Preparation method of sulfur-calcium powder

Abstract

The invention discloses a preparation method of sulfur calcium powder. The method comprises the following steps: (1) sequentially spraying an amino silane coupling agent solution and a vitamin C solution on the surface of attapulgite to obtain modified attapulgite; (2) sequentially spraying an amino silane coupling agent solution and a resveratrol solution on the surface of quick lime to obtain modified quick lime; (3) compounding the modified attapulgite and the modified quicklime by a mechanochemical method to obtain composite powder; and (4) contacting sulfur steam with the composite powder to coat the surface of the composite powder with sulfur to obtain the sulfur-calcium powder. Compared with the traditional lime sulfur, the sulfur-calcium powder prepared by the invention is convenient to store and transport, can be used for preventing and treating various plant diseases, and can also be used for producing rubber products.

Description

Technical Field

[0001] The invention relates to a method for preparing calcium sulphate powder. Background Art

[0002] Elemental sulfur, commonly known as sulfur, is mainly used to make dyes, pesticides, matches, gunpowder, rubber, rayon, etc. In the agricultural field, it is used to treat a variety of plant diseases. It is an important variety of inorganic pesticides. It is safe for humans and animals and is not likely to cause pesticide damage to crops. In the rubber field, it is often used as a vulcanization accelerator to produce vulcanized rubber.

[0003] Calcium oxide, commonly known as quicklime, is mainly used for soil improvement in the agricultural field. It can neutralize acidic substances in the soil, increase the soil pH value, thereby improving soil structure and promoting crop growth. In addition, quicklime has a bactericidal effect and can effectively prevent and control soil-borne diseases. Lime sulfur, which is made by mixing sulfur powder and quicklime in a certain proportion, can be used as a garden cleaning agent to clean and disinfect orchards and protect trees, reducing the spread of diseases and the loss of fruit trees. However, lime sulfur is not easy to store and transport. Summary of the invention

[0004] The object of the present invention is to provide a method for preparing calcium sulphate powder which is convenient for storage and transportation.

[0005] To achieve the above object, the present invention adopts the following technical solution: A method for preparing calcium sulphate powder comprises the following steps: (1) spraying an aminosilane coupling agent solution and a vitamin C solution on the surface of attapulgite in sequence to obtain modified attapulgite; (2) spraying the aminosilane coupling agent solution and the resveratrol solution on the surface of quicklime in sequence to obtain modified quicklime; (3) Compounding the modified attapulgite and modified quicklime by a mechanochemical method to obtain a composite powder; (4) The sulfur vapor is brought into contact with the composite powder so that the sulfur is coated on the surface of the composite powder to obtain calcium sulfur powder.

[0006] Preferably, the amount of aminosilane coupling agent is 1-5% of the mass of attapulgite, and the amount of vitamin C is 2-10% of the mass of attapulgite.

[0007] Preferably, the amount of aminosilane coupling agent is 3-7% of the mass of quicklime, and the amount of resveratrol is 5-15% of the mass of quicklime.

[0008] Preferably, the particle size of attapulgite is smaller than that of quicklime.

[0009] More preferably, the particle size of the attapulgite is above 3000 mesh, and the particle size of the quicklime is between 1000 and 1500 mesh.

[0010] Preferably, during compounding, the mass ratio of the modified attapulgite to the modified quicklime is 1:50-100.

[0011] Preferably, the mass ratio of sulfur to composite powder is 1:1-5.

[0012] Compared with traditional lime sulfur mixture, the calcium sulfur powder prepared by the present invention is easy to store and transport, and can be used not only for the prevention and treatment of various plant diseases, but also for the production of rubber products. DETAILED DESCRIPTION

[0013] The technical solution of the present invention is further described in detail below in conjunction with embodiments.

[0014] Example 1 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0015] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0016] Vitamin C (VC) was dissolved in methanol to prepare a saturated solution.

[0017] The amount of KH-550 was 1% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, the VC saturated solution (the amount of VC was 2% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0018] 2. Preparation of resveratrol grafted modified quicklime Crush quicklime to 1000 mesh.

[0019] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0020] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0021] The amount of KH-550 was 3% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime. After high-speed stirring for 10 minutes, it was dried. Then, a saturated resveratrol solution (resveratrol amount was 5% of the mass of quicklime) was evenly sprayed on the surface of KH-550-modified quicklime to obtain resveratrol grafted modified quicklime.

