CN115926893B - 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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- CN115926893B CN115926893B CN202111223155.8A CN202111223155A CN115926893B CN 115926893 B CN115926893 B CN 115926893B CN 202111223155 A CN202111223155 A CN 202111223155A CN 115926893 B CN115926893 B CN 115926893B
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims description 8
- -1 primary amine compounds Chemical class 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 23
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 7
- 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
- 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 abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 106
- 239000000243 solution Substances 0.000 claims description 103
- 239000003921 oil Substances 0.000 claims description 88
- 235000019198 oils Nutrition 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 239000007864 aqueous solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000000926 separation method Methods 0.000 claims description 29
- 239000010687 lubricating oil Substances 0.000 claims description 27
- 230000001105 regulatory effect Effects 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 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 description 10
- 238000000034 method Methods 0.000 claims description 10
- 229960001716 benzalkonium Drugs 0.000 claims description 9
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 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 5
- 238000005238 degreasing Methods 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- CJAAPVQEZPAQNI-UHFFFAOYSA-N (2-methylphenyl)methanamine Chemical group 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 230000009471 action Effects 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 229960002233 benzalkonium bromide Drugs 0.000 claims description 2
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 2
- 150000003939 benzylamines Chemical class 0.000 claims description 2
- 239000002173 cutting fluid Substances 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
- 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
- 230000003449 preventive effect Effects 0.000 claims description 2
- 239000011734 sodium Substances 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 48
- 150000002466 imines Chemical class 0.000 description 29
- 239000007788 liquid Substances 0.000 description 29
- 229910001220 stainless steel Inorganic materials 0.000 description 29
- 239000010935 stainless steel Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 28
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 24
- 238000012360 testing method Methods 0.000 description 22
- 206010057239 Post laminectomy syndrome Diseases 0.000 description 20
- 229920000742 Cotton Polymers 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 17
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 17
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010494 dissociation reaction Methods 0.000 description 12
- 230000005593 dissociations Effects 0.000 description 12
- 241000252212 Danio rerio Species 0.000 description 10
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- 238000003756 stirring Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 7
- 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
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 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
- 238000010521 absorption reaction Methods 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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- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
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- 231100000820 toxicity test Toxicity 0.000 description 2
- SHHKMWMIKILKQW-UHFFFAOYSA-N 2-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=O SHHKMWMIKILKQW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000250967 Branchia Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 231100000215 acute (single dose) toxicity testing Toxicity 0.000 description 1
- 238000011047 acute toxicity test Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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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- 229920003023 plastic Polymers 0.000 description 1
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- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- Detergent Compositions (AREA)
Abstract
The invention belongs to the field of cleaning agents, and in particular relates to a recyclable cleaning agent, which comprises the following raw materials: primary amine compounds and compounds containing reactive aldehyde groups; the primary amine compound is selected from one, two or more of hydroxylamine, fatty amine, benzyl amine, aromatic amine and the like; the compound containing active aldehyde group is selected from a compound of formula I and/or a compound of formula II, wherein X ‑ is selected from F ‑,Cl‑,Br‑,I‑,SO3 ‑,COO‑ or HSO 4 ‑,Y+ is selected from Na + or K +. The cleaning agent provided by the invention has high use recyclability and 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
Industrial cleaning belongs to the technical field of multidisciplinary fusion, and the effective industrial cleaning not only can remove industrial dirt and improve the appearance quality of industrial products, but also can 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 wide industrial fields such as the fields of automobiles, trains, ships, aviation, household appliances, optics, electronics, hardware, electroplating and the like. Industrial cleaning is essentially required by using industrial cleaning agents, which play an important role in cleaning. Current industrial cleaners have gradually transitioned from organic solvent cleaners, semi-organic solvent cleaners, to fully aqueous based cleaners. The water-based cleaning agent is prepared by taking water as a solvent, taking a surfactant as a main component, and adding a defoaming agent, an antirust agent or other additives. Water-based cleaners have been attracting attention because of their water-to-oil replacement, energy conservation, environmental friendliness, safety in use, and low cost.
