TWI427154B - Method for recycling metal from tungsten-containing waste catalysis - Google Patents

Description

Metal recovery method in tungsten-containing waste catalyst

The invention relates to a metal recovery method in a waste catalyst, in particular to a method for recovering metal in the tungsten-containing waste catalyst by using a highly oxidizing acid liquid.

In the petroleum refining process, the catalyst system is used in a large amount in various processes, such as hydrorefining, hydrocracking, hydrodesulfurization, and the like. Among them, a tungsten-containing catalyst is widely used in the processes, and the tungsten-containing catalyst is made of γ-alumina to fix different metals having active components on the surface of the alumina carrier. Thus, in the tungsten-containing catalyst catalytic process, a large amount of iron, phosphorus and the like are easily adsorbed, and the tungsten-containing catalyst fails to form a waste catalyst, and a large amount of the tungsten-containing waste catalyst is easily treated without effective treatment. Severe environmental poisoning.

In fact, the tungsten-containing catalyst is rich in a large amount of metal, and depending on the batch, there may be some differences, which may contain tungsten, molybdenum and nickel metal, or only tungsten, molybdenum or tungsten, nickel metal. Even if the active component containing the tungsten catalyst is fixed on the surface of the alumina carrier, a large amount of aluminum metal remains in the tungsten-containing waste catalyst, and the metals can be widely used in the metal industry. For this reason, most of the industry's efforts to recover metals from various waste catalysts are based on environmental protection and resource reuse considerations, in order to obtain a large amount of metals from them, and to use these metals as secondary resources.

Traditionally, methods for extracting metals such as tungsten and molybdenum, and metal concentrates as the main extraction raw materials, such as the Chinese Patent No. 101824533A, "Tungsten-molybdenum concentrate concentrated acid pretreatment for the extraction of tungsten trioxide and molybdenum trioxide" patent case, The tungsten-molybdenum concentrate is treated with a concentrated acid pretreatment, leaching, molybdenum, roasting to produce molybdenum trioxide, ammonia leaching, concentration, cooling crystallization, and roasting to produce tungsten trioxide, to obtain tungsten trioxide. And molybdenum trioxide.

However, these steps are not only cumbersome and time consuming, but also require a large amount of acid and alkali solution, which not only fails to achieve the effect of extracting metal quickly and with high quality; even the tungsten-molybdenum concentrate treated by the patent only contains tungsten and molybdenum only. Two kinds of metals, so tungsten trioxide and molybdenum trioxide can be easily obtained after the above method is treated. However, if the method is applied to metal recovery in a tungsten-containing waste catalyst, the following problems are easily derived:

Since the tungsten-containing waste catalyst may be rich in nickel or aluminum metal, and the nickel metal itself is not easily sodiumized, the nickel metal may not be smoothly poured out during the sodium roasting process, so that the tungsten-containing waste catalyst is sodium. The process of roasting can only recover tungsten and molybdenum metal, and the solid waste dumped after sodium roasting still contains a large amount of unrecoverable nickel metal, so that the effect of recovering metal from the tungsten-containing waste catalyst is obvious. It is not obvious; it is more likely to affect the quality of the tungsten and molybdenum products due to the aluminum metal remaining in the subsequent preparation of tungsten and molybdenum products, which will cause serious troubles in the process.

In addition, since the tungsten-containing catalyst may be derived from the catalytic process of hydrodesulfurization, and at the same time adsorbing a large amount of sulfur or a compound thereof, the sulfur or its compound is dispersed in the air in a high temperature environment, thereby causing air quality. Poor, in severe cases, the sulfur or its compounds are acidified after mixing with rainwater, resulting in pollution of rivers, lakes, and people's live drinking water.

To this end, the industry further treats the tungsten-containing waste catalyst by other metal extraction methods (such as wet alkali picking extraction method and roasting acid picking extraction method), in order to be expected to be applied to metal recovery in the waste catalyst, and at the same time Solve the phenomenon of incomplete metal recovery in waste catalysts.

