Coal-based agricultural mineral oil as well as preparation method and application thereof

Abstract

The invention discloses agricultural coal-based mineral oil as well as a preparation method and application thereof, and belongs to the technical field of agricultural mineral oil, the preparation method of the agricultural coal-based mineral oil comprises the following steps: stirring No.1 oil at normal temperature, then adding No.2 oil, and stirring while keeping the temperature stable to obtain an oil product; the No.1 oil is prepared by indirectly liquefying coal; the No.2 oil is prepared by coal liquefaction and hydrogenation; characterizing the oil product, and selecting an emulsifier according to a characterization result; and adding an emulsifier into the oil product, and stirring to obtain the coal-based agricultural mineral oil. The coal-based agricultural mineral oil prepared by the invention has the characteristics of low cost, good use effect and wide use range, in addition, the oil products adopted by the invention are extracted from nature, and the emulsifier is biodegradable, so that the coal-based agricultural mineral oil also has the characteristics of greenness and environmental protection.

Description

Technical Field

[0001] This invention relates to the field of agricultural mineral oil technology, specifically a coal-based agricultural mineral oil, its preparation method, and its application. Background Technology

[0002] Agricultural mineral oil is a pesticide used to control pests. It is diluted 100 to 200 times with water and sprayed onto the trunk, stems, and leaves of plants. Through physical action, it forms an oil film on the surface of the insect body, eggshell, and mycelium, sealing the stomata and causing them to suffocate and die. It is safe for humans, animals, the environment, and natural enemies. It can decompose under sunlight and has the advantages of broad spectrum, extremely low toxicity, low dosage, long-lasting effect, and no resistance. Therefore, it is a green and environmentally friendly pesticide that meets the requirements of national strategy.

[0003] Currently, all agricultural mineral oils available on the domestic market are obtained through petroleum refining, resulting in high production costs and prices ranging from approximately 15,000 to 20,000 yuan per ton.

[0004] Therefore, there is an urgent need to develop a low-cost, high-performance agricultural mineral oil to replace existing petroleum-based agricultural mineral oils. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing coal-based agricultural mineral oil to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0007] A method for preparing a coal-based agricultural mineral oil includes the following steps:

[0008] Oil No. 1 is stirred at room temperature, and then Oil No. 2 is added and stirred again, while maintaining a stable temperature, to obtain the oil product; Oil No. 1 is prepared by indirect coal liquefaction; Oil No. 2 is prepared by coal liquefaction hydrogenation;

[0009] The oil product is characterized, and an emulsifier is selected based on the characterization results;

[0010] Emulsifier is added to the oil and stirred to obtain coal-based agricultural mineral oil; the mass ratio of No. 1 oil, No. 2 oil and emulsifier is (30~80):(20~70):(1~10).

[0011] Furthermore, the No. 1 oil contains alkanes, with a mass percentage of 50% to 100%, wherein the carbon chain length is C. 12 ~C 36 The viscosity of the No. 1 oil is 3.0~11.0 mm. 2 / s, density is 0.3~0.8g / cm³ 3 .

[0012] Furthermore, the No. 2 oil contains cycloalkanes, with a mass percentage of 30% to 100% and a carbon number of C. 12 ~C 36 The viscosity of the No. 2 oil is 5.0~14.0 mm. 2 / s, density is 0.4~0.94g / cm³ 3 .

[0013] Furthermore, the preparation method of the No. 1 oil includes the following steps:

[0014] After the coal is crushed and dried, it is then subjected to dust removal and desulfurization treatment under conditions of 1370-1380℃ and 6.0-8.0MPa, and then reacted under a cobalt-based catalyst support to produce kerosene primary product.

[0015] Kerosene crude product is reacted under nickel-based catalyst conditions to produce alkane-based oil, which is then fractionated to obtain No. 1 oil.

[0016] Furthermore, the preparation method of the No. 2 oil includes the following steps:

[0017] After the coal is broken and dried, it is dispersed into circulating oil to produce coal slurry;

[0018] Coal slurry was reacted under iron-based catalyst conditions to obtain crude oil;

[0019] The crude oil was hydrogenated to produce naphthenic oil, which was then fractionated to obtain No. 2 oil.