The surfactant is the most main component of the water-based cleaning agent, and the commonly used surfactants at present 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 diethanolamide (6501, 6502 and 6503) and the like. By regulating the compounding proportion of the surfactants, a plurality of efficient water-based cleaning agent formulas can be obtained, and the water-based cleaning agent formulas have the function of cleaning dirt on the surfaces of various metal solids. Although the cleaning effect of water-based cleaning agents is continuously improved, industrial cleaning is also faced with a major problem of recycling the cleaning agents, which has not been solved so far. The existing cleaning agent is difficult to recycle, and is usually only needed once, and when the cleaning agent is used again, the cleaning efficiency can be greatly reduced or the cleaning effect is not achieved, so that the cleaning agent is required to be continuously supplemented to maintain high-efficiency cleaning. This leads to a considerable 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 agents can pollute the environment and is unfavorable to the ecological environment and life health. The emulsion formed by the cleaning agent and the greasy dirt is relatively stable, the purification treatment of the wastewater is very difficult, and the cost required for reaching the wastewater treatment emission standard is extremely high.
Therefore, development of efficient recyclable cleaning agents is needed, the service life of the cleaning agents 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 technical problems, the invention aims to provide a cleaning agent, a preparation method and application thereof, and the cleaning agent has high use recyclability and service life.
The invention provides a cleaning agent, which comprises the following raw materials: primary amine compounds and compounds containing reactive aldehyde groups;
the primary amine compound is selected from one, two or more of hydroxylamine, fatty amine, benzyl amine, aromatic amine and the like;
The compound containing active aldehyde group is selected from the compound of formula I and/or the compound of formula II,
Wherein X - is selected from F -,Cl-,Br-,I-,SO3 -,COO- or HSO 4 -,Y+ is 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 present invention, the benzylamine may be selected from substituted or unsubstituted benzylamines, such as o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, benzylamine, 3, 4-dimethylbenzylamine, 2-methyl-3-chlorobenzylamine, N-methylbenzylamine, or α -methylbenzylamine.
According to an embodiment of the present 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 fatty amine may be selected from C3-20 linear or branched fatty amines, preferably C3-C20 linear fatty amines, preferably the fatty amine comprises one, two or more selected from C6-C18 linear fatty amines, such as hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine.
According to embodiments of the present 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 beFor example, one, two or three of 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 like.
According to an embodiment of the present invention, the cleaning agent contains a compound having an imine bond-c=n-formed by dynamic covalent bonding between the primary amine compound and a compound containing an active aldehyde group.
According to an embodiment of the invention, the molar ratio of the primary amine compound to the active aldehyde group containing compound is from 1:3 to 3:1, preferably the molar ratio of the primary amine compound to the active aldehyde group containing compound is from 1:1 to 2:1, for example 1:1.
According to an embodiment of the invention, the feedstock further comprises water, a lower alcohol, preferably at least one of methanol, ethanol, propanol, butanol, and a halide salt, preferably NaBr, KCl or NaCl, for example the feedstock further comprises water, ethanol and NaBr.
According to an embodiment of the invention, the cleaning agent is prepared from the above raw materials.
According to an embodiment of the invention, the cleaning agent has a recyclable property.
When the cleaning agent is alkaline, the pH of the cleaning agent is 7.5 to 14, preferably the pH of the cleaning agent is 8 to 11 or 9 to 10, and exemplified by 7.5, 9.45, 9.5, 10.3, 10.6, 11, 11.3, 11.5, and the cleaning agent contains a compound having an imine bond-c=n-, and the cleaning agent has an ability to clean greasy dirt. At this time, the cleaning agent is milky white. Preferably, the mass fraction of the cleaning agent is 0.3-1.0%, for example 0.4-0.8%, exemplary 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, and exemplified as 2, 2.5.
When the cleaning agent is non-alkaline, the imine bond of the compound with imine bond-C=N-in the cleaning agent is dissociated to obtain primary amine compound and compound containing active aldehyde group, so that oil stain can be quickly released, and oil-water separation can be 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 the active aldehyde group, water, lower alcohol and halogenated 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 group compound;
3) Mixing the primary amine compound aqueous solution and the active aldehyde compound aqueous solution, and then adding lower alcohol and halogenated salt to obtain a dynamic imine bond surfactant solution;
4) And regulating 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 primary amine compound solution in step 1) is 0.1 to 1mol/L, preferably the concentration of the aqueous primary amine compound solution is 0.2 to 0.8mol/L, more preferably the concentration of the aqueous primary amine compound solution is 0.3 to 0.6mol/L, still more preferably the concentration of the aqueous primary amine compound solution is 0.4 to 0.5mol/L.
Preferably, the aqueous primary amine compound 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 in step 2) is 1 to 5mol/L, preferably the concentration of the aqueous solution containing an active aldehyde group 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 aqueous solution of the primary amine compound after mixing and dilution in step 3) is 5 to 60mM, and the concentration of the aqueous solution of the compound containing an active aldehyde group after mixing and dilution is 5 to 60mM.
