Efficient organic inhibitor for arsenopyrite and preparation method and application thereof

Abstract

The present application belongs to the technical field of beneficiation reagent, and relates to a high-efficiency organic depressor for arsenopyrite and a preparation method and application thereof, in particular to a composite depressor for separating sulfur-arsenic minerals. The depressor comprises the following raw materials in parts by mass: 25-45 parts of O-ethyl N-naphthalene sulfonic acid sodium thioaminoformate, 35-45 parts of 2-dihydroxydipropenyl sulfide, 2-5 parts of sodium humate, 10-29 parts of water and 0.5-5 parts of industrial heptane. According to the synergistic effect of the reagent, the present application selects a hydrophilic compound capable of being combined with arsenopyrite as a combined depressor in combination with the structural difference between pyrite and arsenopyrite. The organic depressor has good inhibiting performance on arsenopyrite in the separation of sulfur-arsenic, and has weak inhibiting performance on pyrite. After the high-efficiency depressor and the flotation method of the present application are used, high-efficiency separation can be realized without adding other inorganic depressors in the separation of copper and sulfur.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing agents, and relates to a high-efficiency organic inhibitor for arsenopyrite, a preparation method and an application thereof, and in particular to a composite inhibitor for the separation of sulfur-arsenic minerals. Background Art

[0002] Arsenic is a hazardous element in the smelting of non-ferrous sulfide ores. Arsenic occurs in a variety of states, with common arsenic minerals including chalcopyrite and arsenopyrite. The most widespread primary arsenic mineral is arsenopyrite (FeAsS). Due to its geochemical affinity for sulfur and siderophilicity, arsenopyrite often coexists closely with pyrite, primarily pyrite. The two minerals share similar crystal structures and surface physicochemical properties, resulting in similar flotation properties and difficulty separating them. Excessive arsenic content in pyrite concentrate increases smelting costs and hinders sales. Most mines are forced to stockpile large quantities of high-arsenic pyrite, which not only consumes land resources but also generates arsenic-containing organic compounds and inorganic arsenates from the oxidation of arsenic-containing minerals, which pollute the environment and endanger human health. Therefore, minimizing the arsenic content in sulfide concentrate is crucial for both improving smelting efficiency and protecting the environment.

[0003] The efficient separation of sulfur-arsenic minerals has long been a major challenge for the clean utilization of sulfide mineral resources in my country and around the world. In the copper-sulfur separation process, arsenopyrite inhibitors play a crucial role. Inhibitors can be divided into inorganic and organic inhibitors based on their molecular structure. Lime, oxidants, carbonates, and sulfur oxides are widely used inorganic inhibitors; commonly used organic inhibitors include hexamethylenediaminetetramethylenephosphonic acid, humates, tannin extracts, lignin sulfonates, and mixtures thereof. Although the technology for suppressing arsenopyrite with inorganic inhibitors is relatively mature, with the increasing amount of lean, fine, and mixed ores, and increasingly stringent requirements for concentrate quality and environmental protection, organic inhibitors that are environmentally friendly, highly stable, selective, low-solubility, and low-cost are gaining increasing attention.

[0004] It is difficult to achieve ideal separation results using a single inhibitor. Based on the differences in inhibitor structure and performance, innovative combinations of inhibitors with different properties can produce synergistic effects to enhance the inhibitory effect on arsenopyrite and reduce the arsenic grade in sulfur concentrates separated from sulfur and arsenic. Therefore, combining inhibitors is an important direction for developing highly efficient arsenopyrite inhibitors and is of great significance for improving separation performance. Summary of the Invention

[0005] In response to the current problems in sulfur-arsenic separation, the purpose of the present invention is to provide a highly efficient organic inhibitor of arsenopyrite, its preparation method and application. The inhibitor of the present invention can significantly reduce the grade and recovery rate of arsenic in sulfur concentrate, and solve the problem of difficulty in inhibiting arsenopyrite in sulfur-arsenic separation.

[0006] To achieve the above objectives, the present invention adopts the following technical solutions.

[0007] A high-efficiency organic inhibitor for arsenopyrite comprises the following raw materials, measured by mass: 25 to 45 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate, 35 to 45 parts of 2-dihydroxydipropylene sulfide, 2 to 5 parts of sodium humate, 10 to 29 parts of water, and 0.5 to 5 parts of industrial heptane.

