Method for preparing silicate cement siliceous raw material from copper sulfide tailings

Abstract

The invention discloses a method for preparing a silicate cement siliceous raw material by using copper sulfide tailings, which comprises the following steps: S1, carrying out size mixing on the copper sulfide tailings, and then carrying out desulfurization flotation operation to obtain desulfurization flotation concentrate and desulfurization flotation tailings; s2, water is added into the desulfurized flotation tailings for size mixing, the desulfurized flotation tailings are fed into a hydrocyclone for grading, and coarse-fraction settled sand and fine-fraction overflow are obtained; s3, water is added into the coarse-fraction settled sand for size mixing, then dealkalization flotation operation is conducted, dealkalization flotation concentrate and quartz sand meeting the quality requirement are obtained, the SiO2 content of the quartz sand is 74.62%-76.78%, the S content is lower than 0.3%, and the K2O content is lower than 3%; according to the method, the copper sulphide tailings can be subjected to deep desulfurization and alkali reduction, components, harmful to fired cement clinker, in the copper sulphide tailings are removed, the quartz sand meeting the requirement for a siliceous raw material of Portland cement is obtained, and bulk consumption of the copper sulphide tailings is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of tailings resource utilization and large-scale disposal, and specifically to a method for preparing silicate cement siliceous raw materials by utilizing copper sulfide tailings. Background Art

[0002] Tailings are a product of mineral sorting operations. Since the content of useful target components in tailings is low, they cannot be effectively recovered under current technical conditions, so they are often discharged directly into tailings ponds or dry piles after dehydration.

[0003] Copper tailings have complex chemical composition, fine particle size, low activity, and usually contain harmful elements such as sulfur, cadmium, and arsenic, which limits its large-scale resource utilization in many fields. Therefore, how to achieve copper tailings reduction, high value and full harmlessness has become the focus of industry attention. Copper tailings are mainly composed of quartz, mica, feldspar, siderite, pyrite, etc., and the chemical composition is mainly SiO2, Al2O3, K2O, Fe2O3, which is similar to the composition of cement siliceous raw materials. It can replace part of cement correction materials for calcining cement clinker. However, due to the high content of impurity elements S and K2O in copper tailings, and the large fluctuations in mineral and particle size composition, the application and incorporation rate of copper tailings in cement clinker firing are seriously affected. The impurity elements S and K2O will have a great impact on the cement clinker burning process. High S content will cause the sulfur oxide compounds in the tail gas to exceed the standard during the cement clinker calcination process, requiring the installation of flue gas desulfurization equipment, which increases production costs. High K2O content is not only not conducive to the production of low-alkali cement, but also makes the rotary kiln prone to crusting and blockage, affecting cement clinker production.

[0004] In view of this, deep desulfurization and alkali reduction of copper tailings and removal of harmful components are the key to increasing the consumption of copper tailings in cement preparation. Summary of the invention

[0005] The invention discloses a method for preparing silicate cement siliceous raw materials by utilizing copper sulfide tailings, so as to solve any of the above and other potential problems in the prior art.

[0006] In order to solve the above technical problems, the technical solution of the present invention is: a method for preparing silicate cement siliceous raw materials using copper sulfide tailings, the method specifically comprising the following steps:

[0007] S1) slurrying the copper sulfide tailings, and then feeding them into a desulfurization flotation operation to obtain a desulfurization flotation concentrate and a desulfurization flotation tailings;

[0008] S2) adding water to the desulfurization flotation tailings obtained in S1) to prepare a slurry, and then sending it to a hydrocyclone for classification to obtain coarse-grained sand settling and fine-grained overflow;

[0009] S3) adding water to the coarse-grained sediment obtained in S2) to prepare a slurry, and then performing a dealkalization flotation operation to obtain a dealkalization flotation concentrate and quartz sand, wherein the quartz sand is the siliceous raw material for silicate cement.

[0010] The SiO2 content of quartz sand is 74.62% to 76.78%, the S content is less than 0.3%, and the K2O content is less than 3%.