According to an embodiment of the invention, the concentration of the lower alcohol in step 3) is 0.5-10%, preferably the concentration of the lower alcohol is 1-8%, more preferably the concentration of the lower alcohol is 2-6%, further preferably the concentration of the lower alcohol is 3-5%, for example 2%, 3%, 5%, 6%, 7%, 8%.
According to an embodiment of the invention, the concentration of the halide salt in step 3) is 1-5%, preferably the concentration of the halide salt is 2-4%, e.g. 1.5%, 2%, 3.5%.
According to an embodiment of the invention, the temperature at the time of mixing in step 3) is 0 to 40 ℃, e.g. 10 to 30 ℃, more preferably 20 to 25 ℃, e.g. 10 ℃,20 ℃, 25 ℃, 30 ℃.
Preferably, step 4) is followed by a step of adjusting the temperature of the system to 0-40 ℃.
The invention also provides an application of the cleaning agent in removing greasy dirt, such as treating oily sewage.
According to an embodiment of the invention, the greasy dirt comprises cutting fluid, machine oil, lubricating oil, rust preventive oil, drawing oil, peanut oil and/or soybean oil.
The invention also provides a method for removing oil stains by adopting 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 of 7.5-14 and a temperature of 0-40 ℃ when in use.
According to an embodiment of the invention, the contacting includes ultrasonic, soaking, spraying and other contacting modes.
According to an embodiment of the invention, the workpiece comprises plastic, rubber, metal, glass, silicon wafer, cotton cloth and/or circuit board parts.
The invention also provides a method for recycling the cleaning agent, which comprises the following steps: the pH value of the degreasing cleaning agent system 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, thus the cleaning function can be recovered.
The oil and water phases may be separated by suction drainage and/or oil absorption by means of oil absorption cotton. For example, the oil-water separation time 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:
The structure of the benzylamine is as follows:
aromatic amine means an amine having one aromatic substituent, i.e., -NH 2, -NH, or a nitrogen-containing group attached to one aromatic hydrocarbon; aromatic hydrocarbons generally contain one or more benzene rings in their structure, i.e., the nitrogen atom is directly linked to a carbon atom of the benzene ring by a chemical bond.
Advantageous effects
The cleaning agent comprises primary amine compounds and active aldehyde group compounds, wherein the primary amine compounds and the active aldehyde group compounds form imine bond (R-C=N-R') compounds in aqueous solution through dynamic covalent bond action, the imine bond compounds can form aggregate structures under the condition of pH value of 7.5-14, oil stains on the surface of an object are wrapped, the wrapped oil stains are transferred into a cleaning system, the aggregate releases the oil stains and forms an oil-water separation system under the condition of pH value of 2-7, the oil stains are separated and regenerated into the cleaning system, the cleaning capability 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 the emission to the ecological environment can be reduced.
Drawings
FIG. 1 is an external view showing the FBSS-7C solution of example 2 and the solutions of comparative examples 1 to 4 of the present invention;
FIG. 2 is a microscopic image of the solution of FBSS-7C in example 2 of the present invention under a microscope;
FIG. 3 is a graph showing a regenerating solution and a cleaning effect of 10 cycles of the FBSS-7C solution for cleaning a stainless steel sheet in test example 1 according to the present invention;
FIG. 4 is a graph showing the cleaning effect and the emulsion treatment before and after the treatment of the control groups 1 to 4 in the test example 1 of the present invention;
FIG. 5 is a graph of dynamic surface tension contrast for the solutions of test group 1FBSS-7C and control groups 1-4 in test example 2 of the present invention;
FIG. 6 is a graph showing the comparison of the oil-water interfacial tension of the test group FBSS-7C solution and the control group 1-4 solutions in test example 3;
FIG. 7 is a graph showing the toxicity test results of the test group FBSS-7C solution of test example 4 and the wastewater discharged from the control groups 1-4 diluted 100 times to zebra fish;
FIG. 8 is an external view and a microscopic view under a microscope of the FBAI-6C solution in example 6;
FIG. 9 is a graph showing the effect of 10 cycles of the cleaning solution of test group FBAI-6C on the regenerating solution for cleaning stainless steel sheet in test example 1;
FIG. 10 is an oil-water interface Zhang Litu of the test group FBAI-6C cleaning solution;
FIG. 11 is a graph showing the toxicity test results of the test group FBAI-6C in test example 4, which was 100-fold diluted with the wastewater discharged from the test group.
