Water-based degreasing agent containing micro-nano molybdenum dioxide for removing dirt from nickel-based high-temperature alloy scraps and preparation method of water-based degreasing agent

Abstract

The invention relates to a water-based degreasing agent containing micro-nano molybdenum dioxide for removing dirt from nickel-based high-temperature alloy scraps and a preparation method of the water-based degreasing agent. The preparation method comprises the following steps: weighing 5% of potassium hydroxide and 77% of water in total mass percentage, and stirring in a stirring barrel; weighing 4% by mass of disodium ethylene diamine tetraacetate, 4% by mass of urea, 2% by mass of borax, 0.2% by mass of sodium benzoate and 0.4% by mass of water glass, and adding into the stirring barrel; after stirring to a certain degree, adding 3% by mass of fatty alcohol-polyoxyethylene ether, 0.5% by mass of molybdenum dioxide, 2% by mass of oleic acid, 1% by mass of triethanolamine and 0.9% by mass of ethyl alcohol, and after stirring is completed, preparing the degreasing agent containing micro-nano molybdenum dioxide after foam disappears. According to the stability theory of an emulsifier, the degreasing agent can be effectively used as the emulsifier to stabilize the formation of an emulsion, and micro-nano molybdenum dioxide can induce the arrangement mode of nonionic surface active micelles, so that the degreasing agent is more stable, the nonionic surface active micelles can be effectively induced, and dirt can be better sheared and stripped.

Description

Technical Field

[0001] The invention relates to the technical field of water-based metal degreasing agents, in particular to a water-based degreasing agent containing micro-nano molybdenum dioxide for removing dirt from nickel-based high-temperature alloy chips and a preparation method thereof. Background Art

[0002] Water-based metal degreasers are composite degreasers mainly composed of surfactants, water and other additives. Compared with the two common degreasing methods of boiling alkaline water degreasing and organic solvent degreasing, the advantages of water-based degreasing agents are that they can be mixed with water in any ratio, have no toxic side effects, have good oil removal effects, are relatively low in cost, are widely used, and meet current environmental protection requirements.

[0003] For example, 201711472683.0 proposes an environmentally friendly functional water-based degreasing agent for use before metal painting, and its preparation method and application. This nitrogen-free and phosphorus-free water-based degreasing agent has high cleaning performance and high oil-water separation properties for several commercially available body stamping oils / drawing oils, and can also reduce the COD value of degreasing waste liquid in pre-painting treatment and reduce the total amount of degreasing waste liquid.

[0004] During the processing of nickel-based high-temperature alloys, a certain amount of chips will be produced, and there will be a certain amount of dirt on the surface of the chips, which will affect the use. The cutting fluid used in the processing of nickel alloys is composed of a series of complex components, which is also the main source of dirt. In order to re-smelt to obtain nickel alloy materials with excellent performance, higher requirements are put forward for surface cleaning. Traditional chemical cleaning has been difficult to meet the requirements, so a specific degreasing agent is needed to comprehensively clean the surface of nickel alloys. Therefore, it is urgent to propose a water-based degreasing agent containing micro-nano molybdenum dioxide for nickel-based high-temperature alloy chip dirt removal and its preparation method to solve the above problems. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention provides a water-based degreasing agent containing micro-nano molybdenum dioxide for removing dirt from nickel-based high-temperature alloy chips and a preparation method thereof, which has the advantages of good cleaning effect and stable degreasing agent, and solves the problem that a certain amount of chips will be generated during the processing of nickel-based high-temperature alloys, and there is a certain amount of dirt on the surface of the chips, which affects the use. The cutting fluid used in the processing of nickel alloys is composed of a series of complex components, which is also the main source of dirt. In order to re-smelt to obtain nickel alloy materials with excellent performance, higher requirements are put forward for surface cleaning. Traditional chemical cleaning has been difficult to meet the requirements, so a specific degreasing agent is needed to comprehensively clean the surface of nickel alloys.