[0011] Furthermore, the slurry concentration of the copper sulfide tailings in S1) after slurry adjustment is 30-45%.

[0012] Furthermore, the desulfurization flotation operation in S1) includes the flotation roughing step and the flotation scavenging step, and the specific steps are:

[0013] The flotation roughing step comprises: adding 40-60 g / t of roughing collector and 10-20 g / t of roughing frother to carry out flotation to obtain desulfurized roughing concentrate and desulfurized roughing tailings;

[0014] The flotation scavenging step is: scavenging the desulfurized rougher tailings 1-3 times, adding 10-30 g / t of scavenging collector and 5-15 g / t of scavenging frother for flotation each time, to obtain desulfurized scavenging concentrate and desulfurized flotation tailings, and the desulfurized scavenging concentrate and the desulfurized rougher concentrate are combined into a desulfurized flotation concentrate.

[0015] Furthermore, the roughing collector and the scavenging collector are one or more of butyl xanthate, amyl xanthate, and isopentyl xanthate;

[0016] The roughing foaming agent and the scavenging foaming agent are both pine oil, 2# oil, BK204, methyl isobutyl carbinol, polyethylene glycol ether or mixed fatty alcohol industrial foaming agents.

[0017] Furthermore, the pulp concentration of the desulfurization flotation tailings after slurry adjustment in S2) is 15-35%.

[0018] Furthermore, the particle size of the fine-grained overflow obtained by the classification operation in S2) is 0-X, where X=0.01-0.03 mm.

[0019] Furthermore, the pulp concentration after the coarse-grained sand settling and slurry adjustment in S3) is 30-45%.

[0020] Further, the dealkalization flotation in S3) includes 1-2 flotation roughing operations, each time adding 100-300 g / t of pH adjuster, 100-300 g / t of anionic ONA collector, 40-100 g / t of cationic DDA collector, and 5-15 g / t of frother for flotation to obtain dealkalization flotation concentrate and quartz sand meeting quality requirements.

[0021] Furthermore, the pH adjuster in S3) is sodium hydroxide, which adjusts the pH of the slurry to 7-10;

[0022] The anionic ONA collector is a combination of sodium cyclopentaneate and sodium oleate, and its weight composition is 6-10 parts of sodium cyclopentaneate and 30-60 parts of sodium oleate. ONA is mixed with water to form an aqueous solution with a weight percentage of 1%-15%.

[0023] The cationic DDA collector is one or more of dodecylamine acetate, dodecylamine hydrochloride, and dodecylamine phosphate;

[0024] The foaming agent is pine oil, 2# oil, BK204, methyl isobutyl carbinol, polyethylene glycol ether or mixed fatty alcohol industrial foaming agent.

[0025] Furthermore, the SiO2 content in the quartz sand is 74.62% to 76.78%, the S content is less than 0.3%, and the K2O content is less than 3%.

[0026] The beneficial effects of the present invention are:

[0027] 1. The present invention adopts the process of "flotation-classification-flotation" to deeply desulfurize and reduce alkali of copper sulfide tailings, and obtains quartz sand that meets the quality requirements of silicate cement siliceous raw materials. The process is simple, low-cost, easy to operate, and the yield of the obtained quartz sand is the highest. It can realize the bulk disposal of copper sulfide tailings, reduce the environmental problems caused by tailings storage, and has significant social benefits.

[0028] 2. The present invention adopts a combination of a composite anionic collector ONA and a cationic collector DDA to achieve flotation separation of aluminosilicate minerals containing alkali metal elements such as mica and quartz under neutral or weakly alkaline conditions, reduce the K2O content of copper sulfide tailings, and alleviate the treatment pressure of acidic mineral processing wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The present invention is a process flow chart of a method for preparing silicate cement siliceous raw materials by utilizing copper sulfide tailings. DETAILED DESCRIPTION

[0030] The specific implementation of the present invention will be further described below in conjunction with the accompanying drawings.

