecyltrimethylammonium bromide solution (DTAB) prepared in comparative example 4 was placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricant was placed, the ultrasonic power was adjusted to 100W, the temperature was set to 25 ℃, and ultrasonic cleaning was carried out for 10min. Adjusting the pH of the solution after cleaning to 2, floating up if oil stains exist, removing the oil stains, adjusting the pH to the pH before cleaning, repeating the cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
The cleaning effect and the oil-water separation effect of the experimental group and the control group are shown in fig. 3,4, and 9.
As can be seen from fig. 3, the FBSS-7C solution at pH7.5 and the FBAI-6C solution at pH10.6 have excellent cleaning ability, can strip and emulsify the oil stain on the stainless steel sheet to form an emulsion, and can break the emulsion at pH2.0 to separate oil and water, and the lower layer solution after oil and water separation is relatively clear and the upper layer is a floating oil layer, as can be seen from fig. 3 and 9.
When the stainless steel sheet with the oil stains is irradiated by ultraviolet light, the parts with the oil stains can emit bright purple, and the parts without the oil stains are black. As can be seen from the figures 3 and 9, the stainless steel sheets cleaned in the 10-time circulation process are all cleaned and are black without bright purple, so that the efficient environment-friendly recyclable cleaning agent FBSS-7C, FBAI-6C can be recycled at least 10 times.
As shown in fig. 4, after the first cleaning with the tertiary water having a pH of 12, the isooctanol polyoxyethylene ether solution (JFC-E) having a pH of 0.5%, the sodium dodecylbenzenesulfonate solution (SDBS) having a pH of 0.5%, and the dodecyltrimethylammonium bromide solution (DTAB) having a pH of 0.5%, the amount of the residual oil on the surface was large, and the cleaning effect was gradually decreased as the number of cycles was increased. The cleaned oily wastewater is still stable after standing for three days, the pH is adjusted to be acidic 2 or alkaline 11, and the oily wastewater cannot be demulsified and is difficult to treat.
Test example 2: dynamic surface tension test of efficient recyclable cleaning agent
Experimental groups: 5mM MFBSS-7C solution (example 2 cleaning solution), pH7.5;
control group 1: tertiary water of pH12 provided in comparative example 1;
control group 2: the 0.5% isooctanol polyoxyethylene ether solution (JFC-E) provided in comparative example 2;
control group 3: a 0.5% sodium dodecylbenzenesulfonate solution (SDBS) as provided in comparative example 3;
control group 4: comparative example 4 provides a 0.5% solution of dodecyltrimethylammonium bromide (DTAB).
The dynamic surface tension of the above solution was measured by the maximum bubble pressure method using a kluyverge BP100 dynamic surface tension meter.
Sample Chi Chushi 70mL of surfactant solution was placed, the diameter of the capillary used to generate the bubbles was 0.210mm, the surface lifetime measured was 8.0ms to 10.0s, and the temperature measured for the experiment was 25.0 ± 0.5 ℃.
As can be seen from FIG. 5, the 5mM FBSS-7C solution in the experimental group had the lowest dynamic surface tension, which was much lower than that in the control groups 1-4.
Test example 3: oil-water interface tension test of efficient recyclable cleaning agent
Experimental group 1:5mMFBSS-7C solution (example 2 washing solution), pH7.5;
experimental group 2:5mMFBAI-6C solution (example 6 wash), pH10.6;
control group 1: tertiary water at pH 12;
control group 2:0.5% isooctanol polyoxyethylene ether solution (JFC-E);
control group 3:0.5% sodium dodecylbenzenesulfonate solution (SDBS);
control group 4:0.5% dodecyl trimethyl ammonium bromide solution (DTAB).
The oil-water interfacial tension of the solution is measured by a TX500C ultra-low interfacial tension measuring instrument, the external phase is the solution, the internal phase is mechanical lubricating oil, the rotating speed is 8000rpm, and the measuring temperature of all experiments is 25.0 +/-0.5 ℃.
As can be seen from FIG. 6, only the oil droplets in the 5mM FBSS-7C solution in the test group were pulled up into a cylindrical shape, the oil-water interfacial tension of the solution corresponding to test group 1 was 4.35mN/m, and the oil-water interfacial tension of the solution corresponding to test group 2 was 9.78mM/m, as shown in FIG. 10.
The oil droplets in the control groups 1-4 adhered to the wall and could not be pulled up, which indicates that the oil-water interface activity is poor, which may be the main reason why the cleaning ability of the FBSS-7C solution is better than that of the control group.
