Deep desulfurization and purification integrated process for high-sulfur tin concentrate

Abstract

The invention discloses a deep desulfurization and purification integrated process for high-sulfur tin concentrate, which comprises the following steps: 1) screening tin rough concentrate by using a 0.2 mm screen, returning oversize products for re-grinding, adding copper sulfate into undersize products for size mixing, and then adding oxalic acid for adjusting the pH value to 5.5-6; (2) carrying out primary roughing and secondary sweeping sulfide removal flotation on the slurry to obtain sulfur concentrate and sulfur flotation tailings, (3) carrying out primary shaking table concentration on the sulfur flotation tailings to obtain tin concentrate, tin middling, tailings and tin secondary concentrate, carrying out secondary shaking table concentration on the tin middling to obtain tin concentrate, tin secondary concentrate and tailings, and carrying out secondary shaking table concentration on the tin middling to obtain tin concentrate, tin secondary concentrate and tailings. And the tin concentrate, the tin secondary concentrate and the tailings obtained through the first-stage table concentration and the second-stage table concentration are correspondingly combined, and the tin concentrate, the table tin secondary concentrate and the table tailings are obtained. According to the method, over-crushing of tin can be effectively reduced, the tin concentrate grade and the recovery process are guaranteed, and the distribution of the tin concentrate and the tin secondary concentrate is more reasonable.

Description

Technical Field

[0001] The invention relates to the technical field of tin concentrate beneficiation, and in particular to an integrated process for deep desulfurization and purification of high-sulfur tin concentrate. Background Art

[0002] Tin concentrate refers to ore containing tin element or tin compounds in ore. It is an important raw material for manufacturing tin products, alloys and electronic equipment. Through smelting and processing, the tin in tin concentrate can be extracted and used to manufacture various tin products, such as tin ingots, tin alloys, tin foil, etc.

[0003] At present, with the continuous mining of tin ore, single tin ore has gradually decreased, and tin ore has been transformed into tin-containing polymetallic sulfide ore. The mineral composition of polymetallic sulfide ore is complex, and it often contains a large amount of pyrite, pyrrhotite, arsenopyrite and other pyrite minerals, and the pyrite minerals have a close symbiotic relationship with cassiterite. Affected by the sulfide ore separation agent, some suppressed sulfide ores have poor floatability and high specific gravity, and are easy to enter into the tin concentrate during gravity separation, resulting in excessive content of impurities such as sulfur and arsenic in the tin concentrate, making it difficult to meet the quality standards of tin concentrate (sulfur grade less than 1.2%, arsenic grade less than 0.8%), and the recovery rate of tin concentrate is low, which not only affects the sales price of tin products, but also brings disadvantages to subsequent smelting and deep processing. Summary of the invention

[0004] The object of the present invention is to provide an integrated process for deep desulfurization and purification of high-sulfur tin concentrate to solve the problems existing in the background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: an integrated process for deep desulfurization and purification of high-sulfur tin concentrate, comprising the following steps: 1) screening the tin coarse concentrate using a 0.2 mm screen, returning the screened material to be re-grinded, adding copper sulfate to the screened material to adjust the slurry, and then adding oxalic acid to adjust the pH value to 5.5-6;

[0006] 2) The above slurry is subjected to one-roughing and two-sweeping flotation to remove sulfide, and sulfur concentrate and floating sulfur tailings are obtained. In the first roughing, 140-150 g / t of butyl xanthate and 20-25 g / t of pine oil are added. In the first sweep, 25-30 g / t of butyl xanthate and 10-13 g / t of pine oil are added. In the second sweep, 16-20 g / t of butyl xanthate and 5-7 g / t of pine oil are added.

[0007] 3) The above-mentioned floating sulfur tailings are subjected to a first-stage shaking table concentration to obtain tin concentrate, tin medium ore, tailings and tin secondary concentrate; the tin medium ore is subjected to a second-stage shaking table concentration to obtain tin concentrate, tin secondary concentrate and tailings; the tin concentrate, tin secondary concentrate and tailings obtained by the first-stage shaking table concentration and the second-stage shaking table concentration are respectively combined to obtain tin concentrate, shaking table tin secondary concentrate and shaking table tailings.

[0008] As a preferred embodiment of the present technical solution, the amount of copper sulfate added is 100-120 g / t.

[0009] As a preferred embodiment of the present technical solution, the slurry concentration in step 1) is 25-30%.

[0010] Beneficial effects of the present invention:

[0011] 1. The present invention can effectively enrich sulfide ores with good floatability such as arsenic and sulfur, and realize flotation desulfurization at a coarse grinding particle size by adding copper sulfide, thereby effectively reducing over-crushing of tin.

[0012] 2. The slurry is adjusted with copper sulfate and oxalic acid, and the suppressed sulfur-arsenic minerals are reactivated, ensuring the removal of sulfur-arsenic by flotation.

