Efficient recovery process for valuable metal in metallurgical solid waste

Abstract

The invention relates to the technical field of solid waste recovery, in particular to a high-efficiency recovery process for valuable metals in metallurgical solid waste, which comprises the following steps: grinding and crushing the metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium to obtain solid waste residues, then adding a binder into the waste residues, uniformly mixing, and compressing into a ball to obtain waste residue pellets; the waste residue pellets are subjected to drying and acid leaching-oxidation treatment, the porosity of the dried waste residue pellets can be improved, and the contact area between the dried waste residue pellets and acid liquor and an oxidizing agent is increased; the synergistic effect of acid leaching and oxidation reaction can improve the leaching rate of valuable metals and improve the recovery efficiency of the valuable metals, in addition, the synergistic leaching technology can achieve a higher leaching effect in a shorter time, and is matched with common chemical extraction methods such as replacement reaction and the like, efficient recovery of organic metals in metallurgical solid wastes can be achieved, and the recovery rate of the organic metals in the metallurgical solid wastes is improved. The recovery rate of zinc, iron, nickel, silver, copper, tin and indium is greater than 99%, and the energy consumption and the cost are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of solid waste recovery, and in particular to a highly efficient recovery process for valuable metals in metallurgical solid waste. Background Art

[0002] Metallurgical solid waste, as waste generated during the smelting process of ore, mainly includes slag, slag, dust, etc. These wastes contain rich valuable metal resources, such as zinc, iron, nickel, silver, copper, tin, indium, etc. With the rapid development of industrialization, the consumption of metal resources has increased sharply, resulting in a growing shortage of metal resources. Therefore, it is particularly important to recover valuable metals from metallurgical solid waste.

[0003] The recovery technology of valuable metals in metallurgical solid waste mainly includes physical treatment, chemical treatment and biological treatment, but the organic metal recovery rate in the existing technology is low and the cost is high. In view of this, we propose an efficient recovery process for valuable metals in metallurgical solid waste. Summary of the invention

[0004] The object of the present invention is to provide a highly efficient process for recovering valuable metals from metallurgical solid wastes, so as to solve the problems raised in the above-mentioned background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A highly efficient process for recovering valuable metals from metallurgical solid wastes, comprising the following steps:

[0007] Step 1, grinding and crushing metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium to obtain solid waste slag;

[0008] Step 2, adding a binder to the waste residue, mixing evenly, and compressing the waste residue into a mass to obtain a waste residue pellet, and drying the waste residue pellet;

[0009] Step 3, transferring the waste residue pellets dried in step 2 to the acid leaching solution, heating and stirring to fully mix the waste residue pellets with the acid leaching solution;

[0010] Step 4, adding an oxidant to the acid leaching solution of step 3, continuing heating and stirring to fully mix the waste slag pellets with the oxidant and the acid leaching solution, filtering and collecting the filtrate after the reaction is completed;

[0011] Step 5, adding a chlorine-containing solution to the filtrate in step 4, filtering after the reaction is complete, and recovering the silver chloride precipitate;

[0012] Step 6, adding alkali solution to the filtrate in step 5, adjusting the pH to 4.5-5.5, and filtering and recovering the iron hydroxide precipitate;

[0013] Step 7: Recover indium, copper, tin and nickel in sequence through replacement reaction of the filtrate in step 6 to obtain a zinc-containing solution.

[0014] Preferably, in step 1, the grinding and crushing includes any one of ball milling, vibration milling, air flow milling and sand milling, and the particle size of the obtained solid waste residue is less than 100 μm.

[0015] Preferably, in step 2, the binder is a suspension composed of an inorganic binder and an organic binder, the mass percentage of the inorganic binder to the organic binder is 10% to 30%, the mass ratio of the inorganic binder to the organic binder is 1 to 2:1, the inorganic binder includes any one of bentonite, clay, and sodium silicate, the organic binder includes any one of tar, humic acid, starch, and lignin, and the amount of the binder added is 5% to 15% of the mass of the waste residue.

[0016] Preferably, in step 2, the drying temperature of the waste slag pellets is 80° C. to 120° C., and the drying time is 6 to 10 hours.

