Composite material for cleaning greasy dirt as well as preparation method and application of composite material
By preparing and encapsulating a composite material in the dishwasher's water circuit, and utilizing a high-temperature treated P123 solution with molecular sieves, cerium precursor salts, and zirconium precursor salts, the environmental and health hazards of detergents are solved, achieving a cleaning effect on oil stains without detergent.
Patent Information
- Application Number
- CN202511057222.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-30
- Publication Date
- 2025-11-18
AI Technical Summary
Existing detergents contain surfactants, which cause environmental pollution and harm to human health. There is a need for a material that can effectively clean oil stains without detergent.
By preparing a P123 solution, mixing molecular sieves, cerium precursor salts and zirconium precursor salts, and then treating it at high temperature, a composite material is obtained and encapsulated in the sealed water circuit of a dishwasher. The material is used to generate strong dipoles in water molecules to remove oil stains.
It achieves effective cleaning of oil stains without detergent, avoiding harm to the environment and human body, and has good chemical stability and promising prospects for industrial applications.
Smart Images
Figure CN120966573A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of cleaning materials, in particular to a composite material for oil stain cleaning and a preparation method and application thereof. BACKGROUND
[0002] The cleaning principle of removing oil stains in a dishwasher is that a series of complex physical and chemical actions occur between the detergent, dirt and the surface of dishes during the washing process, and the mechanical force is used to make the dirt fall off the surface of the objects, suspended and dissolved in the detergent medium to be removed.
[0003] However, the commonly used dishwashing powder and rinsing agent usually contains sodium dodecyl benzene sulfonate, an anionic surfactant, which has surface tension, capacity, emulsification, adsorption and foaming effect, thereby achieving the cleaning of oil stains. Although this chemical detergent can effectively remove oil stains, it is harmful to the environment and human health.
[0004] According to relevant research, most of the surfactants in chemical detergents will pollute water sources, not only changing the quality of water, volatilizing harmful gases, producing foam or emulsification, but also blocking the exchange of oxygen in water, affecting the growth of aquatic organisms and destroying the balance of the water ecosystem. In addition, the adsorption of surfactants on soil will change the physical and chemical properties of soil, causing damage to the soil. Moreover, long-term use of chemical detergents can irritate the skin, cause the skin to age, and cause a certain degree of damage. In severe cases, it can cause epidermal necrosis, necrosis, and rupture. At the same time, at different mass fractions, surfactants can activate and inhibit enzymes in the human body, disrupting normal physiological functions.
[0005] In addition, surfactants can generally enter the human body through oral administration, affecting digestion and absorption functions, dissolving the fat of the digestive tract mucosa, changing its permeability, thereby affecting the absorption of nutrients and threatening people's health.
[0006] Therefore, there is an urgent need for a material that can replace detergents and enable ordinary household water to have oil stain removal function without adding washing liquid. SUMMARY
[0007] Therefore, the technical problem to be solved by the present application is how to solve the problem that the existing oil stain cleaning requires the use of washing liquid with surfactants, which in turn causes harm to the environment and human health, so as to provide a composite material for oil stain cleaning and a preparation method and application thereof, which can replace detergents and achieve the purpose of oil stain cleaning without detergents.
[0008] A preparation method of a composite material for oil stain cleaning comprises:
[0009] Obtaining P123 solution: P123 is mixed with anhydrous ethanol and stirred, and nitric acid is added and stirred to obtain a P123 solution;
[0010] Preparation of mixed solution: molecular sieve is stirred with the P123 solution, and cerium precursor salt and zirconium precursor salt are added and stirred; the mass ratio of molecular sieve to P123 is (15-170):1; the mass percentage of cerium is 3-10wt.% and the mass percentage of zirconium is 3-10wt.% based on the amount of molecular sieve;
[0011] Solvent evaporation: the mixed solution is subjected to solvent evaporation to obtain a semi-finished product;
[0012] High-temperature treatment: the semi-finished product is heated to 500-600℃ at a heating rate of 1-5℃ / min and kept for 2-4h to obtain a finished composite material.