Conventionally, the tungsten-containing waste catalyst system has a conventional method in which the waste aluminum-based catalyst is mixed and calcined at a high temperature of 600 to 900 ° C for 0.5 to 2 hours, and then heated at 80 to 90 ° C for roasting. The clinker is leached; then, the water leaching residue after the hot water leaching is acid leached with mineral acid to recover nickel and cobalt metal, and then strontium hydroxide or barium aluminate is added to the water leaching residue, from sodium aluminate The tungsten and molybdenum metals are sequentially separated from the solution; carbon dioxide is introduced into the sodium aluminate solution, and aluminum hydroxide is formed by a carbon method, and then calcined at a high temperature to form alumina. In order to improve the metal recovery rate of 91%, and at the same time reduce the pollution caused by the environment. Alternatively, the clinker after the sodium roasting is directly leached with mineral acid, and after roasting with sodium sulphate, a large amount of nickel metal can be decanted by sulfuric acid leaching, and the molybdenum and tungsten metals present in the leaching slag after sulphuric acid leaching are all In the unoxidized state, since the unoxidized molybdenum and tungsten metal cannot be easily extracted, the tungsten and molybdenum metals must be oxidized in the subsequent treatment process. This process improves the heterogeneity of the water leaching solution and is more likely to cause tungsten. The effect of co-precipitation of molybdenum metal, and the unoxidized metal present in the residue must be treated by high-temperature roasting, so that the respective decantation rates of tungsten and molybdenum metals are significantly reduced, and the recovery of tungsten and molybdenum metal cannot be achieved. rate.

Although the conventional treatment method can simultaneously recover a plurality of metals in the waste catalyst, the sulfur or a compound thereof contained in the waste catalysts cannot be removed by sodium roasting and sulfuric acid leaching, and is easy. Deriving the problems described above, causing serious environmental pollution.

In addition, the active components of the catalysts are fixed on the surface of the alumina carrier, so that a large amount of aluminum metal is present in the waste catalysts, and the aluminum metal is present in the slag of the sodium roasting leaching. In the subsequent processing procedures for the dumping slag, aluminum salt precipitation is easily generated, which seriously affects the recovery rate of other metals; even the conventional treatment method requires additional carbon dioxide in the sodium aluminate solution to The high temperature satin burns out the aluminum metal in the waste catalyst to make alumina. In this way, not only the recycling effect of various metals is reduced, but also the cost and time required for the waste catalyst treatment process are increased, and even the recycling quality of the metals is more worrying.

In view of the above various shortcomings, the metal recovery method in the tungsten-containing waste catalyst is still necessary for improvement.

The main object of the present invention is to improve the above disadvantages, and to provide a metal recovery method in a tungsten-containing waste catalyst, which is capable of removing sulfur or a compound thereof in the tungsten-containing waste catalyst to reduce the dispersion of sulfur or a compound thereof. Pollution.

A second object of the present invention is to provide a metal recovery method in a tungsten-containing waste catalyst, which is capable of directly decanting a metal in an oxidation state to reduce the difficulty of subsequent treatment and to enhance the metal pouring rate.

Still another object of the present invention is to provide a metal recovery method in a tungsten-containing waste catalyst which is capable of avoiding the phenomenon of aluminum precipitation during metal pouring to ensure the recovery quality of various metals.

Another object of the present invention is to provide a metal recovery method in a tungsten-containing waste catalyst, which is capable of directly obtaining a metal residue in an oxidation state, thereby reducing the time and cost required for a subsequent metal recovery process, and increasing the metal in the residue. Recovery rate.

Another object of the present invention is to provide a metal recovery method in a tungsten-containing waste catalyst, which is capable of directly recovering the oxidized acid radical formed by the reaction with sulfur to reuse it to reduce the amount of acid used.