[0006] To achieve the above purpose, the present invention provides the following technical solution: a water-based degreasing agent containing micro-nano molybdenum dioxide, comprising the following raw materials in mass percentage: 5-7% potassium hydroxide, 70-80% water, 1-4% disodium ethylenediaminetetraacetic acid, 2-5% urea, 0.5-3% borax, 0.1-0.5% sodium benzoate, 0.2-0.8% water glass, 3-9% fatty alcohol polyoxyethylene ether, 0.2-0.5% molybdenum dioxide, 2-5% oleic acid, 1-3% triethanolamine, and 0.5-1.5% ethanol.

[0007] A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide, including a method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide, wherein the preparation method is specifically as follows:

[0008] Step 1: Weigh potassium hydroxide and water in the formula mass percentage and pour them into a mixing bucket for thorough stirring;

[0009] Step 2: Weigh the total mass percentage of EDTA disodium, urea, borax, sodium benzoate and water glass into a mixing bucket and stir for 30-40 minutes;

[0010] Step 3: Finally, add fatty alcohol polyoxyethylene ether, molybdenum dioxide, oleic acid, triethanolamine and ethanol in the total mass percentage of the formula, and stir thoroughly to obtain a degreasing agent containing micro-nano molybdenum dioxide.

[0011] Preferably, in step 2, the ratio of disodium ethylenediaminetetraacetate, urea and borax is 2:2:1, and the stirring temperature is 20-40°C.

[0012] Preferably, in step 3, the ratio of fatty alcohol polyoxyethylene ether to oleic acid triethanolamine is 3:2:1, and the stirring temperature is 20-60°C.

[0013] Preferably, the preparation method of the molybdenum dioxide is as follows:

[0014] 1) Take (NH4)6Mo7O 24 4H2O, after being fully ground and evenly placed in an alumina porcelain boat, the alumina porcelain boat is then placed in a tubular atmosphere furnace and argon is introduced for half an hour at a volume flow rate of 200sccm;

[0015] 2) heating from room temperature to 400-600° C. at a heating rate of 5-15° C. / min, and keeping the temperature for 1-3 hours. During the keeping temperature, the gas volume flow rate of argon gas is controlled to be 0-120 sccm. After the reaction is completed, the reaction is cooled to room temperature. During the cooling process to room temperature, the gas volume flow rate of argon gas is controlled to be 0-200 sccm.

[0016] 3) After washing the product obtained in step 2), dry it under vacuum at 50-90° C. for 12-24 hours.

[0017] Preferably, the preparation method of disodium ethylenediaminetetraacetate is as follows:

[0018] 1) Add 292 kg of ethylenediaminetetraacetic acid and 1200 L of water to a 2000 L enamel reaction tank, add 270 kg of 30% sodium hydroxide solution under stirring, and heat until the reaction is complete;

[0019] 2) Add hydrochloric acid to pH = 4.5, heat to 90°C, concentrate, and filter;

[0020] 3) Cool the filtrate and filter out the crystals

[0021] 4) Wash with water and dry at 70°C to obtain disodium ethylenediaminetetraacetate.

[0022] Preferably, the sodium benzoate is prepared by first oxidizing toluene with air in the presence of a cobalt naphthenate catalyst to produce benzoic acid, then using benzoic acid as a raw material, neutralizing with sodium bicarbonate, decolorizing with activated carbon, and then filtering, drying, and pulverizing.

[0023] Preferably, the water glass is liquid sodium silicate, the fatty alcohol polyoxyethylene ether uses sodium hydroxide as a catalyst, and is produced by a ring-opening polymerization reaction of a long-chain fatty alcohol with ethylene oxide in the absence of water and oxygen.

[0024] Preferably, the preparation method of the molybdenum dioxide is as follows:

[0025] 1) Molybdenum trioxide is placed in a porcelain dish and heated to 450°C in a hydrogen stream for 5 to 7 hours to react and generate molybdenum dioxide mixed with molybdenum trioxide;

[0026] 2) Put 170-325 mesh molybdenum trioxide powder into a porcelain plate and send it to a high-temperature dried reaction tube;

[0027] 3) Hydrogen is passed to completely replace the air in the reaction tube, and the temperature is raised to 550-700°C in the hydrogen flow and maintained for about 1 hour, and all the molybdenum trioxide is reduced to molybdenum dioxide.