[0017] Preferably, in step 3, the acid leaching solution is an aqueous solution of any one of hydrochloric acid, nitric acid and sulfuric acid, the concentration of the acid leaching solution is 2 to 8 mol / L, the ratio of waste slag pellets to the acid leaching solution is 1 g: 10 to 30 mL, the heating temperature is 40°C to 60°C, and the stirring time is 2 to 5 hours.

[0018] Preferably, in step 4, the oxidant is hydrogen peroxide, the amount of the oxidant added is 5% to 10% of the volume of the acid leaching solution, the heating temperature is 40° C. to 60° C., and the stirring time is 2 to 5 hours.

[0019] Preferably, in step 5, the chlorine-containing solution is any one of sodium chloride, potassium chloride and ammonium chloride, the concentration of the chlorine-containing solution is 2 to 4 mol / L, and the volume ratio of the added amount of the chlorine-containing solution to the filtrate is 1 to 5:1.

[0020] Preferably, in step 6, the alkali solution is sodium hydroxide or potassium hydroxide, and the concentration of the alkali solution is 1 to 4 mol / L.

[0021] Preferably, in step 7, the replacement reaction comprises the following steps:

[0022] Step 71, adding metallic copper powder to the filtrate in step 6, stirring thoroughly until no more precipitation is produced, and filtering to recover metallic indium;

[0023] Step 72, adding metallic tin powder to the filtrate obtained by filtering in step 71, stirring sufficiently until no precipitation is generated, and filtering to recover metallic copper;

[0024] Step 73, adding metallic nickel powder to the filtrate obtained by filtering in step 72, stirring sufficiently until no precipitation is produced, and filtering to recover metallic tin;

[0025] Step 74, adding metallic zinc powder to the filtrate obtained by filtration in step 73, stirring thoroughly until no more precipitation is produced, filtering to recover metallic tin, and obtaining a zinc-containing solution.

[0026] Preferably, the particle sizes of the metal copper powder, tin powder, nickel powder and zinc powder are all less than 10 μm.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The efficient recovery process of valuable metals in metallurgical solid waste comprises the following steps: grinding and crushing metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium to obtain solid waste slag, then adding a binder to the slag and mixing them evenly, compressing them into agglomerates to obtain slag pellets, and drying and acid leaching-oxidation treatment the slag pellets. The dried slag pellets can increase their porosity and increase their contact area with acid solution and oxidant; the synergistic effect of acid leaching and oxidation reaction can increase the leaching rate of valuable metals and improve their recovery efficiency. In addition, the synergistic leaching technology can achieve a higher leaching effect in a shorter time, and can achieve efficient recovery of organic metals in metallurgical solid waste in combination with common chemical extraction methods such as replacement reaction. The recovery rate of zinc, iron, nickel, silver, copper, tin and indium is greater than 99%, and energy consumption and cost are reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The present invention is a flow chart of a process for efficiently recovering valuable metals from metallurgical solid waste. DETAILED DESCRIPTION

[0030] 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.

[0031] Example 1

[0032] A highly efficient process for recovering valuable metals from metallurgical solid wastes, comprising the following steps:

[0033] Step 1: Grinding and crushing metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium by ball milling to obtain solid waste residue, wherein the particle size of the obtained solid waste residue is less than 100 μm;

[0034] Step 2, adding a binder to the waste residue and mixing evenly, the binder is a suspension composed of an inorganic binder and an organic binder, the mass percentage of the inorganic binder to the organic binder is 10%, the mass ratio of the inorganic binder to the organic binder is 1:1, the inorganic binder is bentonite, the organic binder is tar, the amount of the binder added is 15% of the mass of the waste residue, and using an extruder to compress it into a mass to obtain a waste residue pellet, and the waste residue pellet is dried, the drying temperature of the waste residue pellet is 80°C, and the drying time is 10 hours;

[0035] Step 3, transfer the dried waste pellets in step 2 to the acid leaching solution, heat and stir to fully mix the waste pellets with the acid leaching solution, the acid leaching solution is an aqueous solution of hydrochloric acid, the concentration of hydrochloric acid is 2 mol / L, the ratio of waste pellets to acid leaching solution is 1 g: 10 mL, the heating temperature is 40 ° C, and the stirring time is 5 hours;

[0036] Step 4, adding hydrogen peroxide as an oxidant to the acid leaching solution of step 3, the amount of the oxidant added is 5% of the volume of the acid leaching solution, and continuing to heat and stir to fully mix the waste slag pellets with the oxidant and the acid leaching solution, the heating temperature is 40°C, the stirring time is 5 hours, and after the reaction is completed, filtering and collecting the filtrate;

