CN117583116B - Method for recycling low-grade fine-grain cassiterite and application thereof - Google Patents

Method for recycling low-grade fine-grain cassiterite and application thereof Download PDF

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CN117583116B
CN117583116B CN202410070281.1A CN202410070281A CN117583116B CN 117583116 B CN117583116 B CN 117583116B CN 202410070281 A CN202410070281 A CN 202410070281A CN 117583116 B CN117583116 B CN 117583116B
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cassiterite
flotation
concentrate
grade
magnetic
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CN117583116A (en
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胡明振
孙晓豪
吴伯增
邱鸿鑫
黄宝兴
黄艳
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Guangxi Huaxi Nonferrous Metals Co ltd
China University of Mining and Technology Beijing CUMTB
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Guangxi Huaxi Nonferrous Metals Co ltd
China University of Mining and Technology Beijing CUMTB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B9/00—General arrangement of separating plant, e.g. flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/018—Mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/04—Frothers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/06—Depressants

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to the technical field of mineral separation, in particular to a method for recycling low-grade fine-grain cassiterite and application thereof. The method for recovering low-grade fine-grained cassiterite comprises the following steps: preparing tin-containing materials into ore pulp, adding gangue mineral inhibitor, cassiterite collector, activator and flotation foaming agent into the ore pulp, performing primary flotation roughing through a cyclone-static micro-bubble flotation column, controlling the circulating pressure to be 0.15-0.22 mpa, controlling the aeration quantity to be 1200-4000L/h, and controlling the thickness of a foam layer to be 5-15 cm to obtain cassiterite rough concentrate; carrying out primary flotation and concentration on cassiterite rough concentrate through a cyclone-static microbubble flotation column to obtain concentrated concentrate; carrying out magnetic separation on the concentrate to obtain magnetic concentrate and magnetic tailings; and (3) carrying out gravity separation on the magnetic separation tailings to obtain the cradle concentrate, namely the high-grade cassiterite. The method can effectively improve the grade and recovery rate of the cassiterite.

Description

Method for recycling low-grade fine-grain cassiterite and application thereof
Technical Field
The invention relates to the technical field of mineral separation, in particular to a method for recycling low-grade fine-grain cassiterite and application thereof.
Background
The cassiterite often co-exists with sulphide ores such as lead, zinc, antimony and the like, under the influence of ore forming conditions. The difference of grindability of tin, lead and zinc is large, the cassiterite is brittle, and the cassiterite is easy to excessively crush in the grinding process, so that a large amount of secondary slime is generated. This fraction of fine-grained cassiterite is difficult to recover efficiently by re-selection and is thus lost in tailings. Thus, fine-grained cassiterite is often recovered by flotation. At present, the flotation recovery rate of fine-grained cassiterite is generally low, and the main reason is that the main structure and the separation mechanism of the adjacent flotation cells are basically the same in a conventional flotation machine mineral separation system adopted in the flotation process. In the separation process, the separation mode and mineralization mode of the cell-by-cell flotation enable the conventional flotation machine to separate into a nearly linear separation process, and are not suitable for nonlinear changes of mineral composition and properties in separation. The factors of relatively high pulp turbulence, bubble size and dispersion state, single mineralization mode, thinner foam layer and the like in the flotation machine tank body are the reasons of poor sorting effect on the micro-fine particle minerals.
Chinese patent CN1721080a discloses a method for beneficiating cassiterite, wherein the tin grade of the flotation concentrate can reach 26% and the recovery rate can reach 80% for the placer with the cassiterite content of 0.6% -2.0% through crushing, grinding, classifying and other operations. However, with the continuous decrease of the cassiterite grade and the gradual reduction of the granularity, the applicability of the method needs to be further explored.
Chinese patent CN1810381a discloses a beneficiation method of tin polymetallic sulphide ore tailings, firstly, desulfurization flotation is performed, the flotation tailings are classified by adopting a spiral classifier and a spiral chute, after classification, multi-channel flotation operation is performed for products of different particle sizes, so as to recover fine-grained cassiterite, but the process flow is complex, and the cassiterite recovery rate is not obviously improved.
Based on the above, the single flotation means using a flotation machine cannot recover the fine-grained cassiterite, and the current comprehensive recovery report of the low-grade fine-grained cassiterite is less. The mineralization efficiency of the low-grade fine-grain cassiterite is low, the consumption of a flotation collector is large, the recovery cost is high, and valuable minerals are lost.
Therefore, the development of the low-grade fine-grain cassiterite high-efficiency beneficiation method has important significance for improving the recovery rate of cassiterite.
In view of this, the present invention has been made.