Test example 4: high-efficiency recyclable cleaning agent wastewater biotoxicity determination method
Experimental group 1: putting 5mM MFBSS-7C solution with pH of 7.5 into an ultrasonic cleaning pool, putting a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to be 25 ℃, and ultrasonically cleaning for 10min. After cleaning, adjusting the pH value of the cleaning solution to 2.0 to initiate oil-water separation, sucking floating oil stains on the water surface, and using oil absorption cotton to absorb oil when the oil stains are less. After the oil stain is removed, the pH is adjusted to 7.0 and the biotoxicity is tested.
Experimental group 2: the conditions were the same as those in Experimental group 1 except that the FBSS-7C solution was replaced with the FBAI-6C solution of pH10.6 provided in example 6.
Control group 1: triple water (not participating) at pH7.0
Control group 2: placing 0.5% isooctanol polyoxyethylene ether solution (JFC-E) in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature at 25 ℃, and performing ultrasonic cleaning for 10min. After cleaning, adjusting the pH value of the cleaning solution to 2.5, sucking floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH is adjusted to 7.0 and the biotoxicity is tested.
Control group 3: placing 0.5% Sodium Dodecyl Benzene Sulfonate (SDBS) solution in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature to 25 ℃, and performing ultrasonic cleaning for 10min. After cleaning, adjusting the pH value of the cleaning solution to 2.5, sucking floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH is adjusted to 7.0 and the biotoxicity is tested.
Control group 4: placing 0.5% dodecyl trimethyl ammonium bromide solution (DTAB) in an ultrasonic cleaning pool, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature at 25 deg.C, and ultrasonic cleaning for 10min. After cleaning, adjusting the pH value of the cleaning solution to 2.5, sucking floating oil stains on the water surface, and when the oil stains are less, using oil absorption cotton to absorb oil. After the oil stain is removed, the pH is adjusted to 7.0 and the biotoxicity is tested.
The zebra fish is an ideal vertebrate model system for aquatic ecotoxicology research, and the acute toxicity test is used for respectively researching the influence of waste liquid (diluted by 100 times) obtained after oil stain is cleaned by 5mMFBSS-7C, 0.5% of isooctanol polyoxyethylene ether (JFC-E), 0.5% of Sodium Dodecyl Benzene Sulfonate (SDBS) and 0.5% of Dodecyl Trimethyl Ammonium Bromide (DTAB) on the aquatic ecotoxicology of the zebra fish.
The method uses native wild type adult zebra fish (5-6 months old), selects the zebra fish which has no obvious diseases or macroscopic deformity and is not treated by medicaments according to the instruction of nursing and using experimental animals, domesticates the zebra fish under the environmental condition the same as the test condition at least 2 weeks before the experiment, and cleans excrement and food residues every day. After domestication for two weeks, selecting zebra fish juvenile fish with average body length of 3.0 +/-0.2 cm and body weight of 0.21 +/-0.01 g, putting the zebra fish juvenile fish into diluted sewage to be discharged for culture, and observing the activity state of the zebra fish.
As can be seen from FIGS. 7 and 11, the 5mMFBSS-7C oily wastewater in the experimental group 1 and the 5mMFBAI-6C oily wastewater in the experimental group 2 after being treated were cultured with the zebra fish in the control group 1 for three times for 1 day, and the zebra fish were normal in activity, sensitive in response, and free from obvious diseases or deformities. The treated wastewater of the control groups 2-4 showed strong biological toxicity to the zebrafish, and the zebrafish gradually decreased in mobility with time in the early culture period (< 1 hour), was unresponsive, was hemorrhagic at gill area, and all died at 1 hour. Therefore, the imine dynamic covalent bond cleaning agent provided by the invention has low biological toxicity, and the oily wastewater generated after use is easy to treat and is environment-friendly after being discharged.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The cleaning agent is characterized by comprising the following raw materials: primary amine compounds and compounds containing active aldehyde groups;
the primary amine compound is selected from one, two or more of hydroxylamine, aliphatic amine, benzylamine and aromatic amine;
the compound containing the active aldehyde group is selected from a compound of a formula I and/or a compound of a formula II,
wherein, X - Is selected from F - ，Cl - ，Br - ，I - ，SO 3 - ，COO - Or HSO 4 - ，Y + Selected from Na + Or K + 。
2. The cleaning agent according to claim 1, wherein the aromatic amine is selected from substituted or unsubstituted aniline, such as p-anisidine, p-nitroaniline, p-chloroaniline.
