A method for comprehensive recovery of copper, tungsten, tin and fluorite resources from copper-tin ore bodies

Abstract

The invention discloses a method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body, comprising the following steps: adopting a copper priority flotation process, then refloating the sulfide ore to avoid affecting subsequent operations, then magnetic separation to remove iron and desludging, then tungsten-tin flotation, tungsten-tin rough concentrate reselection, and finally fluorite flotation. After a series of reagent and process optimization tests were conducted in the laboratory of the invention, the open circuit test results were obtained as follows: the copper ore grade was 0.23%, the copper concentrate grade was 19.03%, and the recovery rate was 59.94%; the fluorite flotation feed grade was 30.91%, and the fluorite concentrate grade was 89.81%, and the recovery rate was 43.18%; the tungsten grade of the tungsten-tin flotation feed was 0.19%, and the tin grade was 0.56%, and the tungsten-tin mixed concentrate was 1.63%, the recovery rate was 49.81%, and the tin grade was 2.96%, and the recovery rate was 31.79%.

Description

Technical Field

[0001] The invention relates to the technical field of copper-tungsten-tin-fluorite recovery, and in particular to a method for comprehensively recovering copper-tungsten-tin-fluorite resources from a copper-tin ore body. Background Art

[0002] In addition to the main useful components Cu, Sn, WO3, and CaF2, the tin ore also contains associated components Zn, S, Ag, Pb, Mo, Bi, garnet, etc., and the ore is of high value. The main useful recoverable metal minerals are chalcopyrite, cassiterite, sphalerite, pyrite, etc.; the recoverable non-metallic minerals are mainly fluorite. The symbiotic relationship between the minerals in the ore samples of this test is complex, the embedded particle size is fine, and the ore dressing process is difficult. Therefore, it is urgent to solve the technical problems of copper, tin, tungsten, zinc, and fluorite recovery, and provide strong technical guarantees for the expansion and development of enterprises. In addition, the development and utilization exploration of copper-tin deposits can not only improve the comprehensive utilization of multi-metal resources, but also have a good driving effect on accelerating the development and utilization of similar minerals in China. Based on this, the present invention provides a method for comprehensive recovery of copper, tungsten, tin, and fluorite resources from copper-tin ore bodies. Summary of the invention

[0003] In view of the defects of the prior art, the purpose of the present invention is to provide a method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body, so as to solve the problems raised in the above background technology.

[0004] The present invention solves the technical problem by adopting the following technical solution:

[0005] The present invention provides a method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body, comprising the following steps:

[0006] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0007] Preferably, the preparation method of the modified sodium humate is:

[0008] Sodium humate is added into a chitosan solution of 2-3 times, and then phosphoric acid is added to adjust the pH value to 5.0, followed by adding 5-10% of the total amount of sodium humate modified nano silicon dioxide, and stirring evenly to obtain modified sodium humate.

[0009] Preferably, the mass fraction of the chitosan solution is 10-20%.

[0010] Preferably, the modification method of the modified nano-silica is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 2-5% of tetradecyltrimethylammonium bromide and 1-5% of strontium titanate based on the total amount of nano-silica, stirring thoroughly, and finally washing with water and drying to obtain modified nano-silica.

[0011] Preferably, the mass fraction of the sodium dodecyl sulfate solution is 5-10%.

[0012] Preferably, the preparation method of the nano-modified liquid is:

[0013] Nano magnesium oxide and nano bentonite are mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution which is 2-4 times the total amount of nano magnesium oxide, stirred evenly, and finally silane coupling agent KH560 which is 2-5% of the total amount of nano magnesium oxide is added, stirred sufficiently, and a nano modified liquid is obtained.

[0014] Preferably, the mass fraction of the hydrochloric acid solution is 10-15%.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] After a series of reagent and process optimization tests were conducted in the laboratory, the open circuit test results were obtained: the copper ore grade was 0.23%, the copper concentrate grade was 19.03%, and the recovery rate was 59.94%; the fluorite flotation feed grade was 30.91%, and the fluorite concentrate grade was 89.81%, and the recovery rate was 43.18%; the tungsten-tin flotation feed tungsten grade was 0.19%, and the tin grade was 0.56%, and the tungsten-tin mixed concentrate was 1.63% tungsten, and the recovery rate was 49.81%, and the tin grade was 2.96%, and the recovery rate was 31.79%. Key points and protection points:

[0017] The use of combined inhibitors ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid can well balance the grade and recovery rate of copper concentrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0019] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body of this embodiment comprises the following steps:

[0021] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0022] The preparation method of the modified sodium humate of this embodiment is:

[0023] Sodium humate is added into a chitosan solution of 2-3 times, and then phosphoric acid is added to adjust the pH value to 5.0, followed by adding 5-10% of the total amount of sodium humate modified nano silicon dioxide, and stirring evenly to obtain modified sodium humate.

[0024] The mass fraction of the chitosan solution in this embodiment is 10-20%.