[0013] The molecular formula of the above-mentioned P123 (polyoxypropylene polyoxyethylene copolymer solution) is C 18 H 36 O5, CAS No. 106392-12-5. Although P123 is a high-molecular non-ionic surfactant, it needs to be subjected to high-temperature treatment in the present application, and P123 is decomposed and carbonized during the high-temperature treatment process, so that the finished composite material obtained finally has no pollution problem.
[0014] Alternatively, the mass ratio of molecular sieve to P123 can be 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, etc.; the mass percentage of cerium is 3wt.%, 4wt.%, 5wt.%, 6wt.%, 7wt.%, 8wt.%, 9wt.%, 10wt.%, etc. based on the amount of molecular sieve; and the mass percentage of zirconium is 3wt.%, 4wt.%, 5wt.%, 6wt.%, 7wt.%, 8wt.%, 9wt.%, 10wt.%, etc.
[0015] Further, in the step of obtaining the P123 solution, the mass ratio of P123 to nitric acid is (0.24-0.64):1, and / or the mass-volume ratio of P123 to anhydrous ethanol is 0.6-1.2g / 20mL.
[0016] Optionally, the mass ratio of P123 to nitric acid can be 0.24:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.64:1, etc.; and the mass-volume ratio of P123 to anhydrous ethanol can be 0.6g / 20mL, 0.7g / 20mL, 0.8g / 20mL, 0.9g / 20mL, 1.0g / 20mL, 1.1g / 20mL, 1.2g / 20mL, etc.
[0017] Further, the specific surface area of the molecular sieve is 300-1000m 2 / g, and / or the porosity of the molecular sieve is 40%-80%.
[0018] Optionally, the specific surface area of the molecular sieve can be 300m 2 / g, 400m 2 / g, 500m 2 / g, 600m 2 / g, 700m 2 / g, 800m 2 / g, 900m 2 / g, 1000m 2 / g, etc.; and the porosity of the molecular sieve can be 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.
[0019] As an optional embodiment, in the obtaining step of the P123 solution, the mixing and stirring mode is magnetic stirring.
[0020] Further, the rotating speed of the magnetic stirring is 800-1200rpm.
[0021] Optionally, the rotating speed of the magnetic stirring can be 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, etc.
[0022] As an optional embodiment, the cerium precursor salt is at least one of cerium acetate, cerium nitrate, and cerium chloride.
[0023] As an optional embodiment, the zirconium precursor salt is at least one of zirconium chloride and zirconium nitrate.
[0024] A composite material for oil stain cleaning is prepared by the above preparation method.
[0025] The application further provides an application of the composite material for oil stain cleaning in a dishwasher.
[0026] Preferably, the composite material is applied by being packaged in a sealed water path of the dishwasher.
[0027] The technical scheme of the present application has the following advantages:
[0028] 1. The preparation method of the composite material for oil stain cleaning provided by the present application comprises the following steps: obtaining a P123 solution by mixing P123 with anhydrous ethanol and stirring, adding nitric acid and stirring to obtain the P123 solution; preparing a mixed solution by stirring and uniformly mixing molecular sieves with the P123 solution and adding cerium precursor salt and zirconium precursor salt and stirring; the mass ratio of the molecular sieves to the P123 is (15-170): 1; the mass percentage of cerium is 3-10 wt.%, and the mass percentage of zirconium is 3-10 wt.%, calculated based on the amount of the molecular sieves; solvent evaporation: performing solvent evaporation on the mixed solution to obtain a semi-finished product; high-temperature treatment: heating the semi-finished product to 500-600℃ at a heating rate of 1-5℃ / min and keeping for 2-4h to obtain a finished product composite material. The preparation process of the present application is simple, can be scaled up for production, and has industrial application prospects; at the same time, the composite material prepared by the preparation process of the present application can effectively replace detergents and dishwashing powder for washing tableware, achieve the purpose of cleaning oil stains on tableware, and will not generate intermediate products to cause secondary pollution in the process of cleaning oil stains, and is friendly to the human body and the environment; and the chemical stability of the composite material is good, and it is suitable for mass production.