Detailed Description
The cleaning agent of the present invention, and the preparation method and application thereof will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Preparing 10mM hexylamine solution and 10mM sodium 2-formylbenzenesulfonate aqueous solution, mixing the above two aqueous solutions at room temperature according to a volume ratio of 1:3, adding 5% ethanol and 3% NaBr, adjusting pH to 10.6, and stirring at low speed for 10min to obtain dynamic imine-type cleaning agent solution FBSS-6C (hereinafter referred to as cleaning agent).
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.5 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, when the oil dirt is less, using the oil-absorbing cotton to absorb the oil, and after the oil dirt is removed, adjusting the pH value to 10.6 to enable the dynamic imine cleaning agent to be formed again, so that the cleaning function is recovered.
Example 2
Preparing a 10mM heptylamine solution and a 10mM sodium 2-formylbenzenesulfonate aqueous solution, mixing the two aqueous solutions according to a volume ratio of 1:2 at room temperature, adding 5% ethanol and 3% NaBr, adjusting the pH to 7.5, and stirring at a low speed for 10min to obtain a dynamic imine-type cleaning agent solution FBSS-7C.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.0 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH is adjusted to 7.5, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 3
Preparing 10mM octylamine solution and 10mM sodium 2-formylbenzenesulfonate aqueous solution, mixing the two aqueous solutions at room temperature according to a volume ratio of 1:1, adding 5% ethanol and 3% NaBr, adjusting pH to 7.5, and stirring at low speed for 10min to obtain dynamic imine-type cleaning agent solution FBSS-8C.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.5 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH is adjusted to 7.5, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 4
1.5MM decylamine solution and 1.5mM 2-formylbenzenesulfonate aqueous solution are prepared, the two aqueous solutions are mixed according to the volume ratio of 3:1 at room temperature, 5% ethanol and 3% NaBr are added, the pH is regulated to 11.3, and the stirring is carried out at a low speed for 10min, so that the dynamic imine-type cleaning agent solution FBSS-10C is obtained.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH value of the cleaning liquid is regulated to 1.5 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH value is adjusted to 11.3, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 5
1.5MM of dodecylamine solution and 1.5mM of 2-formylsodium benzenesulfonate aqueous solution are prepared, the two aqueous solutions are mixed according to the volume ratio of 1:1 at room temperature, 5% of ethanol and 3% of NaBr are added, the pH is regulated to 11, and the mixture is stirred at a low speed for 10min, so that the dynamic imine-type cleaning agent solution FBSS-12C is obtained.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.5 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt 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 benzalkonium 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, regulating the pH value to 10.6, and stirring at a low speed for 10min to obtain a dynamic imine type cleaning agent solution FBAI-6C.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.0 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH is adjusted to 10.6, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 7
Preparing a 10mM heptylamine solution and a 10mM 4-formyl N, N, N-trimethyl benzalkonium iodide aqueous solution, mixing the two aqueous solutions according to a volume ratio of 1:1 at room temperature, adding 8% of ethanol and 2% of NaBr, regulating the pH value to 11.5, and stirring at a low speed for 10min to obtain a dynamic imine-type cleaning agent solution FBAI-7C.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.0 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH value is adjusted to 11.5, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 8
Preparing 10mM octylamine solution and 10mM 4-formyl N, N, N-trimethyl benzalkonium 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, regulating the pH value to 9.5, and stirring at a low speed for 10min to obtain a dynamic imine type cleaning agent solution FBAI-8C.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.5 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH value is adjusted to 9.5, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 9
2MM decylamine solution and 2mM 4-formyl N, N, N-trimethyl benzalkonium iodide aqueous solution are prepared, the two aqueous solutions are mixed according to the volume ratio of 1:1 at room temperature, 8% of ethanol and 2% of NaBr are added, the pH is regulated to 10.3, and stirring is carried out for 10min at a low speed, so that a dynamic imine type cleaning agent solution FBAI-10C is obtained.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH value of the cleaning liquid is regulated to 2 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of oil stains and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH is adjusted to 10.3, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Example 10
Preparing a 0.5mM dodecylamine solution and a 0.5mM 4-formylN, N, N-trimethyl benzalkonium iodide aqueous solution, mixing the two aqueous solutions according to a volume ratio of 1:1 at room temperature, adding 8% of ethanol and 2% of NaBr, regulating the pH value to 9.45, and stirring at a low speed for 10min to obtain a dynamic imine type cleaning agent solution FBAI-12C.
Placing the cleaning agent solution into an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH value of the cleaning liquid is adjusted to 2 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of oil stains and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH value is adjusted to 9.45, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered.
Comparative example 1: preparing tertiary water with pH of 12, placing the tertiary water into an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
Comparative example 2: preparing 0.5% isooctyl alcohol polyoxyethylene ether solution (JFC-E), placing the solution in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and performing ultrasonic cleaning for 10min.
