CN115678659A - Cyclic application method of water-based product for metal and water-based product combination for metal - Google Patents
Cyclic application method of water-based product for metal and water-based product combination for metal Download PDFInfo
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- CN115678659A CN115678659A CN202211295761.5A CN202211295761A CN115678659A CN 115678659 A CN115678659 A CN 115678659A CN 202211295761 A CN202211295761 A CN 202211295761A CN 115678659 A CN115678659 A CN 115678659A
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- cutting fluid
- acid
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The invention discloses a recycling application method of a water-based product for metal and a water-based product combination for metal. The method comprises the following steps: in the liquid changing period of the water-based cutting fluid working solution, the waste liquid of the water-based metal cleaner working solution and/or the waste liquid of the water-based antirust fluid working solution is used as a replenishing solution and is injected into a water-based cutting fluid tank for metal processing; the chelating agent, the alkaline agent, the fatty acid and the corrosion inhibitor which are respectively contained in the water-based metal cleaner, the water-based antirust liquid and the water-based cutting fluid for preparing the corresponding working fluid are respectively the same components; the water-based cutting fluid optionally contains a first surfactant which cannot be a nonionic surfactant but is an anionic surfactant; the second surfactant contained in the water-based metal cleaner is a low-foaming surfactant; the pH values of the water-based metal cleaner working solution and the water-based antirust working solution are both below 10. The method provided by the invention meets the use requirement of the cutting fluid, reduces the discharge of waste fluid, and realizes energy conservation and emission reduction.
Description
Technical Field
The invention belongs to the technical field of metal protection, and particularly relates to a cyclic application method of a water-based product for metal and a water-based product combination for metal.
Background
In the production process of the industries of automobiles, machining, hardware and the like, chemicals such as water-based cutting fluid, water-based metal cleaner, water-based antirust fluid and the like are generally used. The chemicals can provide lubricating performance in processing, cleanliness of metal parts and components, and metal rust prevention and protection in the process of transferring among working procedures.
In the actual use process, a large amount of waste liquid is generated in the water-based products, so that the trouble of increasing the waste liquid treatment cost of customers is caused. With the increasing requirements of the state on environmental protection policies, enterprises are under greater pressure to treat waste liquid, and the waste liquid treatment pressure is already emerging in some areas. The Jiangzhe area limits the sewage discharge of factories and requires quantitative discharge every month; wastewater treatment costs in coastal areas have also risen by nearly 3 times. The generated waste liquid causes great trouble for customers.
At present, automobile main engine plants usually use centralized liquid tanks for management, the used water-based cutting fluid realizes a fluid change period of 2-3 years, but the water-based metal cleaning agent and the water-based antirust fluid are still in the fluid change period stage of about 0.5-2 months. The water-based metal cleaning agent and the water-based antirust liquid have short liquid changing period, and can cause great trouble for the treatment of customer waste liquid.
Disclosure of Invention
The invention aims to provide a recycling application method of a water-based product for metal and a water-based product combination, which are used for recycling waste liquid of a water-based metal cleaner working solution and/or waste liquid of a water-based antirust solution working solution into a water-based cutting fluid working solution, so that the waste liquid discharge of customers is reduced under the condition that the mixed water-based cutting fluid working solution meets the use requirements of the water-based cutting fluid working solution, the operation cost is reduced for customers, and energy conservation and emission reduction are realized.
In order to achieve the above object, an aspect of the present invention provides a method for recycling an aqueous metal product, the method comprising: in the fluid changing period of the water-based cutting fluid working fluid, the waste liquid of the water-based metal cleaner working fluid and/or the waste liquid of the water-based antirust fluid working fluid are used as a replenishing fluid and injected into a water-based cutting fluid tank for metal processing;
wherein, the water-based metal cleaning agent, the water-based antirust liquid and the water-based cutting fluid which are used for preparing the corresponding working fluid respectively contain the chelating agent, the alkaline agent, the fatty acid and the corrosion inhibitor which are all corresponding to the same components;
the aqueous cutting fluid optionally contains a first surfactant, which cannot be a nonionic surfactant, and which is an anionic surfactant;
the water-based metal cleaner contains a second surfactant, and the second surfactant is a low-foaming surfactant;
the pH values of the water-based metal cleaner working solution and the water-based antirust working solution are both below 10.
According to the present invention, preferably, the fluid change cycle of the water-based cutting fluid working fluid is 2 to 3 years;
the waste liquid of the working solution of the water-based metal cleaner is the working solution exceeding the solution change period of the working solution of the water-based metal cleaner;
the waste liquid of the water-based antirust liquid working solution is the working solution exceeding the liquid change period of the water-based antirust liquid working solution.
According to the present invention, preferably, when the generated waste liquid of the water-based metal cleaner working fluid and/or the waste liquid of the water-based rust preventive working fluid cannot be entirely filled into the water-based cutting fluid bath at a time as a replenishment liquid, the remaining waste liquid of the water-based metal cleaner working fluid and/or the waste liquid of the water-based rust preventive working fluid is temporarily stored and is filled into the water-based cutting fluid bath as a replenishment liquid when next replenishment is performed.
In the metal processing application, the commercially available aqueous metal product is usually diluted with water and then applied to the metal processing procedure, so the water-based metal cleaner working solution, the water-based antirust working solution and the water-based cutting fluid working solution are respectively diluted with water according to a certain proportion.
When the water-based cutting fluid working fluid is used for metal processing, certain loss can be generated, so that fluid needs to be replenished into a water-based cutting fluid tank every day or for a certain time, and the water level in the water-based cutting fluid tank is ensured not to be lower than the lowest operating water level line; fluid replacement is usually performed using water as a make-up fluid; the recycling application method can take the generated waste liquid of the working solution of the water-based metal cleaner and/or the waste liquid of the working solution of the water-based antirust liquid as a supplementary solution for fluid replacement; when the waste liquid is generated, the waste liquid can be injected into the water-based cutting liquid tank to replace water for liquid supplement when liquid supplement is needed, if all the waste liquid cannot be injected into the water-based cutting liquid tank at the next time, the waste liquid can be temporarily stored in a container, and when the liquid supplement is needed next time, the waste liquid is injected into the water-based cutting liquid tank again.
The invention provides a recycling application method of water-based products for metals, which relates to 3 products such as water-based cutting fluid, water-based metal cleaning agent, water-based antirust fluid and the like. When the water-based metal cleaning agent is applied on site, the waste liquid of the used water-based metal cleaning agent working solution and the water-based antirust liquid working solution can be recycled into the water-based cutting fluid working solution, so that the discharge of the waste liquid can be reduced, and the waste liquid treatment cost can be reduced for customers; although the cleaning performance and the rust-proof performance of the used water-based metal cleaner working solution and the waste liquid of the water-based rust-proof liquid working solution are slightly reduced, after the waste liquid is recycled to the water-based cutting fluid working solution, the rust-proof performance and the bacteria resistance of the water-based cutting fluid working solution can be improved, and meanwhile, other performances are not influenced.