[0029] 2. By encapsulating the synthesized composite material with the function of cleaning oil stains in a dishwasher, the present application can effectively replace detergents and solve the damage of adding detergents in the dishwasher to the human body and the environment; specifically, by encapsulating the composite material in a sealed water path of the dishwasher, water passing through the sealing material forms water with cleaning function, and after the water with cleaning function is introduced into the dishwasher, the removal of oil stains on tableware in the dishwasher can still be achieved without adding detergents; the mechanism by which the water passing through the sealing material can achieve the effect of having cleaning function is that the composite material can make water molecules have strong polarity, reduce the surface tension of water, and remove pollutants on tableware in the form of "water-in-oil". BRIEF DESCRIPTION OF DRAWINGS
[0030] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the description of the specific embodiments or the prior art. Obviously, the drawings described below are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creating any inventive labor.
[0031] Figure 1 is a structural schematic view of the composite material of the present application encapsulated in a sealed water path of a dishwasher.
[0032] In the drawings, the reference signs are explained as follows:
[0033] 1 - water inlet of waterway, 2 - composite material, 3 - water outlet of waterway. DETAILED DESCRIPTION
[0034] The following examples are provided to better enable those skilled in the art to further understand the application and are not intended to limit the scope of the application. Any product that is the same as or similar to the present application that is derived from the present application or from the combination of the present application and other prior art features falls within the scope of the present application.
[0035] The specific experimental steps or conditions not mentioned in the examples can be carried out according to the conventional experimental steps described in the literature in the art or the operation or conditions. The reagents or instruments not mentioned by the manufacturer are conventional reagent products that can be obtained by purchase.
[0036] Example 1
[0037] A method for preparing a composite material for oil cleaning, comprising:
[0038] (1) Obtain P123 solution: weigh 0.6 g of P123 and dissolve in 20 mL of anhydrous ethanol at room temperature, magnetically stir at 800 rpm, slowly add 1.4 mL of 67% mass fraction nitric acid, and stir for 30 min.
[0039] (2) Preparation of mixed solution: add 50 g of molecular sieve to the above P123 solution, stir for 30 min, then add cerium precursor salt and zirconium precursor salt in turn, continue to stir at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate and the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 5 wt.%, and the mass percentage of zirconium is 5 wt.%, which is converted to 11.64 wt.% of the mass percentage of cerium precursor salt and 18.6 wt.% of the mass percentage of zirconium precursor salt; the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0040] (3) Solvent evaporation: transfer the mixed solution to a culture dish and place it in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0041] (4) Add the above semi-finished product to a muffle furnace, slowly heat to 550°C at a heating rate of 2°C / min and keep for 4 h to obtain the final composite material.
[0042] Example 2
[0043] A method for preparing a composite material for oil cleaning, comprising:
[0044] (1) Preparation of P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0045] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and after stirring for 30 min, cerium precursor salt and zirconium precursor salt were sequentially added, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate, and the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 5 wt.%, and the mass percentage of zirconium is 10 wt.% based on the content of the molecular sieve; the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0046] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0047] (4) The above semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0048] Example 3
[0049] A method for preparing a composite material for oil cleaning, comprising:
[0050] (1) Preparation of P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0051] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and after stirring for 30 min, cerium precursor salt and zirconium precursor salt were sequentially added, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate, and the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 5 wt.%, and the mass percentage of zirconium is 10 wt.% based on the content of the molecular sieve; the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0052] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0053] (4) The semi-finished product is added to a muffle furnace, slowly heated to 550℃ at a heating rate of 2℃ / min for 4h, to obtain the final composite material.
[0054] Example 4
[0055] A method for preparing a composite material for oil cleaning, comprising:
[0056] (1) Obtain P123 solution: weigh 0.6g P123 and dissolve in 20mL anhydrous ethanol at room temperature, magnetic stirring at 800rpm, slowly add 1.4mL 67% mass fraction nitric acid, stir for 30min.
