An environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys, its preparation method and application

Abstract

The present invention relates to the technical field of metal processing lubrication, and particularly relates to an environment-friendly hot rolling emulsion oil for aluminum and aluminum alloys, its preparation method and application. The present invention uses an aromatic hydrocarbon-hydrotreated naphthenic oil containing an appropriate amount as the base oil, and its high evaporation loss characteristic enables the emulsion to have good detergency, which can reduce the residue on the surface of the aluminum plate after rolling and improve the surface quality and detergency of the aluminum plate. The present invention also uses a composite emulsifier. In addition to playing an emulsifying role, the multi-functional groups on its molecular structure can achieve functions such as improving rust prevention and lubrication. At the same time, the composite process of the emulsifier can promote the solubility of the emulsifier in the base oil. In addition, the present invention also makes appropriate compatibility of other additives according to the application scenario and environment, and has the characteristics of good dispersion stability, good additive compatibility, less coke residue, non-toxic and harmless, no obvious odor, less oil sludge, and easy maintenance.

Description

Technical Field

[0001] The present invention relates to the technical field of metal processing lubrication, and particularly relates to an environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys, a preparation method thereof and an application thereof. Background Art

[0002] During the aluminum hot-rolling process, the rolled piece is in a high-temperature, high-pressure and high-friction environment, and surface defects of the rolled plate such as sticking rolls are extremely likely to occur. Therefore, an emulsion must be used for lubrication and cooling. The emulsion is an important factor in controlling the surface quality such as the shape and color difference of aluminum and aluminum alloy plates.

[0003] Most of the current aluminum hot-rolling emulsions on the market use paraffin-based oil as the base oil and use a large amount of toxic additives to ensure that the emulsion has good lubrication and cooling properties. Moreover, they have disadvantages such as poor detergency, strong toxicity, pungent odor, and easy generation of sludge, which will cause serious environmental pollution and inconvenience to production.

[0004] The aluminum hot-rolling process is different from cold working conditions such as cold rolling and cutting. Aluminum hot-rolling is generally in a high-temperature environment above 400°C. After the aluminum hot-rolling emulsion plays a role in lubrication and cooling, it evaporates rapidly on the surface of the aluminum plate. Therefore, compared with cold working conditions, more attention is paid to the high-temperature evaporation residue of the emulsion. Most traditional aluminum hot-rolling emulsions use paraffin-based oil as the base oil. Due to the small evaporation loss, some oil will not evaporate completely and form residual carbon on the surface of the aluminum plate, affecting the surface detergency of the aluminum plate and deteriorating the surface quality. Summary of the Invention

[0005] In view of the problems of the prior art, the present invention provides an environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys, its preparation method and application. The present invention uses an aromatic hydrocarbon-hydrotreated naphthenic oil containing an appropriate amount as the base oil, and its high evaporation loss characteristics enable the emulsion to have good detergency, which can reduce the residue on the surface of the aluminum plate after rolling, and improve the surface quality and detergency of the aluminum plate. At the same time, the single-ring aromatic hydrocarbons in the base oil can improve the performance of the base oil, increase the ability of the emulsion to resist miscellaneous oils, avoid the destruction of the lubricity of the emulsion by the sludge and aluminum powder generated during the hot-rolling process, and improve the anti-wear and friction-reducing performance of the emulsion; in addition, the aromatic hydrocarbon-hydrotreated naphthenic oil containing an appropriate amount can effectively reduce the dosage of additives due to its good compatibility with additives, while ensuring that the emulsion has sufficient lubrication and cooling performance. The present invention also uses a composite emulsifier, which can not only play an emulsifying role, but also the multi-functional groups on its molecular structure can improve the functions such as rust prevention and lubrication. At the same time, the composite process of the emulsifier can promote the dissolution ability of the emulsifier in the base oil. The present invention has a low fatty acid content and is not easy to generate metal soaps with metal ions, so it can reduce the generation of solid wastes such as sludge, is easy to clean after use, and reduces the difficulty of subsequent treatment. In addition, the present invention also makes appropriate compatibility of other additives according to the application scenario and environment, and has the characteristics of good dispersion stability, good additive compatibility, less residual carbon, non-toxic and harmless, no obvious odor, less sludge, and easy maintenance, solving the disadvantages of traditional aluminum hot-rolling emulsion such as high additive content, strong toxicity, pungent odor, easy generation of sludge, and great harm to the environment. At the same time, the present invention also has excellent lubricity and cooling performance.