[0022] 3. Preparation of calcium sulphate powder The vitamin C grafted modified attapulgite and the resveratrol grafted modified quicklime were mixed evenly at a mass ratio of 1:50, and then ground in a high-speed ball mill to obtain a composite powder.

[0023] Sulfur is heated and evaporated in a nitrogen atmosphere, the generated sulfur vapor is introduced into the composite powder, and a sulfur coating is formed on the surface of the composite powder after cooling, so as to obtain calcium sulfur powder, wherein the mass ratio of sulfur to the composite powder is 1:1.

[0024] Example 2 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0025] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0026] Vitamin C was dissolved in methanol to prepare a saturated solution.

[0027] The amount of KH-550 was 2% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, a saturated VC solution (the amount of VC was 10% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0028] 2. Preparation of resveratrol grafted modified quicklime Crush quicklime to 1500 mesh.

[0029] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0030] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0031] The amount of KH-550 was 4% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime, stirred at high speed for 10 minutes and then dried, and then the resveratrol solution (resveratrol amount was 15% of the mass of quicklime) was evenly sprayed on the surface of KH-550 modified quicklime to obtain resveratrol grafted modified quicklime.

[0032] 3. Preparation of calcium sulphate powder The vitamin C grafted modified attapulgite and the resveratrol grafted modified quicklime were mixed evenly at a mass ratio of 1:60, and then ground in a high-speed ball mill to obtain a composite powder.

[0033] Sulfur is heated and evaporated in a nitrogen atmosphere, the generated sulfur vapor is introduced into the composite powder, and a sulfur coating is formed on the surface of the composite powder after cooling, so as to obtain calcium sulfur powder, wherein the mass ratio of sulfur to the composite powder is 1:2.

[0034] Example 3 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0035] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0036] Vitamin C was dissolved in methanol to prepare a saturated solution.

[0037] The amount of KH-550 was 3% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, a saturated VC solution (the amount of VC was 5% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0038] 2. Preparation of resveratrol grafted modified quicklime Crush quicklime to 1000 mesh.

[0039] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0040] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0041] The amount of KH-550 was 5% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime, and then dried after high-speed stirring for 10 minutes. Then, the resveratrol solution (the amount of resveratrol was 10% of the mass of quicklime) was evenly sprayed on the surface of KH-550-modified quicklime to obtain resveratrol-grafted quicklime.

[0042] 3. Preparation of calcium sulphate powder The vitamin C grafted modified attapulgite and the resveratrol grafted modified quicklime were mixed evenly at a mass ratio of 1:80, and then ground in a high-speed ball mill to obtain a composite powder.

[0043] Sulfur is heated and evaporated in a nitrogen atmosphere, the generated sulfur vapor is introduced into the composite powder, and a sulfur coating is formed on the surface of the composite powder after cooling, so as to obtain calcium sulfur powder, wherein the mass ratio of sulfur to the composite powder is 1:3.

[0044] Example 4 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0045] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0046] Vitamin C was dissolved in methanol to prepare a saturated solution.

[0047] The amount of KH-550 was 4% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, a saturated VC solution (the amount of VC was 7% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0048] 2. Preparation of resveratrol grafted modified quicklime Crush quicklime to 1000 mesh.

[0049] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0050] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0051] The amount of KH-550 was 6% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime, stirred at high speed for 10 minutes and then dried, and then the resveratrol solution (resveratrol amount was 12% of the mass of quicklime) was evenly sprayed on the surface of KH-550 modified quicklime to obtain resveratrol grafted modified quicklime.

[0052] 3. Preparation of calcium sulphate powder The vitamin C grafted modified attapulgite and the resveratrol grafted modified quicklime were mixed evenly at a mass ratio of 1:90, and then ground in a high-speed ball mill to obtain a composite powder.

[0053] Sulfur is heated and evaporated in a nitrogen atmosphere, the generated sulfur vapor is introduced into the composite powder, and a sulfur coating is formed on the surface of the composite powder after cooling, so as to obtain calcium sulfur powder, wherein the mass ratio of sulfur to the composite powder is 1:4.