Disclosure of Invention
The first aim of the invention is to provide a method for recycling low-grade fine-grained cassiterite, which improves the mineralization efficiency of fine grains by adopting a cyclone-static microbubble flotation column to form microbubbles in a self-priming jet bubbling mode and separating out supersaturated dissolved gas; if the material separated by the pipe flow is not mineralized, the material can enter the cyclone separation section again, and the above process is repeated to form multiple separation cycles until mineralization recovery is obtained; the circulation separation mechanism can greatly reduce the grade of tailings, especially-19 mu m micro-fine cassiterite, thereby improving the recovery rate of cassiterite. Solves the problems of low collision probability of the micro-fine cassiterite and bubbles, low flotation recovery rate, resource waste and high recovery cost.
A second object of the present invention is to provide the use of cassiterite obtained by the process for recovering low-grade fine-grained cassiterite for the production of tinplate, alloys, electroplated parts, dyes, enamels, porcelain and glass.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention firstly provides a method for recycling low-grade fine-grain cassiterite, which comprises the following steps:
preparing tin-containing materials into ore pulp, adding gangue mineral inhibitor, cassiterite collector, activator and flotation foaming agent into the ore pulp, performing primary flotation roughing through a cyclone-static micro-bubble flotation column, controlling the circulating pressure to be 0.15-0.22 mpa, and obtaining cassiterite rough concentrate, wherein the aeration quantity is 1200-4000L/h and the thickness of a foam layer is 5-15 cm;
carrying out primary flotation and concentration on the cassiterite rough concentrate through the cyclone-static micro-bubble flotation column to obtain concentrated concentrate;
carrying out magnetic separation on the concentrate to obtain magnetic concentrate and magnetic tailings;
re-selecting the magnetic separation tailings to obtain a shaking table concentrate, namely the high-grade cassiterite;
wherein, in the tin-containing material, the proportion of particles with the granularity of less than 0.074mm is 95% -97%, and the proportion of particles with the granularity of less than 0.038mm is 65% -75%.
Further, the grade of the cassiterite in the tin-containing material is less than or equal to 0.30 percent based on tin element.
Further, the mass fraction of the ore pulp is 30% -35%.
Further, the gangue mineral inhibitor includes at least one of sodium silicate and 1-aminopropyl phosphoric acid.
Further, the mass of the gangue mineral inhibitor added into each ton of ore pulp is 1000-1500 g.
Further, the cassiterite collector comprises benzoic hydroxamic acid.
Further, the mass of the cassiterite collector added into each ton of ore pulp is 50-100 g.
Further, the activator includes at least one of lead nitrate and hydroxylamine.
Further, the mass of the activator added into each ton of ore pulp is 20-50 g.
Further, the flotation frother comprises at least one of a pinitol oil and an ethereal alcohol oil.
Further, the mass of the flotation foaming agent added into each ton of ore pulp is 10-30 g.
Further, the magnetic flux of the magnetic separator used for magnetic separation is 250-280 MT.
Further, the magnetic concentrate is recovered.
Further, the stroke of the shaking table used for reselection is 8-15 mm, the stroke frequency is 300-400 r/min, the transverse gradient is 1-3 degrees, and the ore feeding concentration is 15-25%.
Further, the tailings obtained by the primary flotation roughing are subjected to twice scavenging to obtain flotation tailings, and middlings obtained by the twice scavenging are sequentially returned to the upper-level flotation to form a flotation closed circuit.
In each scavenging process, the mass of the collector added into each ton of ore pulp is 20-60 g.
Further, the grade of cassiterite in the table concentrate is >45% calculated by tin element.
The invention also provides application of the cassiterite obtained by the method for recycling low-grade fine-grain cassiterite in the production of tinplate, alloy, electroplating parts, dye, enamel, porcelain and glass.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for recycling low-grade fine-grain cassiterite, the cyclone-static microbubble flotation column is adopted, microbubbles are formed in a self-priming jet bubbling mode, supersaturated dissolved gas is separated out, and the mineralization efficiency of fine grains is improved; if the material separated by the pipe flow is not mineralized, the material can enter the cyclone separation section again, and the above process is repeated to form multiple separation cycles until mineralization recovery is obtained; the circulating separation mechanism can greatly reduce the tailing grade and improve the cassiterite recovery rate.
(2) The method for recycling the low-grade fine-grain cassiterite provided by the invention can realize the efficient recycling of the low-grade fine-grain cassiterite by adopting a method combining gravity separation and floatation, and particularly can realize the efficient recycling of the fine-grain cassiterite with the particle size of less than-0.001 mm.
(3) According to the method for recycling the low-grade fine-grain cassiterite, primary flotation roughing is carried out by adopting the cyclone-static microbubble flotation column, and the mineralization of the cassiterite in fine grains and micro-grains can be realized by controlling the circulating pressure to be 0.15-0.22 mpa, the aeration quantity to be 1200-4000L/h and the thickness of the foam layer to be 5-15 cm.
