A method for preparing silicate cement siliceous raw material by using copper sulphide tailings

Abstract

The application discloses a method for preparing silicate cement siliceous raw material from copper sulfide tailings, comprising the following steps: S1, the copper sulfide tailings are slurried, and then desulfurization flotation operation is carried out to obtain desulfurization flotation concentrate and desulfurization flotation tailings; S2, the desulfurization flotation tailings are slurried with water, and then fed into a hydrocyclone for grading to obtain coarse-grained sand and fine-grained overflow; S3, the coarse-grained sand is slurried with water, and then subjected to alkali removal flotation operation to obtain alkali removal flotation concentrate and quartz sand meeting quality requirements, 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%; the method can deeply remove sulfur and alkali from the copper sulfide tailings, remove harmful components in the copper sulfide tailings for sintering cement clinker, obtain quartz sand meeting the requirements of silicate cement siliceous raw material, and realize large-scale consumption of the copper sulfide tailings.

Description

Technical Field

[0001] The present 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. Due to the low content of useful target components in tailings, 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 a complex chemical composition, fine particle size, low activity, and often contain harmful elements such as sulfur, cadmium, and arsenic, which limits their large-scale resource utilization in multiple fields. Therefore, how to achieve copper tailings reduction, high value, and complete harmlessness has become a focus of industry attention. Copper tailings are mainly composed of quartz, mica, feldspar, siderite, pyrite, etc., and their chemical composition is mainly SiO2, Al2O3, K2O, and Fe2O3. They are similar to the composition of cement siliceous raw materials and can replace some cement correction materials for calcining cement clinker. However, due to the high content of impurities such as S and K2O in copper tailings, as well as 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 have a significant impact on the cement clinker firing process. High S content will cause sulfur oxide compounds in the tail gas during cement clinker calcination to exceed the standard, 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 clogging, 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 absorption capacity of copper tailings in cement preparation. Summary of the Invention

[0005] The present 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 siliceous raw materials for Portland cement 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 feeding it into a hydrocyclone for classification to obtain a coarse-grained sediment and a fine-grained overflow;

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

[0010] 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%.

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

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

[0013] The flotation roughing step is to add a roughing collector 40-60 g / t and a roughing frother 10-20 g / t for flotation to obtain a desulfurization roughing concentrate and a desulfurization roughing tailings;

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

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

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

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

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

[0019] Further, the slurry concentration of the coarse-grained settled sand in S3) after slurry preparation is 30-45%.

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

[0021] Further, the pH regulator in S3) is sodium hydroxide, and the pH of the ore slurry is adjusted to 7-10.

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

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

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

[0025] Further, the SiO2 content in the quartz sand is 74.62%-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 application are:

[0027] 1. The present application adopts the process flow of "flotation-classification-flotation", which is used for deep desulfurization and alkali reduction of copper sulfide tailings, and quartz sand meeting the quality requirements of silicate cement silicon raw materials is obtained. The process flow is simple, the cost is low, the operation is convenient, the yield of the obtained quartz sand is maximum, the bulk consumption of copper sulfide tailings can be realized, the environmental problems caused by tailings storage are reduced, and the social benefits are remarkable.

[0028] 2. The present application adopts the combination of the complex anionic collector ONA and the cationic collector DDA to realize the flotation separation of mica and other alkali metal element-containing aluminosilicate minerals and quartz under neutral or weak alkaline conditions, reduce the K2O content of copper sulfide tailings, and relieve the treatment pressure of acidic mineral processing wastewater. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The process flow chart of the method for preparing silicate cement silicon raw materials from copper sulfide tailings. DETAILED DESCRIPTION

[0030] The specific embodiments of the present application will be further described below in combination with the drawings.

[0031] The present application aims to provide a method for preparing silicate cement silicon raw materials from copper sulfide tailings, which can perform deep desulfurization and alkali reduction on copper tailings, and obtain quartz sand meeting the quality requirements of silicate cement silicon raw materials. In addition, the method can realize the flotation separation of mica and other alkali metal element-containing aluminosilicate minerals and quartz under neutral or weak alkaline conditions, and relieve the treatment pressure of acidic mineral processing 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 feeding it into 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 a slurry, and then performing a dealkalization flotation operation to obtain a dealkalization flotation concentrate and quartz sand, wherein the quartz sand has an SiO2 content of 74.62% to 76.78%, an S content of less than 0.3%, and a K2O content of less than 3%.