[0057] (2) Preparation of mixed solution: add 50g molecular sieve to the above P123 solution, stir for 30min, then add cerium precursor salt and zirconium precursor salt in sequence, continue to stir at room temperature for 6h to obtain the mixed solution; wherein the cerium precursor salt is cerium nitrate, the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 3wt.%, the mass percentage of zirconium is 3wt.%, the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500m 2 / g, and the porosity of the molecular sieve is 60%.
[0058] (3) Solvent evaporation: transfer the mixed solution to a culture dish, place it in a 70℃ oven for solvent evaporation for 48h to obtain a semi-finished product.
[0059] (4) The semi-finished product is added to a muffle furnace, slowly heated to 550℃ at a heating rate of 2℃ / min for 4h, to obtain the final composite material.
[0060] Example 5
[0061] A method for preparing a composite material for oil cleaning, comprising:
[0062] (1) Obtain P123 solution: weigh 0.6g P123 and dissolve in 20mL anhydrous ethanol at room temperature, magnetic stirring at 800rpm, slowly add 1.4mL 67% mass fraction nitric acid, stir for 30min.
[0063] (2) Preparation of mixed solution: add 50g molecular sieve to the above P123 solution, stir for 30min, then add cerium precursor salt and zirconium precursor salt in sequence, continue to stir at room temperature for 6h to obtain the mixed solution; wherein the cerium precursor salt is cerium nitrate, the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 10wt.%, the mass percentage of zirconium is 5wt.%, the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500m 2 / g, and the porosity of the molecular sieve is 60%.
[0064] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0065] (4) The semi-finished product was added to a muffle furnace, slowly heated to 550°C at a heating rate of 2°C / min, and kept for 4 h to obtain a final composite material.
[0066] Example 6
[0067] A method for preparing a composite material for oil cleaning, comprising:
[0068] (1) Obtaining a P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0069] (2) Preparation of a mixed solution: 30 g of molecular sieves was added to the P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in sequence, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate, and the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 5 wt.%, and the mass percentage of zirconium is 5 wt.% based on the content of the molecular sieves; the molecular sieves are silicoaluminate molecular sieves (SAPO), the specific surface area of the molecular sieves is 500 m 2 / g, and the porosity of the molecular sieves is 60%.
[0070] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0071] (4) The semi-finished product was added to a muffle furnace, slowly heated to 550°C at a heating rate of 2°C / min, and kept for 4 h to obtain a final composite material.
[0072] Example 7
[0073] A method for preparing a composite material for oil cleaning, comprising:
[0074] (1) Obtaining a P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0075] (2) Preparation of mixed solution: 30 g of molecular sieve was added to the above P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in sequence, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt was cerium nitrate, and the zirconium precursor salt was zirconium nitrate; the mass percentage of cerium was 5 wt.%, the mass percentage of zirconium was 5 wt.%, and the molecular sieve was silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve was 500 m 2 / g, and the porosity of the molecular sieve was 60%.
[0076] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0077] (4) The semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0078] Example 8
[0079] A preparation method of a composite material for oil cleaning, comprising:
[0080] (1) Obtain P123 solution: weigh 0.6 g of P123 and dissolve in 20 mL of anhydrous ethanol at room temperature, magnetically stir at 800 rpm, and slowly add 1.4 mL of 67% mass fraction nitric acid, and stir for 30 min.
[0081] (2) Preparation of mixed solution: 100 g of molecular sieve was added to the above P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in sequence, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt was cerium nitrate, and the zirconium precursor salt was zirconium nitrate; the mass percentage of cerium was 5 wt.%, the mass percentage of zirconium was 5 wt.%, and the molecular sieve was silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve was 500 m 2 / g, and the porosity of the molecular sieve was 60%.