[0037] Step 5, adding a 2 mol / L sodium chloride solution to the filtrate in step 4, wherein the volume ratio of the sodium chloride solution to the filtrate is 5:1, filtering after the reaction is complete, and recovering the silver chloride precipitate;

[0038] Step 6, adding sodium hydroxide solution to the filtrate in step 5, wherein the concentration of the sodium hydroxide solution is 1 mol / L, adjusting the pH to 4.5, and filtering and recovering the ferric hydroxide precipitate;

[0039] Step 7: Recover indium, copper, tin and nickel in sequence from the filtrate in step 6 through a replacement reaction to obtain a zinc-containing solution. The replacement reaction comprises the following steps:

[0040] Step 71, adding metallic copper powder to the filtrate in step 6, stirring thoroughly until no more precipitation is produced, and filtering to recover metallic indium;

[0041] Step 72, adding metallic tin powder to the filtrate obtained by filtering in step 71, stirring sufficiently until no precipitation is generated, and filtering to recover metallic copper;

[0042] Step 73, adding metallic nickel powder to the filtrate obtained by filtering in step 72, stirring sufficiently until no precipitation is produced, and filtering to recover metallic tin;

[0043] Step 74, adding metallic zinc powder to the filtrate obtained by filtration in step 73, stirring thoroughly until no more precipitation is produced, filtering to recover metallic tin, and obtaining a zinc-containing solution.

[0044] In steps 71 to 74, the particle sizes of the metal copper powder, tin powder, nickel powder and zinc powder are all less than 10 μm.

[0045] Example 2

[0046] A highly efficient process for recovering valuable metals from metallurgical solid wastes, comprising the following steps:

[0047] Step 1: Grinding and crushing metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium by a vibration mill to obtain solid waste residue, wherein the particle size of the obtained solid waste residue is less than 100 μm;

[0048] Step 2, adding a binder to the waste residue and mixing evenly, the binder is a suspension composed of an inorganic binder and an organic binder, the mass percentage of the inorganic binder to the organic binder is 20%, the mass ratio of the inorganic binder to the organic binder is 1.5:1, the inorganic binder is clay, the organic binder is humic acid, the amount of the binder added is 10% of the mass of the waste residue, and using an extruder to compress it into a mass to obtain a waste residue pellet, and the waste residue pellet is dried, the drying temperature of the waste residue pellet is 100°C, and the drying time is 8 hours;

[0049] Step 3, transfer the dried waste slag pellets in step 2 to the acid leaching solution, heat and stir to fully mix the waste slag pellets and the acid leaching solution, the acid leaching solution is an aqueous solution of nitric acid, the concentration of the acid leaching solution is 5 mol / L, the ratio of the waste slag pellets to the acid leaching solution is 1 g: 20 mL, the heating temperature is 50 ° C, and the stirring time is 4 hours;

[0050] Step 4, adding hydrogen peroxide as an oxidant to the acid leaching solution of step 3, the amount of the oxidant added is 8% of the volume of the acid leaching solution, and continuing to heat and stir to fully mix the waste slag pellets with the oxidant and the acid leaching solution, the heating temperature is 50°C, the stirring time is 4 hours, and after the reaction is completed, filtering and collecting the filtrate;

[0051] Step 5, adding a 3 mol / L potassium chloride solution to the filtrate in step 4, wherein the volume ratio of the potassium chloride solution to the filtrate is 3:1, filtering after the reaction is complete, and recovering the silver chloride precipitate;

[0052] Step 6, adding sodium hydroxide solution to the filtrate in step 5, wherein the concentration of the sodium hydroxide solution is 2 mol / L, adjusting the pH to 5, and filtering and recovering the ferric hydroxide precipitate;

[0053] Step 7: Recover indium, copper, tin and nickel in sequence from the filtrate in step 6 through a replacement reaction to obtain a zinc-containing solution. The replacement reaction comprises the following steps:

[0054] Step 71, adding metallic copper powder to the filtrate in step 6, stirring thoroughly until no more precipitation is produced, and filtering to recover metallic indium;

[0055] Step 72, adding metallic tin powder to the filtrate obtained by filtering in step 71, stirring sufficiently until no precipitation is generated, and filtering to recover metallic copper;

[0056] Step 73, adding metallic nickel powder to the filtrate obtained by filtering in step 72, stirring sufficiently until no precipitation is produced, and filtering to recover metallic tin;

[0057] Step 74, adding metallic zinc powder to the filtrate obtained by filtration in step 73, stirring thoroughly until no more precipitation is produced, filtering to recover metallic tin, and obtaining a zinc-containing solution.