[0020] Furthermore, the emulsifier includes one or more of tetraethylene glycol monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene oleate, polyoxyethylene monooleate, and polyoxyethylene monostearate.

[0021] Another object of the present invention is to provide a coal-based agricultural mineral oil prepared by the above preparation method.

[0022] Furthermore, the viscosity of the coal-based agricultural mineral oil is 8.0~13.0 mm. 2 / s, density is 0.7~0.9g / cm³ 3 Non-sulfonated content ≥99%, distillation range difference ≤25℃ (10%~90%), carbon chain length C 21 ~C 25 The average number of carbon atoms is C. 22 ~C 24 .

[0023] Another object of the present invention is to provide an application of the above-mentioned coal-based agricultural mineral oil in the control of pests.

[0024] Furthermore, the pest in question is an aphid.

[0025] The method for preparing coal-based agricultural mineral oil provided by this invention uses oils derived from coal mines, reducing dependence on petroleum and conforming to my country's resource characteristics of "abundant coal and scarce oil." This method breaks away from traditional petroleum-based agricultural mineral oils, effectively reducing production costs and dependence on petroleum products. The resulting coal-based agricultural mineral oil is characterized by low cost, good performance, and wide applicability. Furthermore, the oils used in this invention are extracted from nature, and the emulsifiers are biodegradable, thus exhibiting green and environmentally friendly characteristics. Attached Figure Description

[0026] Figure 1 The image shows the control effect of coal-based agricultural mineral oil prepared according to an embodiment of the present invention on apple aphids.

[0027] Figure 2 This image shows the control effect of coal-based agricultural mineral oil prepared according to an embodiment of the present invention on peach aphids.

[0028] Figure 3 This image shows the control effect of coal-based agricultural mineral oil prepared according to an embodiment of the present invention on pepper aphids. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] In one embodiment of the present invention, a method for preparing coal-based agricultural mineral oil is provided, comprising the following steps:

[0031] S1. Stir No. 1 oil at room temperature for 20-30 minutes, then add No. 2 oil and stir for 60-90 minutes, keeping the temperature stable during the process, to obtain the oil product; No. 1 oil is prepared by indirect coal liquefaction; No. 2 oil is prepared by coal liquefaction hydrogenation;

[0032] S2. Characterize the oil product and select an emulsifier based on the characterization results;

[0033] S3. Add emulsifier to the oil and stir to obtain coal-based agricultural mineral oil; the mass ratio of No. 1 oil, No. 2 oil and emulsifier is (30~80):(20~70):(1~10).

[0034] Specifically, the No. 1 oil contains alkanes, with a mass percentage of 50% to 100%, wherein the carbon chain length is C. 12 ~C 36 The viscosity of the No. 1 oil is 3.0~11.0 mm. 2 / s, density is 0.3~0.8g / cm³ 3 Preferably, the alkane content is ≥75%, and the chain length is C. 15 ~C 34 .

[0035] The No. 2 oil contains cycloalkanes, with a mass percentage of 30% to 100% and a carbon number of C. 12 ~C 36 The viscosity of the No. 2 oil is 5.0~14.0 mm. 2 / s, density is 0.4~0.94g / cm³ 3 Preferably, the cycloalkanes account for ≥50%, and the number of carbon atoms is C. 15 ~C 34 .

[0036] The preparation method of No. 1 oil includes the following steps: after crushing and drying coal, oxygen and water vapor are introduced under the conditions of 1370-1380℃ and 6.0-8.0MPa, and dust removal and desulfurization treatment is carried out. Then, the reaction is carried out under a cobalt-based catalyst support to produce kerosene primary product; the kerosene primary product is reacted under the conditions of nickel-based catalyst to obtain alkane-based oil, and No. 1 oil is obtained by fractionation.

[0037] The preparation method of the No. 2 oil includes the following steps: after breaking and drying the coal, it is dispersed into the circulating oil to obtain coal slurry; the coal slurry is reacted under the condition of iron-based catalyst to obtain crude oil; the crude oil is hydrogenated to obtain naphthenic oil, and then fractionated to obtain No. 2 oil.

[0038] The emulsifiers include, but are not limited to, one or more of the following: tetraethylene glycol monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene oleate, polyoxyethylene monooleate, and polyoxyethylene monostearate.