[0028] Compared with the prior art, the technical solution of this application has the following beneficial effects:

[0029] 1. The micro-nano molybdenum dioxide of the present invention can stabilize the degreasing agent on the one hand, and on the other hand, the addition of micro-nano molybdenum dioxide has a small particle size and can more effectively peel off the dirt on the surface of the scraps.

[0030] 2. According to the stability theory of emulsifiers, the present invention can effectively act as an emulsifier to stabilize the formation of emulsions. Micro-nano-scale molybdenum dioxide can induce the arrangement of non-ionic surfactant micelles, making the degreasing agent more stable. It can effectively induce non-ionic surfactant micelles and better shear and peel off dirt. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the XRD diagram of the water-based degreasing agent containing micro-nano molybdenum dioxide of the present invention;

[0032] Figure 2 This is a SEM image of the water-based degreasing agent containing micro-nano molybdenum dioxide of the present invention. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Embodiment 1:

[0035] 1) Weigh 5% potassium hydroxide and 77% water in a mixing bucket and stir;

[0036] 2) Weigh 4% of disodium ethylenediaminetetraacetate, 4% of urea, 2% of borax, 0.2% of sodium benzoate and 0.4% of water glass by total mass and add them into a mixing tank;

[0037] 3) After stirring to a certain extent, 3% of fatty alcohol polyoxyethylene ether, 0.5% of molybdenum dioxide, 2% of oleic acid, 1% of triethanolamine and 0.9% of ethanol were added in total mass percentage, and after stirring, the foam was allowed to subside to prepare a degreasing agent A containing micro-nano molybdenum dioxide.

[0038] Embodiment 2:

[0039] 1) Weigh 6% potassium hydroxide and 75% water in a mixing bucket and stir;

[0040] 2) Weigh 2% of disodium ethylenediaminetetraacetate, 2% of urea, 1% of borax, 0.4% of sodium benzoate and 0.8% of water glass by total mass and add them into a mixing tank;

[0041] 3) After stirring to a certain extent, add 6% of fatty alcohol polyoxyethylene ether, 0.3% of molybdenum dioxide, 4% of oleic acid, 2% of triethanolamine and 0.5% of ethanol by total mass percentage, and wait for the foam to subside after stirring to prepare a degreasing agent B containing micro-nano molybdenum dioxide.

[0042] Embodiment 3:

[0043] 1) Weigh 7% potassium hydroxide and 74% water in a mixing bucket and stir;

[0044] 2) Weigh 3% of disodium ethylenediaminetetraacetate, 3% of urea, 1.5% of borax, 0.3% of sodium benzoate and 0.6% of water glass by total mass and add them into a mixing tank;

[0045] 3) After stirring to a certain extent, 4.5% of fatty alcohol polyoxyethylene ether, 0.4% of molybdenum dioxide, 3% of oleic acid, 1.5% of triethanolamine and 1.2% of ethanol were added in total mass percentage, and after stirring, the foam was allowed to subside to prepare a degreasing agent C containing micro-nano molybdenum dioxide.

[0046] In the above embodiment, the preparation method of molybdenum dioxide is as follows:

[0047] 1) Take (NH4)6Mo7O 24 ·4H2O·4H2O, after being fully ground and evenly placed in an alumina porcelain boat, the alumina porcelain boat is then placed in a tubular atmosphere furnace and argon is introduced for half an hour at a volume flow rate of 200sccm;

[0048] 2) heating from room temperature to 400-600° C. at a heating rate of 5-15° C. / min, and keeping the temperature for 1-3 hours. During the keeping temperature, the gas volume flow rate of argon gas is controlled to be 0-120 sccm. After the reaction is completed, the reaction is cooled to room temperature. During the cooling process to room temperature, the gas volume flow rate of argon gas is controlled to be 0-200 sccm.

