White oil for mosquito-repellent liquid and preparation method thereof

Abstract

The present application relates to the field of white oil, and specifically to a white oil for mosquito coil liquid and a preparation method thereof. A preparation method for white oil for mosquito coil liquid comprises the following steps: Step 1: adding raw materials to a hydrogenation reactor, and the mixed materials and hydrogen pass through a first catalyst bed and a second catalyst bed to undergo a hydrogenation reaction to obtain a primary product; Step 2: subjecting the primary product to multiple oil-gas separations, and the oil phase obtained by separation is the product; the first catalyst bed and the second catalyst bed are filled with a modified catalyst; the preparation method for the modified catalyst comprises the following steps: Step a: preparing a carrier; Step b: loading a precious metal. The white oil obtained by the preparation method of the present application is specially designed for electric mosquito coil liquid for mothers and infants, improves the quality of the white oil, gives the electric mosquito coil liquid moderate volatility, and effectively enables each component in the mosquito coil liquid to fully exert the mosquito repellent effect.

Description

Technical Field

[0001] The present application relates to the field of white oil, and more specifically, to a white oil for mosquito-repellent liquid and a preparation method thereof. Background Art

[0002] With the improvement of living standards, people have higher and higher requirements for the quality of life, especially in the field of maternal and child products, where safety and environmental protection have become the focus of consumers. As a common mosquito repellent product, the safety and stability of the ingredients of electric mosquito repellent liquid are directly related to the health of mothers and babies. In the preparation process of electric mosquito repellent liquid, white oil is an important solvent and stabilizer, and its quality directly affects the overall performance of the product.

[0003] The traditional production process of white oil mainly includes concentrated sulfuric acid sulfonation method, sulfur trioxide sulfonation method and hydrogenation refining method. Among them, the concentrated sulfuric acid sulfonation method has been gradually eliminated due to unstable product quality, low yield, large raw material loss and serious environmental pollution. Although the sulfur trioxide sulfonation method has improved the quality of white oil to a certain extent, the environmental pollution problem has not been fundamentally solved. The hydrogenation refining method has gradually become the mainstream production process due to its low environmental pollution, high product yield, stable quality and ability to produce high-viscosity and high-quality white oil.

[0004] However, although the existing white oil products can meet general industrial purposes, they still have some shortcomings in the application of specific fields such as electric mosquito repellent liquid for mothers and infants. In the production process of white oil, precious metal catalysts (such as platinum, palladium, etc.) play a vital role. As catalysts for hydrogenation reactions, they can significantly improve the efficiency and selectivity of hydrogenation reactions, thereby promoting the hydrogenolysis of non-hydrocarbon compounds such as sulfur, nitrogen, and oxygen in the feedstock oil, as well as the selective hydrogenation saturation of olefins and aromatics. The catalytic effect of the catalyst has a great influence on the quality of white oil. High-quality white oil can enable the various components in the mosquito repellent liquid to fully exert the mosquito repellent effect.

[0005] Therefore, developing a white oil specially designed for electric mosquito repellent liquid for mothers and infants has important market significance and application value. Summary of the invention

[0006] In order to improve the quality of white oil, the present application provides a white oil for mosquito-repellent liquid and a preparation method thereof.

[0007] In the first aspect, the present application provides a method for preparing white oil for mosquito coil liquid, using the following technical solution:

[0008] A method for preparing white oil for mosquito-repellent liquid comprises the following steps:

[0009] Step 1: adding raw materials into a hydrogenation reactor, and the mixed materials and hydrogen pass through the first catalyst bed and the second catalyst bed to undergo a hydrogenation reaction to obtain a primary product;

[0010] Step 2: The primary product is subjected to multiple oil-gas separations, and the oil phase obtained by separation is the product;

[0011] The first catalyst bed and the second catalyst bed are filled with modified catalysts, and the volume ratio of the modified catalysts filled in the first catalyst bed to the second catalyst bed is 1:1.5;

[0012] The preparation method of the modified catalyst comprises the following steps:

[0013] Step a: Preparation of carrier:

[0014] Step a1: crushing and mixing betel nut shells and coconut shells to obtain biological raw materials;

[0015] Step a2: mixing the biological raw material with the alcohol solution and placing it at -20°C to -10°C for 12-24 hours to obtain a frozen raw material;

[0016] Step a3: treating the frozen raw material with a microwave at 150-200 W for 15-30 min, and then filtering, and the solid part is the microwave raw material;

[0017] Step a4: soaking the microwave raw material in an activation solution to obtain an activated raw material;

[0018] Step a5: treating the activated raw material at 700-800° C. for 60-90 min to obtain a carrier;

[0019] Step b: Loading precious metals:

[0020] Step b1: prepare a slurry with the carrier and water for standby use;

[0021] Step b2: mixing the solution containing the precious metal compound with the slurry at 70-80° C., adjusting the pH to greater than 9, to obtain a mixture;

[0022] Step b3: mixing the mixture with formaldehyde aqueous solution for reaction;

[0023] Step b4: Filter the material of step b3, and the obtained solid part is the modified catalyst.