[0039] Emulsifiers are selected based on the HLB value of the oil. The HLB values ​​of various types of emulsifiers are shown in Table 1. Different emulsifiers can also be compounded to prepare emulsifiers with different HLB values ​​for later use. The formula for calculating the HLB value of compound emulsifiers is shown below:

[0040] ;

[0041] Where: X represents the percentage of emulsifier A; Y represents the percentage of emulsifier B.

[0042] Table 1

[0043]

[0044] This invention provides a coal-based agricultural mineral oil prepared through coal liquefaction, cracking, and hydrogenation processes. Compared to agricultural mineral oils on the domestic market, this product has a higher content of non-sulfonated components (non-sulfonated ≥99%), a shorter distillation range (10%~90% distillation range ≤25℃), and a moderate carbon chain length (carbon chain length of C). 21 ~C 25 The average number of carbon atoms is C. 22 ~C 24 Additionally, the viscosity of this coal-based agricultural mineral oil is 8.0~13.0 mm. 2 / s, density is 0.7~0.9g / cm³ 3 It can be used to control pests. Among these pests are, but are not limited to, scale insects, aphids, and mites.

[0045] Example 1: This example provides a method for preparing coal-based agricultural mineral oil, including the following steps:

[0046] S1. Add 30g of No. 1 oil to the mixing vessel and stir at room temperature for 20 minutes. Then add 60g of No. 2 oil to the mixing vessel and stir for 90 minutes. During this period, use circulating water to ensure that the temperature inside the vessel is stable, and the oil product is obtained.

[0047] Among them, No. 1 oil is produced by indirect coal liquefaction. Specifically, coal is crushed to a particle size ≤3mm and dried to reduce the moisture content to below 5%. The furnace temperature is set at 1375℃ and the pressure at 7.0MPa. Oxygen and water vapor are mixed in at an oxygen-to-coal ratio of 0.85:0.95. After a residence time of 3-5 seconds, the resulting gas undergoes dust removal and desulfurization treatment. Then, under a cobalt-based catalyst support, the reaction temperature is set at 230℃, the pressure at 2.9MPa, and the space velocity at 2330h⁻¹. -1 The kerosene was then processed into a primary product. This primary kerosene was then passed through a fixed-bed reactor under nickel-based catalyst conditions, with the following settings: temperature 310℃, pressure 7.6 MPa, hydrogen-to-oil volume ratio 770:1, and space velocity 1.9 h⁻¹. -1 High-quality alkane-based oils are produced, and No. 1 oil that meets the requirements can be obtained through fractionation and cutting.

[0048] Oil No. 2 is produced by coal liquefaction and hydrogenation. Specifically, coal is crushed, dried, dispersed in circulating oil, and additives are added to prepare coal slurry. The reactor temperature is set at 430℃ and the pressure at 20MPa. Under iron-based catalyst conditions, the reaction residence time is 70 min, and the hydrogen-to-coal ratio is 850 N·m. 3 / kg, to obtain crude oil; then the crude oil is subjected to catalytic hydrogenation in a 0.35 L / h fixed-bed hydrogenation unit at a reaction temperature of 385℃, a reaction pressure of 14.5 MPa, a hydrogen-to-oil ratio of 700:1, and a space velocity of 0.65 h⁻¹. -1 High-quality naphthenic oils were prepared under hydrogenation process conditions, and No. 2 oil that met the requirements was obtained by fractionation.

[0049] S2. Take out a portion of the well-stirred oil for characterization, and the characterization results are shown in Table 2. Based on the characterization results, select emulsifier No. 5, polyoxyethylene oxypropylene oleate, from Table 1.

[0050] S3. Add 10g of the selected emulsifier to the oil and stir for 40 minutes to obtain coal-based agricultural mineral oil.

[0051] Example 2: This example provides a method for preparing coal-based agricultural mineral oil, including the following steps:

[0052] S1. Add 50g of No. 1 oil to a mixing vessel and stir at room temperature for 24 minutes. Then add 42g of No. 2 oil to the mixing vessel and stir for 80 minutes. During this period, use circulating water to keep the temperature inside the vessel stable to obtain the oil product. The preparation methods of No. 1 oil and No. 2 oil are the same as in Example 1.

