TWI432584B - A method for extracting metal from manganese residue - Google Patents

Description

Method for extracting valuable metals from manganese slag

The invention relates to a method for extracting valuable metals from waste residue, in particular to a method for extracting valuable metals from manganese residues by using titanium white waste acid supplemented with vanadium containing steel slag.

Various types of process wastes are often produced in various fields of industry. Most of the wastes need to be disposed of properly to reduce the environmental damage caused by emissions or accumulation, so as to implement the principle of parallel development of industrial development and environmental protection.

At present, most of the industrial process wastes are mainly metal residues or waste acid liquids, such as a large amount of manganese slag and vanadium-containing steel slag remaining in the steel refining, chemical industry or light industry processes, and even titanium production in the titanium white production industry. Titanium white waste acid derived from white powder is a thorny issue in the current industrial environmental protection and disposal.

In short, after the manganese ore smelting or ferromanganese process, a large amount of waste residue is easily produced, and the waste residue contains metals such as barium, aluminum, calcium and manganese, and the content of manganese may be as much as 10 to 20%. The waste residue is manganese slag. In addition, vanadium-containing steel slag is produced from the vanadium-containing molten iron metallurgy process. The vanadium-containing steel slag contains complex components, among which calcium and iron are mostly present, and vanadium and manganese are second. As described above, the valuable metals such as manganese, iron and vanadium in the manganese slag and the vanadium-containing steel slag have the value of recovery and extraction for reuse. Therefore, the manganese acid is extracted from the manganese slag by the method of sulfuric acid leaching. However, the cost is often caused by the high price of sulfuric acid, and the use of energy must be relatively increased in response to complicated processes. Moreover, since the vanadium-containing steel slag is rich in a large amount of calcium, most of the methods for treating the vanadium-containing steel slag cause a large loss of manganese, vanadium and iron in the extraction process due to the influence of calcium, and instead derive the valuable metal extraction. Inefficiency and other issues.

In addition, the titanium white manufacturing industry produces up to 4 tons of titanium white waste acid in the process of producing per ton of titanium dioxide by the sulfuric acid process. A large amount of waste acid emissions is undoubtedly a major concern for the environment, even if it is high. The monovalent calcium carbonate reacts with the sulfate-rich titanium white waste acid to form calcium sulfate as a chemical fertilizer and reduce the direct discharge of waste acid. However, the treatment of traditional titanium white waste acid tends to have high cost of treatment, low product price, and unstable pH due to sulfate, which is not only cumbersome but also inconsistent with the industrial economy.

In view of this, it is indeed necessary to develop a method for easily recovering and extracting valuable metals from manganese slag and vanadium-containing steel slag to solve various problems as described above, and to impregnate manganese slag with titanium white waste acid, and supplemented with vanadium The steel slag regulates the pH therein, and the valuable metals are smoothly recovered.

The main object of the present invention is to improve the above disadvantages to provide a method for extracting valuable metals from manganese slag, which is capable of reducing the cost of separately treating titanium white waste acid, vanadium containing steel slag or manganese slag, thereby simultaneously increasing the price of waste slag. The efficiency of metal recycling.

The second object of the present invention is to provide a method for extracting valuable metals from manganese slag, which can reduce the environmental pollution of metal residues and waste acid liquid, and improve the effect of environmental protection.

In order to achieve the foregoing object, the method for extracting valuable metals from a manganese slag of the present invention comprises: an acid leaching step of immersing the manganese slag in the titanium white waste acid, and in the titanium white waste acid mixed with the manganese slag Further adding vanadium containing steel slag to form an acid leaching mixture, and adjusting the pH value of the acid leaching mixture by the vanadium containing steel slag to react the acid leaching mixture to form calcium sulphate; Calcium sulphate in the mixed solution to obtain a first leaching solution, adjusting the pH of the first leaching solution to the trivalent iron in the first leaching solution to filter out the ferric iron and a second leaching solution; and an extraction step Adding an oxidant to the second leachate, and adjusting the pH of the second leachate to the valuable metal in the second leachate to filter out a solid precipitate, the solid precipitate is rich in manganese Valuable metals such as vanadium or iron.