In the invention, the used water-based metal cleaner working solution and the waste liquid of the water-based antirust working solution are not required to be discharged and directly returned to the water-based cutting solution tank, so that the performance of the cutting solution in subsequent use is not influenced. In the use process of the concentrated liquid tank, the water-based cutting fluid working solution has the service life of 2-3 years, and the waste liquid discharge of the water-based metal cleaning agent working solution and the water-based antirust solution working solution can be reduced for customers within 2-3 years.
In the invention, the chelating agent, the alkaline agent, the fatty acid and the corrosion inhibitor contained in the water-based metal cleaning agent, the water-based antirust liquid and the water-based cutting fluid respectively are similar components, which means that the chelating agent, the alkaline agent, the fatty acid and the corrosion inhibitor in three aqueous products are similar components respectively, taking the chelating agent as an example, the chelating agent in the three aqueous products is similar components, and the corresponding descriptions of the other alkaline agent, the fatty acid and the corrosion inhibitor are the same as the chelating agent. The same kind of components in the invention belong to the same class as chemical components; preferably, the water-based metal cleaner, the water-based antirust liquid and the water-based cutting fluid respectively contain a chelating agent, an alkaline agent, a fatty acid and a corrosion inhibitor which are respectively and correspondingly identical chemical components.
In the invention, the water-based cutting fluid, the water-based metal cleaner, the water-based antirust fluid and other products are designed in a systematization way, so that the mutual influence among the products during mixing is reduced. In the product design process, the water-based cutting fluid does not use a nonionic surfactant, but uses an anionic surfactant (the anionic surfactant can be added independently or generated by the reaction of lubricating grease in the water-based cutting fluid and an alkaline agent); the water-based metal cleaner uses a surfactant with low foaming and poor emulsifying capacity, and the factors such as the selection of an alkaline agent, the pH value and the like need to be considered in the consubstantialization design.
In the invention, the pH values of the water-based metal cleaner working solution and the water-based antirust working solution (namely the working solution which is prepared just after being diluted by water and is not used in metal processing) are ensured to be less than 10, so that the problem of hydrolysis of the lubricating grease in the water-based cutting fluid by alkali can be reduced, and the lubricating performance of the water-based cutting fluid is ensured.
According to the present invention, preferably, the second surfactant is a C8-C12 polyoxyethylene ether-based surfactant.
In the invention, the water-based metal cleaning agent product should select a low-foam surfactant, preferably a C8-C12 polyoxyethylene ether surfactant, and the surfactant does not influence the foam and emulsified particle size of the whole water-based cutting fluid in the subsequent mixing process, so that the stable performance of the water-based cutting fluid is ensured, and the field operation condition is met.
According to the present invention, preferably, the water-based cutting fluid includes, in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0.01-25 parts of lubricating grease, 0.01-5 parts of coupling agent, 10-40 parts of base oil and 5-30 parts of deionized water;
the water-based metal cleaner comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0-5 parts of second surfactant and 50-80 parts of deionized water;
the water-based antirust liquid comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor and 50-80 parts of deionized water;
the water-based cutting fluid, the water-based metal cleaner and the water-based antirust fluid are the same or different in unit weight parts.
According to the present invention, preferably, the chelating agent is at least one of ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid disodium salt, ethercarboxylic acid, hydroxyethylidene diphosphonic acid, nitrilotriacetic acid, and organic amine ester;
the alkaline agent is at least one of monoethanolamine, diethanolamine, triethanolamine, diglycolamine, 2-amino-2-methyl-1-propanol, isopropanolamine, N-methyldiethanolamine, dicyclohexylamine and sodium hydroxide;
the fatty acid is at least one of mono-n-octanoic acid, neodecanoic acid, caprylic-capric acid, isononanoic acid, sebacic acid, oleic acid, tall oil acid, tribasic acid, dodecanedioic acid and tetrabasic acid;
the corrosion inhibitor is at least one of sodium metasilicate, siloxane, benzotriazole, methyl benzotriazole, modified amino acid, phosphate, phosphite ester and phosphonate ester;
the second surfactant is at least one of fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether and fatty acid polyoxyethylene ether.
In the present invention, the fatty alcohol-polyoxyethylene ether is preferably at least one of JFC-2 of Haian petrochemical plant of Jiangsu province, antarox BL-240 of Fisher-Tropsch trade, inc. of Foshan, antarox LF-224 of Fisher-Tropsch trade, DF-61 of Nanjing Cutian chemical industry, and L-64 of Nanjing Cutian chemical industry.
According to the present invention, preferably, the grease is at least one of ricinoleic acid ester, oleic acid ester, tetrapolyricinoleic acid ester, self-emulsifying fat, polyester and ethylene oxide condensate, and trimethylolpropane oleate;
the coupling agent is at least one of carbon 14-carbon 15 mixed alcohol, diethylene glycol monobutyl ether, guerbet alcohol, carbon 18 mixed diol and dipropylene glycol methyl ether;
the base oil is at least one of naphthenic base oil, 60SN, 70SN and 100 SN.
In the present invention, the naphthenic base oil is preferably C N Not less than 40 percentA naphthenic base oil. C N The naphthenic base oil with the content of more than or equal to 40 percent refers to the naphthenic base oil with the content of more than or equal to 40 percent of naphthenes.
In the present invention, the polyester and ethylene oxide condensate is preferably obtained from Shenyang Shuangcheng Biotech Co., ltd, trade name ES545.
In one embodiment of the present invention, the emulsification of the water-based cutting fluid is adjusted without using a conventional nonionic emulsifier, but is adjusted by adjusting the emulsification balance with an anionic surfactant obtained by reacting a specific grease with an alkaline agent, and the stability of the product is ensured by adding a small amount of a coupling agent.
According to the present invention, preferably, the amount of the waste liquid of the water-based metal cleaner working solution added is not more than 28.8% based on the total volume of the water-based cutting fluid working solution which is first injected into the water-based cutting fluid tank; the addition amount of the waste liquid of the water-based antirust liquid working solution is not more than 10.8%.
In the scheme, the maximum addition amount of the waste liquid of the working solution of the water-based metal cleaner and the waste liquid of the working solution of the water-based antirust liquid is obtained through simulation of the mixing ratio; the method comprises the following specific steps:
the mixing proportion of the working solution of the water-based metal cleaning agent and the working solution of the water-based antirust solution in the 3-year service cycle (one service cycle of the water-based cutting fluid) is calculated by simulating the water-based cutting fluid collecting tank. Since the influence of the mixing ratio is more accurately observed as the mixing ratio is larger, a concentrated liquid tank capable of holding at least 10T of the water-based cutting fluid is selected for the simulation.
Simulation of a water-based cutting fluid concentrated fluid tank: 10T flume/1/3 year change/10% dilution.
Simulation of a water-based metal cleaning agent liquid tank: 500L of the stock solution tank/2 weeks change/4% dilution (1 tank 5%,2 tank 3%, after averaging to obtain a 4% ratio).
Simulation of a water-based antirust liquid tank: 500L of the fluid bath/1/2 weeks change/3% dilution.