[0049] 3) After washing the product obtained in step 2), dry it under vacuum at 50-90° C. for 12-24 hours.

[0050] In the above embodiment, the preparation method of disodium edetate is as follows:

[0051] 1) Add 292 kg of ethylenediaminetetraacetic acid and 1200 L of water to a 2000 L enamel reaction tank, add 270 kg of 30% sodium hydroxide solution under stirring, and heat until the reaction is complete;

[0052] 2) Add hydrochloric acid to pH = 4.5, heat to 90°C, concentrate, and filter;

[0053] 3) Cool the filtrate and filter out the crystals

[0054] 4) Wash with water and dry at 70°C to obtain disodium ethylenediaminetetraacetate.

[0055] In the above embodiment, sodium benzoate is prepared by first oxidizing toluene with air in the presence of a cobalt naphthenate catalyst to produce benzoic acid, then using benzoic acid as a raw material, neutralizing with sodium bicarbonate, decolorizing with activated carbon, and then filtering, drying, and pulverizing.

[0056] In the above embodiment, water glass is liquid sodium silicate, and the fatty alcohol polyoxyethylene ether uses sodium hydroxide as a catalyst. The long-chain fatty alcohol undergoes a ring-opening polymerization reaction with ethylene oxide in the absence of water and oxygen.

[0057] In the above embodiment, the preparation method of molybdenum dioxide is as follows:

[0058] 1) Molybdenum trioxide is placed in a porcelain dish and heated to 450°C in a hydrogen stream for 5 to 7 hours to react and generate molybdenum dioxide mixed with molybdenum trioxide;

[0059] 2) Put 170-325 mesh molybdenum trioxide powder into a porcelain plate and send it to a high-temperature dried reaction tube;

[0060] 3) Hydrogen is passed to completely replace the air in the reaction tube, and the temperature is raised to 550-700°C in the hydrogen flow and maintained for about 1 hour, and all the molybdenum trioxide is reduced to molybdenum dioxide.

[0061] By adopting the above technical solution, reference Figure 1 and Figure 2 For cleaning of dirt, the temperature setting should not only consider the degree of cleaning, but also the stability of the cleaning system, so as to facilitate operation. Factors such as the latitude of the factory will affect the boiling point of water. To avoid excessive evaporation of water and ensure the stability of the cleaning solution, the treatment temperature is 60-90°C. Under normal circumstances, 75-90°C can achieve the cleaning effect and ensure the stability of the system. The cleaning of scraps at 80°C, the degreasing agent A containing micro-nano molybdenum dioxide / the degreasing agent B containing micro-nano molybdenum dioxide and the degreasing agent C containing micro-nano molybdenum dioxide prepared by the present invention have a cleaning effect greater than 95%.

[0062] In summary, the micro-nano-scale molybdenum dioxide of the present invention can stabilize the degreasing agent on the one hand, and on the other hand, the addition of micro-nano-scale molybdenum dioxide has a small particle size and can more effectively peel off the dirt on the surface of the chips. According to the stability theory of emulsifiers, it can effectively serve as an emulsifier to stabilize the formation of emulsions. Micro-nano-scale molybdenum dioxide can induce the arrangement of non-ionic surfactant micelles, making the degreasing agent more stable. It can effectively induce non-ionic surfactant micelles to better shear and peel off dirt, solving the problem that a certain amount of chips will be generated during the processing of nickel-based high-temperature alloys, and there will be certain dirt on the surface of the chips, which affects the use. The cutting fluid used in the processing of nickel alloys is composed of a series of complex components, which is also the main source of dirt. In order to re-smelt to obtain nickel alloy materials with excellent performance, higher requirements are put forward for surface cleaning. Traditional chemical cleaning has been difficult to meet the requirements, so a specific degreasing agent is needed to comprehensively clean the surface of nickel alloys.