[0006] Specifically, the technical solution of the present invention includes:

[0007] In the first aspect, an environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys, by mass percentage, its composition includes: vegetable oil 5.00% - 10.00%, composite emulsifier 5.00% - 10.00%, extreme pressure agent 1.00% - 2.00%, rust inhibitor 1.00% - 5.00%, oiliness agent 4.00% - 5.00%, antioxidant 1% - 1.5%, defoamer 0.02% - 0.10%, and the balance is base oil; the base oil is an aromatic hydrocarbon-hydrotreated naphthenic oil.

[0008] Preferably, for the aromatic hydrocarbon-hydrotreated naphthenic oil, its kinematic viscosity at 40°C should be controlled at 40 - 70 mm 2 / s, the aromatic hydrocarbon content is 5% - 9%, and PCA < 3%.

[0009] The composite emulsifier is a compound of sorbitan oleate and polyoxyethylene sorbitan oleate, and the mass ratio is 1:1.5 - 4.

[0010] The extreme pressure agent is di-n-butyl phosphite or ammonium thiophosphate.

[0011] The rust inhibitor is sodium petroleum sulfonate or sodium alkylbenzene sulfonate.

[0012] The oiliness agent is a compound of pentaerythritol oleate and butyl stearate, and the mass ratio is 1:3.

[0013] The vegetable oil can be selected according to the existing conventional technology; preferably, the vegetable oil is one or a mixture of two of palm oil and rapeseed oil.

[0014] The antioxidant can be selected according to the existing conventional technology; preferably, the antioxidant is one or a mixture of two of 2,6-di-tert-butyl-p-cresol and dialkyldithiocarbamate.

[0015] The defoamer is ethylene diamine PO-EO block copolymer.

[0016] In the second aspect of the present invention, a preparation method of the above-mentioned environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys is provided, and the specific steps include:

[0017] Step 1: Prepare a composite emulsifier: Mix sorbitan oleate and polyoxyethylene sorbitan oleate, heat to 40-50 °C, and stir with a magnetic stirrer at a speed of 300-400 r / min for 5-10 min to obtain a composite emulsifier.

[0018] Preferably, sorbitan oleate and polyoxyethylene sorbitan oleate are mixed in a mass ratio of 1:1.5-4.

[0019] Step 2: Prepare aluminum hot-rolling emulsion oil: Add vegetable oil, composite emulsifier and rust inhibitor to the base oil in sequence. Under the heating condition of 70-80 °C, stir at a speed of 300-400 r / min until it is uniformly transparent, and then add extreme pressure agent, oiliness agent, antioxidant and defoamer in sequence. Under the heating condition of 40-50 °C, stir at a speed of 400-600 r / min for 15-20 min to obtain the environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys. Step 2 is to ensure that the composite emulsifier and other additives achieve good synergistic effects, and the appearance of the oil product is transparent.

[0020] In the third aspect of the present invention, an application method of the above-mentioned environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys is provided, and the emulsion oil is emulsified into an emulsion with deionized water for application.

[0021] More preferably, the emulsification process of the emulsion oil is specifically: Dilute the emulsion oil with deionized water to a concentration of 3%-5%, and stir at a speed of 600-800 r / min for 15-20 min to obtain the environment-friendly hot-rolling emulsion for aluminum and aluminum alloys.

