A method for preparing calcium sulphide powder

Abstract

The application discloses a preparation method of calcium sulfide powder. The method comprises the following steps: (1) spraying an amino silane coupling agent solution and a vitamin C solution on the surface of a palygorskite in sequence to obtain modified palygorskite; (2) spraying an amino silane coupling agent solution and a white wine solution on the surface of a quicklime in sequence to obtain modified quicklime; (3) compounding the modified palygorskite and the modified quicklime by a mechanical chemical method to obtain a composite powder; and (4) contacting sulfur steam with the composite powder to coat the sulfur on the surface of the composite powder to obtain the calcium sulfide powder. Compared with a traditional stone sulfur mixture, the calcium sulfide powder prepared by the method is convenient to store and transport, and can be used for the prevention and treatment of various plant diseases and the production of rubber products.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of sulfur-calcium powder. BACKGROUND

[0002] Elemental sulfur, commonly known as sulfur powder, is mainly used for manufacturing dyes, pesticides, matches, gunpowder, rubber, rayon, etc. In the agricultural field, it is used for treating various plant diseases and is an important variety of inorganic pesticides, which is safe to humans and livestock and is not easy to cause crop damage. In the rubber field, it is often used as a vulcanization aid for producing 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 the soil structure and promoting crop growth. In addition, quicklime also has a sterilization effect and can effectively prevent soil-borne diseases. The stone sulfur mixture prepared by mixing sulfur powder and quicklime in a certain proportion can be used as a garden cleaning agent for garden cleaning and disinfection and tree protection, reducing the spread of diseases and the loss of fruit trees, but the stone sulfur mixture is not easy to store and transport. SUMMARY

[0004] The application aims to provide a preparation method of sulfur-calcium powder which is convenient to store and transport.

[0005] To achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0006] A preparation method of sulfur-calcium powder comprises the following steps:

[0007] (1) Spraying an amino silane coupling agent solution and a vitamin C solution on the surface of the attapulgite in sequence to obtain modified attapulgite;

[0008] (2) Spraying an amino silane coupling agent solution and a resveratrol solution on the surface of the quicklime in sequence to obtain modified quicklime;

[0009] (3) Compounding the modified attapulgite and the modified quicklime by a mechanochemical method to obtain a composite powder;

[0010] (4) Contacting sulfur steam with the composite powder so that the sulfur is coated on the surface of the composite powder to obtain sulfur-calcium powder.

[0011] Preferably, the amount of the amino silane coupling agent is 1-5% of the mass of the attapulgite, and the amount of the vitamin C is 2-10% of the mass of the attapulgite.

[0012] Preferably, the amount of the amino silane coupling agent is 3-7% of the mass of the quicklime, and the amount of the resveratrol is 5-15% of the mass of the quicklime.

[0013] Preferably, the particle size of the attapulgite is smaller than that of the quicklime.

[0014] More preferably, the particle size of the attapulgite is above 3000 mesh, and the particle size of the quicklime is 1000-1500 mesh.

[0015] Preferably, the mass ratio of the modified attapulgite to the modified quicklime is 1:50-100 during the compounding.

[0016] Preferably, the mass ratio of the sulfur to the compound powder is 1:1-5.

[0017] Compared with the traditional stone sulfur mixture, the calcium sulfide powder prepared by the application is convenient 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

[0018] The technical solutions of the application are further described in detail below in combination with examples.

[0019] Example 1

[0020] I. Preparation of vitamin C grafted modified attapulgite

[0021] The attapulgite is crushed to above 3000 mesh.

[0022] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0023] Vitamin C (VC) is dissolved in methanol to prepare a saturated solution.

[0024] The silane coupling agent solution is uniformly sprayed on the surface of the attapulgite at a dosage of 1% of the mass of the attapulgite, and then high-speed stirring is performed for 20 minutes followed by drying. Then, the VC saturated solution is uniformly sprayed (the dosage of VC is 2% of the mass of the attapulgite) on the surface of the KH-550 modified attapulgite to obtain the vitamin C grafted modified attapulgite.

[0025] II. Preparation of resveratrol grafted modified quicklime

[0026] The quicklime is crushed and passed through a 1000 mesh sieve.

[0027] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0028] Resveratrol is dissolved in methanol to prepare a resveratrol saturated solution.