[0024] Selected betel nut shells and coconut shells are used as green biological raw materials. Through freezing pretreatment combined with microwave technology, they are quickly crushed after freezing, thereby pre-inducing the formation of a unique carbon structure framework. This pretreatment step ensures that these special carbon structures are retained and optimized during the high-temperature carbonization process, laying a good foundation for the subsequent loading of precious metals.

[0025] The precious metals are loaded on this uniquely structured carrier, firmly anchored and evenly dispersed on the carrier, thus preparing an advanced modified catalyst. The excellence of this catalyst lies in that it not only significantly enhances the stability of the precious metals, but also greatly improves the efficiency and selectivity in the hydrogenation reaction, which means a qualitative leap in product quality for the production process of white oil.

[0026] The high-quality white oil produced by this modified catalyst, especially in the mother-infant grade electric mosquito repellent liquid, can be used as the core solvent. With its moderate volatility, it can quickly and evenly diffuse into the air, effectively repelling mosquitoes and creating a fresh and undisturbed sleeping environment for babies and mothers. At the same time, its mild and non-irritating characteristics ensure that it will not cause any discomfort to the human body even if used for a long time, and is particularly suitable for mothers and infants who have extremely high safety requirements.

[0027] Preferably, the mass ratio of the betel nut shell to the coconut shell is (0.8-1.2): (0.8-1.2).

[0028] By adopting the above technical solution, the mass ratio of betel nut shell to coconut shell is further limited. Both betel nut shell and coconut shell have natural porous structures. In the process of conversion into carriers, these pore structures are further developed and refined to form a rich micropore and mesopore system. This high specific surface area characteristic greatly enhances the adsorption capacity of the carrier and can more firmly load more precious metals.

[0029] Betel nut shell and coconut shell not only have strong adsorption capacity, but also have high mechanical strength and good thermal stability. The specific ratio of the mixture of the two enables the prepared carrier to maintain stable adsorption performance in a wide range of temperatures and under a variety of environmental conditions, and is not easy to break or deform, making it suitable for a variety of demanding application scenarios.

[0030] As by-products of the agricultural and forestry industries, betel nut shells and coconut shells are produced in large quantities and are renewable. Using them as raw materials for carriers not only reduces waste emissions, but also realizes the resource utilization of agricultural waste and promotes the development of a green circular economy.

[0031] Preferably, in the step a1, betel nut shells and coconut shells are mixed at 1200-1500 r / min until they are uniform.

[0032] By adopting the above technical solution, the mixing conditions of betel nut shell and coconut shell are further limited so that the two can be fully mixed, which is convenient for the subsequent formation of a special structure.

[0033] Preferably, the betel nut shell and coconut shell are mixed and then crushed to 30-40 mesh.

[0034] Preferably, the noble metal compound is Pd(NH 3 ) 4 (NO3 ) 2 、Pd(NH 3 ) 4 Cl 2 、Pt(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 Cl 2 A mixture of one or more of the above.

[0035] Preferably, the noble metal compound is Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 The mass ratio is 1:1.

[0036] As active ingredients in catalysts, precious metals can adsorb reactants, reduce reaction activation energy, and promote reaction rate. However, the more precious metal content, the better. Too high or too low a content may affect the catalytic efficiency. Therefore, through the above technical solution, the ratio of precious metals is further limited, which can ensure better coordination with the carrier and enable the modified catalyst to achieve the best catalytic effect under reaction conditions.

[0037] Preferably, the activation solution is one of zinc chloride solution, potassium hydroxide solution, calcium chloride solution and phosphoric acid solution.

[0038] Preferably, in the hydrogenation reactor, the reaction pressure is 12-16 MPa, the temperature is 240-290°C, the hydrogen-oil ratio (v / v) is (500-1000):1, and the space velocity is 0.5-1.5h -1 .

[0039] In a second aspect, the present application provides a white oil.

[0040] The high-quality white oil produced by this application is particularly excellent in the application of maternal and infant grade electric mosquito repellent liquid. As the core solvent of this product, this white oil can quickly diffuse in the air with its just the right volatility, achieving a uniform and efficient mosquito repellent effect, creating a quiet and fresh sleeping space for the baby and mother. More importantly, its unique mild formula and non-irritating characteristics ensure that it can maintain absolute safety and comfort for the human body even during long-term use, perfectly meeting the extremely high requirements of the mother and baby group for product safety, making every night of sleep a safe and healthy enjoyment.

[0041] In summary, this application has the following beneficial effects:

[0042] 1. This application has significantly improved the quality standard of white oil by innovating and optimizing the hydrorefining process without increasing the cost of purchasing additional equipment, making it perfectly suitable for the needs of maternal and infant grade electric mosquito repellent liquid. This improvement not only broadens the application field of white oil, but also lays a solid foundation for its extensive promotion in the maternal and infant product market, demonstrating its huge market potential and social value.