Among them, every 100 grams of manganese slag is immersed in 3000 to 12000 grams of titanium white waste acid, and 500 to 3000 grams of vanadium containing steel slag is added thereto. Moreover, in the acid leaching step, the pH of the acid immersion mixture is less than 1, and the reaction is continued at a temperature of 90 to 95 ° C for 1 to 5 hours. In the initial sedimentation step, the pH of the first leachate is 1-3, and the operating temperature is 90-95 °C.

The oxidizing agent added in the extraction step is oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide.

In the extraction step, the present invention operates a vanadium precipitation step, a iron precipitation step and a manganese precipitation step to sequentially extract vanadium, iron and manganese metal from the second leachate.

In detail, the step of depositing vanadium is carried out by introducing oxygen or air into the second leachate to precipitate a vanadium-containing concentrate from the second leachate, and filtering out the vanadium-containing concentrate to obtain a first residual liquid, and The vanadium-containing concentrate is further immersed in an alkaline solution to leach vanadium, and ammonium chloride is added to the vanadium leaching solution to form ammonium metavanadate, wherein the alkaline solution is sodium hydroxide or sodium carbonate. The step of ironing is to pass the oxidant into the first remaining liquid, and adjust the pH of the first remaining liquid to the ferrous iron in the first remaining liquid, wherein the pH of the first remaining liquid The value is 2~4; after the step of removing manganese, the second residual liquid is obtained by filtering the ferrous iron, and the oxidant is introduced into the second residual liquid, and the pH of the second residual liquid is adjusted to the second The manganese in the remaining liquid is precipitated, wherein the pH of the first remaining liquid is 4-6.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

Referring to FIG. 1, which is a preferred embodiment of the present invention, the method for extracting valuable metals from manganese slag comprises an acid leaching step S1, a preliminary precipitation step S2, and an extraction step S3.

The acid leaching step S1 immerses the manganese slag in the titanium white waste acid, and further adds the vanadium-containing steel slag to the titanium white waste acid mixed with the manganese slag to form an acid leaching mixture, and is regulated by the vanadium-containing steel slag. The pH of the acid immersion mixture causes the acid leaching mixture to react to form calcium sulfate.

More specifically, the present invention uses the sulfate-rich titanium white waste acid produced in the titanium white process as an acid immersion liquid to impregnate the manganese slag in the titanium white waste acid, and additionally contains a high calcium component. Vanadium steel slag is configured to complete the acid leaching mixture. Thereby, the pH value of the acid leaching mixture can be controlled by the vanadium-containing steel slag, and the pH of the acid leaching mixture is preferably less than 1, so that the calcium in the vanadium-containing steel slag can be easily combined with the titanium white waste acid. The sulfate reaction produces a large amount of calcium sulfate to achieve the effect of simultaneously reducing the sulfate ion to stabilize the pH of the subsequent reaction, and removing the calcium ions from the reaction with other valuable metals to cause the valuable metal to be difficult to separate. Among them, each 100 g of manganese slag is preferably immersed in 3000-12000 g of titanium white waste acid, and 500-3000 g of vanadium-containing steel slag is specially added thereto, and the temperature of the acid leaching step S1 is maintained at 90-95. °C, to continue the reaction for 1 to 5 hours to completely generate a large amount of calcium sulfate.

The initial step S2 filters out the calcium sulfate in the acid leaching mixture to obtain a first leaching solution, and adjusts the pH of the first leaching solution to the trivalent iron in the first leaching solution to be filtered to obtain a trivalent value. Iron and a second leachate. More specifically, the acid leaching mixture having a large amount of calcium sulfate precipitated through the acid leaching step S1 is filtered to remove the solid calcium sulfate to obtain the first leaching solution, and the first leaching solution contains not only the leaching from the manganese slag. The manganese and iron further contain vanadium and iron leached from the vanadium-containing steel slag, and the iron contained in the first leaching solution contains ferric iron and divalent iron, and in the initial step S2, The pH of the first leachate is adjusted to 1 to 3 to facilitate the precipitation of the ferric iron and to remove the precipitated ferric iron, thereby obtaining a second leachate rich in manganese, vanadium and ferrous iron. In particular, the temperature of the preliminary precipitation step S2 is maintained at 90 to 95 ° C to completely precipitate the ferric iron in the first leachate.