(4) According to the method for recycling the low-grade fine-particle cassiterite, provided by the invention, the cyclone-static microbubble flotation column is adopted for primary flotation roughing, and the column-magnetic-bed combined process is adopted, so that the high-efficiency recycling of the low-grade fine-particle cassiterite can be realized. Under the condition that the ore feeding grade is below 0.30%, the cassiterite concentrate grade is above 45%, and the recovery rate is improved by above 2% compared with the original process.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present invention, unless specifically stated otherwise, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity or as implicitly indicating the importance or quantity of the indicated technical feature. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the present invention, "one or more" or "at least one" means any one, any two or more of the listed items unless specifically stated otherwise. Wherein "several" means any two or more.
In a first aspect, the present invention provides a method for recovering low-grade fine-grained cassiterite based on a column-magnetic-bed combined process, comprising the steps of:
and (3) dewatering the tin-containing materials in the thickening tank, placing the dewatered tin-containing materials in a stirring barrel, and adding water into the stirring barrel to mix to obtain ore pulp.
Wherein, the particle with the granularity lower than 0.074mm accounts for 95% -97% of the tin-containing material, including but not limited to any one point value or any range value between the two points of 95%, 95.5%, 96%, 96.5% and 97%; the ratio of the particles with the granularity lower than 0.038mm in the tin-containing material is 65% -75%, including but not limited to any one point value or any range value between any two of 65%, 66%, 68%, 70%, 72%, 74% and 75%.
The method provided by the invention is used for recycling the fine particles and the micro-fine particles of cassiterite, and can be used for recycling the cassiterite in the fine-particle tin-containing materials with the particle size range, and has high recycling rate, and the recycling rate can be influenced if the particle size is too coarse.
Adding gangue mineral inhibitor, cassiterite collector, activator and flotation foaming agent into the ore pulp, performing primary flotation roughing through a cyclone-static micro-bubble flotation column, and controlling the circulating pressure of the cyclone-static micro-bubble flotation column to be 0.15-0.22 Mpa, including but not limited to any one of 0.15Mpa, 0.16Mpa, 0.17Mpa, 0.19Mpa, 0.2Mpa, 0.21Mpa and 0.22Mpa or a point value between any two of the two values; the inflation amount is 1200-4000L/h, including but not limited to a point value of any one of 1200L/h, 1300L/h, 1500L/h, 1800L/h, 2000L/h, 2200L/h, 2500L/h, 2800L/h, 3000L/h, 3300L/h, 3500L/h, 3800L/h and 4000L/h or a range value between any two of the two; the thickness of the foam layer is 5-15 cm, including but not limited to any one of point values or range values between any two of 5cm, 7cm, 8cm, 10cm, 12cm, 14cm and 15cm, and the cassiterite rough concentrate is obtained after one-time flotation roughing is completed.
The gangue mineral inhibitor mainly inhibits silicate and carbonate gangue ores, the cassiterite collector mainly collects tin oxide and tin sulfide, the activator mainly activates the tin oxide and the tin sulfide, and the flotation foaming agent mainly mineralizes minerals.
And carrying out primary flotation and concentration on the cassiterite rough concentrate through the cyclone-static micro-bubble flotation column to obtain concentrated concentrate.
The circulating pressure of the cyclone-static micro-bubble flotation column is controlled to be 0.15-0.22 mpa in the primary flotation selection process, the aeration quantity is 1200-4000L/h, and the thickness of a foam layer is 5-15 cm.
And carrying out magnetic separation on the concentrate to obtain magnetic concentrate and magnetic tailings.
And (3) carrying out shaking table gravity separation on the magnetic separation tailings to obtain shaking table concentrate, shaking table middlings and shaking table tailings, wherein the shaking table concentrate is the high-grade cassiterite, the shaking table middlings can be recycled, and the shaking table tailings are discarded. The purpose of shaking table reselection is to retrieve the tin metal in the magnetic separation tailing, realizes the high-efficient recovery of tin resource.
According to the invention, by adopting the cyclone-static microbubble flotation column, microbubbles are formed in a self-priming jet bubbling mode, supersaturated dissolved gas is separated out, and the mineralization efficiency of fine particles is improved; if the material separated by the pipe flow is not mineralized, the material can enter the cyclone separation section again, and the above process is repeated to form multiple separation cycles until mineralization recovery is obtained; the circulating separation mechanism can greatly reduce the tailing grade and improve the cassiterite recovery rate.
Meanwhile, the invention can realize the mineralization of cassiterite in fine grains and micro-fine grains by controlling the circulating pressure, the aeration quantity and the thickness of the foam layer.