[0058] In steps 71 to 74, the particle sizes of the metal copper powder, tin powder, nickel powder and zinc powder are all less than 10 μm.

[0059] Example 3

[0060] A highly efficient process for recovering valuable metals from metallurgical solid wastes, comprising the following steps:

[0061] Step 1: Grinding and crushing metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium by sand milling to obtain solid waste residue, wherein the particle size of the obtained solid waste residue is less than 100 μm;

[0062] Step 2, adding a binder to the waste residue and mixing evenly, the binder is a suspension composed of an inorganic binder and an organic binder, the mass percentage of the inorganic binder to the organic binder is 30%, the mass ratio of the inorganic binder to the organic binder is 2:1, the inorganic binder is sodium silicate, the organic binder is lignin, the amount of the binder added is 5% of the mass of the waste residue, and using an extruder to compress it into a mass to obtain a waste residue pellet, and the waste residue pellet is dried, the drying temperature of the waste residue pellet is 120°C, and the drying time is 6 hours;

[0063] Step 3, transfer the dried waste pellets in step 2 to the acid leaching solution, heat and stir to fully mix the waste pellets with the acid leaching solution, the acid leaching solution is an aqueous solution of sulfuric acid, the concentration of the acid leaching solution is 8 mol / L, the ratio of the waste pellets to the acid leaching solution is 1 g: 30 mL, the heating temperature is 60 ° C, and the stirring time is 2 hours;

[0064] Step 4, adding hydrogen peroxide as an oxidant to the acid leaching solution of step 3, the amount of the oxidant added is 10% of the volume of the acid leaching solution, and continuing to heat and stir to fully mix the waste slag pellets with the oxidant and the acid leaching solution, the heating temperature is 60°C, the stirring time is 2 hours, and after the reaction is completed, filtering and collecting the filtrate;

[0065] Step 5, adding a 4 mol / L ammonium chloride solution to the filtrate in step 4, wherein the volume ratio of the ammonium chloride solution to the filtrate is 1:1, filtering after the reaction is complete, and recovering the silver chloride precipitate;

[0066] Step 6, adding potassium hydroxide solution to the filtrate in step 5, wherein the concentration of the potassium hydroxide solution is 4 mol / L, adjusting the pH to 5.5, and filtering and recovering the ferric hydroxide precipitate;

[0067] Step 7: Recover indium, copper, tin and nickel in sequence from the filtrate in step 6 through a replacement reaction to obtain a zinc-containing solution. The replacement reaction comprises the following steps:

[0068] Step 71, adding metallic copper powder to the filtrate in step 6, stirring thoroughly until no more precipitation is produced, and filtering to recover metallic indium;

[0069] Step 72, adding metallic tin powder to the filtrate obtained by filtering in step 71, stirring sufficiently until no precipitation is generated, and filtering to recover metallic copper;

[0070] Step 73, adding metallic nickel powder to the filtrate obtained by filtering in step 72, stirring sufficiently until no precipitation is produced, and filtering to recover metallic tin;

[0071] Step 74, adding metallic zinc powder to the filtrate obtained by filtration in step 73, stirring thoroughly until no more precipitation is produced, filtering to recover metallic tin, and obtaining a zinc-containing solution.

[0072] In steps 71 to 74, the particle sizes of the metal copper powder, tin powder, nickel powder and zinc powder are all less than 10 μm.

[0073] In the above embodiments 1 to 3, metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium is ground and crushed to obtain solid waste slag, and then a binder is added to the slag to mix evenly, and it is compressed into a mass to obtain slag pellets, and the slag pellets are dried and acid-leached-oxidized. The dried slag pellets can increase their porosity and increase their contact area with the acid solution and the oxidant; the synergistic effect of acid leaching and oxidation reaction can increase the leaching rate of valuable metals and improve their recovery efficiency. In addition, the synergistic leaching technology can achieve a higher leaching effect in a shorter time, and can achieve efficient recovery of organic metals in metallurgical solid waste in combination with common chemical extraction methods such as replacement reaction. The recovery rate of zinc, iron, nickel, silver, copper, tin and indium is greater than 99%, and energy consumption and cost are reduced.