The extracting step S3 is to add an oxidizing agent to the second leaching solution, and adjust the pH value of the second leaching liquid to the valuable metal in the second leaching solution to be filtered to obtain a solid precipitate, and the solid precipitate is rich. Contains valuable metals such as manganese, vanadium or iron. The oxidant may be oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide. The selection of a suitable oxidant according to the extraction process of different valuable metals can be understood by those skilled in the art. More specifically, in the extracting step S3, a plurality of processes for extracting valuable metals can be performed according to the needs of the operator, in particular, the valuable metals such as manganese, vanadium and iron rich in the manganese slag and the vanadium-containing steel slag. Thereby, a high-priced and high-content recycled metal is obtained. The process of extracting the metal of the present invention is understood by those skilled in the art, and only a brief description of the preferred embodiment of the present invention will be given below.

Referring to FIG. 2, the present invention selects a vanadium precipitation step S31, a stepping iron step 32 and a sedimentation manganese step S33 in the extracting step S3 to sequentially extract vanadium and iron from the second leachate. And manganese metal.

The vanadium precipitation step S31 is: introducing oxygen or air into the second leachate to precipitate a vanadium-containing concentrate from the second leachate, filtering out the vanadium-containing concentrate to obtain a first residual liquid, and obtaining the first liquid The vanadium concentrate is then immersed in an alkaline solution to leach vanadium. In particular, the present invention selectively performs the vanadium precipitation step S31 by oxygen or air, such that the oxygen or air can react with the vanadium in the second leachate to form a vanadium-containing concentrate, and after filtering out the precipitate. The vanadium-bearing concentrate is obtained by obtaining a first remaining liquid rich in iron and manganese, and the first remaining liquid is subjected to a subsequent extraction step of other metals, and at the same time, the leaching of the vanadium-containing concentrate is performed with an alkaline solution to leach the vanadium. . Among them, the alkaline solution may be selected from sodium hydroxide or sodium carbonate. Further, in the vanadium precipitation step S31, ammonium chloride may be added to the leached vanadium solution to form ammonium metavanadate, whereby ammonium metavanadate is recovered and reused.

The stepping iron step S32 is to pass an oxidant into the first remaining liquid, and adjust the pH of the first remaining liquid to sinter of the ferrous iron in the first remaining liquid. In detail, a large amount of ferrous iron and manganese are still present in the first remaining liquid obtained by the step V31, and the oxidant is first introduced and the pH of the first remaining liquid is adjusted to 2 to 4, thereby facilitating The divalent iron in the first remaining liquid is first precipitated. Wherein, the oxidant may be selected from oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide as described above to facilitate precipitation of ferrous iron from the first remaining liquid.

After the manganese precipitation step S33 filters out the ferrous iron, a second residual liquid is obtained, the oxidant is introduced into the second residual liquid, and the pH of the second residual liquid is adjusted to the manganese deposition in the second residual liquid. . In detail, a large amount of manganese is still present in the second remaining liquid obtained by the stepping iron step S32, and the oxidizing agent is again introduced and the pH of the second remaining liquid is adjusted to 4-6, so as to facilitate the second remaining The manganese in the liquid sinks. Wherein, the oxidizing agent may also be selected as oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide as described above to facilitate precipitation of manganese from the second residual liquid.

Finally, the tail liquid produced after the extraction by all the steps of the present invention can be neutralized with a small amount of calcium carbonate to form calcium sulfate, and the calcium sulfate after the reaction can be filtered to discharge the harmless tail liquid.