In order to achieve the foregoing object, the metal recovery method in the tungsten-containing waste catalyst of the present invention comprises: an acid leaching step of immersing a mixture containing a tungsten waste catalyst in a highly oxidizing acid liquid, so that The sulfur in the mixture reacts with the acid to form a sulfur-containing compound and an oxidized acid radical, and the oxidized acid radical is re-reacted into a reusable highly oxidizing acid liquid, and the sulfur in the mixture is reacted with the acid liquid. After completion, a decanting liquid and a residue body having an oxidized metal are obtained; and a recovery and purification step is performed by extracting and extracting a metal rich in the tungsten-containing waste catalyst from the decanting liquid.

The invention may further operate a roasting and refining step, wherein the residue body is calcined, and the residue body is immersed to form a residue liquid, and then extracted and precipitated from the residue liquid is rich in the tungsten-containing waste contact. The metal in the medium.

In addition, an auxiliary acid may be further added to the acid leaching step, and the auxiliary acid is a strongly acidic solution, wherein the auxiliary acid is added to the acid solution in a concentration percentage of 1 to 50%.

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

The metal recovery method of the invention can treat tungsten-containing waste catalyst recovered from different petrochemical processes (such as hydrorefining, hydrocracking, hydrodesulfurization, etc.), especially obtained by hydrodesulfurization. Tungsten waste catalyst. The mixture of the tungsten-containing waste catalyst is different according to the recycling batch, and the metal contained therein has a partial difference, and may contain tungsten, molybdenum and nickel metal, or only tungsten, molybdenum or tungsten, nickel metal, and The tungsten-containing catalyst further includes sulfur or a compound thereof attached after the hydrodesulfurization process, and aluminum metal remaining in the alumina carrier. Here, a tungsten-containing waste catalyst containing tungsten, molybdenum, nickel, aluminum, and sulfur is taken as an example, and the operation means of the present invention will be described in detail below.

Referring to FIG. 1 , in a preferred embodiment of the present invention, the metal recovery method in the tungsten-containing waste catalyst comprises an acid leaching step S1 and a recovery and purification step S2. In the present invention, depending on the different products obtained in the acid leaching step S1, another calcination refining step S3 may be operated after the recovery and refining step S2, or the recovery refining step S2 and the roasting may be simultaneously operated after the acid leaching step S1. Purification step S3. Thereby, the comprehensive effect of recovering metal from the tungsten-containing waste catalyst is achieved.

The acid leaching step S1 is a mixture of a tungsten-containing waste catalyst, immersed in a highly oxidizing acid liquid, so that the sulfur in the mixture reacts with the acid solution to form a sulfur-containing compound and an oxidized acid radical. The oxidized acid radical is re-reacted into a reusable highly oxidizing acid solution, and after the sulfur in the mixture is completely reacted with the acid solution, a decanted liquid having a oxidized metal and a residue are obtained.

More specifically, the tungsten-containing spent catalyst mixture is rich in tungsten, molybdenum, nickel, and aluminum metals having different compositions, and sulfur or a compound thereof attached after the hydrodesulfurization process. Soaking the mixture in the highly oxidizing acid solution to thoroughly react with the sulfur in the mixture through the acid solution to form a sulfur-containing compound and an oxidized acid radical, and the oxidized acid radical can be recovered into the The acid solution is further reused in the acid leaching step to reduce the amount of the acid solution used in the acid leaching step S1, and the sulfur-containing compound can also lower the pH of the acid solution to enhance immersion in the acid solution. The mixture in the mixture pours out the effect of the metal.

Furthermore, while the vulcanization reaction is carried out, the mixture immersed in the acid solution pours a large amount of decanted liquid rich in tungsten, molybdenum, nickel and a small amount of aluminum metal, and generates a large amount of aluminum metal and a small amount of tungsten, a solid residue of molybdenum or nickel metal, wherein the high oxidation property of the acid liquid simultaneously oxidizes tungsten, molybdenum, nickel and aluminum metal in the decanting liquid and the residue body, and a small amount of unreacted sulfur element, so that The tungsten and molybdenum metals in the decanting liquid and the residue are converted into tungsten and molybdenum in an easily extracted oxidation state, and the phenomenon of co-precipitation of tungsten and molybdenum is not easy to occur, and a small amount of unreacted sulfur element is attached to the decantation. Sulfur dioxide is formed in the liquid or residue to increase its vaporization point and reduce the possibility of subsequent dissipation in the recovery and purification step S2 and the calcination refining S3. Among them, the acid solution may be selected from highly oxidizing solutions such as nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, and concentrated sulfuric acid.