[0074] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions are only preferred examples of the present invention and are not intended to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A highly efficient process for recovering valuable metals from metallurgical solid waste, characterized in that: The following steps are involved: Step 1, grinding and crushing metallurgical solid waste containing zinc, iron, nickel, silver, copper, tin and indium to obtain solid waste slag; Step 2, adding a binder to the waste residue, mixing evenly, and compressing the waste residue into a mass to obtain a waste residue pellet, and drying the waste residue pellet; Step 3, transferring the waste residue pellets dried in step 2 to the acid leaching solution, heating and stirring to fully mix the waste residue pellets with the acid leaching solution; Step 4, adding an oxidant to the acid leaching solution of step 3, continuing heating and stirring to fully mix the waste slag pellets with the oxidant and the acid leaching solution, filtering and collecting the filtrate after the reaction is completed; Step 5, adding a chlorine-containing solution to the filtrate in step 4, filtering after the reaction is complete, and recovering the silver chloride precipitate; Step 6, adding alkali solution to the filtrate in step 5, adjusting the pH to 4.5-5.5, and filtering and recovering the iron hydroxide precipitate; Step 7: Recover indium, copper, tin and nickel in sequence through replacement reaction of the filtrate in step 6 to obtain a zinc-containing solution.

2. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In the step 1, the grinding and crushing includes any one of ball milling, vibration milling, air flow milling and sand milling, and the particle size of the obtained solid waste residue is less than 100 μm.

3. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In the step 2, the binder is a suspension composed of an inorganic binder and an organic binder, the mass percentage of the inorganic binder to the organic binder is 10% to 30%, the mass ratio of the inorganic binder to the organic binder is 1 to 2:1, the inorganic binder includes any one of bentonite, clay, and sodium silicate, the organic binder includes any one of tar, humic acid, starch, and lignin, and the amount of the binder added is 5% to 15% of the mass of the waste residue.

4. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In the step 2, the drying temperature of the waste slag pellets is 80° C. to 120° C., and the drying time is 6 to 10 hours.

5. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In step 3, the acid leaching solution is an aqueous solution of any one of hydrochloric acid, nitric acid and sulfuric acid, the concentration of the acid leaching solution is 2 to 8 mol / L, the ratio of waste slag pellets to the acid leaching solution is 1 g: 10 to 30 mL, the heating temperature is 40° C. to 60° C., and the stirring time is 2 to 5 hours.

6. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In step 4, the oxidant is hydrogen peroxide, the amount of the oxidant added is 5% to 10% of the volume of the acid leaching solution, the heating temperature is 40° C. to 60° C., and the stirring time is 2 to 5 hours.

7. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In step 5, the chlorine-containing solution is any one of sodium chloride, potassium chloride, and ammonium chloride, the concentration of the chlorine-containing solution is 2 to 4 mol / L, and the volume ratio of the added amount of the chlorine-containing solution to the filtrate is 1 to 5:

1.

8. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In step 6, the alkali solution is sodium hydroxide or potassium hydroxide, and the concentration of the alkali solution is 1 to 4 mol / L.

9. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 1, characterized in that: In step 7, the replacement reaction comprises the following steps: Step 71, adding metallic copper powder to the filtrate in step 6, stirring thoroughly until no more precipitation is produced, and filtering to recover metallic indium; Step 72, adding metallic tin powder to the filtrate obtained by filtering in step 71, stirring sufficiently until no precipitation is generated, and filtering to recover metallic copper; Step 73, adding metallic nickel powder to the filtrate obtained by filtering in step 72, stirring sufficiently until no precipitation is generated, and filtering to recover metallic tin; Step 74, adding metallic zinc powder to the filtrate obtained by filtration in step 73, stirring thoroughly until no more precipitation is produced, filtering to recover metallic tin, and obtaining a zinc-containing solution.

10. The efficient recovery process of valuable metals in metallurgical solid waste according to claim 9, characterized in that: The particle sizes of the metal copper powder, tin powder, nickel powder and zinc powder are all less than 10 μm.

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