[0063] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0064] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A water-based degreasing agent containing micro-nano molybdenum dioxide, It is characterized in that The invention comprises the following raw materials in percentage by mass: 5-7% potassium hydroxide, 70-80% water, 1-4% disodium ethylenediaminetetraacetate, 2-5% urea, 0.5-3% borax, 0.1-0.5% sodium benzoate, 0.2-0.8% water glass, 3-9% fatty alcohol polyoxyethylene ether, 0.2-0.5% molybdenum dioxide, 2-5% oleic acid, 1-3% triethanolamine and 0.5-1.5% ethanol.

2. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide, comprising the method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 1, It is characterized in that The preparation method is specifically as follows: Step 1: Weigh potassium hydroxide and water in the formula mass percentage and pour them into a mixing bucket for thorough stirring; Step 2: Weigh the total mass percentage of EDTA disodium, urea, borax, sodium benzoate and water glass into a mixing bucket and stir for 30-40 minutes; Step 3: Finally, add fatty alcohol polyoxyethylene ether, molybdenum dioxide, oleic acid, triethanolamine and ethanol in the total mass percentage of the formula, and stir thoroughly to obtain a degreasing agent containing micro-nano molybdenum dioxide.

3. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that In the step 2, the ratio of disodium ethylenediaminetetraacetate, urea and borax is 2:2:1, and the stirring temperature is 20-40°C.

4. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that In the step 3, the ratio of fatty alcohol polyoxyethylene ether to oleic acid triethanolamine is 3:2:1, and the stirring temperature is 20-60°C.

5. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that The preparation method of the molybdenum dioxide is as follows: 1) Take (NH 4 )6Mo 7 O 24 ·4H 2 O, after being fully ground and evenly placed in an alumina porcelain boat, the alumina porcelain boat is then placed in a tubular atmosphere furnace and argon is introduced for half an hour at a volume flow rate of 200 sccm; 2) heating from room temperature to 400-600° C. at a heating rate of 5-15° C. / min, and keeping the temperature for 1-3 hours. During the keeping temperature, the gas volume flow rate of argon gas is controlled to be 0-120 sccm. After the reaction is completed, the reaction is cooled to room temperature. During the cooling process to room temperature, the gas volume flow rate of argon gas is controlled to be 0-200 sccm. 3) After washing the product obtained in step 2), dry it under vacuum at 50-90° C. for 12-24 hours.

6. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that The preparation method of disodium ethylenediaminetetraacetate is as follows: 1) Add 292 kg of ethylenediaminetetraacetic acid and 1200 L of water to a 2000 L enamel reaction tank, add 270 kg of 30% sodium hydroxide solution under stirring, and heat until the reaction is complete; 2) Add hydrochloric acid to pH = 4.5, heat to 90°C, concentrate, and filter; 3) Cool the filtrate and filter out the crystals 4) Wash with water and dry at 70°C to obtain disodium ethylenediaminetetraacetate.

7. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that The sodium benzoate is prepared by first oxidizing toluene with air in the presence of a cobalt naphthenate catalyst to produce benzoic acid, then using the benzoic acid as a raw material, neutralizing it with sodium bicarbonate, decolorizing it with activated carbon, and then filtering, drying, and crushing it.

8. A method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that The water glass is liquid sodium silicate, and the fatty alcohol polyoxyethylene ether uses sodium hydroxide as a catalyst. The long-chain fatty alcohol undergoes a ring-opening polymerization reaction with ethylene oxide in the absence of water and oxygen.

9. The method for preparing a water-based degreasing agent containing micro-nano molybdenum dioxide according to claim 2, It is characterized in that The preparation method of the molybdenum dioxide is as follows: 1) Molybdenum trioxide is placed in a porcelain dish and heated to 450°C in a hydrogen stream for 5 to 7 hours to react and generate molybdenum dioxide mixed with molybdenum trioxide; 2) Put 170-325 mesh molybdenum trioxide powder into a porcelain plate and send it to a high-temperature dried reaction tube; 3) Hydrogen is passed to completely replace the air in the reaction tube, and the temperature is raised to 550-700°C in the hydrogen flow and maintained for about 1 hour, and all the molybdenum trioxide is reduced to molybdenum dioxide.

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