[0008] The structural formula of sodium O-ethyl N-n-phenylsulfonylthiocarbamate is shown in Formula 1, and the structural formula of 2-dihydroxydipropylene sulfide is shown in Formula 2:

[0009] Formula (1)

[0010] Formula (2).

[0011] A method for preparing a highly efficient organic inhibitor for arsenopyrite comprises the following steps: adding a certain amount of water to a reaction vessel, adding sodium O-ethyl N-n-phenylsulfonylthiocarbamate and sodium humate under stirring, fully dissolving the mixture, adding industrial heptane and 2-dihydroxydipropylene sulfide, and stirring for 1 hour to obtain an oily liquid inhibitor.

[0012] The application of the arsenopyrite organic inhibitor of the present invention is the application in the sulfur-arsenic separation of sulfur concentrate or the sulfur-arsenic flotation separation agent of high-arsenic pyrite, and the application comprises the following steps:

[0013] Step 1: adding lime to the ore sample, grinding and slurrying to obtain slurry;

[0014] Step 2: adding organic inhibitor, ethyl xanthate and pine oil to the ore pulp of step 1 for the first roughing;

[0015] Step 3: If the arsenic grade in the sulfur concentrate meets the standard after the first roughing, but the sulfur recovery rate does not meet the standard, a second roughing can be carried out to improve the sulfur recovery rate in the sulfur concentrate, and ethyl xanthate and organic inhibitors are added in the second roughing; if the arsenic grade in the sulfur concentrate does not meet the standard, but the sulfur recovery rate meets the standard, a sulfur concentrate can be obtained through a first roughing to reduce the arsenic grade in the sulfur concentrate.

[0016] Furthermore, in step 1, the pH of the slurry is 10-11.

[0017] Furthermore, in step 1, the amount of lime added is 500-1200 g / t.

[0018] Furthermore, in step 2, the amount of the crude organic inhibitor added is 200-2000 g / t.

[0019] Furthermore, in step 2, the collector is ethyl xanthate, the addition amount is 30-200 g / t, and the addition amount of pine oil is 20-100 g / t.

[0020] Furthermore, in step 3, the amount of the organic inhibitor added in the second roughing and fine selection is 1 / 3 to 1 / 5 of that in the first roughing, and the amount of the diethyl xanthate added in the roughing is 1 / 3 to 1 / 5 of that in the first roughing.

[0021] The technical principle of the present invention is:

[0022] Xanthate collectors are commonly used in the flotation separation of iron sulfide and arsenopyrite. Sodium O-ethyl N-n-phenylsulfonylthiocarbamate forms a stronger compound with arsenopyrite, occupying the surface of the mineral. The sulfonic acid group in this compound is a hydrophilic complexing group with a specific effect on arsenopyrite. This reaction with arsenopyrite removes the xanthate collector from the mineral surface, reducing its hydrophobicity.

[0023] The ionic composition of the surface of arsenopyrite and pyrite is different. The 2-dihydroxydipropylene sulfide molecule contains two hydroxyl groups and is partially hydrophilic. 3+ The ions form complexes and are fixed on the surface of arsenopyrite, preventing the adsorption of xanthate collectors on the surface of arsenopyrite and making the surface hydrophilic.

[0024] Sodium humate is characterized by its large molecular weight and long molecular chain. When it reacts with minerals, it can not only form a hydrophilic adsorption layer, but also mask the collector adsorbed on the surface of the mineral, shielding the hydrophobic effect of the collector, causing the mineral to become hydrophilic and inhibiting the complexation of Fe. 3+ And generate a hydrophilic film that is selectively adsorbed on the surface of arsenopyrite.

[0025] Industrial heptane and water are used as solvents to ensure a stable combination of the three inhibitors without stratification.

[0026] Compared with the prior art, the present invention has the following beneficial effects.

[0027] 1. Based on the synergistic effect of the reagents, sodium O-ethyl N-n-phenylsulfonylthiocarbamate, 2-dihydroxydipropylene sulfide, and sodium humate are used as inhibitors for the separation of sulfur and arsenic. The inhibitor has good inhibitory performance on arsenopyrite minerals, but weak inhibitory ability on pyrite, and can achieve efficient separation of iron sulfide minerals and arsenopyrite.