[0043] 2. The high-quality white oil of this application plays a vital role in the mother-infant grade electric mosquito repellent liquid. As the core solvent, it can quickly diffuse and evenly distribute in the air with just the right volatility, effectively dispel mosquitoes, and build a pure and quiet sleeping atmosphere for the baby and the mother. In addition, the white oil, with its mild and non-irritating characteristics, ensures that it can remain extremely gentle and safe to the human body even during long-term use, perfectly meeting the strict requirements of the mother-infant group for product safety, and becoming an ideal choice for protecting family health.

[0044] 3. This application uses specially selected betel nut shells and coconut shells as natural biological raw materials, and uses freezing pretreatment technology combined with microwave heating to allow the raw materials to freeze quickly at low temperatures, and then crush them at high speed to pre-shape a unique carbon structure framework. This pretreatment step presets the morphology of the carbon structure, ensuring that this special carbon structure can be stably retained and further optimized during the high-temperature carbonization process, thereby firmly loading the precious metals, enhancing the stability of the precious metals, and extending the service life of the modified catalyst; and significantly improves the catalytic efficiency and product selectivity in the hydrogenation reaction, effectively improving the quality of white oil. DETAILED DESCRIPTION

[0045] The present application is further described in detail below with reference to the embodiments.

[0046] The raw materials used in the following examples and comparative examples are all commercially available products.

[0047] Example

[0048] Example 1

[0049] A method for preparing white oil for mosquito-repellent liquid comprises the following steps:

[0050] Step 1: Add the raw materials into the hydrogenation reactor, set the reaction pressure to 15MPa, the reaction temperature of the first catalyst bed to 290℃, the reaction temperature of the second catalyst bed to 250℃, the hydrogen-oil ratio (v / v) to 750:1, and the space velocity to 1h -1 .

[0051] The mixed material and hydrogen flow into the hydrogenation reactor from the top, pass through the first catalyst bed and the second catalyst bed, undergo hydrogenation reaction, and flow out from the bottom to obtain the primary product.

[0052] The raw material is cyclohexane oil N4006.

[0053] Step 2: The initial product enters the high-pressure separation tank for oil and gas separation, and the separated oil phase enters the low-pressure separation tank for further oil and gas separation. The gas phases of the high and low pressure separators enter the alkali washing tank, and the oil phase enters the stripping tower for gas-liquid separation under the action of nitrogen. The gas phase obtained after gas stripping also enters the alkali washing tank, and the obtained liquid phase is the product.

[0054] The first catalyst bed and the second catalyst bed are filled with modified catalysts, and the volume ratio of the modified catalysts filled in the first catalyst bed to that in the second catalyst bed is 1:1.5.

[0055] In this example, the hydrogenation reactor used has a specification of 500 mL, and the total loading amount of the modified catalyst is 300 mL.

[0056] The preparation method of the modified catalyst comprises the following steps:

[0057] Step a: Preparation of carrier:

[0058] Step a1: The mass ratio of betel nut shell to coconut shell powder is 1:1. In this embodiment, the betel nut shell is 1 kg and the coconut shell powder is 1 kg.

[0059] Crush the betel nut shell and coconut shell to 35 mesh.

[0060] Then, the mixture is mixed at a rotation speed of 1400 r / min and stirred until uniform to obtain a biological raw material.

[0061] Step a2: The biological raw material is mixed with a 70% ethanol solution at a mass ratio of 1:5, and placed at -15°C for 18 hours to obtain a frozen raw material.

[0062] Step a3: The frozen raw material was microwaved at 180 W for 25 min.

[0063] The solid and liquid are separated by filtration, and the solid part is dried (dried with hot air at 40°C to constant weight). The dried solid part is the microwave raw material.

[0064] Step a4: Weigh zinc chloride according to the microwave raw material and zinc chloride in a mass ratio of 1:0.2, and then prepare an activation solution (zinc chloride solution) in a ratio of zinc chloride to water of 1:10.

[0065] The microwave raw material was placed in the activation solution and soaked for 30 minutes, then the solid and liquid were separated, and the solid part was dried to constant weight to obtain the activated raw material.

[0066] Step a5: The activated raw material is treated at 750° C. for 70 min, and the carrier is obtained after natural cooling.

[0067] Step b: Loading precious metals:

[0068] Step b1: prepare a slurry with a carrier and water in a ratio of 1:5 for standby use.

[0069] Step b2: The noble metal compound is Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , the mass ratio is 1:1.

[0070] The solvent of the solution containing the precious metal compound is water; the solution containing the precious metal compound contains Pd(NH 3 ) 4 (NO 3 ) 2 The concentration of Pt(NH 3 ) 4 (NO 3 ) 2 The concentration is 0.002g / mL.