[0013] 3. The multi-stage shaking table concentration process can not only ensure the grade of tin concentrate and the recovery process, but also make the distribution of tin concentrate and tin sub-concentrate more reasonable, thus optimizing the product structure. DETAILED DESCRIPTION

[0014] The technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Example 1: In this example, the contents of the tin crude concentrate are as follows: Sn 9.45%, S 3.46%, As 1.02%, Fe 7.68%, SiO 2 47.34%, Al 2 O 3 8.4%, CaO 2.21%, MgO 0.45%, F 1.32%, and WO 3 0.012%.

[0016] The integrated process of deep desulfurization and purification of high-sulfur tin concentrate comprises the following steps: 1) screening the tin coarse concentrate with a 0.2 mm screen, returning the screened material to be re-grinded, adding copper sulfate to the screened material for slurry adjustment, wherein the amount of copper sulfate added is 100 g / t, the slurry concentration is 30%, and then adding oxalic acid to adjust the pH value to 6; 2) removing sulfide from the above slurry by one coarse and two sweeps, and flotation to obtain sulfur concentrate and floating sulfur tailings, adding 140 g / t of butyl xanthate and 25 g / t of pine oil in the first coarse, adding 25 g / t of butyl xanthate and 10 g / t of pine oil in the first sweep, and adding 20 g / t of butyl xanthate and 5 g / t of pine oil in the second sweep;

[0017] 3) The above-mentioned floating sulfur tailings are subjected to a first-stage shaking table concentration to obtain tin concentrate, tin medium ore, tailings and tin secondary concentrate; the tin medium ore is subjected to a second-stage shaking table concentration to obtain tin concentrate, tin secondary concentrate and tailings; the tin concentrate, tin secondary concentrate and tailings obtained by the first-stage shaking table concentration and the second-stage shaking table concentration are respectively combined to obtain tin concentrate, shaking table tin secondary concentrate and shaking table tailings.

[0018] After the completion of this embodiment, the grade of elements in the tin concentrate is: S0.25%, As0.052%, Sn48.23%, recovery rate S1.25%, As0.64%, Sn86.47%, the grade of elements in the sulfur concentrate is: S28.75%, As10.12%, Sn4.15%, recovery rate S94.52%, As95.43%, Sn6.02%.

[0019] Example 2: In this example, the contents of the tin crude concentrate are as follows: Sn 8.31%, S 4.23%, As 2.21%, Fe 6.48%, SiO 2 39.43%, Al 2 O 3 5.3%, CaO 1.54%, MgO 0.68%, F 2.03%, and WO 3 0.02%.

[0020] The integrated process of deep desulfurization and purification of high-sulfur tin concentrate comprises the following steps: 1) screening the tin coarse concentrate with a 0.2 mm screen, returning the screened material to be re-grinded, adding copper sulfate to the screened material for slurry adjustment, wherein the amount of copper sulfate added is 120 g / t, the slurry concentration is 25%, and then adding oxalic acid to adjust the pH value to 5.5; 2) removing sulfide from the above slurry by one coarse and two sweeps to obtain sulfur concentrate and floating sulfur tailings, adding 150 g / t of butyl xanthate and 20 g / t of pine oil in the first coarse, adding 30 g / t of butyl xanthate and 13 g / t of pine oil in the first sweep, and adding 16 g / t of butyl xanthate and 7 g / t of pine oil in the second sweep;

[0021] 4) The above-mentioned floating sulfur tailings are subjected to a first-stage shaking table concentration to obtain tin concentrate, tin medium ore, tailings and tin sub-concentrate; the tin medium ore is subjected to a second-stage shaking table concentration to obtain tin concentrate, tin sub-concentrate and tailings; the tin concentrate, tin sub-concentrate and tailings obtained by the first-stage shaking table concentration and the second-stage shaking table concentration are respectively combined to obtain tin concentrate, shaking table tin sub-concentrate and shaking table tailings.

[0022] After the completion of this embodiment, the grade of elements in the tin concentrate is: S0.17%, As0.068%, Sn51.12%, recovery rate S1.03%, As0.43%, Sn85.37%; the grade of elements in the sulfur concentrate is: S32.12%, As11.02%, Sn3.41%, recovery rate S93.21%, As94.13%, Sn5.13%.

[0023] Example 3: In this example, the contents of the tin crude concentrate are as follows: Sn 7.92%, S 3.76%, As 1.52%, Fe 7.87%, SiO 2 45.24%, Al 2 O 3 9.32%, CaO 2.35%, MgO 0.65%, F 1.47%, and WO 3 0.017%.