[0025] The modification method of the modified nano-silica in this embodiment is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 2-5% of tetradecyltrimethylammonium bromide and 1-5% of strontium titanate to the total amount of nano-silica, stirring well, and finally washing and drying to obtain modified nano-silica.

[0026] The mass fraction of the sodium dodecyl sulfate solution in this embodiment is 5-10%.

[0027] The preparation method of the nano-modified liquid of this embodiment is:

[0028] Nano magnesium oxide and nano bentonite are mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution which is 2-4 times the total amount of nano magnesium oxide, stirred evenly, and finally silane coupling agent KH560 which is 2-5% of the total amount of nano magnesium oxide is added, stirred sufficiently, and a nano modified liquid is obtained.

[0029] The mass fraction of the hydrochloric acid solution in this embodiment is 10-15%.

[0030] Embodiment 1:

[0031] A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body of this embodiment comprises the following steps:

[0032] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0033] The preparation method of the modified sodium humate of this embodiment is:

[0034] Sodium humate was added into a chitosan solution of 2 times, and then phosphoric acid was added to adjust the pH value to 5.0, and then 5% of the total amount of sodium humate was added with modified nano-silicon dioxide, and the mixture was stirred evenly to obtain modified sodium humate.

[0035] The mass fraction of the chitosan solution in this embodiment is 1%.

[0036] The modification method of the modified nano-silica in this embodiment is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 2% of tetradecyltrimethylammonium bromide and 1% of strontium titanate based on the total amount of nano-silica, stirring thoroughly, and finally washing with water and drying to obtain modified nano-silica.

[0037] The mass fraction of the sodium dodecyl sulfate solution in this embodiment is 5%.

[0038] The preparation method of the nano-modified liquid of this embodiment is:

[0039] Nano magnesium oxide and nano bentonite were mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution twice the total amount of nano magnesium oxide, stirred evenly, and finally added silane coupling agent KH560 at 2% of the total amount of nano magnesium oxide, stirred sufficiently, and a nano modified liquid was obtained.

[0040] The mass fraction of the hydrochloric acid solution in this embodiment is 10%.

[0041] Embodiment 2:

[0042] A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body of this embodiment comprises the following steps:

[0043] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0044] The preparation method of the modified sodium humate of this embodiment is:

[0045] Sodium humate was added into a chitosan solution of 3 times, and then phosphoric acid was added to adjust the pH value to 5.0, and then 10% of the total amount of sodium humate was added with modified nano-silicon dioxide, and the mixture was stirred evenly to obtain modified sodium humate.

[0046] The mass fraction of the chitosan solution in this embodiment is 20%.

[0047] The modification method of the modified nano-silica in this embodiment is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 5% of tetradecyltrimethylammonium bromide and 5% of strontium titanate based on the total amount of nano-silica, stirring thoroughly, and finally washing and drying to obtain modified nano-silica.

[0048] The mass fraction of the sodium dodecyl sulfate solution in this embodiment is 10%.

[0049] The preparation method of the nano-modified liquid of this embodiment is:

[0050] Nano magnesium oxide and nano bentonite were mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution 4 times the total amount of nano magnesium oxide, stirred evenly, and finally added silane coupling agent KH560 5% of the total amount of nano magnesium oxide, stirred sufficiently, and obtained a nano modified liquid.

[0051] The mass fraction of the hydrochloric acid solution in this embodiment is 15%.

[0052] Embodiment 3:

[0053] A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body of this embodiment comprises the following steps:

[0054] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0055] The preparation method of the modified sodium humate of this embodiment is:

[0056] Sodium humate was added into a 2.5 times chitosan solution, and then phosphoric acid was added to adjust the pH value to 5.0, and then 7.5% of the total amount of sodium humate was added with modified nano-silicon dioxide, and the mixture was stirred evenly to obtain modified sodium humate.

[0057] The mass fraction of the chitosan solution in this embodiment is 15%.

[0058] The modification method of the modified nano-silica in this embodiment is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 3.5% of tetradecyltrimethylammonium bromide and 3% of strontium titanate to the total amount of nano-silica, stirring well, and finally washing and drying to obtain modified nano-silica.

[0059] The mass fraction of the sodium dodecyl sulfate solution in this embodiment is 7.5%.

[0060] The preparation method of the nano-modified liquid of this embodiment is:

[0061] Nano magnesium oxide and nano bentonite were mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution 3 times the total amount of nano magnesium oxide, stirred evenly, and finally added silane coupling agent KH560 3.5% of the total amount of nano magnesium oxide, stirred sufficiently, and obtained a nano modified liquid.

[0062] The mass fraction of the hydrochloric acid solution in this embodiment is 12%.

[0063] Embodiment 4:

[0064] A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body of this embodiment comprises the following steps:

[0065] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0066] The preparation method of the modified sodium humate of this embodiment is:

[0067] Sodium humate was added into a chitosan solution of 2 times, and then phosphoric acid was added to adjust the pH value to 5.0, and then 6% of the total amount of sodium humate was added with modified nano-silicon dioxide, and the mixture was stirred evenly to obtain modified sodium humate.