And (3) calculating:
waste liquid mixing amount of water-based metal cleaner working solution: 0.5 (T) × 2 (fluid bath) × 2 (change frequency per month) × 36 (3 years) × 0.04 (dilution ratio)/10T (volume of cutting fluid in the cutting fluid bath) × 100% =28.8%;
mixing amount of waste liquid of water-based antirust liquid working solution: 0.5 (T) × 1 (fluid bath) × 2 (change frequency per month) × 36 (3 years) × 0.03 (dilution ratio)/10T (volume of cutting fluid in the cutting fluid bath) × 100% =10.8%;
according to simulation calculation, the maximum addition amounts of the waste liquid of the water-based metal cleaner working solution and the waste liquid of the water-based antirust solution working solution in the water-based cutting solution working solution with the service cycle of 3 years are respectively 28.8% and 10.8% (based on the total volume of the water-based cutting solution which is firstly injected into the water-based cutting solution tank).
The method for circularly applying the water-based product for metals comprises the steps of continuously injecting waste liquid of the working solution of the water-based metal cleaner and/or the working solution of the water-based antirust solution, which reach the solution change period of the working solution of the water-based metal cleaner and/or the working solution of the water-based antirust solution, into a liquid tank of the water-based cutting solution in the solution change period of the working solution of the water-based cutting solution (the solution change period is 3 years), wherein the maximum injection amount of the waste liquid of the working solution of the water-based metal cleaner is 28.8 percent and the maximum injection amount of the waste liquid of the working solution of the water-based antirust solution is 10.8 percent in the solution change period of the working solution of the water-based cutting solution.
In a further aspect the invention provides an aqueous metal product composition for use in the above described cyclic application process, the aqueous metal product composition comprising: water-based metal cleaning agents, water-based antirust fluids and water-based cutting fluids;
wherein the water-based metal cleaning agent, the water-based antirust liquid and the water-based cutting fluid respectively contain a chelating agent, an alkaline agent, fatty acid and a corrosion inhibitor which are all corresponding to the same components;
the water-based cutting fluid optionally contains a first surfactant, the first surfactant being not a nonionic surfactant, the first surfactant being an anionic surfactant;
the water-based metal cleaner contains a second surfactant, wherein the second surfactant is a low-foaming surfactant, and is preferably a C8-C12 polyoxyethylene ether surfactant;
the pH values of the water-based metal cleaner working solution and the water-based antirust working solution are both below 10.
According to the present invention, preferably, the water-based cutting fluid includes, in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0.01-25 parts of lubricating grease, 0.01-5 parts of coupling agent, 10-40 parts of base oil and 5-30 parts of deionized water;
the water-based metal cleaner comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0-5 parts of second surfactant and 50-80 parts of deionized water;
the water-based antirust liquid comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor and 50-80 parts of deionized water;
the water-based cutting fluid, the water-based metal cleaner and the water-based antirust fluid are the same or different in unit weight parts.
The invention has the following beneficial effects:
according to the recycling application method of the water-based product for metals, provided by the invention, through the same systematization design of the water-based product, after waste liquid of the water-based metal cleaner working solution and/or the water-based antirust working solution is mixed into the water-based cutting solution working solution, the performances of the water-based cutting solution working solution can be ensured to meet the requirements of field application, meanwhile, the performances of antirust property, antibacterial property and the like of the water-based cutting solution working solution can be improved, and through a recycling mode, troubles brought by environmental protection pressure are solved for customers, the waste liquid discharge is reduced, the environmental protection treatment cost is reduced, and the operation cost of the customers is reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 is a graph showing an infrared chromatographic analysis of a water-based cutting fluid before and after mixing according to a simulated comparative example 2 of the present invention. Wherein red represents an unmixed water-based cutting fluid, blue represents a mixed water-based cutting fluid, and transmittince on the vertical axis represents an emission peak.
Figure 2 shows a product diagram of a test sumicidin tablet according to the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention is further illustrated by the following examples:
the parts referred to in the following examples and comparative examples are parts by weight.
The fatty alcohol-polyoxyethylene ethers used in the following examples and comparative examples were purchased from JFC-2 of Haian petrochemical plant of Jiangsu province, antarox BL-240 of Fisley trade company, foshan, or DF-61 of Nanjing Gutian chemical;
the fatty acid polyoxyethylene ether is purchased from the chemical industry Co., ltd of Jinyaoda, and the trade mark is AEO-9; the carbon 14-carbon 15 mixed alcohol is purchased from Shanghai Jingtong chemical Co., ltd, and is available under the trademark of ISALCHEM145; the tribasic acid is purchased from Guangzhou Kaihen chemical engineering Co., ltd, and the brand is NEUF485; the quaternary acid is purchased from Hefeitai biotechnology limited and is under the brand name NEUF985; the tolytriazole is purchased from Nanjing Shengbai International trade company Limited under the trademark TTA; the self-emulsifying fat is purchased from Shanghai Milin chemical Co., ltd, and is provided with the mark ML-955; the organic amine ester is purchased from Ningbo high-new area Bai hydrated science and technology Co., ltd under the brand name TPP; the polyester and ethylene oxide condensate is preferably purchased from Shenyang Shuangcheng Biotech, inc., under the trade designation ES545; the naphthenic base oil used is C N Greater than or equal to 40 percent of naphthenic base oil.
Example 1
This embodiment provides an aqueous metal product composition comprising: water-based metal cleaning agents, water-based antirust fluids and water-based cutting fluids; the method comprises the following specific steps:
water-based cutting fluid:
2 parts of ethylene diamine tetraacetic acid tetrasodium salt, 8 parts of monoethanolamine, 5 parts of triethanolamine, 2 parts of dicyclohexylamine, 3 parts of dodecanedioic acid, 3 parts of neodecanoic acid, 0.4 part of sodium metasilicate, 0.2 part of benzotriazole, 2 parts of ricinoleate, 8 parts of hexapolyricinoleate, 5 parts of trimethylolpropane oleate, and naphthenic base oil (C) N Not less than 40 percent), 35 parts of diethylene glycol monobutyl ether, 2 parts of deionized water and 24.4 parts of deionized water
The water-based cutting fluid is prepared by the following steps:
(1) Accurately weighing each additive for later use.
(2) 21.4 parts of deionized water and 2 parts of ethylenediaminetetraacetic acid tetrasodium salt are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 8 parts of monoethanolamine, 5 parts of triethanolamine, 2 parts of dicyclohexylamine, 3 parts of dodecanedioic acid, 3 parts of neodecanoic acid, 0.2 part of benzotriazole, 2 parts of ricinoleate and 8 parts of hexapolyricinoleate into the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) 5 parts trimethylolpropane oleate, 35 parts of naphthenic base oil (C) N Not less than 40 percent) and 3 parts of diethylene glycol monobutyl ether are added into the second mixed solution to play a role of cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) And adding 3 parts of deionized water and 0.4 part of sodium metasilicate into another container in sequence. Stirring at normal temperature for 20min until the solution is clear and transparent to obtain a fourth mixed solution.
(6) The fourth mixed solution was added to the third mixed solution, and stirred for 20min until the solution was clear and transparent, to obtain the water-based cutting fluid of example 1.