[0024] The integrated process of deep desulfurization and purification of high-sulfur tin concentrate comprises the following steps: 1) screening the tin coarse concentrate with a 0.2 mm screen, returning the screened material to be re-grinded, adding copper sulfate to the screened material for slurry adjustment, wherein the amount of copper sulfate added is 110 g / t, and the slurry concentration is 28%, and then adding oxalic acid to adjust the pH value to 5.7; 2) removing sulfide from the above slurry by one coarse and two scavenging flotation to obtain sulfur concentrate and floating sulfur tailings, adding 145 g / t of butyl xanthate and 23 g / t of pine oil in the first coarse, adding 26 g / t of butyl xanthate and 12 g / t of pine oil in the first scavenging, and adding 17 g / t of butyl xanthate and 6 g / t of pine oil in the second scavenging;

[0025] 3) The above-mentioned floating sulfur tailings are subjected to a first-stage shaking table concentration to obtain tin concentrate, tin medium ore, tailings and tin secondary concentrate; the tin medium ore is subjected to a second-stage shaking table concentration to obtain tin concentrate, tin secondary concentrate and tailings; the tin concentrate, tin secondary concentrate and tailings obtained by the first-stage shaking table concentration and the second-stage shaking table concentration are respectively combined to obtain tin concentrate, shaking table tin secondary concentrate and shaking table tailings.

[0026] After the completion of this embodiment, the grade of elements in the tin concentrate is: S0.17%, As0.068%, Sn51.12%, recovery rate S1.03%, As0.43%, Sn85.37%; the grade of elements in the sulfur concentrate is: S32.12%, As11.02%, Sn3.41%, recovery rate S93.21%, As94.13%, Sn5.13%.

[0027] Example 4: In this example, the contents of the tin crude concentrate are as follows: Sn 8.31%, S 4.57%, As 2.51%, Fe 6.25%, SiO 2 42.67%, Al 2 O 3 6.5%, CaO 3.81%, MgO 0.86%, F 1.75%, and WO 3 0.016%.

[0028] The integrated process of deep desulfurization and purification of high-sulfur tin concentrate comprises the following steps: 1) screening the tin coarse concentrate with a 0.2 mm screen, returning the screened material to be re-grinded, adding copper sulfate to the screened material for slurry adjustment, wherein the amount of copper sulfate added is 115 g / t, the slurry concentration is 22%, and then adding oxalic acid to adjust the pH value to 6; 2) removing sulfide from the above slurry by one coarse and two scavenging flotation to obtain sulfur concentrate and floating sulfur tailings, adding 140 g / t of butyl xanthate and 24 g / t of pine oil in the first coarse, adding 28 g / t of butyl xanthate and 13 g / t of pine oil in the first scavenging, and adding 19 g / t of butyl xanthate and 5 g / t of pine oil in the second scavenging;

[0029] 3) The above-mentioned floating sulfur tailings are subjected to a first-stage shaking table concentration to obtain tin concentrate, tin medium ore, tailings and tin secondary concentrate; the tin medium ore is subjected to a second-stage shaking table concentration to obtain tin concentrate, tin secondary concentrate and tailings; the tin concentrate, tin secondary concentrate and tailings obtained by the first-stage shaking table concentration and the second-stage shaking table concentration are respectively combined to obtain tin concentrate, shaking table tin secondary concentrate and shaking table tailings.

[0030] After the completion of this embodiment, the grade of elements in the tin concentrate is: S0.26%, As0.11%, Sn53.03%, recovery rate S1.28%, As0.68%, Sn82.12%; the grade of elements in the sulfur concentrate is: S35.06%, As9.87%, Sn3.43%, recovery rate S95.04%, As93.61%, Sn4.56%.

Claims

1. A deep desulfurization and purification integrated process for high-sulfur tin concentrate, characterized in that: The following steps are involved: 1) The tin concentrate is screened using a 0.2 mm sieve, the sieved material is returned for re-grinding, the sieved material is added with copper sulfate for slurry preparation, and then oxalic acid is added to adjust the pH value to 5.5-6; 2) The above slurry is subjected to one-roughing and two-sweeping flotation to remove sulfide, and sulfur concentrate and floating sulfur tailings are obtained. In the first roughing, 140-150 g / t of butyl xanthate and 20-25 g / t of pine oil are added. In the first sweep, 25-30 g / t of butyl xanthate and 10-13 g / t of pine oil are added. In the second sweep, 16-20 g / t of butyl xanthate and 5-7 g / t of pine oil are added. 3) The above-mentioned floating sulfur tailings are subjected to a first-stage shaking table concentration to obtain tin concentrate, tin medium ore, tailings and tin secondary concentrate; the tin medium ore is subjected to a second-stage shaking table concentration to obtain tin concentrate, tin secondary concentrate and tailings; the tin concentrate, tin secondary concentrate and tailings obtained by the first-stage shaking table concentration and the second-stage shaking table concentration are respectively combined to obtain tin concentrate, shaking table tin secondary concentrate and shaking table tailings.

2. The integrated process for deep desulfurization and purification of high-sulfur tin concentrate according to claim 1, characterized in that: The amount of copper sulfate added is 100-120 g / t.

3. The integrated process for deep desulfurization and purification of high-sulfur tin concentrate according to claim 2, characterized in that: The slurry concentration in step 1) is 25-30%.