For example, in this embodiment, the tungsten-containing waste catalyst mixture is immersed in a concentration of 5 to 40% of nitric acid, and the mixture is rich in 5% aluminum, 13.7% tungsten, 8.8% molybdenum, and 8.2. % nickel metal, and a part of sulfur or a compound thereof, and the relative weight ratio of the nitric acid to the mixture (nitrate/mixture) is preferably selected from 1 to 4, wherein the proportion of the metal rich in the mixture is based on each There are differences in batch recycling of tungsten-containing waste catalysts. In this way, the mixture is immersed in the acid solution for 2 to 4 hours, so that the sulfur in the mixture reacts with the nitric acid to form sulfuric acid and nitrogen oxide gas, and the vaporized nitrogen acid is collected by the pumping device, and Nitric acid is reused in the acid leaching step S1 (as shown in Chemical Formulas 1 and 2).

HO-NO ₂ +2H ₂ SO ₄ →NO ₂ ⁺ +2H ₂ SO ₄ ^- +H ₃ O ⁺ [Chemical Formula 1]

NO ₂ ⁺ +H ₂ O→HNO ₃ [Chemical Formula 2]

In addition, in the acid leaching step S1, an eluate rich in a large amount of oxidized tungsten, molybdenum, nickel and a small amount of oxidized aluminum metal, and a large amount of oxidized aluminum metal and a small amount of unexposed oxidized metal are simultaneously obtained. And the residue of the tungsten, molybdenum, and nickel metal, and in the subsequent recovery and purification step S2, selecting the metal present in the tungsten-containing waste catalyst from the decanting liquid, and optionally operating the roasting and refining step S3 The residual tungsten, molybdenum, nickel metal and a large amount of aluminum metal are obtained from the residue.

The recovery and purification step S2 extracts from the decanted liquid to precipitate a metal rich in the tungsten-containing waste catalyst. In more detail, the recovery and purification step S2 is first co-extracting the tungsten and molybdenum metal in the decanting liquid with an extracting agent to obtain a total extraction liquid, and then reacting the co-extraction liquid with an alkaline solution. After extracting a stripping solution, the tungsten and molybdenum metal are obtained by sinking tungsten and molybdenum with the stripping solution respectively; then, a residual liquid of tungsten and molybdenum metal is extracted, and the solution is re-extracted. The extracting agent extracts aluminum metal and performs stripping with an acidic solution to obtain a trace amount of the aluminum-containing compound; finally, a noble liquid after removing tungsten, molybdenum and aluminum metal is directly deposited, and a large amount of nickel metal is taken out.

For example, after the decanting liquid is obtained by the acid leaching step S1, and the recovery and purification step S2 is directly operated, tungsten, molybdenum, and nickel metal having a recovery rate of 70 to 95% can be obtained from the decanting liquid. Wherein, the extracting agent may be selected from the group consisting of N-235, Alamine 336, Aliquit 306, P204, P507, N236, cyaney and TOA; the alkaline solution for the extraction may be selected from sodium hydroxide and sodium chloride. Or sodium carbonate; the acidic solution for the extraction may be selected from nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid.

In addition, the present invention may further operate a calcination purification step S3 after the recovery and purification step S2, or simultaneously operate the recovery and purification step S2 and the calcination purification step S3 after the acid dip step S1. In the roasting and purifying step S3, the residue is calcined, and the residue is immersed in the residue to form a residue liquid, and the residue is further extracted and precipitated to be rich in the metal contained in the tungsten-containing waste catalyst. More specifically, the roasting and refining step S3 is to mix the residue with an alkali powder, and calcined at 300 to 800 ° C for 1 hour, preferably at 600 to 700 ° C, and then calcined and cured. The body is leached with hot water to obtain the residue liquid, and the residue liquid is extracted by the same technical means as in the above-mentioned recovery and purification step S2 to precipitate tungsten, molybdenum, nickel and aluminum metal contained therein. The techniques for extracting, stripping, and depositing tungsten, molybdenum, nickel, or aluminum are easily exemplified by those skilled in the art and are not characteristic of the present invention, and thus are not described in detail herein.