[0022] The beneficial effects of the present invention are as follows:

[0023] The main component of the composite emulsifier used in the present invention is a non-ionic emulsifier, and its molecular structure contains multifunctional groups such as hydroxyl groups and ester groups with rust prevention functions. On the one hand, it has good emulsifying ability, can make the particle size distribution of the emulsion uniform, has good dispersion stability, and can be stored for a long time at room temperature. On the other hand, the groups in the molecular structure of the composite emulsifier enable the emulsifier to have multifunctional characteristics, thereby reducing the use of additives and preventing antagonistic effects with other active ingredients. In addition, the polar end of the sorbitan oleate molecule adsorbs on the metal surface to form an adsorption film, preventing water, oxygen, and corrosive substances from reaching the metal surface, and can improve the surface quality after rolling. Other additives in the composite emulsifier can achieve good synergistic effects, improve the surface smoothness of the rolled plate, and reduce the thickness of the rolled plate.

[0024] The aromatic hydrocarbons contained in the hydrogenated naphthenic oil with appropriate aromatic hydrocarbons used in the present invention are monocyclic aromatic hydrocarbons, which have no carcinogenic effect compared with polycyclic aromatic hydrocarbons; they have strong antioxidant properties and can inhibit the oxidation of oil products; and they can make oil droplets easily adsorb on the surface of aluminum plates to form a thin adsorption film to improve anti-wear and friction reduction performance; they can also improve the solubility of the base oil, reduce the influence of aluminum powder and sludge generated during hot rolling, and improve the anti-impurity oil ability of the emulsion. At the same time, aromatic hydrocarbons can reduce the viscosity index of the base oil and prevent large changes in the fluidity of oil products in low-temperature and high-temperature environments.

[0025] The aluminum hot rolling process is generally in a high-temperature environment above 400 °C. After the aluminum hot rolling emulsion plays a lubricating and cooling role, it evaporates rapidly on the surface of the aluminum plate. Most of the base oils of traditional aluminum hot rolling emulsions are paraffin-based oils, which are not easy to volatilize during hot rolling and form coke residues on the surface of the aluminum plate, thus affecting the surface quality and surface cleanliness. The high evaporation loss characteristics of the hydrogenated naphthenic oil with appropriate aromatic hydrocarbons enable the emulsion to have good cleanliness, can reduce the residues on the surface of the aluminum plate after rolling, reduce the coke residue content, and improve the surface cleanliness. At the same time, the hydrogenated naphthenic oil with appropriate aromatic hydrocarbons used in the present invention has good compatibility. Compared with traditional paraffin-based aluminum hot rolling emulsions, naphthenic oil can give full play to the anti-wear and friction reduction effects of extreme pressure agents and oiliness agents, and is easy to emulsify, saving the amount of emulsifier used, thereby reducing costs.

[0026] The additives used in the present invention are green and environmentally friendly, contain no harmful substances, have no obvious odor, and are an environmentally friendly type of emulsion. The present invention has a low fatty acid content and is not easy to react with metal ions to form metal soaps, thereby avoiding the formation of solid impurities such as oil sludge by substances such as impurity oil in the emulsion circulation system, facilitating the maintenance of the emulsion system, and also playing a positive role in protecting the ecological environment and promoting sustainable development.

[0027] The present invention has excellent anti-wear and lubricating properties, which are better than some domestic and foreign brand aluminum hot rolling emulsions on the current market. It can play a good role in lubricating and cooling during the aluminum hot rolling process and can be widely used in the hot rolling of aluminum plates and strips. Brief Description of the Drawings

[0028] Figure 1 It is a comparison chart of the oil separation and soap separation of the emulsion in Example 2 and Comparative Example 3.

[0029] Figure 2 It is the residue situation on the surface of a high-temperature aluminum plate in the experiment of using the EXXON annealing box method for the emulsions in Example 2 and Comparative Example 3.

[0030] Figure 3 It is the appearance of the emulsified oil and emulsion in Examples 1-3.

[0031] Figure 4 It is the wear scar morphology after the four-ball long-term wear experiment in Examples 1-3 and Comparative Examples 1-3. Detailed Embodiments

[0032] The following is a further detailed description of the above content of the present invention through specific embodiments in the form of examples, but this should not be construed as limiting the scope of the above subject matter of the present invention to the following examples. All technologies implemented based on the above content of the present invention belong to the scope of the present invention. Unless otherwise specified, the following examples are all completed using conventional technical operations.