[0071] The solution containing the precious metal compound was added dropwise to the slurry by an equal volume impregnation method. After the addition was completed, the temperature was maintained at 75° C., the reaction was stirred for 2 hours, and the pH was adjusted to 9.5 using a 5% sodium hydroxide aqueous solution to obtain a mixed material.

[0072] Step b3: According to Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2Prepare 37% formaldehyde aqueous solution in a 1:6 molar ratio of formaldehyde to substance.

[0073] Add formaldehyde aqueous solution to the mixture and stir at warm temperature for 60 minutes.

[0074] Step b4: Filter the material of step b3, wash and dry the solid part to obtain a modified catalyst.

[0075] Example 2

[0076] A method for preparing white oil for mosquito-repellent liquid comprises the following steps:

[0077] Step 1: Add the raw materials into the hydrogenation reactor, set the reaction pressure to 12MPa, the reaction temperature of the first catalyst bed to 290℃, the reaction temperature of the second catalyst bed to 240℃, the hydrogen-oil ratio (v / v) to 500:1, and the space velocity to 0.5h -1 .

[0078] The mixed material and hydrogen flow into the hydrogenation reactor from the top, pass through the first catalyst bed and the second catalyst bed, undergo hydrogenation reaction, and flow out from the bottom to obtain the primary product.

[0079] The raw material is cyclohexane oil N4006.

[0080] Step 2: The initial product enters the high-pressure separation tank for oil and gas separation, and the separated oil phase enters the low-pressure separation tank for further oil and gas separation. The gas phases of the high and low pressure separators enter the alkali washing tank, and the oil phase enters the stripping tower for gas-liquid separation under the action of nitrogen. The gas phase obtained after gas stripping also enters the alkali washing tank, and the obtained liquid phase is the product.

[0081] The first catalyst bed and the second catalyst bed are filled with modified catalysts, and the volume ratio of the modified catalysts filled in the first catalyst bed to that in the second catalyst bed is 1:1.5.

[0082] In this example, the hydrogenation reactor used has a specification of 500 mL, and the total loading amount of the modified catalyst is 300 mL.

[0083] The preparation method of the modified catalyst comprises the following steps:

[0084] Step a: Preparation of carrier:

[0085] Step a1: The mass ratio of betel nut shell to coconut shell powder is 0.8:1.2. In this embodiment, the betel nut shell is 0.8 kg and the coconut shell powder is 1.2 kg.

[0086] Crush the betel nut shell and coconut shell into 3-40 mesh.

[0087] Then, the mixture is mixed at a rotation speed of 1200 r / min and stirred until uniform to obtain a biological raw material.

[0088] Step a2: The biological raw material is mixed with a 70% ethanol solution at a mass ratio of 1:5, and placed at -20°C for 12 hours to obtain a frozen raw material.

[0089] Step a3: The frozen raw material was microwaved at 150 W for 30 min.

[0090] The solid and liquid are separated by filtration, and the solid part is dried (dried with hot air at 40°C to constant weight). The dried solid part is the microwave raw material.

[0091] Step a4: Weigh zinc chloride according to the microwave raw material and zinc chloride in a mass ratio of 1:0.1, and then prepare an activation solution (zinc chloride solution) in a ratio of zinc chloride to water of 1:10.

[0092] The microwave raw material was placed in the activation solution and soaked for 30 minutes, then the solid and liquid were separated, and the solid part was dried to constant weight to obtain the activated raw material.

[0093] Step a5: The activated raw material is treated at 700° C. for 90 min, and the carrier is obtained after natural cooling.

[0094] Step b: Loading precious metals:

[0095] Step b1: prepare a slurry with a carrier and water in a ratio of 1:5 for standby use.

[0096] Step b2: The noble metal compound is Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , the mass ratio is 1:1.

[0097] The solvent of the solution containing the precious metal compound is water; the solution containing the precious metal compound contains Pd(NH 3 ) 4 (NO 3 ) 2 The concentration of Pt(NH 3 ) 4 (NO 3 ) 2 The concentration is 0.001g / mL.

[0098] The solution containing the precious metal compound was added dropwise to the slurry by an equal volume impregnation method. After the addition was completed, the temperature was maintained at 70° C., the reaction was stirred for 2 hours, and the pH was adjusted to 9.5 using a 5% sodium hydroxide aqueous solution to obtain a mixture.

[0099] Step b3: According to Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 Prepare 37% formaldehyde aqueous solution in a 1:6 molar ratio of formaldehyde to substance.

[0100] Add formaldehyde aqueous solution to the mixture and stir at warm temperature for 60 minutes.

[0101] Step b4: Filter the material of step b3, wash and dry the solid part to obtain a modified catalyst.

[0102] Example 3

[0103] A method for preparing white oil for mosquito-repellent liquid comprises the following steps:

[0104] Step 1: Add the raw materials into the hydrogenation reactor, set the reaction pressure to 16MPa, the reaction temperature of the first catalyst bed to 2850℃, the reaction temperature of the second catalyst bed to 245℃, the hydrogen-oil ratio (v / v) to 1000:1, and the space velocity to 1.5h -1 .