[0028] 2. The arsenopyrite inhibitor of the present invention is liquid, has a simple production process, can be stored for a long time, is easy to use, and is easy to automate.

[0029] 3. After adopting the high-efficiency inhibitor and flotation method of the present invention, efficient separation can be achieved during copper-sulfur separation without adding other inorganic inhibitors. The inhibitor is green, environmentally friendly and easy to degrade. DETAILED DESCRIPTION

[0030] The present invention is further described below with reference to the embodiments, but the present invention is not limited in any way. Any changes and substitutions made based on the teachings of the present invention fall within the scope of protection of the present invention.

[0031] A high-efficiency organic inhibitor for arsenopyrite comprises the following raw materials, measured by mass: 25 to 45 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate, 35 to 45 parts of 2-dihydroxydipropylene sulfide, 2 to 5 parts of sodium humate, 10 to 29 parts of water, and 0.5 to 5 parts of industrial heptane.

[0032] The structural formula of sodium O-ethyl N-n-phenylsulfonylthiocarbamate is shown in Formula 1, and the structural formula of 2-dihydroxydipropylene sulfide is shown in Formula 2:

[0033] Formula (1)

[0034] Formula (2).

[0035] A method for preparing a highly efficient organic inhibitor for arsenopyrite comprises the following steps: adding a certain amount of water to a reaction vessel, adding sodium O-ethyl N-n-phenylsulfonylthiocarbamate and sodium humate under stirring, fully dissolving the mixture, adding industrial heptane and 2-dihydroxydipropylene sulfide, and stirring for 1 hour to obtain an oily liquid inhibitor.

[0036] The application of the arsenopyrite organic inhibitor of the present invention is the application in the sulfur-arsenic separation of sulfur concentrate or the sulfur-arsenic flotation separation agent of high-arsenic pyrite, and the application comprises the following steps:

[0037] Step 1: adding lime to the ore sample, grinding and slurrying to obtain slurry;

[0038] Step 2: adding organic inhibitor, ethyl xanthate and pine oil to the ore pulp of step 1 for the first roughing;

[0039] Step 3: If the arsenic grade in the sulfur concentrate meets the standard after the first roughing, but the sulfur recovery rate does not meet the standard, a second roughing can be carried out to improve the sulfur recovery rate in the sulfur concentrate, and ethyl xanthate and organic inhibitors are added in the second roughing; if the arsenic grade in the sulfur concentrate does not meet the standard, but the sulfur recovery rate meets the standard, a sulfur concentrate can be obtained through a first roughing to reduce the arsenic grade in the sulfur concentrate.

[0040] Furthermore, in step 1, the pH of the slurry is 10-11.

[0041] Furthermore, in step 1, the amount of lime added is 500-1200 g / t.

[0042] Furthermore, in step 2, the amount of the crude organic inhibitor added is 200-2000 g / t.

[0043] Furthermore, in step 2, the collector is ethyl xanthate, the addition amount is 30-200 g / t, and the addition amount of pine oil is 20-100 g / t.

[0044] Furthermore, in step 3, the amount of the organic inhibitor added in the second roughing and fine selection is 1 / 3 to 1 / 5 of that in the first roughing, and the amount of the diethyl xanthate added in the roughing is 1 / 3 to 1 / 5 of that in the first roughing.

[0045] Example 1: Separation of sulfur and arsenic from a sulfur concentrate in Inner Mongolia (I).

[0046] A method for preparing a highly effective organic inhibitor for arsenopyrite comprises the following steps: adding 15 parts of water to a reaction vessel, adding 40 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate and 5 parts of sodium humate while stirring, and after fully dissolving, adding 1 part of industrial heptane and 39 parts of 2-dihydroxydipropylene sulfide, and stirring for 1 hour to obtain an oily liquid inhibitor. The inhibitor is added in the original solution.