[0029] The silane coupling agent solution is uniformly sprayed on the surface of the quicklime according to the amount of KH-550 being 3% of the mass of the quicklime, and then dried after high-speed stirring for 10 minutes; then the resveratrol saturated solution (the amount of resveratrol being 5% of the mass of the quicklime) is uniformly sprayed on the surface of the KH-550 modified quicklime, so as to obtain the resveratrol grafted modified quicklime.

[0030] III. Preparation of calcium sulfide powder

[0031] The vitamin C grafted modified palygorskite and the resveratrol grafted modified quicklime are uniformly mixed according to a mass ratio of 1:50, and then grinded in a high-speed ball mill to obtain a composite powder.

[0032] Sulfur is heated and evaporated under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the composite powder, so that a sulfur coating film is formed on the surface of the composite powder after cooling, thereby obtaining the calcium sulfide powder, wherein the mass ratio of sulfur to the composite powder is 1:1.

[0033] Example 2

[0034] I. Preparation of vitamin C grafted modified palygorskite

[0035] The palygorskite is crushed to more than 3000 meshes.

[0036] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0037] Vitamin C is dissolved in methanol to prepare a saturated solution.

[0038] The silane coupling agent solution is uniformly sprayed on the surface of the palygorskite according to the amount of KH-550 being 2% of the mass of the palygorskite, and then dried after high-speed stirring for 20 minutes; then the VC saturated solution (the amount of VC being 10% of the mass of the palygorskite) is uniformly sprayed on the surface of the KH-550 modified palygorskite, so as to obtain the vitamin C grafted modified palygorskite.

[0039] II. Preparation of resveratrol grafted modified quicklime

[0040] The quicklime is crushed and passed through a 1500-mesh sieve.

[0041] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0042] Resveratrol is dissolved in methanol to prepare a resveratrol saturated solution.

[0043] The silane coupling agent solution is uniformly sprayed on the surface of the quicklime according to the amount of KH-550 being 4% of the mass of the quicklime, and then dried after high-speed stirring for 10 minutes; then the resveratrol solution (the amount of resveratrol being 15% of the mass of the quicklime) is uniformly sprayed on the surface of the KH-550 modified quicklime, so as to obtain the resveratrol grafted modified quicklime.

[0044] III. Preparation of calcium sulfide powder

[0045] The vitamin C grafted modified palygorskite and the resveratrol grafted modified quicklime are uniformly mixed according to a mass ratio of 1:60, and then grinded in a high-speed ball mill to obtain a composite powder.

[0046] Sulfur is evaporated by heating under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the composite powder, so that a sulfur coating film is formed on the surface of the composite powder after cooling, thereby obtaining the calcium sulfide powder, wherein the mass ratio of sulfur to the composite powder is 1:2.

[0047] Example 3

[0048] I. Preparation of vitamin C grafted modified palygorskite

[0049] The palygorskite is crushed to more than 3000 meshes.

[0050] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0051] Vitamin C is dissolved in methanol to prepare a saturated solution.

[0052] The silane coupling agent solution is uniformly sprayed on the surface of the palygorskite according to the amount of KH-550 being 3% of the mass of the palygorskite, and then dried after high-speed stirring for 20 minutes; then the VC saturated solution (the amount of VC being 5% of the mass of the palygorskite) is uniformly sprayed on the surface of the KH-550 modified palygorskite, so as to obtain the vitamin C grafted modified palygorskite.

[0053] II. Preparation of resveratrol grafted modified quicklime

[0054] The quicklime is crushed and passed through a 1000-mesh sieve.

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

[0056] Resveratrol is dissolved in methanol to prepare a resveratrol saturated solution.

[0057] The silane coupling agent solution is uniformly sprayed on the surface of the quicklime according to the amount of KH-550 being 5% of the mass of the quicklime, and then dried after high-speed stirring for 10 minutes; then the resveratrol solution (the amount of resveratrol being 10% of the mass of the quicklime) is uniformly sprayed on the surface of the KH-550 modified quicklime, so as to obtain the resveratrol grafted modified quicklime.

[0058] III. Preparation of calcium sulfide powder

[0059] The vitamin C grafted modified palygorskite and the resveratrol grafted modified quicklime are uniformly mixed according to a mass ratio of 1:80, and then grinded in a high-speed ball mill to obtain a composite powder.