[0105] The mixed material and hydrogen flow into the hydrogenation reactor from the top, pass through the first catalyst bed and the second catalyst bed, undergo hydrogenation reaction, and flow out from the bottom to obtain the primary product.

[0106] The raw material is cyclohexane oil N4006.

[0107] Step 2: The initial product enters the high-pressure separation tank for oil and gas separation, and the separated oil phase enters the low-pressure separation tank for further oil and gas separation. The gas phases of the high and low pressure separators enter the alkali washing tank, and the oil phase enters the stripping tower for gas-liquid separation under the action of nitrogen. The gas phase obtained after gas stripping also enters the alkali washing tank, and the obtained liquid phase is the product.

[0108] The first catalyst bed and the second catalyst bed are filled with modified catalysts, and the volume ratio of the modified catalysts filled in the first catalyst bed to that in the second catalyst bed is 1:1.5.

[0109] In this example, the hydrogenation reactor used has a specification of 500 mL, and the total loading amount of the modified catalyst is 300 mL.

[0110] The preparation method of the modified catalyst comprises the following steps:

[0111] Step a: Preparation of carrier:

[0112] Step a1: The mass ratio of betel nut shell to coconut shell powder is 1.2:0.8. In this embodiment, the betel nut shell is 1.2 kg and the coconut shell powder is 0.8 kg.

[0113] Crush the betel nut shell and coconut shell into 40 mesh.

[0114] Then, the mixture is mixed at a rotation speed of 1500 r / min and stirred until uniform to obtain a biological raw material.

[0115] Step a2: The biological raw material is mixed with a 70% ethanol solution at a mass ratio of 1:5, and placed at -10°C for 24 hours to obtain a frozen raw material.

[0116] Step a3: The frozen raw material was microwaved at 200 W for 15 min.

[0117] The solid and liquid are separated by filtration, and the solid part is dried (dried with hot air at 40°C to constant weight). The dried solid part is the microwave raw material.

[0118] Step a4: Weigh zinc chloride according to the microwave raw material and zinc chloride in a mass ratio of 1:0.3, and then prepare an activation solution (zinc chloride solution) in a ratio of zinc chloride to water of 1:10.

[0119] The microwave raw material was placed in the activation solution and soaked for 30 minutes, then the solid and liquid were separated, and the solid part was dried to constant weight to obtain the activated raw material.

[0120] Step a5: The activated raw material is treated at 800° C. for 60 min, and the carrier is obtained after natural cooling.

[0121] Step b: Loading precious metals:

[0122] Step b1: prepare a slurry with a carrier and water in a ratio of 1:5 for standby use.

[0123] Step b2: The noble metal compound is Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , the mass ratio is 1:1.

[0124] The solvent of the solution containing the precious metal compound is water; the solution containing the precious metal compound contains Pd(NH 3 )4 (NO 3 ) 2 The concentration of Pt(NH 3 ) 4 (NO 3 ) 2 The concentration is 0.003g / mL.

[0125] The solution containing the precious metal compound is added dropwise to the slurry by an equal volume impregnation method. After the addition is completed, the temperature is maintained at 80° C., the reaction is stirred for 2 hours, and the pH is adjusted to 9.5 using a 5% sodium hydroxide aqueous solution to obtain a mixed material.

[0126] Step b3: According to Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 Prepare 37% formaldehyde aqueous solution in a 1:6 molar ratio of formaldehyde to substance.

[0127] Add formaldehyde aqueous solution to the mixture and stir at warm temperature for 60 minutes.

[0128] Step b4: Filter the material of step b3, wash and dry the solid part to obtain a modified catalyst.

[0129] Example 4

[0130] A method for preparing white oil for mosquito coil liquid, which is different from that of Example 1 in that the mass ratio of betel nut shell to coconut shell powder in step a1 is 0.2:1.8. In this embodiment, the betel nut shell is 0.2 kg and the coconut shell powder is 1.8 kg.

[0131] Comparative Example

[0132] Comparative Example 1

[0133] A method for preparing white oil for mosquito coil liquid, which is different from that of Example 1 in that the betel nut shell in step a1 is replaced by walnut shell, that is, the betel nut shell is 0, the walnut shell is 1kg, and the coconut shell is 1kg.

[0134] Comparative Example 2

[0135] A method for preparing white oil for mosquito coil liquid, which is different from that of embodiment 1 in that the coconut shell in step a1 is replaced by betel nut shell, that is, the betel nut shell is 2kg and the coconut shell is 0.

[0136] Comparative Example 3

[0137] A method for preparing white oil for mosquito-repellent liquid, which is different from that of Example 1 in that:

[0138] The preparation method of the modified catalyst comprises the following steps:

[0139] Step a: Preparation of carrier:

[0140] Step a1: The mass ratio of betel nut shell to coconut shell powder is 1:1. In this embodiment, the betel nut shell is 1 kg and the coconut shell powder is 1 kg.