[0047] Sulfur-arsenic mixed concentrate: The test ore had an S grade of 30.18% and an As grade of 3.14%. A single-roughing, single-concentrating process was used with 800 g / t of calcium oxide, a pH of 10, 100 g / t of ethyl xanthate, and 50 g / t of pine oil. The roughing inhibitor dosage was 500 g / t, and the concentrating inhibitor dosage was 120 g / t. A sulfur concentrate with an S grade of 44.98%, a S recovery of 71%, and an As grade of 0.55% was obtained.

[0048] In the comparative example, calcium hypochlorite was used as an inhibitor to obtain a sulfur concentrate with an S grade of 41.16%, an S recovery rate of 70%, and an As grade of 0.84%. Potassium permanganate was used as an inhibitor to obtain a sulfur concentrate with an S grade of 41.12%, an S recovery rate of 69%, and an As grade of 0.69%.

[0049] Compared with the comparative reagent, the inhibitor of the present invention has better selectivity for arsenopyrite while maintaining the grade and recovery rate.

[0050] Example 2: Separation of sulfur and arsenic from a high-arsenic sulfur concentrate in Inner Mongolia (II).

[0051] A method for preparing a highly effective organic inhibitor for arsenopyrite comprises the following steps: adding 15 parts of water to a reaction vessel, adding 40 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate and 5 parts of sodium humate while stirring, and after fully dissolving, adding 1 part of industrial heptane and 39 parts of 2-dihydroxydipropylene sulfide, and stirring for 1 hour to obtain an oily liquid inhibitor. The inhibitor is added in the original solution.

[0052] Arsenic sulfide in sulfur concentrate exists primarily as arsenopyrite, while pyrite is primarily pyrrhotite and pyrite, along with trace amounts of chalcopyrite, arsenic pyroxene, native bismuth, bismuthinite, limonite, sphalerite, and other metallic minerals. Gangue minerals primarily include quartz and siderite, with minor amounts of dolomite, biotite, and chlorite.

[0053] Sulfur-arsenic mixed concentrate: The test ore had an sulfur grade of 39.88% and an arsenic grade of 6.92%. A secondary roughing process was used with 800 g / t of calcium oxide, a pH of 10, 60 g / t of ethyl xanthate, and 30 g / t of pine oil. The primary roughing depressant used in this invention was 1500 g / t, the secondary roughing depressant was 500 g / t, and 20 g / t of ethyl xanthate. The resulting sulfur concentrate had an sulfur grade of 44.98%, a sulfur recovery of 76.21%, and an arsenic grade of 1.55%.

[0054] In the comparative example, dextrin was used as an inhibitor to obtain a sulfur concentrate with an S grade of 46.88%, an S recovery rate of 74.92%, and an arsenic grade of 5.02%.

[0055] Compared with dextrin, the inhibitor of the present invention has better selectivity for arsenopyrite while maintaining the grade and recovery rate.

[0056] Example 3: Separation of sulfur and arsenic from a sulfur concentrate in Inner Mongolia (III).

[0057] A method for preparing a highly effective organic inhibitor for arsenopyrite comprises the following steps: adding 20 parts of water to a reaction vessel, adding 39 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate and 3 parts of sodium humate while stirring, and after fully dissolving, adding 2 parts of industrial heptane and 36 parts of 2-dihydroxydipropylene sulfide, and stirring for 1 hour to obtain an oily liquid inhibitor. The inhibitor is added in the original solution.

[0058] Sulfur-arsenic mixed concentrate: The test ore contained 36% sulfur and 7.9% asarsenic. A single-rougher and single-concentrator process was used, using 1000 g / t calcium oxide, a pH of 11, 100 g / t ethyl xanthate, 40 g / t pine oil, 1500 g / t rougher inhibitor, and 500 g / t concentrator inhibitor. The resulting sulfur concentrate had an sulfur grade of 46.98%, a sulfur recovery of 76%, and an asarsenic grade of 1.38%.

[0059] In the comparative example, calcium hypochlorite was used as an inhibitor to obtain a sulfur concentrate with an S grade of 45.16%, an S recovery rate of 75.88%, and an As grade of 4.56%.

[0060] Compared with calcium hypochlorite, the inhibitor of the present invention has better selectivity for arsenopyrite while maintaining the grade and recovery rate.

[0061] Example 4: Arsenic pyrite tailings in Yunnan.