[0082] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0083] (4) The semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0084] Example 9
[0085] A preparation method of a composite material for oil cleaning, comprising:
[0086] (1) Preparation of P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.6 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0087] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and after stirring for 30 min, cerium precursor salt and zirconium precursor salt were sequentially added, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate, and the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 5 wt.%, and the mass percentage of zirconium is 5 wt.% based on the content of the molecular sieve; the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0088] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0089] (4) The semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0090] Example 10
[0091] A method for preparing a composite material for oil cleaning, comprising:
[0092] (1) Preparation of P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0093] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and after stirring for 30 min, cerium precursor salt and zirconium precursor salt were sequentially added, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium acetate, and the zirconium precursor salt is zirconium chloride; the mass percentage of cerium is 5 wt.%, and the mass percentage of zirconium is 5 wt.% based on the content of the molecular sieve; the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0094] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0095] (4) The semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0096] Example 11
[0097] A method for preparing a composite material for oil cleaning, comprising:
[0098] (1) Obtaining a P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, magnetic stirring at 800 rpm, slowly adding 1.4 mL of 67% nitric acid, stirring for 30 min.
[0099] (2) Preparation of a mixed solution: 50 g of molecular sieve was added to the above P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in turn, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium chloride, the zirconium precursor salt is zirconium chloride; the mass percentage of cerium is 5 wt.%, the mass percentage of zirconium is 5 wt.%, and the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0100] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0101] (4) The above semi-finished product was added to a muffle furnace, slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0102] Example 12
[0103] A method for preparing a composite material for oil cleaning, comprising:
[0104] (1) Obtaining a P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, magnetic stirring at 800 rpm, slowly adding 1.4 mL of 67% nitric acid, stirring for 30 min.
[0105] (2) Preparation of a mixed solution: 50 g of molecular sieve was added to the above P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in turn, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium chloride, the zirconium precursor salt is zirconium chloride; the mass percentage of cerium is 5 wt.%, the mass percentage of zirconium is 5 wt.%, and the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0106] (3) Solvent evaporation: transfer the mixed solution to a culture dish, place it in a 70°C oven for solvent evaporation for 48h to obtain a semi-finished product.
[0107] (4) The above semi-finished product is added to a muffle furnace, slowly heated to 500°C at a heating rate of 1°C / min and kept for 4h to obtain the final composite material.
[0108] Example 13
[0109] A method for preparing a composite material for oil cleaning, comprising:
[0110] (1) Obtain P123 solution: weigh 0.6g P123 and dissolve it in 20mL anhydrous ethanol at room temperature, magnetically stir at 800rpm, slowly add 1.4mL 67% mass fraction nitric acid, and stir for 30min.
[0111] (2) Preparation of mixed solution: add 50g molecular sieve to the above P123 solution, stir for 30min, then add cerium precursor salt and zirconium precursor salt in sequence, continue to stir at room temperature for 6h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate and the zirconium precursor salt is zirconium nitrate; the mass percentage of cerium is 5wt.%, the mass percentage of zirconium is 5wt.%, the molecular sieve is silicoaluminate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500m 2 / g, and the porosity of the molecular sieve is 60%.
[0112] (3) Solvent evaporation: transfer the mixed solution to a culture dish, place it in a 70°C oven for solvent evaporation for 48h to obtain a semi-finished product.
[0113] (4) The above semi-finished product is added to a muffle furnace, slowly heated to 500°C at a heating rate of 1°C / min and kept for 4h to obtain the final composite material.
[0114] Example 14
[0115] A method for preparing a composite material for oil cleaning, comprising:
[0116] (1) Obtain P123 solution: weigh 0.6g P123 and dissolve it in 20mL anhydrous ethanol at room temperature, magnetically stir at 800rpm, slowly add 1.4mL 67% mass fraction nitric acid, and stir for 30min.
[0117] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in sequence, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt was cerium nitrate, and the zirconium precursor salt was zirconium nitrate; the mass percentage of cerium was 5 wt.%, the mass percentage of zirconium was 5 wt.%, and the molecular sieve was a phosphoaluminate molecular sieve (AlPO4), the specific surface area of the molecular sieve was 300 m 2 / g, and the porosity of the molecular sieve was 40%.