[0141] Crush the betel nut shell and coconut shell to 35 mesh.

[0142] Then, the mixture is mixed at a rotation speed of 1400 r / min and stirred until uniform to obtain a biological raw material.

[0143] Step a2: The biological raw material was mixed with a 70% ethanol solution at a mass ratio of 1:5, and then subjected to microwave treatment at 180 W for 25 min.

[0144] The solid and liquid are separated by filtration, and the solid part is dried (dried with hot air at 40°C to constant weight). The dried solid part is the microwave raw material.

[0145] Step a3: Weigh zinc chloride according to the microwave raw material and zinc chloride in a mass ratio of 1:0.2, and then prepare an activation solution (zinc chloride solution) in a ratio of zinc chloride to water of 1:10.

[0146] The microwave raw material was placed in the activation solution and soaked for 30 minutes, then the solid and liquid were separated, and the solid part was dried to constant weight to obtain the activated raw material.

[0147] Step a4: The activated raw material is treated at 750° C. for 70 min, and the carrier is obtained after natural cooling.

[0148] Step b: Loading precious metals:

[0149] Step b1: prepare a slurry with a carrier and water in a ratio of 1:5 for standby use.

[0150] Step b2: The noble metal compound is Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , the mass ratio is 1:1.

[0151] The solvent of the solution containing the precious metal compound is water; the solution containing the precious metal compound contains Pd(NH 3 ) 4 (NO3 ) 2 The concentration of Pt(NH 3 ) 4 (NO 3 ) 2 The concentration is 0.002g / mL.

[0152] The solution containing the precious metal compound was added dropwise to the slurry by an equal volume impregnation method. After the addition was completed, the temperature was maintained at 75° C., the reaction was stirred for 2 hours, and the pH was adjusted to 9.5 using a 5% sodium hydroxide aqueous solution to obtain a mixed material.

[0153] Step b3: According to Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 Prepare 37% formaldehyde aqueous solution in a 1:6 molar ratio of formaldehyde to substance.

[0154] Add formaldehyde aqueous solution to the mixture and stir at warm temperature for 60 minutes.

[0155] Step b4: Filter the material of step b3, wash and dry the solid part to obtain a modified catalyst.

[0156] Comparative Example 4

[0157] A method for preparing white oil for mosquito-repellent liquid, which is different from that of Example 1 in that:

[0158] The preparation method of the modified catalyst comprises the following steps:

[0159] Step a: Preparation of carrier:

[0160] Step a1: The mass ratio of betel nut shell to coconut shell powder is 1:1. In this embodiment, the betel nut shell is 1 kg and the coconut shell powder is 1 kg.

[0161] Crush the betel nut shell and coconut shell to 35 mesh.

[0162] Then, the mixture is mixed at a rotation speed of 1400 r / min and stirred until uniform to obtain a biological raw material.

[0163] Step a2: The biological raw material was mixed with a 70% ethanol solution at a mass ratio of 1:5, and placed at -15°C for 18 hours.

[0164] Thaw naturally, filter to separate the solid and liquid, dry the solid part (dry with hot air at 40°C to constant weight), and the dried solid part is the frozen raw material.

[0165] Step a3: Weigh zinc chloride according to the frozen raw material and zinc chloride in a mass ratio of 1:0.2, and then prepare an activation solution (zinc chloride solution) in a ratio of zinc chloride to water of 1:10.

[0166] The microwave raw material was placed in the activation solution and soaked for 30 minutes, then the solid and liquid were separated, and the solid part was dried to constant weight to obtain the activated raw material.

[0167] Step a4: The activated raw material is treated at 750° C. for 70 min, and the carrier is obtained after natural cooling.

[0168] Step b: Loading precious metals:

[0169] Step b1: prepare a slurry with a carrier and water in a ratio of 1:5 for standby use.

[0170] Step b2: The noble metal compound is Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , the mass ratio is 1:1.

[0171] The solvent of the solution containing the precious metal compound is water; the solution containing the precious metal compound contains Pd(NH 3 ) 4 (NO 3 ) 2 The concentration of Pt(NH 3 ) 4 (NO 3 ) 2 The concentration is 0.002g / mL.

[0172] The solution containing the precious metal compound was added dropwise to the slurry by an equal volume impregnation method. After the addition was completed, the temperature was maintained at 75° C., the reaction was stirred for 2 hours, and the pH was adjusted to 9.5 using a 5% sodium hydroxide aqueous solution to obtain a mixed material.

[0173] Step b3: According to Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 Prepare 37% formaldehyde aqueous solution in a 1:6 molar ratio of formaldehyde to substance.

[0174] Add formaldehyde aqueous solution to the mixture and stir at warm temperature for 60 minutes.

[0175] Step b4: Filter the material of step b3, wash and dry the solid part to obtain a modified catalyst.