Water-based metal cleaner:
2 parts of ethylenediaminetetraacetic acid tetrasodium salt, 8 parts of monoethanolamine, 5 parts of triethanolamine, 3 parts of dodecanedioic acid, 3 parts of neodecanoic acid, 0.4 part of sodium metasilicate, 0.2 part of benzotriazole, 2 parts of fatty alcohol-polyoxyethylene ether (DF-61) and 76.4 parts of deionized water.
The water-based metal cleaner is prepared as follows:
(1) Accurately weighing each additive for later use.
(2) 23.4 parts of deionized water and 2 parts of ethylenediaminetetraacetic acid tetrasodium salt are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) 8 parts of monoethanolamine, 5 parts of triethanolamine, 3 parts of dodecanedioic acid, 3 parts of neodecanoic acid and 0.2 part of benzotriazole are added to the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 2 parts of fatty alcohol-polyoxyethylene ether DF-61 and 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) Another container is sequentially added with 3 parts of water and 0.4 part of sodium metasilicate. Stirring at normal temperature for 20min until the solution is clear and transparent to obtain a fourth mixed solution.
(6) The fourth mixed solution was added to the third mixed solution to obtain the water-based metal cleaner of example 1.
Water-based antirust liquid:
2 parts of ethylenediaminetetraacetic acid tetrasodium salt, 8 parts of monoethanolamine, 5 parts of triethanolamine, 3 parts of dodecanedioic acid, 3 parts of neodecanoic acid, 0.4 part of sodium metasilicate, 0.2 part of benzotriazole and 78.4 parts of deionized water.
The preparation process of the water-based antirust liquid is as follows:
(1) Accurately weighing each additive for later use.
(2) 25.4 parts of deionized water and 2 parts of ethylenediaminetetraacetic acid tetrasodium salt are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) 8 parts of monoethanolamine, 5 parts of triethanolamine, 3 parts of dodecanedioic acid, 3 parts of neodecanoic acid and 0.2 part of benzotriazole are added to the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) Another container is sequentially added with 3 parts of water and 0.4 part of sodium metasilicate. Stirring at normal temperature for 20min until the solution is clear and transparent to obtain a fourth mixed solution.
(6) The fourth mixed solution was added to the third mixed solution to obtain the water-based rust inhibitive liquid of example 1.
Example 2
This embodiment provides an aqueous metal product composition comprising: water-based metal cleaning agents, water-based antirust fluids and water-based cutting fluids; the method comprises the following specific steps:
water-based cutting fluid:
2 parts of ethylene diamine tetraacetic acid disodium salt, 4 parts of monoethanolamine, 3 parts of dicyclohexylamine, 5 parts of tribasic acid, 3 parts of isononanoic acid, 1 part of phosphonate, 0.2 part of methylbenzotriazole, 2 parts of oleate, 10 parts of tetrapoly ricinoleate, 8 parts of trimethylolpropane oleate and naphthenic base oil (C) N Not less than 40 percent), 1 part of C14-C15 mixed alcohol and 25.8 parts of deionized water
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 25.8 parts of deionized water and 2 parts of disodium ethylene diamine tetraacetate are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 4 parts of monoethanolamine, 3 parts of dicyclohexylamine, 5 parts of tribasic acid, 3 parts of isononanoic acid, 1 part of phosphonate, 0.2 part of methyl benzotriazole, 2 parts of oleate and 10 parts of tetrapoly ricinoleate into the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) 8 parts trimethylolpropane oleate, 35 parts of naphthenic base oil (C) N Not less than 40 percent), and 1 part of C14-C15 mixed alcohol is added into the second mixed liquid and has the function of reducing the temperature. After stirring for 30min, the solution was clear and transparent, and the water-based cutting fluid of example 2 was obtained.
Water-based metal cleaner:
2 parts of ethylene diamine tetraacetic acid disodium salt, 4 parts of monoethanolamine, 5 parts of tribasic acid, 3 parts of isononanoic acid, 1 part of phosphonate, 0.2 part of methylbenzotriazole, 3 parts of fatty alcohol-polyoxyethylene ether (JFC-2) and 81.8 parts of deionized water.
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 31.8 parts of deionized water and 2 parts of disodium ethylene diamine tetraacetate are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) 4 parts of monoethanolamine, 5 parts of tribasic acid, 3 parts of isononanoic acid, 1 part of phosphonate ester and 0.2 part of methylbenzotriazole are added to the first mixed solution. And heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) And adding 3 parts of fatty alcohol-polyoxyethylene ether (JFC-2) to the third mixed solution. Stirring for 30min until the solution is clear and transparent, and obtaining the water-based metal cleaner in the example 2.
Water-based antirust liquid:
2 parts of ethylene diamine tetraacetic acid disodium salt, 4 parts of monoethanolamine, 5 parts of tribasic acid, 3 parts of isononanoic acid, 1 part of phosphonate, 0.2 part of benzotriazole and 84.8 parts of deionized water.
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 34.8 parts of deionized water and 2 parts of disodium ethylene diamine tetraacetate are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) 4 parts of monoethanolamine, 5 parts of triacid, 3 parts of isononanoic acid, 1 part of phosphonate and 0.2 part of methylbenzotriazole are added to the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain the water-based antirust liquid of example 2.
Example 3
This embodiment provides an aqueous metal product composition comprising: water-based metal cleaning agents, water-based antirust fluids and water-based cutting fluids; the method comprises the following specific steps:
water-based cutting fluid:
2 parts of organic amine ester, 4 parts of monoethanolamine, 10 parts of triethanolamine, 1 part of dicyclohexylamine, 3 parts of tetrabasic acid, 4 parts of neodecanoic acid, 1 part of phosphate, 0.2 part of methyl benzotriazole, 2 parts of siloxane, 4 parts of self-emulsifying fat, 5 parts of tetrapoly ricinoleate, 5 parts of polyester and ethylene oxide condensate, 10 parts of trimethylolpropane oleate and naphthenic base oil (C) N Not less than 40 percent), 2 parts of carbon 14-carbon 15 mixed alcohol and 11.8 parts of deionized water
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 11.8 parts of deionized water and 2 parts of organic amine ester are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 4 parts of monoethanolamine, 10 parts of triethanolamine, 1 part of dicyclohexylamine, 3 parts of tetrabasic acid, 4 parts of neodecanoic acid, 1 part of phosphate, 0.2 part of methylbenzotriazole, 4 parts of self-emulsifying fat, 5 parts of tetrapoly ricinoleate and 5 parts of polyester and ethylene oxide condensate into the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) 10 parts of trimethylolpropane oleate35 parts of naphthenic base oil (C) N Not less than 40 percent), 2 parts of C14-C15 mixed alcohol is added into the second mixed liquid, and the cooling effect is achieved. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) 2 parts of silicone hydride was added to the third mixed solution, and stirred for 20 minutes until the solution was clear and transparent, to obtain the water-based cutting fluid of example 3.
Water-based metal cleaner:
2 parts of organic amine ester, 4 parts of monoethanolamine, 10 parts of triethanolamine, 3 parts of tetrabasic acid, 4 parts of neodecanoic acid, 1 part of phosphate, 0.2 part of methylbenzotriazole, 2 parts of siloxane, 4 parts of fatty alcohol-polyoxyethylene ether (Antarox BL-240) and 69.8 parts of deionized water.