[0118] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0119] (4) The semi-finished product was added to a muffle furnace, slowly heated to 550°C at a heating rate of 2°C / min, and kept for 4 h to obtain the final composite material.
[0120] Example 15
[0121] A preparation method of a composite material for oil stain cleaning, comprising:
[0122] (1) Obtaining P123 solution: 0.6 g of P123 was weighed and dissolved in 20 mL of anhydrous ethanol at room temperature, and stirred at 800 rpm by magnetic stirring, and 1.4 mL of 67% mass fraction nitric acid was slowly added and stirred for 30 min.
[0123] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, stirred for 30 min, and then cerium precursor salt and zirconium precursor salt were added in sequence, and stirring was continued at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt was cerium nitrate, and the zirconium precursor salt was zirconium nitrate; the mass percentage of cerium was 5 wt.%, the mass percentage of zirconium was 5 wt.%, and the molecular sieve was a phosphoaluminate molecular sieve (AlPO4), the specific surface area of the molecular sieve was 300 m 2 / g, and the porosity of the molecular sieve was 40%.
[0124] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0125] (4) The semi-finished product was added to a muffle furnace, slowly heated to 550°C at a heating rate of 2°C / min, and kept for 4 h to obtain the final composite material.
[0126] Comparative Example 1
[0127] A preparation method of a composite material for oil stain cleaning, comprising:
[0128] (1) Preparation of P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0129] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and stirred for 30 min, and then stirred at room temperature for 6 h to obtain a mixed solution; wherein the molecular sieve is a silicate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0130] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0131] (4) The above semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0132] Comparative Example 2
[0133] A preparation method of a composite material for oil cleaning, comprising:
[0134] (1) Preparation of P123 solution: 0.6 g of P123 was dissolved in 20 mL of anhydrous ethanol at room temperature, and 1.4 mL of 67% nitric acid was slowly added under magnetic stirring at 800 rpm for 30 min.
[0135] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and stirred for 30 min, and then added with cerium precursor salt and stirred at room temperature for 6 h to obtain a mixed solution; wherein the cerium precursor salt is cerium nitrate; the mass percentage of cerium is 5 wt.% based on the content of the molecular sieve, the molecular sieve is a silicate molecular sieve (SAPO), the specific surface area of the molecular sieve is 500 m 2 / g, and the porosity of the molecular sieve is 60%.
[0136] (3) Solvent evaporation: the mixed solution was transferred to a culture dish and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0137] (4) The above semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min and kept for 4 h to obtain the final composite material.
[0138] Comparative Example 3
[0139] A preparation method of a composite material for oil cleaning, comprising:
[0140] (1) Preparation of P123 solution: 0.6 g of P123 was weighed and dissolved in 20 mL of anhydrous ethanol at room temperature, and stirred at 800 rpm by magnetic stirring. Then, 1.4 mL of 67% nitric acid was slowly added, and stirred for 30 min.
[0141] (2) Preparation of mixed solution: 50 g of molecular sieve was added to the above P123 solution, and stirred for 30 min. Then, zirconium precursor salt was added, and stirred for 6 h at room temperature to obtain a mixed solution; wherein the zirconium precursor salt was zirconium nitrate; the mass percentage of zirconium was 5 wt.% based on the content of the molecular sieve; the molecular sieve was silicoaluminate molecular sieve (SAPO); the specific surface area of the molecular sieve was 500 m 2 / g; and the porosity of the molecular sieve was 60%.
[0142] (3) Solvent evaporation: the mixed solution was transferred to a culture dish, and placed in a 70°C oven for solvent evaporation for 48 h to obtain a semi-finished product.
[0143] (4) The semi-finished product was added to a muffle furnace, and slowly heated to 550°C at a heating rate of 2°C / min, and kept for 4 h to obtain the final composite material.