Comparative example 3: preparing 0.5% sodium dodecyl benzene sulfonate solution (SDBS), placing the sodium dodecyl benzene sulfonate solution in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and performing ultrasonic cleaning for 10min.
Comparative example 4: preparing 0.5% dodecyl trimethyl ammonium bromide solution (DTAB), placing the solution in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
As shown in FIG. 1, which is a physical diagram of the solution of FBSS-7C of example 2 and the solutions prepared in comparative examples 1-4, the solution of FBSS-7C of example 2 was milky white, indicating that larger aggregates were formed, and the solutions of comparative examples 1-4 were colorless transparent liquids, indicating that no aggregates were formed or that the aggregate size was small.
As can be seen from fig. 2 and 8, the solutions of example 2 and example 6 formed spherical aggregates with larger sizes, and the solutions were rich in liquid phase, thus resulting in cloudiness of the solutions, and the spherical aggregates were milky white in size, with the size of the spherical aggregates ranging from 1 to 10 micrometers.
Test example 1: efficient recyclable cleaning agent cleaning effect and oil-water separation effect test
Experiment group 1: example 2 provides a dynamic imine-type cleaner solution FBSS-7C.
Placing the FBSS-7C solution into an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min. After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.0 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH is adjusted to 7.5, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered. The cleaning effect and the oil-water separation effect in the process of 10 cycles were tested.
Experiment group 2: the dynamic imine-type detergent solution provided in example 6 is FBAI-6C.
Placing the cleaning liquid in an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min.
After the cleaning is finished, the pH of the cleaning liquid is regulated to 2.0 to trigger the dissociation of the dynamic imine cleaning agent, thereby leading to the rapid release of greasy dirt and realizing the oil-water separation in a short time. Sucking oil dirt floating on the water surface, and when the oil dirt is less, using the oil-absorbing cotton to absorb oil. After the greasy dirt is removed, the pH is adjusted to 10.6, so that the dynamic imine cleaning agent is formed again, and the cleaning function is recovered. The cleaning effect and the oil-water separation effect in the process of 10 cycles were tested.
Control group 1: the three times of water with the pH of 12 prepared in comparative example 1 is placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricating oil is placed, ultrasonic power is adjusted to 100W, the temperature is set to 25 ℃, and ultrasonic cleaning is performed for 10min. And (3) adjusting the pH value of the solution after cleaning to 2, if oil stains float upwards, removing the oil stains, adjusting the pH value to the pH value before cleaning the solution, repeatedly cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
Control group 2: the 0.5% isooctyl alcohol polyoxyethylene ether solution (JFC-E) prepared in comparative example 2 was placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricating oil was placed, the ultrasonic power was adjusted to 100W, the temperature was set to 25 ℃, and ultrasonic cleaning was performed for 10min. And (3) adjusting the pH value of the solution after cleaning to 2, if oil stains float upwards, removing the oil stains, adjusting the pH value to the pH value before cleaning the solution, repeatedly cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
Control group 3: the 0.5% sodium dodecyl benzene sulfonate solution (SDBS) prepared in comparative example 3 was placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricating oil was placed, the ultrasonic power was adjusted to 100W, the temperature was set to 25℃and ultrasonic cleaning was performed for 10min. And (3) adjusting the pH value of the solution after cleaning to 2, if oil stains float upwards, removing the oil stains, adjusting the pH value to the pH value before cleaning the solution, repeatedly cleaning for 3 times, and observing the cleaning effect and the oil-water separation effect.
Control group 4: comparative example 4 was prepared with 0.5% dodecyltrimethylammonium bromide solution (DTAB), placed in an ultrasonic cleaning tank, placed in a stainless steel sheet coated with mechanical lubricating oil, and ultrasonically cleaned for 10min with ultrasonic power adjusted to 100W and temperature set at 25 ℃. And (3) adjusting the pH value of the solution after cleaning to 2, if oil stains float upwards, removing the oil stains, adjusting the pH value to the pH value before cleaning the solution, repeatedly 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 pH 7.5 and the FBAI-6C solution at pH 10.6 have excellent cleaning ability, and can be used for stripping and emulsifying oil stains on stainless steel sheets to form emulsion, and can be demulsified to realize oil-water separation at pH2.0, and as can be seen from fig. 3 and 9, the lower solution after oil-water separation is clear, and the upper layer is a floating oil layer.