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 19.8 parts of deionized water and 2 parts of organic amine ester are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 4 parts of monoethanolamine, 10 parts of triethanolamine, 3 parts of tetrabasic acid, 4 parts of neodecanoic acid, 1 part of phosphate and 0.2 part of methylbenzotriazole into the first mixed solution. And heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) And adding 2 parts of silicone into the third mixed solution, and stirring for 20min until the solution is clear and transparent to obtain a fourth mixed solution.
(5) And adding 4 parts of fatty alcohol-polyoxyethylene ether (Antarox BL-240) into the fourth mixed solution. Stirring for 30min until the solution is clear and transparent to obtain the water-based metal cleaner of example 3.
Water-based antirust liquid:
2 parts of organic amine ester, 4 parts of monoethanolamine, 10 parts of triethanolamine, 3 parts of tetrabasic acid, 4 parts of neodecanoic acid, 1 part of phosphate, 0.2 part of methyl benzotriazole, 2 parts of siloxane and 73.8 parts of deionized water.
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 23.8 parts of deionized water and 2 parts of organic amine ester are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 4 parts of monoethanolamine, 10 parts of triethanolamine, 3 parts of tetrabasic acid, 4 parts of neodecanoic acid, 1 part of phosphate and 0.2 part of methylbenzotriazole into the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously performing a cooling function. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) And adding 2 parts of silane ketone into the third mixed solution, and stirring for 20min until the solution is clear and transparent to obtain the water-based antirust liquid in the example 3.
Comparative example 1
This comparative example provides an aqueous metal working combination comprising: water-based metal cleaning agents, water-based antirust fluids and water-based cutting fluids; the method comprises the following specific steps:
water-based cutting fluid:
2 parts of ethylene diamine tetraacetic acid disodium salt, 10 parts of monoethanolamine, 3 parts of triethanolamine, 2 parts of dicyclohexylamine, 3 parts of sebacic acid, 3 parts of caprylic-capric acid, 1 part of phosphite ester, 0.2 part of methylbenzotriazole, 6 parts of self-emulsifying fat, 4 parts of tetrapoly ricinoleate, 4 parts of polyester and ethylene oxide condensate (ES 545), 7 parts of trimethylolpropane oleate, 2.5 parts of nonylphenol polyoxyethylene ether (NP-10), and cycloparaffin base oil (C) N Not less than 40 percent), 1 part of C14-C15 mixed alcohol, 0.5 part of diethylene glycol monobutyl ether and 15.8 parts of deionized water
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 15.8 parts of deionized water and 2 parts of disodium ethylene diamine tetraacetate are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 10 parts of monoethanolamine, 3 parts of triethanolamine, 2 parts of dicyclohexylamine, 3 parts of sebacic acid, 3 parts of neodecanoic acid, 1 part of phosphite ester, 0.2 part of methylbenzotriazole, 6 parts of self-emulsifying lipid, 4 parts of tetrapolyricinoleate and 4 parts of ES545 to the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) 7 parts of trimethylolpropane oleate, 35 parts of naphthenic base oil (C) N Not less than 40 percent), 2.5 parts of NP-10,1 parts of C14-C15 mixed alcohol and 0.5 part of diethylene glycol monobutyl ether are added into the second mixed solution, and the effect of cooling is achieved at the same time. Stirring for 30min until the solution becomes clear and transparent, to obtain the water-based cutting fluid of comparative example 1.
Water-based metal cleaner:
3 parts of organic amine ester, 15 parts of monoethanolamine, 4 parts of tribasic acid, 2 parts of isononanoic acid, 1 part of phosphate ester, 0.2 part of benzotriazole, 3 parts of fatty acid polyoxyethylene ether (AEO-9) and 71.8 parts of deionized water
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 21.8 parts of deionized water and 3 parts of organic amine ester are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) Adding 15 parts of monoethanolamine, 4 parts of tribasic acid, 2 parts of isononanoic acid, 1 part of phosphate and 0.2 part of benzotriazole into the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) And adding 3 parts of fatty acid polyoxyethylene ether into the third mixed solution. Stirring for 30min until the solution is clear and transparent, and obtaining the water-based metal cleaner in the comparative example 1.
Water-based antirust liquid:
2 parts of ethylene diamine tetraacetic acid tetrasodium salt, 10 parts of monoethanolamine, 3 parts of triethanolamine, 3 parts of sebacic acid, 4 parts of caprylic-capric acid, 0.4 part of sodium metasilicate, 0.2 part of tolyltriazole and 77.4 parts of deionized water.
The preparation process comprises the following steps:
(1) Accurately weighing each additive for later use.
(2) 24.4 parts of deionized water and 2 parts of ethylenediaminetetraacetic acid tetrasodium salt are sequentially added into a reaction kettle. Stirring for 20min at normal temperature until the solution is clear and transparent to obtain a first mixed solution.
(3) 10 parts of monoethanolamine, 3 parts of triethanolamine, 3 parts of sebacic acid, 4 parts of octadecanoic acid and 0.2 part of methylbenzotriazole are added to the first mixed solution. Heating the reaction kettle to 50-60 ℃, stirring for 30min until the solution is clear and transparent, and stopping heating to obtain a second mixed solution.
(4) And adding 50 parts of deionized water into the second mixed solution, and simultaneously cooling. Stirring for 30min until the solution is clear and transparent to obtain a third mixed solution.
(5) Another container is sequentially added with 3 parts of water and 0.4 part of sodium metasilicate. Stirring at normal temperature for 20min until the solution is clear and transparent to obtain a fourth mixed solution.
(6) The fourth mixed solution was added to the third mixed solution to obtain a water-based rust inhibitive liquid of comparative example 1.
Example 4
The embodiment provides a recycling application method of a water-based product for metal, which comprises the following steps: in the liquid changing period of the water-based cutting fluid working solution, the waste liquid of the water-based metal cleaner working solution and/or the waste liquid of the water-based antirust fluid working solution is used as a replenishing solution and is injected into a water-based cutting fluid tank for metal processing;
wherein the liquid changing period of the water-based cutting fluid working solution is 2-3 years;
the waste liquid of the working solution of the water-based metal cleaner is the working solution exceeding the solution change period of the working solution of the water-based metal cleaner;
the waste liquid of the water-based antirust liquid working solution is a working solution exceeding the liquid change period of the water-based antirust liquid working solution;
when the generated waste liquid of the water-based metal cleaner working solution and/or the waste liquid of the water-based antirust liquid working solution cannot be completely injected into the water-based cutting fluid tank as a replenishing solution at one time, the residual waste liquid of the water-based metal cleaner working solution and/or the waste liquid of the water-based antirust liquid working solution is temporarily stored, and is used as the replenishing solution to be injected into the water-based cutting fluid tank when the next fluid replenishing is performed.
The addition amount of the waste liquid of the water-based metal cleaning agent working solution is not more than 28.8 percent based on the total volume of the water-based cutting fluid working solution which is firstly injected into the water-based cutting fluid tank; the addition amount of the waste liquid of the water-based antirust liquid working solution is not more than 10.8%.