In this way, the residue obtained by the acid leaching step S1 can be obtained by secondly obtaining the recovered tungsten, molybdenum, and nickel metal through the baking and purifying step S3, and simultaneously extracting the aluminum metal in a large amount to precipitate the aluminum-containing product. Preferred metal pouring efficiency. Wherein, the calcined alkali powder may be selected from sodium carbonate, sodium hydroxide or sodium chloride.

In addition, referring to FIG. 3, the present invention may also operate a pre-treatment step S01 before the acid leaching step S1, which removes the heavy oil adhered to the tungsten-containing waste catalyst mixture. More specifically, the tungsten-containing spent catalyst mixture is placed in a reactor to remove the heavy oil attached to the mixture at 150-800 °C. Thereby, the heavy oil component is prevented from affecting the treatment effect of the mixture in the subsequent acid leaching step S1 to enhance the metal pouring effect in the mixture. Furthermore, the present invention may also add an auxiliary acid in the acid leaching step S1, and reduce the pH value of the acid solution by the auxiliary acid to increase the metal pouring rate of the mixture immersed in the acid solution. The auxiliary acid may be selected from a strongly acidic solution such as hydrochloric acid or sulfuric acid, and the concentration of the auxiliary acid added to the acid solution is preferably from 1 to 50% by weight.

According to the above, the present invention selects a highly oxidizing acid acid immersion mixture of the tungsten-containing waste catalyst, which can directly react with the sulfur rich in the mixture through the high oxidizability of the acid solution to generate a sulfur-containing compound and an oxidized acid radical, and the oxidized acid radical can be further converted into the acid liquid for reuse in the acid leaching step S1, thereby maintaining a preferred pH value of the acid liquid, and stabilizing the acid liquid pair The pouring effect of the metal in the mixture can further reduce the amount of the acid solution used; and the sulfur-containing compound is in an oxidation state to increase the vaporization temperature thereof, so that the subsequent purification and purification step S2 or the calcination purification step S3 is processed. At the same time, the sulfur-containing compound is not easily dispersed in the air or rainwater, thereby reducing the damage caused to the ecological environment.

In addition, the highly oxidizing acid liquid can oxidize the tungsten, molybdenum, nickel and aluminum metal rich in the mixture during the acid leaching of the metal, so that the decanted liquid and the residue body Tungsten and molybdenum metals are converted into easily extracted oxidized tungsten and molybdenum to facilitate extraction of the decanted liquid and residue into tungsten, molybdenum, nickel and aluminum; even due to the residual metal in the residue All of them are in an oxidation state. Therefore, when the calcination refining step S3 is subsequently carried out, the residue liquid having the metals can be poured out from the residue body without further high temperature higher than 850 ° C, and the tungsten is twice recovered. , molybdenum and nickel metal, and at the same time a large number of extraction and precipitation of aluminum-containing products. Thus, the present invention can achieve the effect of improving the metal pouring rate and ensuring the quality of metal recovery under the conditions of low energy consumption and short time processing, and comprehensively recycling and recycling the metal.

In order to prove that the present invention soaks the tungsten-containing waste catalyst mixture with a highly oxidizing acid solution, it has the advantages of increasing the metal, tungsten, nickel and aluminum metal pouring rate, and comprehensively recovering the metal in the tungsten-containing waste catalyst. The effect of this example is the following experimental analysis using nitric acid as the main acid leaching system.