The stainless steel sheet with greasy dirt is irradiated by ultraviolet light, the greasy dirt part can emit bright purple, and the greasy dirt part is black. As can be seen from the figures 3 and 9, the stainless steel sheet cleaned in the 10-time circulation process is clean, black and has no bright purple, so that the efficient and environment-friendly recyclable cleaning agent FBSS-7C, FBAI-6C can be recycled for at least 10 times.
As can be seen from fig. 4, after the first washing with water having a pH of 12, 0.5% isooctyl alcohol polyoxyethylene ether solution (JFC-E), 0.5% sodium dodecyl benzene sulfonate solution (SDBS), and 0.5% dodecyltrimethylammonium bromide solution (DTAB), the surface was more greasy, and the washing effect gradually decreased with the increase of the number of cycles. The cleaned oily wastewater is still stable after standing for three days, and can not be demulsified after the pH is regulated to be acidic 2 or alkaline 11, so that the oily wastewater is difficult to treat.
Test example 2: dynamic surface tension test of high-efficiency recyclable cleaning agent
Experimental group: 5mMFBSS-7C solution (cleaning solution of example 2), pH7.5;
control group 1: comparative example 1 provides a tertiary water of pH 12;
Control group 2: comparative example 2 provided a 0.5% solution of isooctanol polyoxyethylene ether (JFC-E);
Control group 3: comparative example 3 provided a 0.5% sodium dodecyl benzene sulfonate solution (SDBS);
Control group 4: comparative example 4 provided a 0.5% solution of dodecyltrimethylammonium bromide (DTAB).
The dynamic surface tension of the above solution was measured by a KluyBP 100 dynamic surface tension meter using the maximum bubble pressure method.
The sample Chi Chushi was placed 70mL of surfactant solution, the diameter of the capillary for bubble generation was 0.210mm, the measured surface lifetime was 8.0 ms-10.0 s, and the experimental measurement temperature 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 far lower than that of the control groups 1-4.
Test example 3: oil-water interfacial tension test for efficient and recyclable cleaning agent
Experiment group 1:5mMFBSS-7C solution (cleaning solution of example 2), pH7.5;
experiment group 2:5mMFBAI-6C solution (cleaning solution of example 6), pH10.6;
Control group 1: triple water at pH 12;
Control group 2:0.5% isooctanol polyoxyethylene ether solution (JFC-E);
Control group 3:0.5% sodium dodecyl benzene sulfonate solution (SDBS);
Control group 4:0.5% dodecyl trimethyl ammonium bromide solution (DTAB).
The oil-water interfacial tension of the above solution was measured by a TX500C ultra-low interfacial tension meter, the external phase was the above solution, the internal phase was a mechanical lubricating oil, the rotational speed was 8000rpm, and the measurement temperature in all experiments was 25.0±0.5 ℃.
As can be seen from FIG. 6, only the oil droplets in the 5mM FBSS-7C solution in the experimental group were pulled up into a cylindrical shape, the oil-water interfacial tension of the corresponding solution in the experimental group 1 was 4.35mN/m, and the oil-water interfacial tension of the corresponding solution in the experimental group 2 was 9.78mM/m, as shown in FIG. 10.
The oil drops in control groups 1-4 stuck on the wall and could not be pulled up, indicating poor oil-water interfacial activity, which may be the main reason why the cleaning ability of the FBSS-7C solution was better than that of the control group.
Test example 4: high-efficiency recyclable detergent wastewater biotoxicity determination
Experiment group 1: placing 5mMFBSS-7C solution with pH of 7.5 into an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min. After the cleaning is finished, the pH value of the cleaning liquid is regulated to 2.0 to trigger oil-water separation, oil stains floating on the water surface are sucked, and when the oil stains are less, the oil absorbing cotton is used for absorbing oil. After removal of the oil stains, the pH was adjusted to 7.0 and tested for biotoxicity.
Experiment group 2: the conditions were the same as in experimental group 1 except that the FBSS-7C solution was replaced with FBAI-6C solution at pH 10.6 as provided in example 6.
Control group 1: triple Water at pH7.0 (not involved)
Control group 2: placing 0.5% isooctyl alcohol polyoxyethylene ether solution (JFC-E) into an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting the ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min. After the cleaning is finished, the pH value of the cleaning liquid is regulated to 2.5, oil floating on the water surface is sucked, and when the oil is less, the oil absorbing cotton is used for absorbing oil. After removal of the oil stains, the pH was adjusted to 7.0 and tested for biotoxicity.