The pH values of the water-based metal cleaner working solution and the water-based antirust working solution are both below 10.
Wherein the water-based metal cleaner, the water-based rust preventive liquid, and the water-based cutting fluid used for preparing the respective working fluids were the water-based metal cleaner, the water-based rust preventive liquid, and the water-based cutting fluid prepared in example 1, respectively.
Example 5
The present embodiment differs from embodiment 4 only in that: wherein the water-based metal cleaner, the water-based rust preventive liquid, and the water-based cutting fluid used for preparing the respective working fluids were the water-based metal cleaner, the water-based rust preventive liquid, and the water-based cutting fluid prepared in example 2, respectively.
Example 6
The present embodiment differs from embodiment 4 only in that: wherein the water-based metal cleaner, the water-based rust preventive liquid, and the water-based cutting fluid used for preparing the respective working fluids were the water-based metal cleaner, the water-based rust preventive liquid, and the water-based cutting fluid prepared in example 3, respectively.
Comparative example 2
The comparative example differs from example 4 only in that: wherein the water-based metal cleaner, the water-based rust-preventive liquid, and the water-based cutting fluid used for preparing the respective working fluids were the water-based metal cleaner, the water-based rust-preventive liquid, and the water-based cutting fluid prepared in comparative example 1, respectively.
Test example
The test example verifies the application effect of the cyclic application methods of examples 4 to 6 and comparative example 2 by a simulation experiment method, and further verifies the application feasibility of the method of the invention.
Simulation of mixing ratio:
the mixing proportion of the waste liquid of the water-based metal cleaner working solution and the waste liquid of the water-based antirust solution working solution in the 3-year service cycle (one service cycle of the water-based cutting solution working solution) is calculated by simulating the water-based cutting solution concentrated solution tank, and after the waste liquids are mixed according to the mixing proportion, the product performance of the mixed product is finally verified. Since the larger the mixing ratio is, the more accurate the influence of the mixing ratio is, the concentrated liquid tank capable of holding at least 10T of the water-based cutting fluid was selected for the simulation.
Simulation of a water-based cutting fluid concentrated fluid tank: the water-based cutting fluid at least can contain 10T of water-based cutting fluid working fluid, 1 fluid tank is replaced in 3 years, and the mass concentration of the water-based cutting fluid working fluid is 10 percent (dilution ratio).
Simulation of a water-based metal cleaning agent liquid tank: 500L liquid tanks and 2 liquid tanks are replaced for 2 weeks, and the mass concentration of the working solution of the water-based metal cleaner is 4% (5% dilution ratio in 1 tank, 3% dilution ratio in 2 tank, and 4% dilution ratio after averaging).
Simulation of a water-based antirust liquid tank: 500L liquid tanks and 1 liquid tank are replaced for 2 weeks, and the mass concentration of the water-based antirust working fluid is 3 percent (dilution ratio).
And (3) calculating:
waste liquid mixing amount of water-based metal cleaner working solution: 0.5 (T). Times.2 (fluid bath). Times.2 (change frequency per month). Times.36 (3 years). Times.0.04 (dilution ratio)/10T (volume of cutting fluid in cutting fluid bath). Times.100% =28.8%
Mixing amount of waste liquid of water-based antirust liquid working solution: 0.5 (T). Times.1 (fluid bath). Times.2 (change frequency per month). Times.36 (3 years). Times.0.03 (dilution ratio)/10T (volume of cutting fluid in cutting fluid bath). Times.100% =10.8%
According to the simulation calculation, the waste liquid of the water-based cleaning agent working solution and the waste liquid of the water-based antirust solution, wherein 28.8 percent of the waste liquid of the water-based cleaning agent working solution and 10.8 percent of the waste liquid of the water-based antirust solution can be mixed into the water-based cutting fluid working solution with the service cycle of 3 years at most, can be obtained.
Because impurities such as metal cuttings, miscellaneous oil and the like in metal processing application can be introduced into the waste liquid of the water-based metal cleaner working solution, the waste liquid of the water-based antirust solution working solution and the water-based cutting solution working solution in practical application, the impurities are specifically simulated as follows: cutting scraps (the test takes cast iron scraps as an example), and miscellaneous oil (150 SN is used for replacing 32# hydraulic oil); according to the monitoring data of a concentrated liquid tank on the site of a certain engine client in the coast for 3 years, the mixing amount of iron powder is about 0.05 percent, and the mixing amount of miscellaneous oil is about 1 percent. For the sake of the severity of the test results, the chip incorporation amount in this test was 5% and the miscellaneous oil incorporation amount was 5% (based on the total volume of the water-based cutting fluid working fluid first injected into the water-based cutting fluid tank). As the miscellaneous oil and the cutting scraps have a synergistic effect on the lubricity of the water-based cutting fluid, the cutting scraps and the miscellaneous oil are not added during the lubricating property test.
Simulation example 4: the simulation example 4 contained, in terms of the total volume of the water-based cutting fluid working fluid which was first injected into the water-based cutting fluid tank: 28.8% of the water-based metal cleaner of example 1 diluted at a dilution ratio of 4%, 10.8% of the water-based rust preventive liquid of example 1 diluted at a dilution ratio of 3%, and 50.4% of the water-based cutting fluid of example 1 diluted at a dilution ratio of 10%.
Simulation example 5: simulation example 5 contained, in terms of the total volume of the water-based cutting fluid working fluid that was first injected into the water-based cutting fluid tank: 28.8% of the water-based metal cleaner of example 2 diluted at a dilution ratio of 4%, 10.8% of the water-based rust preventive liquid of example 2 diluted at a dilution ratio of 3%, and 50.4% of the water-based cutting fluid of example 2 diluted at a dilution ratio of 10%.
Simulation example 6: the simulation example 6 contained, in terms of the total volume of the water-based cutting fluid working fluid which was first injected into the water-based cutting fluid tank: 28.8% of the water-based metal cleaner of example 3 diluted at a dilution ratio of 4%, 10.8% of the water-based rust preventive liquid of example 3 diluted at a dilution ratio of 3%, and 50.4% of the water-based cutting fluid of example 3 diluted at a dilution ratio of 10%.
Simulation of comparative example 2: the simulation comparative example 2 contained, in terms of the total volume of the water-based cutting fluid working fluid first injected into the water-based cutting fluid tank: 28.8% of the water-based metal cleaner of comparative example 1 at a dilution ratio of 4%, 10.8% of the water-based rust preventive liquid of comparative example 1 at a dilution ratio of 3%, and 50.4% of the water-based cutting fluid of comparative example 1 at a dilution ratio of 10%.
Whether or not the simulated impurities (i.e., 5% of the chips and 5% of the miscellaneous oil) need to be added in the above simulated examples 4 to 6 and the simulated comparative example 2 depends on the following specific test items, and whether or not the addition is reflected in the following specific test items, and the specific addition or not is shown in the following test items.