[0176] Comparative Example 5

[0177] A method for preparing white oil for mosquito-repellent liquid, which is different from that of Example 1 in that:

[0178] The preparation method of the modified catalyst comprises the following steps:

[0179] Step a: Preparation of carrier:

[0180] Step a1: The mass ratio of betel nut shell to coconut shell powder is 1:1. In this embodiment, the betel nut shell is 1 kg and the coconut shell powder is 1 kg.

[0181] Crush the betel nut shell and coconut shell to 35 mesh.

[0182] Then, the mixture is mixed at a rotation speed of 1400 r / min and stirred until uniform to obtain a biological raw material.

[0183] Step a2: The biological raw material was mixed with a 70% ethanol solution in a mass ratio of 1:5, and subjected to microwave treatment at 180 W for 25 min to obtain a microwave raw material.

[0184] Step a3: Place the microwave material at -15°C for 18 h.

[0185] Thaw naturally, filter to separate the solid and liquid, dry the solid part (dry with hot air at 40°C to constant weight), and the dried solid part is the frozen raw material.

[0186] Step a4: Weigh zinc chloride according to the frozen raw material and zinc chloride in a mass ratio of 1:0.2, and then prepare an activation solution (zinc chloride solution) in a ratio of zinc chloride to water of 1:10.

[0187] The frozen raw material is placed in the activation solution and soaked for 30 minutes. Then the solid and liquid are separated and the solid part is dried to constant weight to obtain the activated raw material.

[0188] Step a5: The activated raw material is treated at 750° C. for 70 min, and the carrier is obtained after natural cooling.

[0189] Step b: Loading precious metals:

[0190] Step b1: prepare a slurry with a carrier and water in a ratio of 1:5 for standby use.

[0191] Step b2: The noble metal compound is Pd(NH 3 ) 4(NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 , the mass ratio is 1:1.

[0192] The solvent of the solution containing the precious metal compound is water; the solution containing the precious metal compound contains Pd(NH 3 ) 4 (NO 3 ) 2 The concentration of Pt(NH 3 ) 4 (NO 3 ) 2 The concentration is 0.002g / mL.

[0193] The solution containing the precious metal compound was added dropwise to the slurry by an equal volume impregnation method. After the addition was completed, the temperature was maintained at 75° C., the reaction was stirred for 2 hours, and the pH was adjusted to 9.5 using a 5% sodium hydroxide aqueous solution to obtain a mixed material.

[0194] Step b3: According to Pd(NH 3 ) 4 (NO 3 ) 2 、Pt(NH 3 ) 4 (NO 3 ) 2 Prepare 37% formaldehyde aqueous solution in a 1:6 molar ratio of formaldehyde to substance.

[0195] Add formaldehyde aqueous solution to the mixture and stir at warm temperature for 60 minutes.

[0196] Step b4: Filter the material of step b3, wash and dry the solid part to obtain a modified catalyst.

[0197] Comparative Example 6

[0198] A method for preparing white oil for mosquito coil liquid is different from that of Example 1 in that: in step a3, the frozen raw material is subjected to microwave treatment at 380 W for 25 min.

[0199] Comparative Example 7

[0200] A method for preparing white oil for mosquito coil liquid is different from that of Example 1 in that: in step a3, the frozen raw material is subjected to microwave treatment at 80 W for 25 min.

[0201] Comparative Example 8

[0202] A method for preparing white oil for mosquito-repellent liquid, which is different from that of Example 1 in that:

[0203] In step a5, the activated raw material is treated at 1000° C. for 70 min, and the carrier is obtained after natural cooling.

[0204] Comparative Example 9

[0205] A method for preparing white oil for mosquito-repellent liquid, which is different from that of Example 1 in that:

[0206] In step a5, the activated raw material is treated at 500° C. for 70 min, and the carrier is obtained after natural cooling.

[0207] Performance test test 1: The performance of the mosquito-repellent liquid prepared in Example 1 was tested with white oil, as shown in Table 1 for details.

[0208] Table 1

[0209]

[0210] According to Table 1, all indicators of the white oil provided in this application meet the requirements and are qualified high-quality products.

[0211] Test 2:

[0212] The BET volumetric gas adsorption method was used to detect the specific surface areas of the carriers of Examples 1-4 and Comparative Examples 1-9.

[0213] Test conditions: After the carriers of Examples 1-4 and Comparative Examples 1-9 were degassed at 120° C. for 24 hours, nitrogen adsorption and desorption experiments were performed under a relative pressure range of 0-1.0.

[0214] The specific surface area of ​​the support is recorded in Table 2.

[0215] Table 2

[0216]

[0217] According to the test data in Table 2, the carriers of Examples 1-4 have larger specific surface areas than those of Comparative Examples 1-9, and can provide more sites for loading precious metals.

[0218] Test three:

[0219] 1. Sample preparation:

[0220] The electric mosquito repellent liquid was prepared according to the following mass percentages: 20% lemon leaf essential oil, 0.2% chlorfluthrin, 0.05% antioxidant BTH, and the solvent was supplemented to a balance of 100%.