In a specific embodiment of the present invention, 1000 g of the tungsten-containing waste catalyst mixture is immersed in a nitric acid solution having a concentration of 20%, and the relative weight ratio (nitric acid/mixing) of the nitric acid solution to the mixture is adjusted to 1 to 4 , each reacted for 4 hours. Here, the vaporized nitrite is first collected by an aspirating device, and nitric acid is reused in the above reaction. After the metal contained in the decanting liquid and the residue body is separately precipitated, the final tailings are analyzed to determine the content of tungsten, molybdenum, nickel and aluminum in the tailings, as shown in Table 1. .

It can be seen from Table 1 that when the relative weight ratio of the nitric acid solution to the mixture (nitrogen:mixture) is higher than 2:1, the recovery of the tungsten, molybdenum and nickel metal can be as high as 99% or more.

According to a second embodiment of the present invention, 1000 g of the tungsten-containing waste catalyst mixture is immersed in a concentration of 5 to 40 under the condition that the relative weight ratio of the nitric acid solution to the mixture (nitrogen:mixing) is 3:1. A solution of % nitric acid was reacted for 4 hours each. Here, the vaporized nitrite is first collected by an aspirating device, and nitric acid is reused in the above reaction. After the metal contained in the decanting liquid and the residue body is separately precipitated, the final tailings are analyzed to determine the content of tungsten, molybdenum, nickel and aluminum in the tailings, as shown in Table 2. .

It can be seen from Table 2 that when the concentration of nitric acid is higher than 10%, the recovery of the tungsten, molybdenum and nickel metal can be as high as 99% or more.

Therefore, it is confirmed from Table 1 and Table 2 that the nitric acid-based acid leaching system of the present invention can improve the recovery efficiency of the tungsten, molybdenum and nickel metal, thereby achieving the comprehensive recovery of the metal in the tungsten-containing waste catalyst. And the cost of recovering the metal in the tungsten-containing waste catalyst is relatively reduced.

In addition, Tables 1 and 2 show that the final tailings have 90-95% of aluminum metal, so it is confirmed that other processes such as tungsten, molybdenum and nickel metal are not affected by the simultaneous dumping of aluminum metal. And can ensure the quality of the metal after pouring. Even after immersing the tungsten-containing waste catalyst mixture with the nitric acid, the sulfur measured in the tail slag is less than 2%, and it is known that most of the sulfur contained in the tungsten-containing waste catalyst is Nitric acid is converted to sulfuric acid and mixed in the acid.

In addition, in a third embodiment of the present invention, 1000 g of the tungsten-containing waste catalyst mixture is immersed in a concentration of 20 under the condition that the relative weight ratio of the nitric acid solution to the mixture (nitrogen:mixing) is 3:1. % nitric acid solution, and 1 to 50% hydrochloric acid was additionally added thereto to react for 4 hours each. Here, the vaporized nitrite is first collected by an aspirating device, and nitric acid is reused in the above reaction. After the reaction was completed, the decanted liquid after the leaching was analyzed, and the recovery rates of the final tungsten, molybdenum, nickel and aluminum metals were measured, as shown in Table 3.

It is known from Table 3 that when the ore acid is assisted in the nitric acid leaching system, the leaching recovery effect of the tungsten, molybdenum and nickel metal is significantly improved. Thereby, it is confirmed that the addition of the auxiliary acid (such as strong acid such as hydrochloric acid or sulfuric acid) can effectively improve the recovery rate of the tungsten, molybdenum and nickel metal.

The metal recovery method in the tungsten-containing waste catalyst of the invention is capable of removing sulfur or a compound thereof in the waste catalyst to reduce the effect of sulfur or its compound floating in the air and mixing in the rainwater to reduce environmental pollution.

The metal recovery method in the tungsten-containing waste catalyst of the invention can directly pour out the metal in the oxidation state to reduce the difficulty of subsequent treatment and achieve the effect of improving the metal pouring rate.

The metal recovery method in the tungsten-containing waste catalyst of the invention can avoid the phenomenon of aluminum precipitation during the metal pouring process, so as to effectively ensure the recovery quality of the metal and achieve the effect of metal recycling and reuse.