Preferably, the benzylamine may be selected from substituted or unsubstituted benzylamines, such as o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, benzylamine, 3,4-dimethylbenzylamine, 2,4-dimethylbenzylamine, 2-methyl-3-chlorobenzylamine, N-methylbenzylamine, or α -methylbenzylamine.
Preferably, the hydroxylamine is selected from 2-hydroxyethylamine polyoxyethylene ether, 3-hydroxypropylamine polyoxyethylene ether, or 4-hydroxybutylamine polyoxyethylene ether.
Preferably, the aliphatic amine may be selected from C3-20 linear or branched aliphatic amines, preferably C3-C20 linear aliphatic amines.
3. The cleaning agent according to claim 1 or 2, wherein the compound of formula I is one, two or three of sodium 2-formylbenzenesulfonate, sodium 3-formylbenzenesulfonate and sodium 4-formylbenzenesulfonate.
Preferably, the compound of formula II may be
For example, 4-formyl N, N, N-trimethyl benzalkonium bromide, 4-formyl N, N, N-trimethyl benzalkonium iodide, 4-formyl N, N, N-trimethyl benzalkonium fluoride and the likeOne, two or three.
4. The cleaning agent according to any one of claims 1 to 3, wherein the cleaning agent comprises a compound having an imine bond-C = N-, wherein the compound having an imine bond-C = N-is formed by a dynamic covalent bond interaction between the primary amine-based compound and a compound having an active aldehyde group.
Preferably, the molar ratio of the primary amine compound to the compound containing the active aldehyde group is 1:3 to 3:1, and more preferably, the molar ratio of the primary amine compound to the compound containing the active aldehyde group is 1:1 to 2:1.
Preferably, the feedstock also comprises water, a lower alcohol and a halide salt;
preferably, the cleaning agent has recyclable performance.
5. The cleaning agent according to any one of claims 1 to 4, wherein when the cleaning agent is alkaline, the pH of the cleaning agent is 7.5 to 14, and the cleaning agent contains a compound having an imine bond-C = N-, the cleaning agent having an ability to clean an oil stain.
Preferably, when the cleaning agent is non-alkaline, the pH value of the cleaning agent is 2-7, the imine bond of the compound with imine bond-C = N-in the cleaning agent is dissociated to obtain a primary amine compound and a compound containing active aldehyde group, so that oil stain can be quickly released, and oil-water separation is realized.
6. A method for preparing the cleaning agent according to any one of claims 1 to 5, which comprises the following steps: and mixing the primary amine compound, the compound containing active aldehyde group, water, lower alcohol and halide salt, and adjusting the pH value of the system to obtain the cleaning agent.
7. The method of claim 6, comprising the steps of:
1) Preparing a primary amine compound aqueous solution;
2) Preparing an aqueous solution containing an active aldehyde compound;
3) Mixing the primary amine compound aqueous solution and the active aldehyde compound aqueous solution, and then adding lower alcohol and halide salt to obtain a dynamic imine bond surfactant solution;
4) And adjusting the pH value of the dynamic imine bond surfactant solution to 7.5-14 to obtain the cleaning agent.
8. The preparation method according to claim 7, wherein the concentration of the primary amine compound aqueous solution in step 1) is 0.1 to 1mol/L, preferably the concentration of the primary amine compound aqueous solution is 0.2 to 0.8mol/L;
preferably, the concentration of the aqueous solution containing the active aldehyde group compound in the step 2) is 1 to 5mol/L, and more preferably, the concentration of the aqueous solution containing the active aldehyde group compound is 2 to 4mol/L.
Preferably, the concentration of the primary amine compound aqueous solution mixed and diluted in the step 3) is 5 to 60mM, and the concentration of the active aldehyde group-containing compound aqueous solution mixed and diluted is 5 to 60mM.
Preferably, the concentration of the lower alcohol in step 3) is 0.5 to 10%.
Preferably, the concentration of the halide salt in step 3) is 1 to 5%.
9. Use of a cleaning agent according to any of claims 1 to 5 for degreasing, for example the treatment of oily sewage.
Preferably, the oil stain comprises a cutting fluid, a machine oil, a lubricating oil, a rust preventative oil, a stretching oil, peanut oil and/or soybean oil.
10. A method for recycling the cleaning agent according to any one of claims 1 to 5, comprising the steps of: the pH value of the cleaner system after oil stain removal is adjusted to 2-7, oil-water separation is carried out, and the pH value of the water phase is adjusted to 7.5-14, so that the cleaning function can be recovered.
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