In addition, the primary flotation roughing is carried out by adopting the cyclone-static microbubble flotation column and the combined process of column-magnetic-bed is adopted, so that the mineralization efficiency of the micro-fine cassiterite and the concentrate quality can be effectively improved, and the recovery rate of the low-grade micro-fine cassiterite is further improved.
The method provided by the invention can recycle low-grade cassiterite. In some embodiments, the grade of cassiterite in the tin-containing material is less than or equal to 0.30% as elemental tin, including, but not limited to, any one of a point value or a range value between any two of 0.05%, 0.1%, 0.15%, 0.18%, 0.2%, 0.23%, 0.25%, 0.28%, 0.30%. The method provided by the invention still has high recovery rate for tin-containing materials with the grade below 0.30%.
In some specific embodiments, the mass fraction of the pulp is 30% -35%, including but not limited to any one of the point values or any range between the two values of 30%, 31%, 32%, 33%, 34%, 35%.
The concentration of the ore pulp can influence the floatability of the cassiterite, so that the recovery rate of fine particles and micro-fine cassiterite is influenced, and the recovery rate of fine particles and micro-fine cassiterite can be improved by adopting the ore pulp with the concentration range, and the cassiterite content in tailings is reduced.
In some embodiments, the gangue mineral inhibitor comprises sodium silicate.
The gangue mineral inhibitor adopting the specific types has the advantages of improving the quality of the cassiterite, reducing the content of gangue minerals in the cassiterite and the like.
In some specific embodiments, the mass of the gangue mineral inhibitor added into each ton of the ore pulp is 1000-1500 g; including but not limited to a point value of any one of 1000g, 1100g, 1200g, 1300g, 1400g, 1500g, or a range value between any two.
In some specific embodiments, the cassiterite collector comprises benzohydroxamic acid.
In some specific embodiments, the mass of the cassiterite collector added into each ton of the ore pulp is 50-100 g; including but not limited to a point value of any one of 50g, 60g, 70g, 80g, 90g, 100g, or a range value therebetween.
In some embodiments, the activator comprises lead nitrate.
In some specific embodiments, the mass of the activator added into each ton of the ore pulp is 20-50 g; including but not limited to a point value of any one of 20g, 30g, 40g, 50g, or a range value between any two.
In some embodiments, the flotation frother comprises at least one of a pinitol oil and an ethereal alcohol oil.
In some embodiments, the mass of the flotation frother added to each ton of the pulp is 10-30 g, including but not limited to a point value of any one of 10g, 15g, 20g, 25g, 30g, or a range between any two.
In some specific embodiments, the magnetic flux of the magnetic separator used for magnetic separation is 250-280 MT; including but not limited to a point value of any one of 250MT, 260MT, 270MT, 280MT, or a range value between any two.
The magnetic flux in the range is adopted in the magnetic separation process, so that the content of magnetite can be increased, the magnetite in cassiterite can be reduced, and the grade of cassiterite can be improved.
In some specific embodiments, the grade of cassiterite in the magnetic separation tailings is 3.5% -5.5% calculated by tin element, including but not limited to any one of 3.5%, 4%, 4.5%, 5%, 5.5% or a range value between any two.
In some specific embodiments, the magnetic concentrate is recovered. The main component of the magnetic concentrate is ferroferric oxide, which can be reused, and the economic added value is improved.
In some specific embodiments, the stroke of the cradle used for the reselection is 8-15 mm, including but not limited to a point value of any one of 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm or a range value between any two; the impulse is 300-400 r/min, including but not limited to any one point value or range value between any two of 300r/min, 320r/min, 340r/min, 350r/min, 380r/min and 400 r/min; the transverse gradient is 1-3 degrees, including but not limited to any one point value or range value between any two of 1 degree, 1 degree 30', 2 degrees 30', 3 degrees; the feed concentration is 15% -25%, including but not limited to any one of 15%, 17%, 18%, 20%, 22%, 23%, 25% or a range between any two.
The gravity separation adopts the range, so that the content of cassiterite in tailings can be reduced, and the recovery rate of cassiterite is improved.
In some specific embodiments, the tailings obtained by the primary flotation roughing are subjected to twice scavenging to obtain flotation tailings, middlings obtained by the twice scavenging are sequentially returned to the upper-level flotation, namely middlings obtained by the second scavenging are returned to the primary scavenging process, and middlings obtained by the primary scavenging are returned to the primary flotation roughing process to form a flotation closed circuit. Thus, the recovery of the cassiterite in the tailings can be realized, and the cassiterite content in the tailings is reduced.
In each scavenging process, the mass of the collector added into each ton of ore pulp is 20-60 g, including but not limited to any one of point values or range values between any two of 20g, 30g, 40g, 50g and 60g.