[0054] Example 5 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0055] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0056] Vitamin C was dissolved in methanol to prepare a saturated solution.

[0057] The amount of KH-550 was 5% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, a saturated VC solution (the amount of VC was 9% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0058] 2. Preparation of resveratrol grafted modified quicklime Crush quicklime to 1000 mesh.

[0059] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0060] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0061] The amount of KH-550 was 7% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime, and then dried after high-speed stirring for 10 minutes. Then, the resveratrol solution (the amount of resveratrol was 8% of the mass of quicklime) was evenly sprayed on the surface of KH-550-modified quicklime to obtain resveratrol-grafted quicklime.

[0062] 3. Preparation of calcium sulphate powder The vitamin C grafted modified attapulgite and the resveratrol grafted modified quicklime were mixed evenly at a mass ratio of 1:100, and then ground in a high-speed ball mill to obtain a composite powder.

[0063] Sulfur is heated and evaporated in a nitrogen atmosphere, the generated sulfur vapor is introduced into the composite powder, and a sulfur coating is formed on the surface of the composite powder after cooling, so as to obtain calcium sulfur powder, wherein the mass ratio of sulfur to the composite powder is 1:5.

[0064] Comparative Example 1 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0065] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0066] Vitamin C was dissolved in methanol to prepare a saturated solution.

[0067] The amount of KH-550 was 5% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, a saturated VC solution (the amount of VC was 9% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0068] 2. Preparation of resveratrol grafted modified quicklime Crush quicklime to 1000 mesh.

[0069] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0070] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0071] The amount of KH-550 was 7% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime, stirred at high speed for 10 minutes and then dried, and then the resveratrol solution (resveratrol amount was 8% of the mass of quicklime) was evenly sprayed on the surface of KH-550 modified quicklime to obtain resveratrol grafted modified quicklime.

[0072] 3. Preparation of calcium sulphate powder The vitamin C grafted modified attapulgite and the resveratrol grafted modified quicklime were mixed evenly at a mass ratio of 1:100, and then ground in a high-speed ball mill to obtain a composite powder.

[0073] The sulfur powder and the composite powder were uniformly mixed in a mass ratio of 1:5 to obtain calcium sulfur powder (DB-1).

[0074] Comparative Example 2 1. Preparation of Vitamin C Grafted Modified Attapulgite The attapulgite was crushed to above 3000 mesh.

[0075] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0076] Vitamin C was dissolved in methanol to prepare a saturated solution.

[0077] The amount of KH-550 was 5% of the mass of attapulgite, and the silane coupling agent solution was evenly sprayed on the surface of attapulgite. After high-speed stirring for 20 minutes, it was dried. Then, a saturated VC solution (the amount of VC was 9% of the mass of attapulgite) was evenly sprayed on the surface of KH-550-modified attapulgite to obtain vitamin C grafted modified attapulgite.

[0078] 2. Preparation of calcium sulphate powder Sulfur is heated and evaporated under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the vitamin C grafted modified attapulgite. After cooling, a sulfur coating film is formed on the surface of the vitamin C grafted modified attapulgite, thereby obtaining calcium sulfur powder (DB-2), wherein the mass ratio of sulfur to the vitamin C grafted modified attapulgite is 1:5.

[0079] Comparative Example 3 1. Preparation of resveratrol grafted quicklime Crush quicklime to 1000 mesh.

[0080] The silane coupling agent KH-550 was dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0081] Resveratrol was dissolved in methanol to prepare a saturated resveratrol solution.

[0082] The amount of KH-550 was 7% of the mass of quicklime, and the silane coupling agent solution was evenly sprayed on the surface of quicklime, and then dried after high-speed stirring for 10 minutes. Then, the resveratrol solution (the amount of resveratrol was 8% of the mass of quicklime) was evenly sprayed on the surface of KH-550-modified quicklime to obtain resveratrol-grafted quicklime.

[0083] 2. Preparation of calcium sulphate powder Sulfur is heated and evaporated under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the resveratrol grafted modified quicklime. After cooling, a sulfur coating film is formed on the surface of the resveratrol grafted modified quicklime, thereby obtaining calcium sulfur powder (DB-3), wherein the mass ratio of sulfur to resveratrol grafted modified quicklime is 1:5.