[0031] The object of the present invention is to provide a method for preparing silicate cement raw materials by using copper sulfide tailings, which can deeply desulfurize and reduce the alkali content of copper tailings to obtain quartz sand that meets the quality requirements of silicate cement raw materials. In addition, the method can realize the flotation separation of aluminum silicate minerals containing alkali metal elements such as mica and quartz under neutral or weakly alkaline conditions, thereby alleviating the treatment pressure of mines on acidic ore dressing wastewater.

[0032] like Figure 1 As shown, the present invention provides a method for preparing silicate cement siliceous raw materials using copper sulfide tailings, comprising the following steps:

[0033] S1) slurrying the copper sulfide tailings, and then performing a desulfurization flotation operation to obtain a desulfurization flotation concentrate and a desulfurization flotation tailings;

[0034] S2) adding water to the desulfurization flotation tailings described in S1) to prepare a slurry, and then sending it to a hydrocyclone for classification to obtain a coarse-grained sediment and a fine-grained overflow;

[0035] S3) adding water to the coarse-grained sediment described in S3) to prepare the slurry, and then performing dealkalization flotation operation to obtain dealkalization flotation concentrate and quartz sand, wherein the SiO2 content of the quartz sand is 74.62% to 76.78%, the S content is less than 0.3%, and the K2O content is less than 3%.

[0036] Furthermore, the slurry concentration of the copper sulfide tailings in S1) after slurry adjustment is 30-45%.

[0037] Furthermore, in step S1, the desulfurization flotation operation includes a flotation roughing step and a flotation scavenging step.

[0038] The flotation roughing step comprises: adding 40-60 g / t of collector and 10-20 g / t of frother to carry out flotation to obtain desulfurized roughing concentrate and desulfurized roughing tailings;

[0039] The flotation scavenging step is: scavenging the desulfurized rougher tailings 1-3 times, adding 10-30 g / t of collector and 5-15 g / t of frother for flotation each time, to obtain desulfurized scavenging concentrate and desulfurized flotation tailings, and combining the desulfurized scavenging concentrate and the desulfurized rougher concentrate into the desulfurized flotation concentrate.

[0040] Further, in step S1, the collector includes one or more of butyl xanthate, amyl xanthate, and isopentyl xanthate;

[0041] The foaming agent includes pine oil, 2# oil, BK204, methyl isobutyl carbinol, polyethylene glycol ether, and mixed fatty alcohol industrial foaming agents.

[0042] Furthermore, in step S2, the slurry concentration of the desulfurization flotation tailings after slurry adjustment is 15-35%.

[0043] Furthermore, in step S2, the particle size of the fine-grained overflow obtained by the classification operation is 0-X, where X=0.01-0.03 mm.

[0044] Furthermore, in step S3, the slurry concentration after coarse-grained sand settling and slurry adjustment is 30-45%.

[0045] Furthermore, in step S3, the dealkalization flotation includes 1-2 flotation roughing operations, each time adding 100-300 g / t of pH adjuster, 100-300 g / t of anionic ONA collector, 40-100 g / t of cationic DDA collector, and 5-15 g / t of frother for flotation, to obtain dealkalization flotation concentrate and quartz sand meeting quality requirements, wherein the SiO2 content of the quartz sand is 76.78% to 78.11%, the S content is less than 0.3%, and the K2O content is less than 3%.

[0046] Furthermore, in step S3, the pH adjuster is sodium hydroxide, and the pH of the slurry is adjusted to 7-10;

[0047] The anionic ONA collector is a combination of sodium cyclopentaneate and sodium oleate, and its weight composition is 6-10 parts of sodium cyclopentaneate and 30-60 parts of sodium oleate. ONA is mixed with water to form an aqueous solution with a weight percentage of 1%-15%.

[0048] The cationic DDA collector is one or more of dodecylamine acetate, dodecylamine hydrochloride, and dodecylamine phosphate;

[0049] The foaming agent includes pine oil, 2# oil, BK204, methyl isobutyl carbinol, polyethylene glycol ether, and mixed fatty alcohol industrial foaming agents.