[0053] S2. Take out a portion of the well-stirred oil for characterization, and the characterization results are shown in Table 2. Based on the characterization results, select emulsifier No. 3 in Table 1, polyoxyethylene sorbitan tristearate.

[0054] S3. Add 8g of the selected emulsifier to the oil and stir for 35 minutes to obtain coal-based agricultural mineral oil.

[0055] Example 3: This example provides a method for preparing coal-based agricultural mineral oil, including the following steps:

[0056] S1. Add 80g of No. 1 oil to a mixing vessel and stir at room temperature for 30 minutes. Then add 15g of No. 2 oil to the mixing vessel and stir for 65 minutes. During this period, use circulating water to keep the temperature inside the vessel stable to obtain the oil product. The preparation methods of No. 1 oil and No. 2 oil are the same as in Example 1.

[0057] S2. Take out a portion of the well-stirred oil for characterization, and the characterization results are shown in Table 2. Based on the characterization results, select emulsifier No. 2 in Table 1, polyoxyethylene sorbitan monooleate.

[0058] S3. Add 5g of the selected emulsifier to the oil and stir for 40 minutes to obtain coal-based agricultural mineral oil.

[0059] Example 4: This example provides a method for preparing coal-based agricultural mineral oil, including the following steps:

[0060] S1. Add 60g of No. 1 oil to a mixing vessel and stir at room temperature for 26 minutes. Then add 33g of No. 2 oil to the mixing vessel and stir for 75 minutes. During this period, use circulating water to keep the temperature inside the vessel stable to obtain the oil product. The preparation methods of No. 1 oil and No. 2 oil are the same as in Example 1.

[0061] S2. Take out a portion of the well-stirred oil for characterization, and the characterization results are shown in Table 2. Based on the characterization results, select emulsifier No. 3 in Table 1, polyoxyethylene sorbitan tristearate.

[0062] S3. Add 7g of the selected emulsifier to the oil and stir for 35 minutes to obtain coal-based agricultural mineral oil.

[0063] Example 5: This example provides a method for preparing coal-based agricultural mineral oil, including the following steps:

[0064] S1. Add 70g of No. 1 oil to a mixing vessel and stir at room temperature for 28 minutes. Then add 25g of No. 2 oil to the mixing vessel and stir for 70 minutes. During this period, use circulating water to ensure the temperature inside the vessel remains stable to obtain the oil product. The preparation methods of No. 1 oil and No. 2 oil are the same as in Example 1.

[0065] S2. Take out a portion of the well-stirred oil for characterization, and the characterization results are shown in Table 2. Based on the characterization results, select emulsifier No. 2 in Table 1, polyoxyethylene sorbitan monooleate.

[0066] S3. Add 5g of the selected emulsifier to the oil and stir for 30 minutes to obtain coal-based agricultural mineral oil.

[0067] Example 6: This example provides a method for preparing coal-based agricultural mineral oil, including the following steps:

[0068] S1. Add 40g of No. 1 oil to a mixing vessel and stir at room temperature for 22 minutes. Then add 50g of No. 2 oil to the mixing vessel and stir for 85 minutes. During this period, use circulating water to keep the temperature inside the vessel stable to obtain the oil product. The preparation methods of No. 1 oil and No. 2 oil are the same as in Example 1.

[0069] S2. Take out a portion of the well-stirred oil for characterization, and the characterization results are shown in Table 2. Based on the characterization results, select emulsifier No. 5, polyoxyethylene oxypropylene oleate, from Table 1.

[0070] S3. Add 10g of the selected emulsifier to the oil and stir for 40 minutes to obtain coal-based agricultural mineral oil.

[0071] Table 2

[0072]

[0073] Through comparisons of Examples 1 to 6, it was found that the coal-based agricultural mineral oil prepared in Example 4 had better overall performance. After being diluted 200 times and sprayed onto apple trees for observation, the results were as follows... Figure 1 As shown, with the increase in the number of days of application of coal-based agricultural mineral oil, the number of apple aphids gradually decreased, and the difference between the number of aphids and the control group (blank) became increasingly larger. The control efficacy of this coal-based agricultural mineral oil against apple aphids gradually increased from 21.6% one day after application to 85.76% fourteen days after application.