In order to further understand the various acid metals (such as manganese, iron and vanadium) and other components [such as calcium and sulfur] which are present in the present invention under different acid leaching times, different amounts of titanium white waste acid and different vanadium containing steel slags. The leaching situation is detailed in Tables 1~3:

100 g of manganese slag containing 11% manganese and 7% calcium is immersed in 6000 g of titanium white waste acid containing 20% sulfur, 7% iron, 0.3% manganese and 0.05% vanadium, and 1000 g of vanadium is added. The vanadium-containing steel slag of %, calcium 40% and iron 15% is formed into an acid leaching mixture, and the pH value of the acid leaching mixture is preferably adjusted by the vanadium-containing steel slag, and the reaction time is constant at 90 ° C for 1~ After 5 hours, a first leachate is obtained by filtering the generated calcium sulfate to detect the contents of manganese, iron, vanadium, calcium and sulfur contained in the first leachate, thereby knowing that the titanium white waste acid acid is soaked The metal leaching rate afterwards is shown in Table 1.

Table 1: Variations in composition of different acid leaching times.

It can be seen from Table 1 that when the reaction time is higher than 4 hours, the leaching rate of manganese and vanadium can be as high as 98%, while the leaching rate of calcium is only 1% residual, even the sulfur present in titanium white waste acid. It can be removed by up to 66.5%. Therefore, under the action of a long time, the use of titanium white waste acid supplemented with vanadium-containing steel slag and manganese slag can greatly leaching valuable metals such as manganese, iron and vanadium, and can also thoroughly affect the subsequent reaction of calcium and sulfur. Calcium sulfate is formed and filtered to enhance the efficiency of subsequent extraction of valuable metals.

Furthermore, 100 g of manganese slag containing 11% manganese and 7% calcium is immersed in 3000~12000 g of titanium white waste acid containing 20% sulfur, 7% iron, 0.3% manganese and 0.05% vanadium, and added 1000 g of vanadium-containing steel slag containing vanadium 2%, calcium 40% and iron 15% to form an acid leaching mixture to adjust the pH of the acid leaching mixture to 1 by the vanadium-containing steel slag, and continuously react at 90 ° C After the time is 4 hours, a first leachate is obtained by filtering the generated calcium sulfate to detect the contents of manganese, iron, vanadium, calcium and sulfur contained in the first leachate, thereby knowing that the titanium white waste is obtained. The metal leaching rate after acid leaching is detailed in Table 2.

Table 2: Variations in the composition of different titanium white waste acids.

It can be seen from Table 2 that when the amount of titanium white waste acid is more than 6000 grams, the leaching rate of manganese and vanadium can be as high as 98%, while the leaching rate of calcium is only 1.4% residual, even in titanium white waste acid. The sulfur in the process can be removed by 67.3%. It is worth noting that when the content of titanium white waste acid is gradually increased to 12,000 g, sulfur and calcium are fully reacted to form calcium sulfate precipitate, which in turn causes an increase in sulfur content. Therefore, the amount of the titanium white waste acid is preferably 6000 g, and the titanium white waste acid is supplemented by the vanadium-containing steel slag and the manganese slag, and the leaching of valuable metals such as manganese, iron and vanadium can also be affected at the same time. The subsequent reaction of calcium and sulfur is completely filtered out by calcium sulfate to improve the efficiency of subsequent extraction of valuable metals.

In addition, 100 g of manganese slag containing 11% manganese and 7% calcium is immersed in 6000 g of titanium white waste acid containing 20% sulfur, 7% iron, 0.3% manganese and 0.05% vanadium, and 500~3000 is added. a vanadium-containing steel slag containing vanadium 2%, calcium 40% and iron 15% to form an acid leaching mixture to adjust the pH of the acid leaching mixture to 1 by the vanadium-containing steel slag, and to continue the reaction time at 90 ° C After 4 hours, a first leachate is obtained by filtering the generated calcium sulfate to detect the contents of manganese, iron, vanadium, calcium and sulfur contained in the first leachate, thereby knowing the waste acid of the titanium white The metal leaching rate after acid leaching is detailed in Table 3.

