Composite desulfurizer and preparation method thereof

Abstract

The invention relates to the technical field of composite desulfurizers and discloses a composite desulfurizer, comprising a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight parts of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material and 5 parts of the desulfurization strengthening raw material; the invention provides the hydrophobic strengthening raw material and the desulfurization strengthening raw material; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, which can promote the formation of a hydrophobic layer on the surface of calcium oxide, so that the surface has good hydrophobicity, thereby improving the stability of the calcium oxide solid superbase; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, all of which have a strong affinity for sulfur, thereby optimizing the reaction effect, and the desulfurization efficiency can be greatly improved by the hydrophobic strengthening raw material and the desulfurization strengthening raw material.

Description

Technical Field

[0001] The invention relates to the technical field of composite desulfurizers, in particular to a composite desulfurizer and a preparation method thereof. Background Art

[0002] Sulfur is a harmful element in pig iron. It will promote the combination of iron and carbon, making the iron hard and brittle, and combine with iron to form low-melting-point iron sulfide, which makes the pig iron hot-brittle and reduces the fluidity of the molten iron. Therefore, the molten iron needs to be desulfurized, and desulfurization requires the use of corresponding desulfurizers. The desulfurizers are combined with the molten iron by spraying or stirring for desulfurization. Most of the existing desulfurizers use lime and calcium carbide as the main raw materials, add fluorite and other slag, and mechanically stir and mix to form a mixture containing lime, fluorite and other substances. The desulfurizer is used for the desulfurization of ordinary molten iron. For the desulfurization of vanadium-titanium molten iron, due to the low temperature and poor fluidity of the vanadium-titanium molten iron, directly using the above-mentioned desulfurizer will cause low desulfurizer utilization and high cost.

[0003] A Chinese patent discloses a vanadium-titanium composite desulfurizer for hot metal and its preparation and use methods (publication number CN108588335A). The components and proportions of the desulfurizer in this patented technology increase the pH of the desulfurizer, reduce the oxidizing properties of the system, and improve the desulfurization rate. The sulfur content of the hot metal after slagging treatment using the desulfurizer in this invention can be reduced to below 0.02%. However, the main component of the desulfurizer is also calcium oxide, i.e., quicklime. Calcium oxide easily absorbs water during use, causing surface poisoning of the calcium oxide, affecting the stability of the calcium oxide superbase, and thus easily affecting the desulfurization efficiency. The calcium oxide is not specially treated to prevent the desulfurization efficiency from being affected by water absorption. Moreover, the desulfurizer cannot improve its affinity and binding force for sulfur in the hot metal, thereby failing to further improve the desulfurization effect. Therefore, the desulfurization effect is relatively mediocre. Therefore, those skilled in the art provide a composite desulfurizer and its preparation method to solve the problems raised in the above background technology. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite desulfurizer and a preparation method thereof to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are composed of the following weight parts: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material and 5 parts of the desulfurization strengthening raw material.

[0007] As a further solution of the present invention: the calcium-based raw materials are composed of calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of calcium oxide, calcium carbide and sodium carbonate is 18-20:1:2.

[0008] As a further solution of the present invention: the magnesium-based raw material consists of purified magnesium.

[0009] As a further solution of the present invention: the hydrophobic strengthening raw material consists of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 1-3:3-5:2:1-3.

[0010] As a further solution of the present invention: the desulfurization strengthening raw material consists of cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:1~3:1~3.

[0011] A method for preparing a composite desulfurizer comprises the following steps:

[0012] S1, placing a certain amount of calcium oxide powder in a calcining box for calcining, taking it out after a period of time, and placing it on a material plate in a drying chamber for natural drying and cooling;

[0013] S2, placing the calcined and cooled calcium oxide powder in a blender, pouring a fixed amount of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate into the blender, and turning on the blender for stirring;

[0014] S3, take out the raw materials stirred in S2, and evenly spread them on the material plate in the drying chamber for natural drying and cooling;

[0015] S4. Place the naturally dried and cooled material in S3 in a blender, and then add a certain amount of calcium carbide, sodium carbonate, purified magnesium, cerium powder, yttrium powder, rhenium powder and titanium powder in sequence, turn on the blender for stirring, and the preparation of the composite desulfurizer is completed after the stirring is completed.

[0016] As a further solution of the present invention: the calcination temperature of the calcium oxide in S1 is 850-900° C., the calcination time is 3.5 hours, and the natural drying and cooling time is 45 minutes.

[0017] As a further solution of the present invention: the stirring time of the stirrer in S2 is 30 minutes, and the stirring temperature is 20-28° C.; the natural cooling time in S3 is 8-12 hours.