[0033] Example 1

[0034] The weight percentages of the emulsified oil in Example 1 are as follows: rapeseed oil 5%, compound emulsifier 5%, dibutyl phosphite 1%, pentaerythritol oleate 1%, butyl stearate 3%, sodium petroleum sulfonate 3%, molybdenum dialkyldithiocarbamate 1%, ethylene diamine PO-EO block copolymer 0.1%, and the balance is a 46# hydrogenated naphthenic oil containing an appropriate amount of aromatics, with a CA value of 8 and a PCA of 1.8%.

[0035] 1) Preparation of the compound emulsifier: Mix the non-ionic surfactant sorbitan oleate and polyoxyethylene sorbitan oleate in a mass ratio of 1:4, and stir with a magnetic stirrer at a speed of 300 r / min for 5 min to obtain a compound emulsifier with rust prevention and emulsification properties.

[0036] 2) Preparation of the aluminum hot-rolling emulsified oil: Sequentially add rapeseed oil, compound emulsifier, and sodium petroleum sulfonate to the base oil, and stir at a speed of 300 r / min until homogeneous and transparent under heating conditions at 70°C. Then sequentially add dibutyl phosphite, pentaerythritol oleate, butyl stearate, molybdenum dialkyldithiocarbamate, and ethylene diamine PO-EO block copolymer, and stir at a speed of 500 r / min for 15 min under heating conditions at 40°C to obtain an environmentally friendly hot-rolling emulsified oil for aluminum and its alloys.

[0037] According to requirements, a hot-rolled emulsion can be prepared: Dilute the emulsifying oil with deionized water to a concentration of 5%, and stir at a speed of 600 r / min for 15 min to obtain an environmentally friendly hot-rolled emulsion for aluminum and aluminum alloys.

[0038] Example 2

[0039] The weight percentages of the emulsifying oil in Example 2 are as follows: palm oil 10%, composite emulsifier 10%, dibutyl phosphite 2%, sodium petroleum sulfonate 5%, pentaerythritol oleate 1.5%, butyl stearate 4.5%, 2,6-di-tert-butyl-p-cresol 1.5%, ethylene diamine PO-EO block copolymer 0.05%, and the balance is 56# hydrogenated naphthenic oil containing appropriate aromatics, with a CA value of 5 and a PCA of 2.1%.

[0040] 1) Prepare the composite emulsifier: Mix the non-ionic surfactants sorbitan oleate and polyoxyethylene sorbitan oleate in a mass ratio of 1:1.5, and stir with a magnetic stirrer at a speed of 300 r / min for 5 min to obtain a composite emulsifier with rust prevention and emulsification properties.

[0041] 2) Prepare the aluminum hot-rolled emulsifying oil: Add palm oil, composite emulsifier, and sodium petroleum sulfonate to the base oil in sequence. Under the heating condition of 70 °C, stir at a speed of 300 r / min until it is uniformly transparent, and then add dibutyl phosphite, pentaerythritol oleate, butyl stearate, 2,6-di-tert-butyl-p-cresol, and ethylene diamine PO-EO block copolymer in sequence. Under the heating condition of 50 °C, stir at a speed of 600 r / min for 15 min to obtain an environmentally friendly hot-rolled emulsifying oil for aluminum and aluminum alloys.

[0042] According to requirements, a hot-rolled emulsion can be prepared: Dilute the emulsifying oil with deionized water to a concentration of 5%, and stir at a speed of 600 r / min for 15 min to obtain an environmentally friendly hot-rolled emulsion for aluminum and aluminum alloys.

[0043] Example 3

[0044] The weight percentages of the emulsifying oil in Example 3 are as follows: palm oil 8%, composite emulsifier 8%, ammonium thiophosphate 1.5%, alkylbenzene sulfonate 4%, pentaerythritol oleate 1.2%, butyl stearate 3.6%, 2,6-di-tert-butyl-p-cresol 1.2%, ethylene diamine PO-EO block copolymer 0.05%, and the balance is 56# hydrogenated naphthenic oil containing appropriate aromatics, with a CA value of 5 and a PCA of 2.1%.