Wherein the diluted water-based products of the above simulation examples 4 to 6 and the simulation comparative example 2 are prepared by mixing the respective products prepared in the respective examples and comparative example 1 with deionized water or hard water at the respective dilution ratios, and the dilution ratios refer to weight percentages based on the total weight of the respective water-based products and water (deionized water or hard water); for example: the water-based metal cleaner of example 1 at a dilution ratio of 4% was prepared by mixing the water-based metal cleaner prepared in example 1 with water (the water being deionized water or hard water) at a dilution ratio of 4wt% (based on the total weight of the water-based metal cleaner and water prepared in example 1); in the following test items, the test samples used in the other test items were prepared with deionized water, except that the bacteriostatic activity and the emulsion stability were prepared with hard water.
And (4) detecting items:
the feasibility of the cyclic application method of the aqueous metal product of the present invention is verified by items such as lubricity, rust prevention, corrosion resistance, bacterial inhibition, emulsion stability and defoaming property, and the specific experimental method is as follows, and the specific results are shown in table 1, table 2 and fig. 1 below.
1. Lubricity test (note 1):
equipment: DMG MORIA MILLTAP 700 (Dammar Gi) speed drilling machining center
The principle is as follows: the 6061 deformation aluminum material is subjected to hole rotating, chamfering and tapping processing. The equipment collects charge data in the processing process through a charge sensor, converts the charge data into a torque value through a charge amplifier and an analog signal device, and determines the lubricity through an average torque value. Generally, the lower the torque value, the more excellent the lubricating property. Different devices and different tools can obtain different torque values, and the lubricating data reference values obtained by the perennial test are as follows: water-based cutting fluid excellent in lubrication: 1800Nm or less; lubricating a common water-based cutting fluid: 1800Nm-2200Nm; poorly lubricated water-based cutting fluids: 2200Nm or more; relative deviation: 2% or less. By tapping torque test, the change of the lubricating property before and after mixing was observed.
In the lubricity test, swarf and miscellaneous oil were not added to the above simulated examples and simulated comparative examples, and the test was performed only with a working fluid containing no simulated impurities.
2. Test of rust inhibitive Property
Single-chip: JB/T4323-2019 (HT 300 cast iron, 10# steel, T3 red copper, H62 brass, 2A12 aluminum)
Laminating: JB/T4323-2019 (HT 300 cast iron, 10# steel, T3 red copper, H62 brass, 2A12 aluminum)
1, antirust property: QB/T2117-1995 (Z3 cast iron, 45# Steel, H62 brass, LY12 aluminum)
2, antirust property: JB/T9189-2016 (ball-milling cast iron)
In the rust inhibitive performance test, chips and miscellaneous oils were not added to the above simulation examples and simulation comparative examples, and only the test was performed with the working fluid containing no simulation impurities.
3. And (3) corrosion test: GB/T6144-2010 (first grade grey cast iron, red copper, LY12 aluminium)
In the corrosion test, swarf and miscellaneous oil were not added to the above simulated examples and simulated comparative examples, and the test was performed only with a working fluid containing no simulated impurities.
4. Bacteriostatic (note 2):
(1) Hard water (500 ppm calcium ion, 500ppm magnesium ion concentration pattern) was prepared using calcium nitrate and magnesium sulfate.
(2) 5%150SN and 5% scrap iron of ball-milled iron (in terms of the total volume of the working fluid of the water-based cutting fluid first injected into the fluid bath of the water-based cutting fluid) were added to the above-described simulation examples 4-6 and simulation comparative example 2, respectively, which were prepared using the hard water prepared in step (1).
(3) 200ml of the impurity-added model sample prepared in step (2) was taken and placed in a 500ml Erlenmeyer flask.
(4) Bacterial liquid: taking out the site odor-causing cutting fluid (Shumei test bacterium slice test bacterium number is 10) 7 )。
(5) Adding bacterial liquid into the sample in the step (3), wherein the adding amount of the bacterial liquid is 10% based on the total volume of the sample in the step (3); then, the sample added with the bacterial liquid is placed into a constant temperature shaking table (a circumferential oscillation constant temperature shaking table controlled by German IKA KS4000 i).
(6) The biological incubator was set at 150RPM and a temperature of 30 ℃.
(7) Continuously adding 2% of bacterial liquid (based on the total volume of the sample in the step (3)) to the sample every day, and testing the bacterial content by using Shumei test bacterium tablets (shown in figure 2) every 3 days.
5. Emulsion stability (Note 3)
(1) Hard water was prepared (500 ppm calcium ion, 500ppm magnesium ion concentration pattern) using calcium nitrate and magnesium sulfate.
(2) 5%150SN and 5% scrap iron of ball-milled iron (in terms of the total volume of the working fluid of the water-based cutting fluid first injected into the fluid bath of the water-based cutting fluid) were added to the above-described simulation examples 4-6 and simulation comparative example 2, respectively, which were prepared using the hard water prepared in step (1).
(3) 500ml of the impurity-added model sample prepared in the step (2) was taken and placed in a 500ml beaker.
(4) The beaker was placed in a dispersion machine. (Germany IKA disperser T25 easy clean digital display high performance disperser)
(5) The beaker is placed in the heating plate, and the heating plate is provided with 70 ℃, and after the temperature is stabilized, the rotating speed of the dispersion machine is set to be 15000RPM and the dispersion machine is rotated for 2 hours.
(6) And (4) taking off the beaker, standing for 1 week at normal temperature, and observing whether the middle liquid phase is layered or not. Typically, the top will float un-emulsified 150SN and the bottom will precipitate iron powder. After the product with poor emulsification is tested, the intermediate liquid phase can be layered, the bottom is colorless and transparent, and the top is white emulsion.
6. Defoaming property test: JB/T4323-2019.
In the defoaming test, chips and miscellaneous oil were not added to the above simulation examples and simulation comparative examples, and only the test was performed with a working fluid containing no simulated impurities.
In the following table 1, the mixed cutting fluids in the simulation examples 4 to 6 and the simulation comparative example 2 refer to the simulated mixed fluids prepared in the corresponding simulation examples 4 to 6 and the simulation comparative example 2; the water-based cutting fluids of the simulated examples 4 to 6 and the simulated comparative example 2 refer to the water-based cutting fluids of the respective examples or comparative example 1 at a dilution ratio of 10% used in the simulated examples 4 to 6 and the simulated comparative example 2.
TABLE 1
TABLE 2 indexes of bacteriostatic properties
TABLE 3
From the specific formulation, the simulated comparative example 2 belongs to a product combination of different systems, high alkalinity and emulsified surfactants;
from the test data, the following conclusions can be drawn:
from the test results, the antirust property and the antibacterial property of the mixed product are improved, but the lubricity and the defoaming property are reduced, wherein the reduction of the simulated comparative example 2 is more obvious.
From the appearance of the working fluid, the water-based cutting fluid in the simulated comparative example 2 contains nonylphenol polyoxyethylene ether, the water-based metal cleaner contains emulsifying surfactants such as fatty acid polyoxyethylene ether, and the like, and after the emulsifying surfactants are mixed, the particle size of the water-based cutting fluid can be refined, so that the lubricating performance is reduced, otherwise, the particle size change of a product can be reduced by a combined system without the emulsifying surfactants.