[0018] As a further solution of the present invention: the stirring time of the stirrer in S4 is 1.5 hours, and the stirring temperature is 20-28°C.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention is suitable for desulfurization of various molten irons including vanadium-titanium molten iron; a hydrophobic strengthening raw material and a desulfurization strengthening raw material are provided; the hydrophobic strengthening raw material consists of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, which can modify calcium oxide, promote the formation of a hydrophobic layer on the surface of the calcium oxide, and make the surface have good hydrophobicity, thereby preventing external water from poisoning the surface of the calcium oxide, thereby improving the stability of the solid superbase of calcium oxide, and thus avoiding affecting the desulfurization effect; the treated calcium oxide can be stored for a long time and can be taken out as needed; the desulfurization strengthening raw material consists of cerium powder, yttrium powder, rhenium powder and titanium powder, all of which have a strong affinity for sulfur and are used to strengthen the binding reaction with sulfur in the molten iron, thereby optimizing the reaction effect; the hydrophobic strengthening raw material and the desulfurization strengthening raw material can jointly greatly improve the desulfurization efficiency. DETAILED DESCRIPTION

[0021] In an embodiment of the present invention, a composite desulfurizer includes a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material, and a desulfurization strengthening raw material. The weight ratios of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material, and the desulfurization strengthening raw material are as follows: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material, and 5 parts of the desulfurization strengthening raw material.

[0022] The calcium-based raw materials are composed of calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of calcium oxide, calcium carbide and sodium carbonate is 18-20:1:2;

[0023] The magnesium-based raw materials consist of purified magnesium;

[0024] The hydrophobic strengthening raw material consists of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 1-3:3-5:2:1-3;

[0025] The desulfurization strengthening raw material consists of cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:1 to 3:1 to 3.

[0026] A method for preparing a composite desulfurizer comprises the following steps:

[0027] S1. Place a certain amount of calcium oxide powder in a calcining box for calcining. After a period of time, take it out and place it on a material plate in a drying chamber for natural drying and cooling. The calcination temperature of calcium oxide is 850-900° C., the calcination time is 3.5 hours, and the natural drying and cooling time is 45 minutes.

[0028] S2. Place the calcined and cooled calcium oxide powder in a blender, add a fixed amount of benzene bromide, methyl acrylate, butyltrichlorosilane, and ethyl bromoacetate into the blender, and start the blender for stirring. Stir for 30 minutes at a temperature of 20 to 28°C.

[0029] S3. Take out the raw materials after mixing in S2, and evenly spread them on the material plate in the drying chamber for natural drying and cooling; the natural cooling time is 8 to 12 hours;

[0030] S4. Place the naturally dried and cooled materials in S3 in a blender, and then add a certain amount of calcium carbide, sodium carbonate, purified magnesium, cerium powder, yttrium powder, rhenium powder and titanium powder in sequence, turn on the blender for stirring, and the preparation of the composite desulfurizer is completed after the stirring is completed; the stirring time of the blender is 1.5 hours, and the stirring temperature is 20-28°C. Example 1

[0031] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight proportions of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of calcium raw material, 30 parts of magnesium raw material, 10 parts of hydrophobic strengthening raw material and 5 parts of desulfurization strengthening raw material; the calcium raw material comprises calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of calcium oxide, calcium carbide and sodium carbonate is 18:1:2; the magnesium raw material comprises purified magnesium; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 1:3:2:1; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:1:1. Example 2

[0032] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight proportions of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material and 5 parts of the desulfurization strengthening raw material; the calcium raw material comprises calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of the calcium oxide, calcium carbide and sodium carbonate is 18.4:1:2; the magnesium raw material comprises purified magnesium; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 1.4:3.4:2:1.4; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of the cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:1.4:1.4. Example 3

[0033] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight proportions of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material and 5 parts of the desulfurization strengthening raw material; the calcium raw material comprises calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of the calcium oxide, calcium carbide and sodium carbonate is 18.8:1:2; the magnesium raw material comprises purified magnesium; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 1.8:3.8:2:1.8; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of the cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:1.8:1.8. Example 4

[0034] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight proportions of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of calcium raw material, 30 parts of magnesium raw material, 10 parts of hydrophobic strengthening raw material and 5 parts of desulfurization strengthening raw material; the calcium raw material comprises calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of calcium oxide, calcium carbide and sodium carbonate is 19.2:1:2; the magnesium raw material comprises purified magnesium; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 2.2:4.2:2:2.2; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:2.2:2.2. Example 5

[0035] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight proportions of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material and 5 parts of the desulfurization strengthening raw material; the calcium raw material comprises calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of the calcium oxide, calcium carbide and sodium carbonate is 19.6:1:2; the magnesium raw material comprises purified magnesium; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 2.6:4.6:2:2.6; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of the cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:2.6:2.6. Example 6

[0036] A composite desulfurizer comprises a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the weight proportions of the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are as follows: 80 parts of calcium raw material, 30 parts of magnesium raw material, 10 parts of hydrophobic strengthening raw material and 5 parts of desulfurization strengthening raw material; the calcium raw material comprises calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of calcium oxide, calcium carbide and sodium carbonate is 20:1:2; the magnesium raw material comprises purified magnesium; the hydrophobic strengthening raw material comprises benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 3:5:2:3; the desulfurization strengthening raw material comprises cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:3:3.