[0084] Comparative Example 4 1. Crush the attapulgite to 3000 mesh.

[0085] 2. Crush the quicklime to 1000 mesh.

[0086] 3. After uniformly mixing attapulgite and quicklime in a mass ratio of 1:100, the mixture is ground in a high-speed ball mill to obtain a composite powder.

[0087] 4. Preparation of calcium sulphate powder Sulfur is heated and evaporated in a nitrogen atmosphere, and the generated sulfur vapor is introduced into the composite powder. After cooling, a sulfur coating is formed on the surface of the composite powder to obtain calcium sulfur powder (DB-4), wherein the mass ratio of sulfur to the composite powder is 1:5.

[0088] Application of calcium sulphate powder 1. Agriculture Usage: Manual dry powder spraying or applying to the soil during tillage. Dry powder spraying 10-50 grams per plant each time; when the land is plowed, the application amount is 100-500 kg / mu.

[0089] Taking cotton as an example, the experimental site with wilt disease was divided into 5 plots according to the treatment group (embodiment) and the control group (comparative examples 1-4). 100 plants with similar disease severity were selected from each plot for treatment, and 25 grams of dry powder was sprayed on each plant. The evaluation effect was divided into five levels, mortality rate (%), no improvement, improvement, significant improvement and cure rate (%). The specific treatment effect of each group is shown in Table 1.

[0090] Table 1 Treatment effect on cotton wilt

[0091] For the treatment of sunflower disk rot, the experimental scheme was similar to that of cotton, wherein 30 g of dry powder was sprayed per plant. The treatment effects of each group are shown in Table 2.

[0092] Table 2 Treatment effect on sunflower disk rot

[0093] 2. Rubber field The calcium sulphate powder product of the present invention is used in rubber composite materials as a vulcanization aid, which can replace 15% to 35% of pure sulphur powder, reduce the cost by about 20 to 40%, and has better mechanical properties than pure sulphur powder.

[0094] Table 3 shows the mechanical properties of the product used in styrene-butadiene rubber. Styrene-butadiene rubber formula: 400 parts of styrene-butadiene rubber, 200 parts of carbon black, 4 parts of stearic acid, 4 parts of TBBS, 7 parts of sulfur, and 12 parts of zinc oxide. In this test, 25% of the sulfur was replaced by the same mass of calcium sulfate powder (products of Example 5 and Comparative Examples 1-4) while the amounts of other components remained unchanged.

[0095] Table 3 Effects on mechanical properties of styrene-butadiene rubber

[0096] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing calcium sulphate powder, comprising the following steps: (1) spraying an aminosilane coupling agent solution and a vitamin C solution on the surface of attapulgite in sequence to obtain modified attapulgite; (2) spraying the aminosilane coupling agent solution and the resveratrol solution on the surface of quicklime in sequence to obtain modified quicklime; (3) Compounding the modified attapulgite and modified quicklime by a mechanochemical method to obtain a composite powder; (4) The sulfur vapor is brought into contact with the composite powder so that the sulfur is coated on the surface of the composite powder to obtain calcium sulfur powder.

2. The preparation method according to claim 1, characterized in that: The amount of aminosilane coupling agent used is 1-5% of the mass of attapulgite, and the amount of vitamin C used is 2-10% of the mass of attapulgite.

3. The preparation method according to claim 1, characterized in that: The amount of aminosilane coupling agent used is 3-7% of the mass of quicklime, and the amount of resveratrol used is 5-15% of the mass of quicklime.

4. The preparation method according to claim 1, characterized in that: The particle size of attapulgite is smaller than that of quicklime. Preferably, the particle size of attapulgite is above 3000 meshes, and the particle size of quicklime is between 1000 and 1500 meshes.

5. The preparation method according to claim 1, characterized in that: During compounding, the mass ratio of modified attapulgite to modified quicklime is 1:50~100.

6. The preparation method according to claim 1, characterized in that: The mass ratio of sulfur to composite powder is 1:1~5.

7. Calcium sulphate powder prepared according to any one of claims 1 to 6.

8. Use of the calcium sulphate powder according to claim 7 in preventing and treating cotton wilt and sunflower disk rot.

9. Application of the calcium sulphate powder according to claim 7 as a vulcanizing agent in the production of rubber products.

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