[0050] Embodiment 1

[0051] The tailings used in this example are flotation tailings of a domestic copper-sulfur mine, which are a mixture of the first-stage tailings after "copper-sulfur mixed flotation" and the second-stage tailings after "copper-sulfur separation-separation tailings sulfur selection". The main chemical composition of the tailings is:

[0052]

[0053] like Figure 1 As shown, the present invention provides a method for preparing silicate cement siliceous raw materials using copper sulfide tailings, comprising the following steps:

[0054] S1. The copper sulfide tailings in the tailings pipeline are slurried to control the slurry concentration to be about 40%, and a desulfurization flotation operation of "one roughing and one scavenging" is performed to obtain a desulfurization flotation concentrate and a desulfurization flotation tailings.

[0055] The desulfurization roughing agent system is: butyl xanthate, the addition amount is 50g / t, methyl isobutyl carbinol, the addition amount is 15g / t; the desulfurization sweeping agent system is: butyl xanthate, the addition amount is 20g / t, methyl isobutyl carbinol, the addition amount is 8g / t.

[0056] S2. Add water to the desulfurization flotation tailings to adjust the pulp, control the pulp concentration to about 20%, and feed it into the hydrocyclone for classification to obtain coarse-grained sand and fine-grained overflow, of which the particle size of the fine-grained overflow is 0-0.02mm, and the rest is coarse-grained sand.

[0057] S3, add water to the coarse-grained sediment to adjust the pulp, control the pulp concentration to about 30%, and carry out a roughing dealkalization flotation operation to obtain dealkalization flotation concentrate and quartz sand that meets the quality requirements. The dealkalization flotation reagent system is: sodium hydroxide, the addition amount is 110g / t, the pulp pH is adjusted to 8-10, the compound anion collector ONA, the addition amount is 200g / t, the cationic collector DDA, the addition amount is 65g / t, and the addition amount of methyl isobutyl carbinol is 10g / t.

[0058] Finally, quartz sand with SiO2 content of 76.78%, S content of 0.24%, K2O content of 2.52% and Al2O3 content of 10.63% is obtained, that is, silicate cement siliceous raw material, and the content of impurity Cr in the quartz sand is only 0.004%.

[0059] Embodiment 2

[0060] The copper sulfide tailings used in this example are the total tailings of a large domestic copper-molybdenum-sulfur mine. The main chemical composition of the tailings is:

[0061]

[0062] like Figure 1 As shown, the present invention provides a method for preparing silicate cement siliceous raw materials using copper sulfide tailings, comprising the following steps:

[0063] S1. Add water to the copper sulfide tailings to adjust the pulp, control the pulp concentration to about 40%, and perform a desulfurization flotation operation of "one roughing and one scavenging" to obtain a desulfurization flotation concentrate and a desulfurization flotation tailings.

[0064] The desulfurization roughing agent system is: butyl xanthate, the addition amount is 40g / t, BK204, the addition amount is 15g / t; the desulfurization sweeping agent system is: butyl xanthate, the addition amount is 15g / t, BK204, the addition amount is 8g / t.

[0065] S2. Add water to the desulfurization flotation tailings to adjust the pulp, control the pulp concentration to about 30%, and feed it into the hydrocyclone for classification to obtain coarse-grained sand and fine-grained overflow, wherein the particle size of the fine-grained overflow is 0-0.03mm, and the rest is coarse-grained sand.

[0066] S3. Add water to the coarse-grained sediment to adjust the pulp, control the pulp concentration to about 35%, and carry out a roughing dealkalization flotation operation to obtain dealkalization flotation concentrate and quartz sand that meets the quality requirements. The dealkalization flotation reagent system is: sodium hydroxide, the addition amount is 120g / t, the pulp pH is adjusted to 8-10, the compound anion collector ONA, the addition amount is 300g / t, the cationic collector DDA, the addition amount is 100g / t, and the addition amount of BK204 is 10g / t.

[0067] Finally, quartz sand with SiO2 content of 74.62%, S content of 0.26%, K2O content of 2.81% and Al2O3 content of 11.27% is obtained, that is, silicate cement siliceous raw material, and the content of impurity Cr in the quartz sand is only 0.005%.