[0221] The solvent is any one of the white oils for mosquito-repellent liquids in Examples 1-4 and Comparative Examples 1-9.

[0222] Lemon leaf essential oil, cyfluthrin and antioxidant BTH are added into white oil and stirred until uniform and transparent to obtain a sample.

[0223] 2. Test:

[0224] The mosquito repellent effect of the samples was tested with the box method according to GB / T 13917.6-2009 "Indoor efficacy test and evaluation of public health insecticides for pesticide registration Part 6 - Electric mosquito repellent liquid". 50 To evaluate the efficacy of KT 50 / min≤6.0 is Class A, KT 50 / min≤10.0 is Class B. Record the class in Table 3.

[0225] The mosquito repellent rate within the observation period is recorded in Table 3. (Kill rate = number of dead or fainted mosquitoes / initial number of mosquitoes*100%) Table 3

[0226] Category <![CDATA[KT 50 / min level]]> Mosquito repellent rate (%) Example 1 A 100 Example 2 A 98 Example 3 A 98 Example 4 A 90 Comparative Example 1 B 70 Comparative Example 2 B 64 Comparative Example 3 B 72 Comparative Example 4 B 70 Comparative Example 5 B 66 Comparative Example 6 B 74 Comparative Example 7 B 72 Comparative Example 8 B 62 Comparative Example 9 B 62

[0227] According to the test data in Table 3, the samples prepared using the white oil for mosquito-repellent liquid in Examples 1-4 have significantly better mosquito-inhibiting effects than those of Comparative Examples 1-9, indicating that the white oil for mosquito-repellent liquid produced by a specific method has better quality, and can be used as the main solvent to prepare electric mosquito-repellent liquid to give it a more appropriate volatilization effect, give full play to the inhibitory effect of chlorfenapyr on mosquitoes, and effectively repel mosquitoes.

[0228] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A method for preparing white oil for mosquito-repellent liquid, characterized in that: The following steps are involved: Step 1: adding raw materials into a hydrogenation reactor, and the raw materials and hydrogen pass through a first catalyst bed and a second catalyst bed to undergo a hydrogenation reaction to obtain a primary product; The raw material is naphthenic oil N4006; Step 2: The primary product is subjected to multiple oil-gas separations, and the oil phase obtained by separation is the product; The first catalyst bed and the second catalyst bed are filled with a modified catalyst, and the preparation method of the modified catalyst comprises the following steps: Step a: Preparation of carrier: Step a1: crushing and mixing betel nut shell and coconut shell to obtain a biological raw material; the mass ratio of the betel nut shell to the coconut shell is (0.8-1.2): (0.8-1.2); Step a2: mixing the biological raw material with the alcohol solution and placing it at -20°C to -10°C for 12-24 hours to obtain a frozen raw material; Step a3: treating the frozen raw material with a microwave at 150-200 W for 15-30 min, and then filtering, and the solid part is the microwave raw material; Step a4: soaking the microwave raw material in an activation solution to obtain an activated raw material; the activation solution is one of zinc chloride solution, potassium hydroxide solution, calcium chloride solution, and phosphoric acid solution; Step a5: treating the activated raw material at 700-800° C. for 60-90 min to obtain a carrier; Step b: Loading precious metals: Step b1: prepare a slurry with the carrier and water for standby use; Step b2: mixing the solution containing the precious metal compound with the slurry at 70-80° C., adjusting the pH to greater than 9, to obtain a mixture; Step b3: mixing the mixture with formaldehyde aqueous solution for reaction; Step b4: Filter the material of step b3, and the obtained solid part is the modified catalyst.

2. The method for preparing white oil for mosquito-repellent liquid according to claim 1, characterized in that: In the step a1, betel nut shells and coconut shells are mixed at 1200-1500 r / min until they are uniform.

3. The method for preparing white oil for mosquito-repellent liquid according to claim 1, characterized in that: The betel nut shell and coconut shell are mixed and crushed into 30-40 meshes.

4. The method for preparing white oil for mosquito-repellent liquid according to claim 1, characterized in that: The precious metal compound is a mixture of one or more of Pd(NH3)4(NO3)2, Pd(NH3)4Cl2, Pt(NH3)4(NO3)2, and Pt(NH3)4Cl2.

5. The method for preparing white oil for mosquito-repellent liquid according to claim 4, characterized in that: The precious metal compounds are Pd(NH3)4(NO3)2 and Pt(NH3)4(NO3)2, and the mass ratio of Pd(NH3)4(NO3)2 to Pt(NH3)4(NO3)2 is 1:

1.

6. The method for preparing white oil for mosquito-repellent liquid according to claim 1, characterized in that: In the hydrogenation reactor, the reaction pressure is 12-16 MPa, the temperature is 240-290°C, the hydrogen-oil volume ratio is (500-1000): 1, and the space velocity is 0.5-1.5h -1 .

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