[0144] Experimental Example
[0145] The composite materials prepared in the above examples and comparative examples were placed in a sealed water path of a dishwasher, as shown in FIG. 1, wherein the two ends of the composite material were the water inlet end and the water outlet end, respectively. The addition amount of the composite material in the sealed water path was 1000 g, the water throughput of a single cleaning was 5 L, and the dishwasher was assembled with 3 sets of tableware, a total of 25 pieces. Then, the washing test was performed according to GB 38383-2019 and GB_T 20290-2016. Meanwhile, a comparative example 4 was set, in which no composite material was added in the sealed water path of the dishwasher, and a comparative example 5 was set, in which no composite material was added in the sealed water path of the dishwasher, but a recommended dosage and type of conventional detergent were added in the dishwasher. Figure 1
[0146] The washing results of the above examples and comparative examples are shown in Table 1.
[0147] Table 1
[0148]
[0149]
[0150] The above washing index = washing score / tableware total / reference machine average; in this experimental example, the reference machine average was 1.5.
[0151] From the data in Table 1, it can be seen that the composite material in the application can greatly improve the cleaning ability of the dishwasher without using a detergent, and by adjusting the proportion of the effective components of the composite material, the cleaning effect can be optimized, and the best washing index obtained can even reach 1.17, exceeding the national standard. By further controlling the mass of cerium ≥ the mass of zirconium and the mass percentage of cerium and zirconium ≥ 15wt.%, the washing index of the examples is all greater than the minimum index 1.12 required by the new national standard, proving that the composite material of the application meets the national standard. In summary, the composite material of the application effectively solves the problem of damage to the human body and the environment caused by the dishwasher detergent.
[0152] Obviously, the above examples are only examples for clearly illustrating, but not limitation to the embodiments. For ordinary skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, all the embodiments need not and cannot be exhausted. The obvious changes or variations derived therefrom are still within the protection scope of the present application.
Claims
1. A method for preparing a composite material for cleaning oil stains, characterized in that, include: Obtaining P123 solution: P123 was mixed with anhydrous ethanol and stirred, and then nitric acid was added and stirred to obtain P123 solution. Preparation of mixed solution: The molecular sieve and P123 solution were stirred and mixed, and cerium precursor salt and zirconium precursor salt were added and stirred. The mass ratio of molecular sieve to P123 is (15-170):1; based on the amount of molecular sieve used, the mass percentage of cerium is 3-10 wt.% and the mass percentage of zirconium is 3-10 wt.%. Solvent evaporation: The mixed solution is subjected to solvent evaporation to obtain a semi-finished product; High temperature treatment: The semi-finished product is heated to 500-600℃ at a heating rate of 1-5℃ / min and held for 2-4 hours to obtain the finished composite material.
2. The preparation method according to claim 1, characterized in that, In the step of obtaining the P123 solution, the mass ratio of P123 to nitric acid is (0.24-0.64):1, and / or the mass-volume ratio of P123 to anhydrous ethanol is 0.6-1.2 g / 20 mL.
3. The preparation method according to claim 1 or 2, characterized in that, The specific surface area of the molecular sieve is 300-1000 m². 2 / g, and / or, the porosity of the molecular sieve is 40%-80%.
4. The preparation method according to claim 1 or 2, characterized in that, In the step of obtaining the P123 solution, the mixing and stirring method is magnetic stirring.
5. The preparation method according to claim 4, characterized in that, The magnetic stirring speed is 800-1200 rpm.
6. The preparation method according to claim 1 or 2, characterized in that, The cerium precursor salt is at least one of cerium acetate, cerium nitrate, and cerium chloride.
7. The preparation method according to claim 1 or 2, characterized in that, The zirconium precursor salt is at least one of zirconium chloride and zirconium nitrate.
8. A composite material for cleaning oil stains, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. The application of the composite material for cleaning oil stains as described in claim 8 in a dishwasher.
10. The application according to claim 9, characterized in that, The composite material is encapsulated within a sealed water passage of the dishwasher for application.