[0068] Finally, it should be noted that the above is only an application example of the present invention and does not impose any form of limitation or restriction on the present invention. Those skilled in the art should understand that within the framework of the technical solution of the present invention, some or all of the technical features can still be changed, modified or replaced by equivalents. These changes, modifications or equivalent replacements do not make the essence of the corresponding technical solution deviate from the scope of the technical solutions of the application examples in the present invention, and therefore still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing silicate cement siliceous raw materials using copper sulfide tailings, characterized in that: The steps include: S1) slurrying the copper sulfide tailings, and then feeding them into a desulfurization flotation operation to obtain a desulfurization flotation concentrate and a desulfurization flotation tailings; S2) adding water to the desulfurization flotation tailings obtained in S1) to prepare a slurry, and then sending it to a hydrocyclone for classification to obtain coarse-grained sand settling and fine-grained overflow; S3) adding water to the coarse-grained sediment obtained in S2) to prepare a slurry, and then performing a dealkalization flotation operation to obtain a dealkalization flotation concentrate and quartz sand, wherein the quartz sand is the siliceous raw material for silicate cement.

2. The method according to claim 1, characterized in that The slurry concentration of the copper sulfide tailings in S1) after slurry adjustment is 30-45%.

3. The method according to claim 1, characterized in that The desulfurization flotation operation in S1) includes the flotation roughing step and the flotation scavenging step, and the specific steps are: The flotation roughing step comprises: adding 40-60 g / t of roughing collector and 10-20 g / t of roughing frother to carry out flotation to obtain desulfurized roughing concentrate and desulfurized roughing tailings; The flotation scavenging step is: scavenging the desulfurized rougher tailings 1-3 times, adding 10-30 g / t of scavenging collector and 5-15 g / t of scavenging frother for flotation each time, to obtain desulfurized scavenging concentrate and desulfurized flotation tailings, and the desulfurized scavenging concentrate and the desulfurized rougher concentrate are combined into a desulfurized flotation concentrate.

4. The method according to claim 3, characterized in that The roughing collector and the scavenging collector are one or more of butyl xanthate, amyl xanthate, and isopentyl xanthate; The roughing foaming agent and the scavenging foaming agent are both pine oil, 2# oil, BK204, methyl isobutyl carbinol, polyethylene glycol ether or mixed fatty alcohol industrial foaming agents.

5. The method according to claim 1, characterized in that The slurry concentration of the desulfurization flotation tailings in S2) after slurry adjustment is 15-35%.

6. The method according to claim 1, characterized in that The particle size of the fine-grained overflow obtained by the classification operation in S2) is 0-X, where X=0.01-0.03 mm.

7. The method according to claim 1, characterized in that The pulp concentration after the coarse-grained sand settling and slurry adjustment in S3) is 30-45%.

8. The method according to claim 1, characterized in that The dealkalization flotation in S3) includes 1-2 flotation roughing operations, each time adding 100-300g / t of pH adjuster, 100-300g / t of anionic ONA collector, 40-100g / t of cationic DDA collector, and 5-15g / t of frother for flotation to obtain dealkalization flotation concentrate and quartz sand meeting quality requirements.

9. The method according to claim 8, characterized in that The pH adjuster in S3) is sodium hydroxide, which adjusts the pH of the slurry to 7-10; The anionic ONA collector is a combination of sodium cyclopentaneate and sodium oleate, and its weight composition is 6-10 parts of sodium cyclopentaneate and 30-60 parts of sodium oleate. ONA is mixed with water to form an aqueous solution with a weight percentage of 1%-15%. The cationic DDA collector is one or more of dodecylamine acetate, dodecylamine hydrochloride, and dodecylamine phosphate; The foaming agent is pine oil, 2# oil, BK204, methyl isobutyl carbinol, polyethylene glycol ether or mixed fatty alcohol industrial foaming agent.

10. The method according to claim 1, characterized in that The SiO2 content in the quartz sand is 74.62% to 76.78%, the S content is lower than 0.3%, and the K2O content is lower than 3%.

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