Control group 3: the 0.5% sodium dodecyl benzene sulfonate solution (SDBS) is placed in an ultrasonic cleaning tank, a stainless steel sheet coated with mechanical lubricating oil is placed in the ultrasonic cleaning tank, the ultrasonic power is adjusted to 100W, the temperature is set to 25 ℃, and the ultrasonic cleaning is carried out for 10min. After the cleaning is finished, the pH value of the cleaning liquid is regulated to 2.5, oil floating on the water surface is sucked, and when the oil is less, the oil absorbing cotton is used for absorbing oil. After removal of the oil stains, the pH was adjusted to 7.0 and tested for biotoxicity.
Control group 4: placing 0.5% dodecyl trimethyl ammonium bromide solution (DTAB) into an ultrasonic cleaning tank, placing a stainless steel sheet coated with mechanical lubricating oil, adjusting ultrasonic power to 100W, setting the temperature to 25 ℃, and carrying out ultrasonic cleaning for 10min. After the cleaning is finished, the pH value of the cleaning liquid is regulated to 2.5, oil floating on the water surface is sucked, and when the oil is less, the oil absorbing cotton is used for absorbing oil. After removal of the oil stains, the pH was adjusted to 7.0 and tested for biotoxicity.
The invention uses an acute toxicity test to respectively study the aquatic ecotoxicology effects of 5mMFBSS-7C, 0.5% isooctyl alcohol polyoxyethylene ether (JFC-E), 0.5% Sodium Dodecyl Benzene Sulfonate (SDBS) and 0.5% Dodecyl Trimethyl Ammonium Bromide (DTAB) after oil stain cleaning on the zebra fish.
According to the invention, native wild type male adult zebra fish (5-6 months old) is used, zebra fish without obvious diseases or macroscopic deformity and without drug treatment are selected according to the instructions for nursing and using experimental animals, and the zebra fish is subjected to domestication under the same environmental conditions as the test conditions at least 2 weeks before the experiment, so that feces and food residues are cleaned every day. After two weeks of domestication, the juvenile zebra fish with the average body length of 3.0+/-0.2 cm and the body weight of 0.21+/-0.01 g is selected and put into the diluted sewage to be discharged for cultivation, and the activity state of the zebra fish is observed.
As can be seen from FIGS. 7 and 11, the oily wastewater of 5mMFBSS-7C in the experimental group 1, the oily wastewater of 5mMFBAI-6C in the experimental group 2 and the zebra fish in the water of the control group 1 are cultured for 1 day after being treated, and the activity is normal, the reaction is sensitive, and no obvious diseases or deformity are caused. The treated wastewater of control groups 2-4 showed strong biotoxicity to zebra fish, and the activity of zebra fish gradually decreased with time at the initial stage of culture (< 1 hour), and the fish branchia bleed and all died at 1 hour. Therefore, the imine type dynamic covalent bond cleaning agent provided by the invention has low biological toxicity, and oily wastewater generated after use is easy to treat and is environment-friendly after discharge.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. The cleaning agent is characterized by comprising the following raw materials: primary amine compounds and compounds containing reactive aldehyde groups; the raw materials also comprise water, lower alcohol and halogenated salt; the molar ratio of the primary amine compound to the compound containing the active aldehyde group is 1:3 to 3:1;
the primary amine compound is selected from one, two or more of hydroxylamine, fatty amine, benzyl amine and aromatic amine;
The compound containing an active aldehyde group is selected from the group consisting of compounds of formula I and/or compounds of formula II,
Wherein X - is selected from F -,Cl-,Br-,I-,COO- or HSO 4 -,Y+ is selected from Na + or K +;
The pH value of the cleaning agent is 7.5-14, the cleaning agent contains a compound with imine bond-C=N-and has the capability of cleaning greasy dirt, and the compound with imine bond-C=N-is formed by the primary amine compound and a compound containing an active aldehyde group through dynamic covalent bond action;
the preparation method of the cleaning agent comprises the following steps:
1) Preparing a primary amine compound aqueous solution;
2) Preparing a compound aqueous solution containing active aldehyde groups;
3) Mixing the primary amine compound aqueous solution and the compound aqueous solution containing active aldehyde groups, and then adding lower alcohol and halide salt to obtain a dynamic imine bond surfactant solution;
4) Regulating the pH value of the dynamic imine bond surfactant solution to 7.5-14 to obtain the cleaning agent;
In the step 3), the concentration of the diluted primary amine compound aqueous solution is 5-60 mM, and the concentration of the diluted compound aqueous solution containing active aldehyde group is 5-60 mM.
2. The cleaning agent according to claim 1, wherein the aromatic amine is selected from substituted or unsubstituted anilines.
3. The cleaning agent according to claim 2, wherein the aromatic amine is selected from the group consisting of p-methoxyaniline, p-nitroaniline and p-chloroaniline.