In some embodiments, the grade of cassiterite in the shaker concentrate is >45% as elemental tin, including, but not limited to, a point value of any one of 45.85%, 46%, 46.3%, 46.5%, 47%, 47.28%, 47.5%, 48%, or a range value between any two.
The cassiterite obtained by the method has high grade.
In a second aspect, the invention provides the use of the cassiterite obtained by the method for recovering low grade fine-grained cassiterite for the production of tinplate, alloys, electroplated parts, dyes, enamels, porcelain and glass.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The method for recovering low-grade fine-grain cassiterite based on the column-magnetic-bed combined process provided by the embodiment adopts mineral raw materials from underflow (including tin-containing materials) of a tin polymetallic ore thickener in Guangxi, and specifically comprises the following steps:
(1) And (5) placing the underflow ore pulp of the thickener into a stirring barrel to adjust the ore pulp to 30% by mass fraction. In the tin-containing material, the proportion of particles with the granularity of less than 0.074mm is 95.40 percent, the proportion of particles with the granularity of less than 0.038mm is 65.70 percent, and the grade of the cassiterite is 0.15 percent calculated by tin element.
(2) Adding 1500g/t of sodium silicate serving as a gangue mineral inhibitor, 100g/t of benzoic hydroxamic acid serving as a cassiterite collector, 50g/t of lead nitrate serving as an activator and 15g/t of pinitol oil serving as a flotation foaming agent (namely, adding 1500g of sodium silicate, 100g of benzoic hydroxamic acid, 50g of lead nitrate and 15g of pinitol oil into each ton of ore pulp) into 30% of ore pulp obtained in the step (1), and performing primary flotation roughing through a cyclone-static micro-bubble flotation column to obtain a cassiterite rough concentrate, wherein the circulating pressure of the cyclone-static micro-bubble flotation column is 0.15Mpa, the aeration amount is 1500L/h, and the thickness of a foam layer is 5cm.
(3) And (3) carrying out primary flotation concentration (circulation pressure, aeration quantity and foam layer thickness are the same as those in the step (2) of the embodiment) on the cassiterite rough concentrate obtained in the step (2) through a cyclone-static microbubble flotation column, so as to obtain the concentrate.
And removing magnetic minerals from the concentrate through magnetic separation, wherein the magnetic flux of the magnetic separator is 250MT, so as to obtain magnetic concentrate and magnetic tailings, and recovering the magnetic concentrate.
(4) And (3) reselecting the magnetic separation tailings obtained in the step (3) by using a shaking table to obtain shaking table concentrate, shaking table middlings and shaking table tailings, wherein the stroke of the shaking table is 8mm, the stroke frequency is 300r/min, the transverse gradient of the surface of the shaking table is 1 DEG 30', the ore feeding concentration is 15%, and the shaking table concentrate is the final product, namely the high-grade cassiterite.
(5) And (3) carrying out twice scavenging on tailings obtained by primary flotation roughing in the step (1) through a cyclone-static microbubble flotation column (the circulating pressure, the air charge and the foam layer thickness are the same as those in the step (2) in the embodiment), obtaining flotation tailings, and sequentially returning middlings obtained by twice scavenging to superior flotation (namely returning middlings obtained by secondary scavenging to a primary scavenging process, and returning middlings obtained by primary scavenging to a primary flotation roughing process), so as to form a flotation closed circuit, wherein 50g of a collector is added into each ton of ore pulp during primary scavenging, and 30g of a collector is added into each ton of ore pulp during secondary scavenging.
In this example, the grade of cassiterite in the table concentrate was 45.85% in terms of tin element, and the recovery rate of raw ore was 5.43%.
Wherein, the recovery rate of the raw ore is = (weight of the table concentrate x stannum grade calculated by tin element in the table concentrate)/(weight of the raw ore x stannum grade calculated by tin element in the raw ore) ×100%.
Example 2
The method for recovering low-grade fine-grain cassiterite based on the column-magnetic-bed combined process provided by the embodiment adopts mineral raw materials from underflow (including tin-containing materials) of a multi-metal ore thickener in some tin in Guizhou, and specifically comprises the following steps:
(1) And (5) placing the underflow ore pulp of the thickener into a stirring barrel to adjust the ore pulp to 33.50% by mass. In the tin-containing material, the proportion of particles with the granularity of less than 0.074mm is 96.50%, the proportion of particles with the granularity of less than 0.038mm is 69.85%, and the grade of the cassiterite is 0.25% based on tin element.
(2) Adding 1380g/t sodium silicate serving as gangue mineral inhibitor, 75g/t benzoic hydroxamic acid serving as cassiterite collector, 35g/t lead nitrate serving as activator and 20g/t pinitol oil serving as flotation foaming agent into 33.50% ore pulp obtained in the step (1), and performing primary flotation roughing through a cyclone-static microbubble flotation column to obtain cassiterite rough concentrate, wherein the circulating pressure of the cyclone-static microbubble flotation column is 0.20Mpa, the aeration amount is 2100L/h, and the thickness of a foam layer is 8cm.