[0062] A method for preparing a highly effective organic inhibitor for arsenopyrite comprises the following steps: adding 20 parts of water to a reaction vessel, adding 39 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate and 3 parts of sodium humate while stirring, and after fully dissolving, adding 2 parts of industrial heptane and 36 parts of 2-dihydroxydipropylene sulfide, and stirring for 1 hour to obtain an oily liquid inhibitor. The inhibitor is added in the original solution.

[0063] Sulfur-arsenic mixed concentrate, with an S grade of 34.22% and an As grade of 1.75% in the test ore. A secondary roughing and primary concentrating process was used, using 800g / t of calcium oxide, a pH of 10, 50g / t of ethyl xanthate, 30g / t of pine oil, 1000g / t of inhibitor for the first roughing, 300g / t of inhibitor for the second roughing, 16g / t of ethyl xanthate, and 200g / t of inhibitor for concentrating. The result was a sulfur concentrate with an S grade of 42.18%, an S recovery of 81.2%, and an As grade of 0.85%.

[0064] In the comparative example, sodium humate was used as an inhibitor to obtain a sulfur concentrate with an S grade of 40.22%, an S recovery rate of 76.8%, and an As grade of 0.97%.

[0065] Compared with sodium humate, the inhibitor of the present invention has better selectivity for arsenopyrite while maintaining the grade and recovery rate.

Claims

1. A highly effective organic inhibitor of arsenopyrite, characterized in that: The raw materials include the following by mass: 25 to 45 parts of sodium O-ethyl N-n-phenylsulfonylthiocarbamate, 35 to 45 parts of 2-dihydroxydipropylene sulfide, 2 to 5 parts of sodium humate, 10 to 29 parts of water, and 0.5 to 5 parts of industrial heptane; The structural formula of the sodium O-ethyl N-n-phenylsulfonylthiocarbamate is as follows: ； The 2-dihydroxydipropylene sulfide is shown in the following formula: 。 2. The highly effective organic inhibitor of arsenopyrite according to claim 1, characterized in that: The inhibitor is used in the flotation separation of sulfur and arsenic.

3. The highly effective organic inhibitor of arsenopyrite according to claim 2, characterized in that: The application comprises the following steps: Step 1: adding lime to the ore sample, grinding and slurrying to obtain slurry; Step 2: adding organic inhibitor, ethyl xanthate and pine oil to the ore pulp of step 1 for the first roughing; Step 3: If the arsenic grade in the sulfur concentrate meets the standard in the first roughing, but the sulfur recovery rate does not meet the standard, a second roughing is performed to improve the sulfur recovery rate in the sulfur concentrate, and ethyl xanthate and organic inhibitors are added in the second roughing; if the arsenic grade in the sulfur concentrate does not meet the standard, but the sulfur recovery rate meets the standard, a sulfur concentrate is obtained after the first roughing to reduce the arsenic grade in the sulfur concentrate.

4. The highly effective organic inhibitor of arsenopyrite according to claim 3, characterized in that: In step 1, the pH of the slurry is 10-11.

5. The highly effective organic inhibitor of arsenopyrite according to claim 3, characterized in that: In step 1, the amount of lime added is 500-1200 g / t.

6. The highly effective organic inhibitor of arsenopyrite according to claim 3, characterized in that: In the step 2, the amount of the crude organic inhibitor added is 200-2000 g / t; the collector is ethyl xanthate, the amount of which is 30-200 g / t; and the amount of pine oil added is 20-100 g / t.

7. The highly effective organic inhibitor of arsenopyrite according to claim 3, characterized in that: In the step 3, the amount of the organic inhibitor added in the rough selection 2 and the fine selection is 1 / 3 to 1 / 5 of that in the rough selection 1, and the amount of the diethyl xanthate added in the rough selection is 1 / 3 to 1 / 5 of that in the rough selection 1.

8. The method for preparing a high-efficiency organic inhibitor of arsenopyrite according to claim 1, wherein: A certain amount of water was added to the reaction vessel, and the sodium O-ethyl N-n-phenylsulfonylthiocarbamate and sodium humate were added under stirring. After they were fully dissolved, industrial heptane and 2-dihydroxydipropylene sulfide were added and stirred for 1 hour to obtain an oily liquid inhibitor.

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