[0037] In order to illustrate the technical effects of the present invention, the following experiments were performed to verify:

[0038] The composite vulcanizing agents produced by Examples 1, 2, 3, 4, 5 and 6 of the present invention are selected and recorded as Experimental Examples A, B, C, D, E and F;

[0039] The third embodiment of the present invention after removing the hydrophobic enhancement raw material and the desulfurization enhancement raw material is recorded as Experimental Example G;

[0040] The composite desulfurizer produced by Example 2 of a vanadium-titanium molten iron composite desulfurizer and its preparation and use method disclosed in a Chinese patent (Publication No. CN108588335A) is recorded as Experimental Example J; the composite desulfurizer produced by adding the hydrophobic strengthening raw material of the present invention to its Example 2 is recorded as Experimental Example K; the composite desulfurizer produced by adding the desulfurization strengthening raw material of the present invention to its Example 2 is recorded as Experimental Example M; the composite desulfurizer produced by adding the hydrophobic strengthening raw material and the desulfurization strengthening raw material of the present invention to its Example 2 is recorded as Experimental Example N;

[0041] A portion of vanadium-titanium molten iron was selected, and its sulfur content before desulfurization was first detected. The molten iron was divided into 11 portions, and each portion was desulfurized using an experimental example. The dosage of each experimental example was equal. The molten iron was desulfurized by injection, and the sulfur content of the molten iron after desulfurization was detected to produce the following table:

[0042] It can be analyzed from the above table that after desulfurization of molten iron in 11 experimental cases, the sulfur content of molten iron was reduced. Experimental cases A, B, C, D, E, F, and N were all reduced to about 0.010%, experimental cases G and J were reduced to about 0.020%, and experimental cases K and M were reduced to 0.014% and 0.013%, respectively.

[0043] From this analysis, it can be concluded that the sulfur content of the molten iron in Experimental Examples A, B, C, D, E, F, and N, which added both the hydrophobic strengthening and desulfurization strengthening raw materials, was significantly reduced, all to around 0.010%. In Experimental Examples G and J, which removed the hydrophobic strengthening and desulfurization strengthening raw materials and did not use either the hydrophobic strengthening and desulfurization strengthening raw materials, the sulfur content of the molten iron was reduced, but remained at around 0.020%, far higher than 0.010%. In Experimental Example K and Experimental Example M, which used only the hydrophobic strengthening raw materials, the sulfur content of the molten iron was reduced to around 0.015%.

[0044] The hydrophobic strengthening raw material and the desulfurization strengthening raw material in the present invention can effectively improve the desulfurization effect of molten iron.

[0045] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0046] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A composite desulfurizer, characterized in that: It includes a calcium raw material, a magnesium raw material, a hydrophobic strengthening raw material and a desulfurization strengthening raw material, wherein the calcium raw material, the magnesium raw material, the hydrophobic strengthening raw material and the desulfurization strengthening raw material are composed of the following parts by weight: 80 parts of the calcium raw material, 30 parts of the magnesium raw material, 10 parts of the hydrophobic strengthening raw material and 5 parts of the desulfurization strengthening raw material; The hydrophobic strengthening raw material is composed of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate, wherein the mass ratio of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate is 1-3:3-5:2:1-3; The desulfurization strengthening raw material consists of cerium powder, yttrium powder, rhenium powder and titanium powder, wherein the mass ratio of cerium powder, yttrium powder, rhenium powder and titanium powder is 2:3:1-3:1-3.

2. A composite desulfurizer according to claim 1, characterized in that: The calcium-based raw materials consist of calcium oxide, calcium carbide and sodium carbonate, wherein the mass ratio of calcium oxide, calcium carbide and sodium carbonate is 18-20:1:

2.

3. A composite desulfurizer according to claim 1, characterized in that: The magnesium-based raw material consists of purified magnesium.

4. A method for preparing the composite desulfurizer according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1, placing a certain amount of calcium oxide powder in a calcining box for calcination, taking it out after a period of time, and placing it on a material plate in a drying chamber for natural drying and cooling; S2, the calcium oxide powder after roasting, natural drying and cooling is placed in a blender, a certain amount of benzene bromide, methyl acrylate, butyltrichlorosilane and ethyl bromoacetate are poured into the blender, and the blender is turned on for stirring; S3, take out the raw materials stirred in S2, and evenly spread them on the material plate in the drying chamber for natural drying and cooling; S4. Place the naturally dried and cooled material in S3 in a blender, and then add a certain amount of calcium carbide, sodium carbonate, purified magnesium, cerium powder, yttrium powder, rhenium powder and titanium powder in sequence, turn on the blender for stirring, and the preparation of the composite desulfurizer is completed after the stirring is completed.

5. The method for preparing a composite desulfurizer according to claim 4, characterized in that: The calcium oxide in S1 is calcined at a temperature of 850-900° C. for 3.5 hours and naturally dried and cooled for 45 minutes.

6. The method for preparing a composite desulfurizer according to claim 4, characterized in that: The stirring time of the stirrer in S2 is 30 minutes, and the stirring temperature is 20-28° C.; the natural cooling time in S3 is 8-12 hours.

7. The method for preparing a composite desulfurizer according to claim 4, characterized in that: The stirring time of the stirrer in S4 is 1.5 hours, and the stirring temperature is 20-28°C.