[0045] 1) Preparation of compound emulsifier: Mix the non-ionic surfactants sorbitan oleate and polyoxyethylene sorbitan oleate in a mass ratio of 1:2, and stir with a magnetic stirrer at a speed of 300 r / min for 5 min to obtain a compound emulsifier with rust prevention and emulsification properties.

[0046] 2) Preparation of aluminum hot-rolling emulsion oil: Add palm oil, compound emulsifier and sodium alkylbenzene sulfonate to the base oil in sequence. Under the heating condition of 80 °C, stir at a speed of 300 r / min until homogeneous and transparent, and then add ammonium thiophosphate, pentaerythritol oleate, butyl stearate, 2,6-di-tert-butyl-p-cresol, and ethylene diamine PO-EO block copolymer in sequence. Under the heating condition of 50 °C, stir at a speed of 600 r / min for 15 min to obtain an environmentally friendly hot-rolling emulsion oil for aluminum and its alloys.

[0047] The hot-rolling emulsion can be prepared according to requirements: Dilute the emulsion oil with deionized water to a concentration of 5%, and stir at a speed of 600 r / min for 15 min to obtain an environmentally friendly hot-rolling emulsion for aluminum and its alloys.

[0048] Comparative Example 1

[0049] It is a domestic brand aluminum hot-rolling emulsion oil. Dilute the emulsion oil with deionized water to a concentration of 5%, and stir at a speed of 600 r / min for 15 min to obtain an aluminum hot-rolling emulsion.

[0050] Comparative Example 2

[0051] It is a foreign brand aluminum hot-rolling emulsion oil. Dilute the emulsion oil with deionized water to a concentration of 5%, and stir at a speed of 600 r / min for 15 min to obtain an aluminum hot-rolling emulsion.

[0052] Comparative Example 3

[0053] Replace the 56# hydrogenated naphthenic oil in Example 2 with 350N paraffin base oil with similar viscosity, and the other technical solutions are the same as those in Example 2.

[0054] (1) Let the emulsion obtained in Example 2 and the emulsion of this comparative example stand for 20 min under the same room temperature condition, and observe the oil separation and soap separation situation as Figure 1 shown. The oil separation and soap separation of the paraffin base oil emulsion used in this Comparative Example 3 are relatively serious, and the emulsion prepared in Example 2 of the technical solution of this application has better stability.

[0055] (2) The EXXON annealing box method experiment is adopted, that is: use an aluminum box with a diameter of Ф70mm×2mm. At the vertices of an equilateral triangle 2mm away from the edge on the surface of the box cover, there are three through holes with a diameter of Ф2mm. Drop 0.125ml of emulsion into the box. After holding at 350°C for 1h, observe the change in the color of the bottom surface of the aluminum box to judge the surface residue situation after annealing as Figure 2 shown. The emulsion of Example 2 shows significantly better detergency than the emulsion of Comparative Example 3.

[0056] Use a four-ball friction and wear tester to measure the performance of each example and comparative example. Refer to GB / T3142-2019 "Determination of the Load-Carrying Capacity of Lubricants (Four-Ball Method)". The maximum non-seizure load is used to reflect the oil film strength. Under the conditions of a load of 392N, a rotational speed of 1200rpm, and a temperature of 25°C, a 60-minute long-term wear experiment is carried out to obtain the average friction coefficient of the emulsion, measure the wear scar diameter, observe the wear scar morphology, and the measured product performance indicators are as follows:

[0057]

[0058] The above table is a comparison of the quality inspection data of the products of the implementation cases of the present invention and ordinary emulsified oil.