(3) And (3) carrying out primary flotation concentration (circulation pressure, aeration quantity and foam layer thickness are the same as those in the step (2) of the embodiment) on the cassiterite rough concentrate obtained in the step (2) through a cyclone-static microbubble flotation column, so as to obtain the concentrate.
And removing magnetic minerals from the concentrate through magnetic separation, wherein the magnetic flux of the magnetic separator is 270MT, so as to obtain magnetic concentrate and magnetic tailings, and recovering the magnetic concentrate.
(4) And (3) reselecting the magnetic separation tailings obtained in the step (3) by using a shaking table to obtain shaking table concentrate, shaking table middlings and shaking table tailings, wherein the stroke of the shaking table is 10mm, the stroke frequency is 360r/min, the horizontal gradient of the surface of the shaking table is 2 degrees, the ore feeding concentration is 20 percent, and the shaking table concentrate is the final product, namely the high-grade cassiterite.
(5) And (3) carrying out twice scavenging on tailings obtained by primary flotation roughing in the step (1) through a cyclone-static microbubble flotation column, wherein the circulating pressure is 0.18Mpa, the aeration quantity is 2000L/h, the thickness of a foam layer is 6cm, flotation tailings are obtained, middlings obtained by twice scavenging are sequentially returned to superior flotation (namely middlings obtained by secondary scavenging are returned to a primary scavenging process, middlings obtained by primary scavenging are returned to a primary flotation roughing process), a flotation closed circuit is formed, 45g of a collecting agent is added into each ton of ore pulp during primary scavenging, and 20g of a collecting agent is added into each ton of ore pulp during secondary scavenging.
In this example, the grade of cassiterite in the table concentrate was 48.20% in terms of tin element, and the recovery rate of the raw ore was 6.77%.
Example 3
The method for recovering low-grade fine-grain cassiterite based on the column-magnetic-bed combined process provided by the embodiment adopts mineral raw materials from the underflow of a multi-metal ore thickener (comprising tin-containing materials) in Guizhou tin, and specifically comprises the following steps:
(1) And (5) placing the underflow ore pulp of the thickener into a stirring barrel to adjust the ore pulp to 34.71% by mass. In the tin-containing material, the proportion of particles with the granularity of less than 0.074mm is 96.80 percent, the proportion of particles with the granularity of less than 0.038mm is 74.50 percent, and the grade of the cassiterite is 0.27 percent calculated by tin element.
(2) Adding 1000g/t sodium silicate serving as a gangue mineral inhibitor, 50g/t benzoic hydroxamic acid serving as a cassiterite collector, 20g/t lead nitrate serving as an activator and 10g/t pinitol oil serving as a flotation foaming agent into the ore pulp with the mass fraction of 34.71% obtained in the step (1), and performing primary flotation roughing through a cyclone-static microbubble flotation column to obtain cassiterite rough concentrate, wherein the circulating pressure of the cyclone-static microbubble flotation column is 0.22Mpa, the aeration rate is 3000L/h, and the thickness of a foam layer is 15cm.
(3) And (3) carrying out primary flotation concentration (circulation pressure, aeration quantity and foam layer thickness are the same as those in the step (2) of the embodiment) on the cassiterite rough concentrate obtained in the step (2) through a cyclone-static microbubble flotation column, so as to obtain the concentrate.
And removing magnetic minerals from the concentrate through magnetic separation, wherein the magnetic flux of the magnetic separator is 280MT, so as to obtain magnetic concentrate and magnetic tailings, and recovering the magnetic concentrate.
(4) And (3) reselecting the magnetic separation tailings obtained in the step (3) by using a shaking table to obtain shaking table concentrate, shaking table middlings and shaking table tailings, wherein the stroke of the shaking table is 14mm, the stroke frequency is 400r/min, the transverse gradient of the surface of the shaking table is 3 degrees, the ore feeding concentration is 25 percent, and the shaking table concentrate is the final product, namely the high-grade cassiterite.
(5) And (3) carrying out twice scavenging on tailings obtained by primary flotation roughing in the step (1) through a cyclone-static microbubble flotation column, wherein the circulating pressure is 0.20Mpa, the aeration quantity is 2800L/h, the thickness of a foam layer is 13cm, flotation tailings are obtained, middlings obtained by twice scavenging are sequentially returned to the upper-level flotation (namely middlings obtained by secondary scavenging are returned to the primary scavenging process, middlings obtained by primary scavenging are returned to the primary flotation roughing process), a flotation closed circuit is formed, 50g of a collecting agent is added into each ton of ore pulp during the primary scavenging, and 25g of a collecting agent is added into each ton of ore pulp during the secondary scavenging.