[0060] Sulfur is heated and evaporated under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the composite powder, so that a sulfur coating film is formed on the surface of the composite powder after cooling, thereby obtaining the calcium sulfide powder, wherein the mass ratio of sulfur to the composite powder is 1:3.

[0061] Example 4

[0062] I. Preparation of vitamin C grafted modified palygorskite

[0063] The palygorskite is crushed to more than 3000 meshes.

[0064] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0065] The vitamin C is dissolved in methanol to prepare a saturated solution.

[0066] The silane coupling agent solution is uniformly sprayed on the surface of the palygorskite according to the amount of KH-550 being 4% of the mass of the palygorskite, and then dried after high-speed stirring for 20 minutes; then the VC saturated solution (the amount of VC being 7% of the mass of the palygorskite) is uniformly sprayed on the surface of the KH-550 modified palygorskite, so as to obtain the vitamin C grafted modified palygorskite.

[0067] II. Preparation of resveratrol grafted modified quicklime

[0068] The quicklime is crushed and passed through a 1000-mesh sieve.

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

[0070] The resveratrol is dissolved in methanol to prepare a resveratrol saturated solution.

[0071] The silane coupling agent solution is uniformly sprayed on the surface of the quicklime according to the amount of KH-550 being 6% of the mass of the quicklime, and then dried after high-speed stirring for 10 minutes; then the resveratrol solution (the amount of resveratrol being 12% of the mass of the quicklime) is uniformly sprayed on the surface of the KH-550 modified quicklime, so as to obtain the resveratrol grafted modified quicklime.

[0072] III. Preparation of calcium sulfide powder

[0073] The vitamin C grafted modified palygorskite and the resveratrol grafted modified quicklime are uniformly mixed according to a mass ratio of 1:90, and then grinded in a high-speed ball mill to obtain a composite powder.

[0074] Sulfur is evaporated by heating under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the composite powder, so that a sulfur coating film is formed on the surface of the composite powder after cooling, thereby obtaining the calcium sulfide powder, wherein the mass ratio of sulfur to the composite powder is 1:4.

[0075] Example 5

[0076] I. Preparation of vitamin C grafted modified palygorskite

[0077] The palygorskite is crushed to more than 3000 meshes.

[0078] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to configure a silane coupling agent solution with a concentration of 10%.

[0079] The vitamin C is dissolved in methanol to configure a saturated solution.

[0080] The silane coupling agent solution is uniformly sprayed on the surface of the palygorskite according to the amount of KH-550 being 5% of the mass of the palygorskite, and then dried after high-speed stirring for 20 minutes; then the VC saturated solution (the amount of VC being 9% of the mass of the palygorskite) is uniformly sprayed on the surface of the KH-550 modified palygorskite, so as to obtain the vitamin C grafted modified palygorskite.

[0081] II. Preparation of resveratrol grafted modified quicklime

[0082] The quicklime is crushed and passed through a 1000-mesh sieve.

[0083] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to configure a silane coupling agent solution with a concentration of 10%.

[0084] The resveratrol is dissolved in methanol to configure a resveratrol saturated solution.

[0085] The silane coupling agent solution is uniformly sprayed on the surface of the quicklime according to the amount of KH-550 being 7% of the mass of the quicklime, and then dried after high-speed stirring for 10 minutes; then the resveratrol solution (the amount of resveratrol being 8% of the mass of the quicklime) is uniformly sprayed on the surface of the KH-550 modified quicklime, so as to obtain the resveratrol grafted modified quicklime.

[0086] III. Preparation of calcium sulfide powder

[0087] The vitamin C grafted modified palygorskite and the resveratrol grafted modified quicklime are uniformly mixed according to a mass ratio of 1:100, and then grinded in a high-speed ball mill to obtain a composite powder.

[0088] Sulfur is heated and evaporated under a nitrogen atmosphere, and the generated sulfur vapor is introduced into the composite powder, so that a sulfur coating film is formed on the surface of the composite powder after cooling, thereby obtaining the calcium sulfide powder, wherein the mass ratio of sulfur to the composite powder is 1:5.