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

[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 comprises: 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 a desulfurized flotation concentrate.

[0040] Furthermore, 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 pulp is adjusted to 7-10;

[0047] The anionic ONA collector is a combination of sodium naphthenate and sodium oleate, which is composed of 6-10 parts of sodium naphthenate and 30-60 parts of sodium oleate by weight. 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] Example 1

[0051] The tailings used in this example are flotation tailings from a domestic copper-sulfur mine. They 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 about 40%, and a desulfurization flotation operation of "one roughing and one scavenging" is performed to obtain desulfurization flotation concentrate and 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 scavenging 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 concentration to about 20%, and feed it into the hydrocyclone for classification to obtain coarse-grained sand and fine-grained overflow. The particle size of the fine-grained overflow is 0-0.02mm, and the rest is coarse-grained sand.

[0057] S3. The coarse-grained sediment is slurried with water to a controlled pulp concentration of approximately 30%. A roughing, dealkalization flotation operation is then performed to obtain a dealkalized flotation concentrate and quartz sand that meets quality requirements. The dealkalization flotation reagent system is as follows: sodium hydroxide at a dosage of 110 g / t, the pulp pH adjusted to 8-10, a compound anionic collector ONA at a dosage of 200 g / t, a cationic collector DDA at a dosage of 65 g / t, and methyl isobutyl carbinol at a dosage of 10 g / t.

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

[0059] Example 2

[0060] The copper sulfide tailings used in this example are the total tailings from 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 desulfurization flotation concentrate and desulfurization flotation tailings.

[0064] The desulfurization roughing agent system is: butyl xanthate, added at 40g / t, BK204, added at 15g / t; the desulfurization scavenging agent system is: butyl xanthate, added at 15g / t, BK204, added at 8g / t.

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

[0066] S3. The coarse-grained sediment is slurried with water to a controlled slurry concentration of approximately 35%. A roughing, dealkalization flotation operation is then performed to obtain a dealkalized flotation concentrate and quartz sand that meets quality requirements. The dealkalization flotation reagent system is as follows: sodium hydroxide at a dosage of 120 g / t, the slurry pH is adjusted to 8-10, and a compound anionic collector, ONA, is added at a dosage of 300 g / t, a cationic collector, DDA, is added at a dosage of 100 g / t, and BK204 is added at a dosage of 10 g / t.

[0067] Finally, quartz sand with a SiO2 content of 74.62%, a S content of 0.26%, a K2O content of 2.81%, and an Al2O3 content of 11.27% is obtained, namely, the siliceous raw material of silicate cement. The content of the 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; and these changes, modifications or equivalent replacements do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of each application example 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 raw materials using copper sulfide tailings, characterized in that: The steps include: S1) slurrying the copper sulfide tailings and then feeding them into the desulfurization flotation process to obtain desulfurization flotation concentrate and desulfurization flotation tailings; The desulfurization flotation operation includes the flotation roughing step and the flotation scavenging step. The specific steps are: The flotation roughing step comprises: adding 40-60 g / t of a roughing collector and 10-20 g / t of a roughing frother to perform flotation to obtain a desulfurized roughing concentrate and a desulfurized roughing tailing; The flotation scavenging step comprises: scavenging the desulfurized rougher tailings 1-3 times, adding 10-30 g / t of scavenging collector and 5-15 g / t of scavenging frother each time for flotation to obtain desulfurized scavenging concentrate and desulfurized flotation tailings, and combining the desulfurized scavenging concentrate and the desulfurized rougher concentrate into a desulfurized flotation concentrate; S2) adding water to the desulfurized flotation tailings obtained in S1) to prepare a slurry, and then feeding it into a hydrocyclone for classification to obtain coarse-grained sediment 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 Portland cement; 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 that meets quality requirements.

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

3. The method according to claim 1, characterized in that The coarse selection 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.

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

5. The method according to claim 1, wherein 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.

6. 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%.

7. The method according to claim 1, 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 naphthenate and sodium oleate, which is composed of 6-10 parts of sodium naphthenate and 30-60 parts of sodium oleate by weight. 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.

8. 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 less than 0.3%, and the K2O content is less than 3%.

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