In this example, the grade of cassiterite in the table concentrate was 47.28% as tin element and the recovery rate of raw ore was 6.15%.
Example 4
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this example is basically the same as that of example 3, except that in step (2), sodium silicate is replaced with equal mass of 1-aminopropyl phosphoric acid, lead nitrate is replaced with equal mass of carboxyamine, and pinitol oil is replaced with equal mass of ethereal alcohol oil.
In this example, the grade of cassiterite in the table concentrate was 46.29% in terms of tin element, and the recovery rate of raw ore was 6.03%.
Comparative example 1
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is basically the same as that of example 3, except that the cyclone-static microbubble flotation column is not used in step (2) but a conventional air-filled flotation machine is used.
In the comparative example, the grade of cassiterite in the table concentrate is 38.30% in terms of tin element, and the recovery rate of the raw ore is 2.15%.
Comparative example 2
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is basically the same as that of example 3, except that in step (2), the circulating pressure of the cyclone-static microbubble flotation column is replaced with 0.3Mpa, the aeration amount is replaced with 5000L/h, and the foam layer thickness is replaced with 20cm.
In this comparative example, the grade of cassiterite in the table concentrate was 35.64% in terms of tin element, and the recovery rate of raw ore was 2.68%.
Comparative example 3
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is basically the same as that of example 3, except that in step (2), the circulating pressure of the cyclone-static micro-bubble flotation column is replaced with 0.1Mpa, the aeration amount is replaced with 500L/h, and the thickness of the foam layer is replaced with 2cm.
In the comparative example, the grade of cassiterite in the table concentrate is 36.84% in terms of tin element, and the recovery rate of the raw ore is 2.98%.
Comparative example 4
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is basically the same as example 3, except that in step (1), the mass fraction of the pulp is replaced with 40%.
In the comparative example, the grade of cassiterite in the table concentrate is 32.18% calculated by tin element, and the recovery rate of the raw ore is 1.98%.
Comparative example 5
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is substantially the same as example 3, except that in step (2), the addition amounts of the respective reagents are replaced with: 800g/t sodium silicate as gangue mineral inhibitor, 30g/t benzoic hydroxamic acid as cassiterite collector, 10g/t lead nitrate as activator, and 5g/t pinitol oil.
In this comparative example, the grade of cassiterite in the table concentrate was 30.58% as tin element, and the recovery rate of raw ore was 1.23%.
Comparative example 6
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is substantially the same as example 3, except that in step (3), the magnetic flux is replaced with 350MT.
In this comparative example, the grade of cassiterite in the table concentrate was 30.12% in terms of tin element, and the recovery rate of raw ore was 1.69%.
Comparative example 7
The method for recovering low-grade fine-grained cassiterite based on the column-magnetic-bed combined process provided in this comparative example is basically the same as that of example 3, except that in step (4), the stroke of the cradle is replaced with 20mm, the stroke frequency is replaced with 500r/min, the lateral gradient of the cradle bed surface is replaced with 4 °, and the ore feeding concentration is replaced with 40%.
In this comparative example, the grade of cassiterite in the table concentrate was 29.69% in terms of tin element, and the recovery rate of raw ore was 1.36%.
As can be seen by comparing example 3 with comparative example 1, the use of a cyclone-static microbubble flotation column instead of the conventional aerated flotation can increase the recovery of low grade fine-grained cassiterite.
As can be seen from a comparison of example 3 and comparative examples 2-3, the grade and recovery of cassiterite can be further improved by using appropriate recycle pressure, aeration quantity and foam layer thickness.
As can be seen from a comparison of example 3 and comparative examples 4-7, the concentration of the raw ore slurry, the amount of the flotation reagent, the magnetic flux during the magnetic separation, and the parameters of the shaking table during the reselection all have a certain influence on the grade or recovery rate of cassiterite. The ore dressing parameters provided by the invention can improve the grade and recovery rate of cassiterite.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.

Claims (10)

1. A method for recovering low grade fine-grained cassiterite, comprising the steps of:
preparing tin-containing materials into ore pulp, adding gangue mineral inhibitor, cassiterite collector, activator and flotation foaming agent into the ore pulp, performing primary flotation roughing through a cyclone-static micro-bubble flotation column, controlling the circulating pressure to be 0.15-0.22 mpa, and obtaining cassiterite rough concentrate, wherein the aeration quantity is 1200-4000L/h and the thickness of a foam layer is 5-15 cm;
carrying out primary flotation and concentration on the cassiterite rough concentrate through the cyclone-static micro-bubble flotation column to obtain concentrated concentrate;
carrying out magnetic separation on the concentrate to obtain magnetic concentrate and magnetic tailings;
re-selecting the magnetic separation tailings to obtain a shaking table concentrate, namely the high-grade cassiterite;
wherein, in the tin-containing material, the proportion of particles with the granularity of less than 0.074mm is 95% -97%, and the proportion of particles with the granularity of less than 0.038mm is 65% -75%.