[0059] It can be seen from the above data that: 1) The friction coefficient of the examples of the present invention is lower than that of Comparative Examples 1 and 2, having excellent anti-friction ability, and can reduce the rolling force and increase the rolling deformation efficiency during the rolling process; 2) The wear scar diameter of the examples of the present invention is smaller than that of the comparative examples, which can play an excellent anti-wear role and improve the surface quality after rolling. 3) The detergency and stability of the emulsion of the examples of the present invention are significantly better than those of Comparative Example 3. In summary, the comprehensive effect of the technical solution of this application is the best, that is, in addition to ensuring the excellent performance of the friction coefficient and wear scar diameter, it can also achieve better stability and detergency!

[0060] The above embodiments are all preferred embodiments of the present invention, which are only used to illustrate the actual effects of the present invention and are not limitations of the present invention. Any other changes, substitutions, and simplifications made without departing from the spirit and principle of the present invention shall be included within the scope of patent protection determined by the claims submitted in the present invention.

Claims

1. An environment-friendly hot-rolling emulsifying oil for aluminum and aluminum alloys, characterized in that, By mass percentage, its composition includes: vegetable oil 5.00% - 10.00%, compound emulsifier 5.00% - 10.00%, extreme pressure agent 1.00% - 2.00%, rust inhibitor 1.00% - 5.00%, oiliness agent 4.00% - 5.00%, antioxidant 1% - 1.5%, defoamer 0.05% - 0.10%, and the balance is base oil; the base oil is an aromatic-containing hydrotreated naphthenic oil; For the aromatic hydrocarbon-containing hydrocycloalkane oil, its kinematic viscosity at 40 °C should be controlled within 40-70 mm 2 / s, the aromatic hydrocarbon content is 5%-9%, and PCA < 3%; The vegetable oil is one or a mixture of two of palm oil and rapeseed oil; The compound emulsifier is a compound of sorbitan oleate and polyoxyethylene sorbitan oleate, and the compound mass ratio of sorbitan oleate and polyoxyethylene sorbitan oleate is 1:1.5 - 4.

2. The environment-friendly hot-rolling emulsifying oil for aluminum and aluminum alloys according to claim 1, characterized in that, The extreme pressure agent is dibutyl phosphite or ammonium thiophosphate; the rust inhibitor is sodium petroleum sulfonate or sodium alkylbenzene sulfonate; the oiliness agent is a compound of pentaerythritol oleate and butyl stearate, and the mass ratio is 1:

3.

3. The environment-friendly hot-rolling emulsifying oil for aluminum and aluminum alloys according to claim 1, characterized in that, The antioxidant is one or a mixture of two of 2,6-di-tert-butyl-p-cresol and dialkyldithiocarbamate; the defoamer is ethylene diamine PO-EO block copolymer.

4. A preparation method of the environment-friendly hot-rolling emulsifying oil for aluminum and aluminum alloys according to claim 1, characterized in that, Its specific steps include: Step 1: Prepare the compound emulsifier: Mix sorbitan oleate and polyoxyethylene sorbitan oleate, heat to 40 - 50 °C, and use a magnetic stirrer to stir at a speed of 300 - 400 r / min for 5 - 10 min to obtain the compound emulsifier; Step 2: Prepare the aluminum hot-rolling emulsion oil: Sequentially add vegetable oil, compound emulsifier, and rust inhibitor to the base oil, under the heating condition of 70 - 80 °C, stir at a speed of 300 - 400 r / min until homogeneous and transparent, then sequentially add the extreme pressure agent, oiliness agent, antioxidant, and defoamer, and stir at a speed of 400 - 600 r / min for 15 - 20 min under the heating condition of 40 - 50 °C to obtain an environment-friendly hot-rolling emulsion oil for aluminum and aluminum alloys.

5. An application method of the environment-friendly hot-rolling emulsifying oil for aluminum and aluminum alloys according to claim 1, characterized in that, Use deionized water to emulsify the emulsion oil into an emulsion for application.

6. The application method of the environment-friendly hot-rolling emulsifying oil for aluminum and aluminum alloys according to claim 5, characterized in that, The specific process of emulsifying the emulsion oil is: Use deionized water to dilute the emulsion oil to a concentration of 3% - 5%, and stir at a speed of 600 - 800 r / min for 15 - 20 min to obtain an environment-friendly hot-rolling emulsion for aluminum and aluminum alloys.

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