[0089] Comparative Example 1

[0090] I. Preparation of vitamin C grafted modified palygorskite

[0091] The palygorskite is crushed to more than 3000 meshes.

[0092] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0093] Vitamin C is dissolved in methanol to prepare a saturated solution.

[0094] The silane coupling agent solution is uniformly sprayed on the surface of the palygorskite according to the amount of KH-550 being 5% of the mass of the palygorskite, and then dried after high-speed stirring for 20 minutes; then the VC saturated solution (the amount of VC being 9% of the mass of the palygorskite) is uniformly sprayed on the surface of the KH-550 modified palygorskite, so as to obtain the vitamin C grafted modified palygorskite.

[0095] II. Preparation of resveratrol grafted modified quicklime

[0096] The quicklime is crushed and passed through a 1000-mesh sieve.

[0097] The silane coupling agent KH-550 is dissolved in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0098] Resveratrol is dissolved in methanol to prepare a resveratrol saturated solution.

[0099] The silane coupling agent solution was uniformly sprayed on the surface of the quicklime at a dosage of 7% of the mass of the quicklime, and then dried after high-speed stirring for 10 minutes. Then, the resveratrol solution (resveratrol dosage was 8% of the mass of the quicklime) was uniformly sprayed on the surface of the quicklime modified by KH-550 to obtain the resveratrol grafted modified quicklime.

[0100] III. Preparation of calcium sulfide powder

[0101] The vitamin C grafted modified palygorskite and the resveratrol grafted modified quicklime were mixed uniformly at a mass ratio of 1:100, and then ground in a high-speed ball mill to obtain a composite powder.

[0102] The sulfur powder and the composite powder were mixed uniformly at a mass ratio of 1:5 to obtain the calcium sulfide powder (DB-1).

[0103] Comparative Example 2

[0104] I. Preparation of vitamin C grafted modified palygorskite

[0105] The palygorskite was crushed to more than 3000 meshes.

[0106] 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%.

[0107] The vitamin C was dissolved in methanol to prepare a saturated solution.

[0108] The silane coupling agent solution was uniformly sprayed on the surface of the palygorskite at a dosage of 5% of the mass of the palygorskite, and then dried after high-speed stirring for 20 minutes. Then, the VC saturated solution (VC dosage was 9% of the mass of the palygorskite) was uniformly sprayed on the surface of the palygorskite modified by KH-550 to obtain the vitamin C grafted modified palygorskite.

[0109] II. Preparation of calcium sulfide powder

[0110] The sulfur was heated and evaporated under a nitrogen atmosphere, and the generated sulfur vapor was introduced into the vitamin C grafted modified palygorskite. After cooling, a sulfur coating film was formed on the surface of the vitamin C grafted modified palygorskite to obtain the calcium sulfide powder (DB-2), wherein the mass ratio of sulfur to vitamin C grafted modified palygorskite was 1:5.

[0111] Comparative Example 3

[0112] I. Preparation of resveratrol grafted modified quicklime

[0113] The quicklime was crushed and passed through a 1000-mesh sieve.

[0114] Dissolve silane coupling agent KH-550 in an ethanol / water mixed solvent to prepare a silane coupling agent solution with a concentration of 10%.

[0115] Dissolve resveratrol in methanol to prepare a resveratrol saturated solution.

[0116] Spray the silane coupling agent solution on the surface of the quicklime at a dosage of 7% of the mass of the quicklime, and dry after high-speed stirring for 10 minutes. Then spray the resveratrol solution on the surface of the KH-550 modified quicklime at a dosage of 8% of the mass of the quicklime, to obtain resveratrol grafted modified quicklime.

[0117] II. Preparation of calcium sulfide powder

[0118] Heat and evaporate sulfur under a nitrogen atmosphere, and introduce the generated sulfur vapor into the resveratrol grafted modified quicklime. After cooling, a sulfur coating film is formed on the surface of the resveratrol grafted modified quicklime, to obtain calcium sulfide powder (DB-3), wherein the mass ratio of sulfur to resveratrol grafted modified quicklime is 1:5.

[0119] Comparative Example 4

[0120] I. Crush attapulgite and pass it through a 3000-mesh sieve.

[0121] II. Crush quicklime and pass it through a 1000-mesh sieve.