2. The method for recovering low-grade fine-grained cassiterite according to claim 1, characterized in that the grade of cassiterite in the tin-containing material is not more than 0.30% in terms of tin element.
3. The method for recovering low-grade fine-grained cassiterite according to claim 1, wherein the mass fraction of the ore pulp is 30% -35%.
4. The method for recovering low-grade fine-grained cassiterite according to claim 1, characterized by comprising at least one of the following features (1) to (8):
(1) The gangue mineral inhibitor comprises at least one of sodium silicate and 1-aminopropyl phosphoric acid;
(2) The mass of the gangue mineral inhibitor added into each ton of ore pulp is 1000-1500 g;
(3) The cassiterite collector comprises benzohydroxamic acid;
(4) The mass of the cassiterite collecting agent added into each ton of ore pulp is 50-100 g;
(5) The activator comprises at least one of lead nitrate and hydroxylamine;
(6) The mass of the activating agent added into each ton of ore pulp is 20-50 g;
(7) The flotation foaming agent comprises at least one of pine alcohol oil and ether alcohol oil;
(8) The mass of the flotation foaming agent added into each ton of ore pulp is 10-30 g.
5. The method for recovering low-grade fine-grained cassiterite according to claim 1, wherein the magnetic flux of the magnetic separator used for magnetic separation is 250-280 MT.
6. The method for recovering low-grade fine-grained cassiterite according to claim 1, characterized in that the magnetic concentrate is recovered.
7. The method for recycling low-grade fine-grained cassiterite according to claim 1, wherein the stroke of a shaking table used for reselection is 8-15 mm, the stroke frequency is 300-400 r/min, the transverse gradient is 1-3 degrees, and the ore feeding concentration is 15-25%.
8. The method for recycling low-grade fine-grained cassiterite according to claim 1, wherein tailings obtained by primary flotation roughing are subjected to twice scavenging to obtain flotation tailings, and middlings obtained by twice scavenging are sequentially returned to superior flotation to form a flotation closed circuit;
in each scavenging process, the mass of the collector added into each ton of ore pulp is 20-60 g.
9. The method of recovering low grade fine-grained cassiterite according to claim 1, characterized in that the cassiterite grade in the table concentrate is >45% based on tin element.
10. Use of the cassiterite obtained by the method for recovering low-grade fine-grained cassiterite according to any one of claims 1 to 9 for the production of tinplate, alloys, electroplated parts, dyes, enamels, porcelain and glass.
CN202410070281.1A 2024-01-18 2024-01-18 Method for recycling low-grade fine-grain cassiterite and application thereof Active CN117583116B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1110643A (en) * 1966-02-23 1968-04-24 Nathaniel Arbiter Benefication of cassiterite ores by froth flotation
CN101884951A (en) * 2010-06-23 2010-11-17 广西华锡集团股份有限公司车河选矿厂 Combined mineral dressing technology of fine grain and micro grain cassiterite
CN102489386A (en) * 2011-12-13 2012-06-13 广州有色金属研究院 Method for separating fine cassiterite
CN112237985A (en) * 2020-10-09 2021-01-19 昆明理工大学 Method for recovering cassiterite from tin-containing sulfide ore
WO2021073162A1 (en) * 2019-10-14 2021-04-22 广东省科学院资源综合利用研究所 Method for intensive recovery of valuable components from rare earth tailings
CN116422457A (en) * 2023-02-09 2023-07-14 广西华锡矿业有限公司铜坑矿业分公司 Method for recycling fine-grained cassiterite

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1110643A (en) * 1966-02-23 1968-04-24 Nathaniel Arbiter Benefication of cassiterite ores by froth flotation
CN101884951A (en) * 2010-06-23 2010-11-17 广西华锡集团股份有限公司车河选矿厂 Combined mineral dressing technology of fine grain and micro grain cassiterite
CN102489386A (en) * 2011-12-13 2012-06-13 广州有色金属研究院 Method for separating fine cassiterite
WO2021073162A1 (en) * 2019-10-14 2021-04-22 广东省科学院资源综合利用研究所 Method for intensive recovery of valuable components from rare earth tailings
CN112237985A (en) * 2020-10-09 2021-01-19 昆明理工大学 Method for recovering cassiterite from tin-containing sulfide ore
CN116422457A (en) * 2023-02-09 2023-07-14 广西华锡矿业有限公司铜坑矿业分公司 Method for recycling fine-grained cassiterite

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