4. The cleaning agent according to claim 1, wherein the benzylamine is selected from substituted or unsubstituted benzylamines.
5. The cleaning agent according to claim 4, wherein the benzylamine is selected from o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, benzylamine, 3, 4-dimethylbenzylamine, 2-methyl-3-chlorobenzylamine, N-methylbenzylamine and α -methylbenzylamine.
6. The cleaning agent according to any one of claims 1 to 5, wherein the hydroxylamine is selected from 2-hydroxyethylamine polyoxyethylene ether, 3-hydroxypropylamine polyoxyethylene ether and 4-hydroxybutylamine polyoxyethylene ether.
7. The cleaning agent according to any one of claims 1 to 5, wherein the fatty amine is selected from a C3-20 linear or branched fatty amine.
8. The cleaning agent according to claim 7, wherein the aliphatic amine is a C3 to C20 linear aliphatic amine.
9. The cleaning agent according to any one of claims 1 to 5, wherein the compound of formula I is one, two or three of sodium 2-formylbenzenesulfonate, sodium 3-formylbenzenesulfonate and sodium 4-formylbenzenesulfonate.
10. The cleaning agent as claimed in any one of claims 1 to 5, wherein the compound of formula II is
11. The cleaning agent according to claim 10, wherein the compound of formula II is one, two or three of 4-formyl N, N-trimethyl benzalkonium bromide, 4-formyl N, N-trimethyl benzalkonium iodide and 4-formyl N, N-trimethyl benzalkonium fluoride.
12. The cleaning agent according to any one of claims 1 to 5, wherein the molar ratio of the primary amine compound to the active aldehyde group-containing compound is 1:1 to 2:1.
13. The cleaning agent according to any one of claims 1 to 5, wherein the cleaning agent has a recyclable property, and when the pH value of the cleaning agent system after degreasing is 2 to 7, the imine bond of the compound having imine bond-c=n-in the cleaning agent is dissociated to obtain a primary amine compound and a compound having an active aldehyde group, which can rapidly release the greasy dirt and realize oil-water separation.
14. The cleaning agent according to any one of claims 1 to 5, wherein the concentration of the lower alcohol in step 3) is 0.5 to 10%.
15. The cleaning agent according to claim 7, wherein the concentration of the halide salt in the step 3) is 1 to 5%.
16. Use of a cleaning agent according to any one of claims 1 to 15 for degreasing.
17. The use according to claim 16, wherein the use comprises treatment of oily sewage.
18. Use according to claim 16 or 17, wherein the greasy dirt comprises cutting fluid, mechanical oil, lubricating oil, rust preventive oil, drawing oil, peanut oil and/or soybean oil.
19. A method of recycling the cleaning agent as claimed in any one of claims 1 to 15, comprising the steps of: the pH value of the degreasing cleaning agent system 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, thus the cleaning function can be recovered.
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| CN110257839A (en) * | 2019-07-23 | 2019-09-20 | 佛山市骏虎表面技术有限公司 | A kind of acid deoiling agent and its application |
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| DE69606011D1 (en) * | 1995-05-08 | 2000-02-10 | Nalco Chemical Co | COPOLYMERS OF DIALLYLDIMETHYLAMMONIUM CHLORIDE AND VINYLTRIALKOXYSILANE AND THEIR USE IN THE TREATMENT OF WASTEWATER |
| EP0971024A1 (en) * | 1998-07-10 | 2000-01-12 | The Procter & Gamble Company | Laundry and cleaning compositions |
| US20040147426A1 (en) * | 1998-07-10 | 2004-07-29 | The Procter & Gamble Company | Laundry and cleaning compositions |
| EP0971027A1 (en) * | 1998-07-10 | 2000-01-12 | The Procter & Gamble Company | Amine reaction compounds comprising one or more active ingredient |
| US20100098650A1 (en) * | 2007-01-30 | 2010-04-22 | Andreas Herrmann | Controlled release of active aldehydes and ketones from equilibrated dynamic mixtures |
| CN111662208B (en) * | 2019-03-06 | 2021-09-17 | 中国科学院化学研究所 | Trimeric quaternary ammonium salt surfactant constructed by dynamic imine bonds, and preparation method and application thereof |
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| CN110257839A (en) * | 2019-07-23 | 2019-09-20 | 佛山市骏虎表面技术有限公司 | A kind of acid deoiling agent and its application |
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| 亚胺表面活性剂判别和活性预测;曹俊;张革新;崔正刚;;计算机与应用化学;20130628(第06期);660 * |
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