The pH of comparative example 2 was simulated to be relatively too high, and the lubricating properties thereof were found to be significantly deteriorated after blending, and it was found that the ester bonds of the mixed water-based cutting fluid were lost by infrared chromatographic observation before and after the blending (see FIG. 1). It follows that when the pH of the aqueous composition is too high, hydrolysis of the grease may result after mixing, ultimately affecting lubricity.
The simulation comparative example 2 is a product matching with a non-homogeneous system, and the emulsion stability test shows that although the emulsion surfactant is added, the emulsion stability of the product is still defective, so that a homogeneous system design can stably mix the product system.
From the aspect of foaming performance, if the system is stable and the foaming is low after mixing, the surfactant in the water-based metal cleaner needs to be a normal-temperature low-foaming surfactant, which is beneficial to the foaming of the mixed water-based cutting fluid.
According to the simulation of various data of the embodiments 4 to 6, the cutting fluid can meet the requirement that the mixed cutting fluid still has original product characteristics through a special formula design, and has synergistic performance in the aspects of rust resistance and bacterial inhibition, so that the mixed cutting fluid can meet the requirement of field application; namely, the cyclic application method of the water-based product for metal can ensure that the mixed water-based cutting fluid still meets the use requirements of metal processing, and has feasibility.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A recycling method of an aqueous product for metals is characterized by comprising the following steps: in the liquid changing period of the water-based cutting fluid working solution, the waste liquid of the water-based metal cleaner working solution and/or the waste liquid of the water-based antirust fluid working solution is used as a replenishing solution and is injected into a water-based cutting fluid tank for metal processing;
wherein, the water-based metal cleaning agent, the water-based antirust liquid and the water-based cutting fluid which are used for preparing the corresponding working fluid respectively contain the chelating agent, the alkaline agent, the fatty acid and the corrosion inhibitor which are all corresponding to the same components;
the water-based cutting fluid optionally contains a first surfactant, the first surfactant being not a nonionic surfactant, the first surfactant being an anionic surfactant;
the water-based metal cleaner contains a second surfactant, and the second surfactant is a low-foaming surfactant;
the pH values of the water-based metal cleaner working solution and the water-based antirust working solution are both below 10.
2. The cyclic application method of claim 1, wherein the fluid change period of the water-based cutting fluid working fluid is 2 to 3 years;
the waste liquid of the working solution of the water-based metal cleaner is the working solution exceeding the solution change period of the working solution of the water-based metal cleaner;
the waste liquid of the water-based antirust liquid working solution is the working solution exceeding the liquid change period of the water-based antirust liquid working solution.
3. The recycling method according to claim 1, wherein when the generated waste liquid of the water-based metal cleaner working fluid and/or the waste liquid of the water-based rust inhibitive fluid working fluid cannot be entirely filled into the water-based cutting fluid tank at a time as a replenishment liquid, the remaining waste liquid of the water-based metal cleaner working fluid and/or the waste liquid of the water-based rust inhibitive fluid working fluid is temporarily stored and is filled into the water-based cutting fluid tank as the replenishment liquid when the next replenishment liquid is performed.
4. The recycling method of claim 1, wherein the second surfactant is a C8-C12 polyoxyethylene ether-based surfactant.
5. The cyclic application method of claim 1,
the water-based cutting fluid comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0.01-25 parts of lubricating grease, 0.01-5 parts of coupling agent, 10-40 parts of base oil and 5-30 parts of deionized water;
the water-based metal cleaner comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0-5 parts of second surfactant and 50-80 parts of deionized water;
the water-based antirust liquid comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor and 50-80 parts of deionized water;
the water-based cutting fluid, the water-based metal cleaner and the water-based antirust fluid are the same or different in unit weight part.
6. The recycling method of any of claims 1 to 5, wherein the chelating agent is at least one of ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid disodium salt, ethercarboxylic acid, hydroxyethylidene diphosphonic acid, nitrilotriacetic acid, and organic amine ester;
the alkaline agent is at least one of monoethanolamine, diethanolamine, triethanolamine, diglycolamine, 2-amino-2-methyl-1-propanol, isopropanolamine, N-methyldiethanolamine, dicyclohexylamine and sodium hydroxide;
the fatty acid is at least one of mono-n-octanoic acid, neodecanoic acid, caprylic-capric acid, isononanoic acid, sebacic acid, oleic acid, tall oil acid, tribasic acid, dodecanedioic acid and tetrabasic acid;
the corrosion inhibitor is at least one of sodium metasilicate, siloxane, benzotriazole, methyl benzotriazole, modified amino acid, phosphate, phosphite ester and phosphonate ester;
the second surfactant is at least one of fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether and fatty acid polyoxyethylene ether.
7. The recycling method according to claim 5, wherein the grease is at least one of ricinoleic acid ester, oleic acid ester, tetrapolyricinoleic acid ester, self-emulsifying grease, condensate of polyester with ethylene oxide, and trimethylolpropane oleate;
the coupling agent is at least one of carbon 14-carbon 15 mixed alcohol, diethylene glycol monobutyl ether, guerbet alcohol, carbon 18 mixed diol and dipropylene glycol methyl ether;
the base oil is at least one of naphthenic base oil, 60SN, 70SN and 100 SN.
8. The cyclic application method of claim 1, wherein the amount of the waste liquid of the water-based metal cleaning agent working fluid added is not more than 28.8% based on the total volume of the water-based cutting fluid working fluid which is first injected into the water-based cutting fluid tank; the addition amount of the waste liquid of the water-based antirust liquid working solution is not more than 10.8%.
9. An aqueous metal product composition for use in the cyclic application process of any one of claims 1 to 8, characterized in that it comprises: water-based metal cleaning agents, water-based antirust fluids and water-based cutting fluids;
wherein the water-based metal cleaning agent, the water-based antirust liquid and the water-based cutting fluid respectively contain a chelating agent, an alkaline agent, fatty acid and a corrosion inhibitor which are all corresponding to the same components;
the water-based cutting fluid optionally contains a first surfactant, the first surfactant being not a nonionic surfactant, the first surfactant being an anionic surfactant;
the water-based metal cleaner contains a second surfactant, wherein the second surfactant is a low-foaming surfactant, and is preferably a C8-C12 polyoxyethylene ether surfactant;
the pH values of the water-based metal cleaner working solution and the water-based antirust working solution are both below 10.
10. Aqueous metal product combination according to claim 9,
the water-based cutting fluid comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0.01-25 parts of lubricating grease, 0.01-5 parts of coupling agent, 10-40 parts of base oil and 5-30 parts of deionized water;
the water-based metal cleaner comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor, 0-5 parts of second surfactant and 50-80 parts of deionized water;
the water-based antirust liquid comprises the following components in parts by weight: 0.01-3 parts of chelating agent, 0.01-15 parts of alkaline agent, 0.01-10 parts of fatty acid, 0.01-3 parts of corrosion inhibitor and 50-80 parts of deionized water;
the water-based cutting fluid, the water-based metal cleaner and the water-based antirust fluid are the same or different in unit weight part.
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| CN115678659B (en) | 2024-01-16 |
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