[0068] The mass fraction of the chitosan solution in this embodiment is 12%.

[0069] The modification method of the modified nano-silica in this embodiment is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 3% of tetradecyltrimethylammonium bromide and 2% of strontium titanate to the total amount of nano-silica, stirring well, and finally washing and drying to obtain modified nano-silica.

[0070] The mass fraction of the sodium dodecyl sulfate solution in this embodiment is 6%.

[0071] The preparation method of the nano-modified liquid of this embodiment is:

[0072] Nano magnesium oxide and nano bentonite were mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution 3 times the total amount of nano magnesium oxide, stirred evenly, and finally added 3% of the total amount of nano magnesium oxide silane coupling agent KH560, stirred sufficiently, to obtain a nano modified liquid.

[0073] The mass fraction of the hydrochloric acid solution in this embodiment is 12%.

[0074] Embodiment 5:

[0075] A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body of this embodiment comprises the following steps:

[0076] A copper priority flotation process was adopted, and then the sulfide ore was floated again to avoid affecting subsequent operations. Magnetic separation was used to remove iron and desludging, and tungsten-tin flotation was carried out. The tungsten-tin rough concentrate was re-selected, and finally fluorite flotation was carried out. The final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation for iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate re-selection-fluorite flotation", in which a combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in flotation.

[0077] The preparation method of the modified sodium humate of this embodiment is:

[0078] Sodium humate was added into a chitosan solution of 3 times, and then phosphoric acid was added to adjust the pH value to 5.0, and then 8% of the total amount of sodium humate was added with modified nano-silicon dioxide, and the mixture was stirred evenly to obtain modified sodium humate.

[0079] The mass fraction of the chitosan solution in this embodiment is 18%.

[0080] The modification method of the modified nano-silica in this embodiment is: adding nano-silica to sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 4% of tetradecyltrimethylammonium bromide and 4% of strontium titanate to the total amount of nano-silica, stirring well, and finally washing and drying to obtain modified nano-silica.

[0081] The mass fraction of the sodium dodecyl sulfate solution in this embodiment is 9%.

[0082] The preparation method of the nano-modified liquid of this embodiment is:

[0083] Nano magnesium oxide and nano bentonite were mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution 3 times the total amount of nano magnesium oxide, stirred evenly, and finally added silane coupling agent KH560 4% of the total amount of nano magnesium oxide, stirred sufficiently, and obtained a nano modified liquid.

[0084] The mass fraction of the hydrochloric acid solution in this embodiment is 14%.

[0085] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0086] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for comprehensively recovering copper, tungsten, tin and fluorite resources from a copper-tin ore body, characterized in that: The following steps are involved: The copper priority flotation process was adopted, and then the sulfide ore was re-floated to avoid affecting the subsequent operations, and then the magnetic separation was used to remove iron and desludging, and then tungsten-tin flotation, tungsten-tin rough concentrate gravity selection, and finally fluorite flotation; the final experimental process was determined to be "copper priority flotation-sulfur flotation-magnetic separation iron removal-cyclone desludging-tungsten-tin mixed flotation, tungsten-tin rough concentrate gravity selection-fluorite flotation", in which the combined depressant ZnSO4+Na2SO3+modified sodium humate and nano-modified liquid were used in the flotation; The preparation method of the modified sodium humate is: The sodium humate is added into a chitosan solution of 2-3 times, and then phosphoric acid is added to adjust the pH value to 5.0, and then 5-10% of the total amount of the sodium humate is added with modified nano-silicon dioxide, and the mixture is stirred evenly to obtain modified sodium humate; The mass fraction of the chitosan solution is 10-20%; The modification method of the modified nano-silicon dioxide is as follows: adding the nano-silicon dioxide to a sodium dodecyl sulfate solution at a weight ratio of 1:5, then adding 2-5% of tetradecyl trimethyl ammonium bromide and 1-5% of strontium titanate based on the total amount of the nano-silicon dioxide, stirring sufficiently, and finally washing with water and drying to obtain the modified nano-silicon dioxide; The mass fraction of the sodium dodecyl sulfate solution is 5-10%.

2. The method for comprehensive recovery of copper, tungsten, tin and fluorite resources from a copper-tin ore body according to claim 1, characterized in that: The preparation method of the nano modified liquid is: Nano magnesium oxide and nano bentonite are mixed in a weight ratio of 4:1, then added into a hydrochloric acid solution which is 2-4 times the total amount of nano magnesium oxide, stirred evenly, and finally silane coupling agent KH560 which is 2-5% of the total amount of nano magnesium oxide is added, stirred sufficiently, and a nano modified liquid is obtained.

3. The method for comprehensive recovery of copper, tungsten, tin and fluorite resources from a copper-tin ore body according to claim 2, characterized in that: The mass fraction of the hydrochloric acid solution is 10-15%.

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