Table 3: Variations in the composition of different vanadium containing steel slags.

It can be seen from Table 3 that when the vanadium-containing steel slag is used in an amount of 500 to 2000 g, the leaching rates of manganese and vanadium can be as high as 90%, but the calcium content is accordingly increased. It is worth noting that if the vanadium-containing steel slag is excessively increased, the pH value during acid leaching is greatly reduced, and the leaching rate is decreased and the calcium content is increased. Therefore, the vanadium-containing steel slag is preferably maintained at a level of between 500 and 1500 grams to assist the titanium white waste acid to act together with the manganese slag, and to leaching a large amount of valuable metals such as manganese, iron and vanadium, which may also affect subsequent reactions. Calcium and sulfur are completely formed by calcium sulfate and filtered to improve the efficiency of subsequent extraction of valuable metals.

In addition, the first leachate after the acid leaching step S1 is passed through the subsequent step S2 and the extraction step S3 to detect the content of the finally obtained valuable metal [including: manganese, vanadium and iron]. This is to know the metal extraction rate and purity after complete treatment by the present invention.

100 g of manganese slag containing 11% manganese and 7% calcium is immersed in 6000 g of titanium white waste acid containing 20% sulfur, 7% iron, 0.3% manganese and 0.05% vanadium, and 1000 g of vanadium is added. %, calcium 40% and iron 15% vanadium-containing steel slag, forming an acid leaching mixture, the pH of the acid leaching mixture is preferably adjusted by the vanadium-containing steel slag, and the reaction time is maintained at 90 ° C for 4 hours. After the calcium sulfate formed is filtered to obtain a first leachate, and the first leachate is subjected to a subsequent preliminary sedimentation step S2 and an extraction step S3, the final total extraction rate and purity of manganese, vanadium and iron are obtained. Table 4.

Table 4: Variations in the composition of different vanadium containing steel slags.

It can be seen from Table 4 that the final total extraction rate of the valuable metals extracted by the present invention, such as manganese, vanadium and iron, can be as high as 90%, and the purity can be as high as 96% or more. Thus, the present invention utilizes titanium white waste acid supplemented with vanadium-containing steel slag to co-operate with manganese slag, and can extract a large amount of valuable metals such as manganese, vanadium and iron with high purity, so as to facilitate the recovery and utilization of the valuable metals, and The invention realizes the effect of conforming to industrial economic benefits through the simple process of co-impregnation of waste acid and waste metal slag.

In summary, the main feature of the method for extracting valuable metals from manganese slag in the present invention is that titanium white waste acid is used together with vanadium-containing steel slag to co-operate with manganese slag, which can be used not only in calcium and titanium white waste acid in vanadium-containing steel slag. Sulfate reacts with each other to form calcium sulfate, so as to avoid excessive sulfuric acid affecting the pH value of the acid leaching process, and also reduce the trouble of calcium ions for subsequent extraction of valuable metals, and effectively improve the leaching of valuable metals such as manganese and iron in the leached manganese slag. Rate, and at the same time in the acid leaching step S1 leaching the vanadium-containing steel slag and the titanium-white waste acid partially rich in valuable metals such as manganese, vanadium and iron, can obtain higher content and purity of manganese in the final extraction step S3 Vanadium and iron metal not only eliminate the cost of separately treating titanium white waste acid, vanadium-containing steel slag or manganese slag, but also solve the problems caused by separately treating the metal waste residue and acid solution, and improve the waste residue and acid solution. The effectiveness of valuable metal recovery efficiency.

In addition, the method for extracting valuable metals from the manganese slag of the present invention can be widely applied to various industrial equipments, especially the common chemical equipments, in order to costly the processing cost and solve the pollution wastes produced by different industrial fields. Moreover, the calcium sulfate obtained by the reaction can be easily neutralized with a small amount of calcium carbonate to form a harmless tail liquid, which can not only reduce the environmental pollution of the metal residue and the waste acid liquid, but also recover the high-priced valuable metal by the invention. In order to thoroughly implement the parallel goal of industrial economic development and environmental protection.