[0122] III. Mix the attapulgite and the quicklime at a mass ratio of 1:100, and then grind them in a high-speed ball mill to obtain a composite powder.

[0123] IV. Preparation of calcium sulfide powder

[0124] Heat and evaporate sulfur under a nitrogen atmosphere, and introduce the generated sulfur vapor into the composite powder. After cooling, a sulfur coating film is formed on the surface of the composite powder, to obtain calcium sulfide powder (DB-4), wherein the mass ratio of sulfur to the composite powder is 1:5.

[0125] Application of calcium sulfide powder

[0126] 1. Agricultural field

[0127] Method of use: spray with artificial dry powder or apply to soil when plowing. Spray with dry powder at 10-50 grams per plant per time; apply at a dosage of 100-500 kg / acre when plowing.

[0128] Cotton was used as an example to illustrate the treatment of cotton wilt. The experimental site where cotton wilt occurred was divided into five plots according to treatment groups (Examples) and control groups (Comparative Examples 1 to 4). 100 plants with similar wilt levels were selected in each plot and treated with 25 g of dry powder per plant. The treatment effects were evaluated in five grades, mortality rate (%), no improvement, improvement, significant improvement, and cure rate (%). The specific treatment effects of each group are shown in Table 1.

[0129] Table 1 Treatment effects on cotton wilt

[0130]

[0131] For the treatment of sunflower disc rot, the experimental scheme was similar to that described above for cotton. In this case, 30 g of dry powder was sprayed per plant, and the treatment effects of each group are shown in Table 2.

[0132] Table 2 Treatment effects on sunflower disc rot

[0133]

[0134] 2. Rubber field

[0135] The sulfur-calcium powder product of the present application can be used in rubber composites as a vulcanization aid, replacing 15% to 35% of the amount of pure sulfur powder, reducing costs by about 20% to 40%, and having better mechanical properties than pure sulfur powder.

[0136] Table 3 shows the mechanical properties of the product when used in styrene-butadiene rubber. The styrene-butadiene rubber formulation was as follows: styrene-butadiene rubber 400 parts, carbon black 200 parts, stearic acid 4 parts, TBBS 4 parts, sulfur 7 parts, and zinc oxide 12 parts. In this test, 25% of the sulfur was replaced with an equal amount of sulfur-calcium powder (the product of Example 5 and Comparative Examples 1 to 4) while the amounts of the other components remained unchanged.

[0137] Table 3 Effects on the mechanical properties of styrene-butadiene rubber

[0138]

[0139] Finally, it should be noted that the above description is only a preferred embodiment of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will still be able to make modifications to the technical solutions described in the foregoing embodiments or make equivalent substitutions of some technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A method for preparing calcium sulfide powder, comprising the following steps: (1) spraying amino silane coupling agent solution and vitamin C solution on the surface of palygorskite in sequence to obtain modified palygorskite; (2) spraying amino silane coupling agent solution and resveratrol solution on the surface of quicklime in sequence to obtain modified quicklime; (3) compounding the modified palygorskite and the modified quicklime by mechanical chemical method to obtain composite powder, and the mass ratio of the modified palygorskite to the modified quicklime is 1:50-100 during compounding; (4) contacting sulfur steam with the composite powder to make sulfur coat on the surface of the composite powder to obtain calcium sulfide powder, and the mass ratio of sulfur to the composite powder is 1:1-5.

2. The production method according to claim 1, characterized by: The amount of amino silane coupling agent is 1-5% of the mass of palygorskite, and the amount of vitamin C is 2-10% of the mass of palygorskite.

3. The method of claim 1, wherein: The amount of amino silane coupling agent is 3-7% of the mass of quicklime, and the amount of resveratrol is 5-15% of the mass of quicklime.

4. The method of claim 1, wherein: The particle size of palygorskite is smaller than that of quicklime.

5. The method of claim 4, wherein: The particle size of palygorskite is above 3000 mesh, and the particle size of quicklime is 1000-1500 mesh.

6. The calcium sulfide powder prepared by the method according to any one of claims 1-5.

7. The use of the calcium sulfide powder according to claim 6 in preventing and treating cotton fusarium wilt and sunflower stem rot.

8. The use of the calcium sulfide powder according to claim 6 as vulcanization aid in rubber product production.

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