[0074] The coal-based agricultural mineral oil prepared in Example 4 was diluted 200 times and sprayed onto peach trees for observation. The results are as follows: Figure 2 As shown, with the increase in the number of days of application of coal-based agricultural mineral oil, the number of peach aphids gradually decreased, and the difference between the number of aphids and the control group (blank) became increasingly larger. The control effect of this coal-based agricultural mineral oil on peach aphids gradually increased from 27.8% one day after application to 87.54% fourteen days after application.

[0075] The coal-based agricultural mineral oil prepared in Example 4 was diluted 200 times and sprayed onto Sichuan pepper trees for observation. The results are as follows: Figure 3 As shown, with the increase in the number of days of application of coal-based agricultural mineral oil, the number of aphids on Sichuan pepper gradually decreased and the difference between the number of aphids and the control group (blank) became increasingly larger. The control effect of this coal-based agricultural mineral oil on Sichuan pepper aphids reached 83.24% on the 4th day, 94.86% on the 14th day after application, and still 89.17% after 18 days.

[0076] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification.

Claims

1. A method for preparing coal-based agricultural mineral oil, characterized in that, Includes the following steps: Oil No. 1 is stirred at room temperature, and then Oil No. 2 is added and stirred again, while maintaining a stable temperature, to obtain the oil product; Oil No. 1 is prepared by indirect coal liquefaction; Oil No. 2 is prepared by coal liquefaction hydrogenation; The oil product is characterized, and an emulsifier is selected based on the characterization results; Emulsifier is added to the oil and stirred to obtain coal-based agricultural mineral oil; the mass ratio of No. 1 oil, No. 2 oil and emulsifier is (30~80):(20~70):(1~10).

2. The method for preparing coal-based agricultural mineral oil according to claim 1, characterized in that, The No. 1 oil contains alkanes, with a mass percentage of 50% to 100%, wherein the carbon chain length is C. 12 ~C 36 The viscosity of the No. 1 oil is 3.0~11.0 mm. 2 / s, density is 0.3~0.8g / cm³ 3 .

3. The method for preparing coal-based agricultural mineral oil according to claim 1, characterized in that, The No. 2 oil contains cycloalkanes, with a mass percentage of 30% to 100% and a carbon number of C. 12 ~C 36 The viscosity of the No. 2 oil is 5.0~14.0 mm. 2 / s, density is 0.4~0.94g / cm³ 3 .

4. The method for preparing coal-based agricultural mineral oil according to claim 1 or 2, characterized in that, The preparation method of the No. 1 oil includes the following steps: After the coal is crushed and dried, it is then subjected to dust removal and desulfurization treatment under conditions of 1370-1380℃ and 6.0-8.0MPa, and then reacted under a cobalt-based catalyst support to produce kerosene primary product. Kerosene crude product is reacted under nickel-based catalyst conditions to produce alkane-based oil, which is then fractionated to obtain No. 1 oil.

5. The method for preparing coal-based agricultural mineral oil according to claim 1 or 3, characterized in that, The preparation method of the No. 2 oil includes the following steps: After the coal is broken and dried, it is dispersed into circulating oil to produce coal slurry; Coal slurry was reacted under iron-based catalyst conditions to obtain crude oil; The crude oil was hydrogenated to produce naphthenic oil, which was then fractionated to obtain No. 2 oil.

6. The method for preparing coal-based agricultural mineral oil according to claim 1, characterized in that, The emulsifier includes one or more of the following: tetraethylene glycol monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene oleate, polyoxyethylene monooleate, and polyoxyethylene monostearate.

7. A coal-based agricultural mineral oil prepared by any one of claims 1-6.

8. The coal-based agricultural mineral oil according to claim 7, characterized in that, The viscosity of the coal-based agricultural mineral oil is 8.0~13.0 mm. 2 / s, density is 0.7~0.9g / cm³ 3 Non-sulfonated content ≥99%, distillation range difference ≤25℃ (10%~90%), carbon chain length C 21 ~C 25 The average number of carbon atoms is C. 22 ~C 24 .

9. The application of a coal-based agricultural mineral oil as described in claim 7 or 8 in the control of pests.

10. The application according to claim 9, characterized in that, The pest in question is an aphid.

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