The method for extracting valuable metals from the manganese slag of the invention can reduce the cost of separately treating the titanium white waste acid, the vanadium-containing steel slag or the manganese slag, so as to achieve the effect of improving the recovery efficiency of the valuable metal in the waste slag.

The method for extracting valuable metals from the manganese slag of the invention can reduce the environmental pollution of the metal residue and the waste acid solution, and achieve the effect of improving environmental protection.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

[this invention]

S1. . . Acid leaching step

S2. . . Initial step

S3. . . Extraction step

S31. . . Step vanadium

S32. . . Iron step

S33. . . Shen manganese step

Figure 1 is a flow chart 1 of a method for extracting valuable metals from manganese slag according to the present invention.

Figure 2: Flow chart 2 of the method for extracting valuable metals from manganese slag according to the present invention.

S1. . . Acid leaching step

S2. . . Initial step

S3. . . Extraction step

Claims (8)

The invention relates to a method for extracting valuable metals from manganese slag, comprising: an acid leaching step, immersing manganese slag in titanium white waste acid, and adding vanadium-containing steel slag to titanium white waste acid mixed with the manganese slag to form one An acid leaching mixture, wherein the pH of the acid leaching mixture is controlled by the vanadium-containing steel slag, and the acid leaching mixture is reacted to form calcium sulphate; in a preliminary step, the calcium sulphate in the acid leaching mixture is filtered to Obtaining a first leachate, adjusting the pH of the first leachate to the trivalent iron in the first leachate to filter out the ferric iron and a second leachate; and an extraction step of adding the second leachate An oxidant, and adjusting the pH of the second leachate to the valuable metal in the second leachate to filter out a solid precipitate, the solid precipitate is rich in valuable metals such as manganese, vanadium or iron; Wherein, in the extracting step, a vanadium precipitation step, a sedimentation iron step and a manganese precipitation step are performed to sequentially extract vanadium, iron and manganese metal from the second leachate through the steps; The second leachate is filled with oxygen or air to self The vanadium-containing concentrate is precipitated in the second leachate, a vanadium-containing concentrate is filtered to obtain a first remaining liquid, and the vanadium-containing concentrate is further immersed in an alkaline solution to leach vanadium, and then the vanadium leachate Adding ammonium chloride to form ammonium metavanadate; the step of iron precipitation is to introduce an oxidant into the first remaining liquid, and adjusting the pH of the first remaining liquid to the divalent iron sink in the first remaining liquid The immersed manganese step is obtained by filtering out the ferrous iron to obtain a second residual liquid, introducing an oxidizing agent into the second residual liquid, and adjusting the pH of the second residual liquid to the second The manganese in the remaining liquid sinks. The method for extracting valuable metals from manganese slag according to claim 1, wherein in the acid leaching step, each 100 g of manganese slag is immersed in 3000-12000 g of titanium white waste acid, and 500~ is added thereto. 3000 grams of vanadium containing steel slag. The method for extracting valuable metals from manganese slag according to claim 1, wherein in the acid leaching step, the pH of the acid immersion mixture is less than 1, and the reaction is continued at a temperature of 90 to 95 ° C for 1 to 5 hour. The method for extracting valuable metals from manganese slag according to claim 1, wherein the pH of the first leaching solution is 1 to 3 and the operating temperature is 90 to 95 ° C. A method for extracting a valuable metal from a manganese slag according to the first aspect of the invention, wherein the oxidizing agent is oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide. A method for extracting a valuable metal from a manganese slag according to the first aspect of the invention, wherein the alkaline solution is sodium hydroxide or sodium carbonate. The method for extracting a valuable metal from a manganese slag according to the first aspect of the patent application, wherein the pH of the first remaining liquid is 2 to 4 in the step of sinking iron. The method for extracting valuable metals from manganese slag according to claim 1, wherein the first remaining liquid has a pH of 4-6.