The metal recovery method in the tungsten-containing waste catalyst of the invention can directly obtain the metal residue in the oxidation state, thereby reducing the time and cost required for the subsequent metal recovery process, and achieving the effect of increasing the metal recovery rate in the residue.

The method for recovering metal in the tungsten-containing waste catalyst of the present invention is capable of directly reacting with sulfur to form an oxidized acid radical for recycling in the treatment procedure of the tungsten-containing waste catalyst, achieving acid state acid reuse, and reducing acid The effect of the amount of use.

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]

S01. . . Pre-processing steps

S1. . . Acid leaching step

S2. . . Recovery and refining step

S3. . . Roasting and refining step

Figure 1 is a flow chart 1 of the operation of the present invention.

Figure 2: Flow chart 2 of the operation of the present invention.

Figure 3: Flow chart 3 of the operation of the present invention.

S1. . . Acid leaching step

S2. . . Recovery and refining step

Claims (13)

A method for recovering metal in a tungsten-containing waste catalyst comprises: an acid leaching step of immersing a mixture of tungsten-containing waste catalyst in a highly oxidizing acid liquid to make the sulfur in the mixture The acid reacts to form a sulfur-containing compound and an oxidized acid radical, and the oxidized acid radical is re-reacted into a reusable highly oxidizing acid liquid, and after the sulfur in the mixture is completely reacted with the acid liquid, a metal having an oxidized state is obtained. a decanting liquid and a residue body; and a recovery and refining step of extracting and depleting the metal rich in the tungsten-containing waste catalyst from the decanting liquid; wherein the highly oxidizing acid liquid is Nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid or nitrous acid. According to the method for recovering metal in the tungsten-containing waste catalyst according to the first aspect of the patent application, a calcination and refining step is further performed, wherein the residue is calcined to form a residue liquid by immersing the residue after aging. Further, the residue is extracted by the residue to precipitate a metal rich in the tungsten-containing waste catalyst. According to the method for recovering metal in the tungsten-containing waste catalyst according to claim 1 or 2, an auxiliary acid is additionally added to the acid leaching step, and the auxiliary acid is a strongly acidic solution. The method for recovering metal in a tungsten-containing waste catalyst according to claim 3, wherein the auxiliary acid is added in the acid solution in a concentration of 1 to 50% by weight. The method for recovering metal in a tungsten-containing waste catalyst according to claim 3, wherein the relative weight ratio of the acid to the mixture (acid/mix) is 1 to 4. The method for recovering metal in a tungsten-containing waste catalyst according to item 3 of the patent application scope, wherein the concentration of the highly oxidizing acid liquid is 5 to 40%. A method for recovering metal in a tungsten-containing waste catalyst comprises: an acid leaching step of immersing a mixture of tungsten-containing waste catalyst in a highly oxidizing acid liquid to make sulfur and the acid in the mixture The liquid reacts to form a sulfur-containing compound and an oxidized acid radical, and the oxidized acid radical is re-reacted into a reusable highly oxidizing acid liquid, and after the sulfur in the mixture is completely reacted with the acid liquid, a metal having an oxidized state is obtained. a decanting liquid and a residue body; and a roasting and refining step, the residue body is calcined, and the residue body is immersed to form a residue liquid, and then extracted and precipitated from the residue liquid is rich in the content The metal in the tungsten waste catalyst; wherein the highly oxidizing acid liquid is nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid or nitrous acid. According to the metal recovery method in the tungsten-containing waste catalyst described in claim 7 of the patent application, an auxiliary acid is additionally added in the acid leaching step, and the auxiliary acid is a strongly acidic solution. The method for recovering metal in a tungsten-containing waste catalyst according to item 8 of the patent application scope, wherein the auxiliary acid is added to the acid solution in a concentration percentage of 1 to 50%. A metal recovery method in a tungsten-containing waste catalyst according to claim 1 or 2 or 7, wherein the relative weight ratio (acid/mixture) of the acid to the mixture is 1 to 4. The method for recovering metal in a tungsten-containing waste catalyst according to claim 1 or 2 or 7, wherein the concentration of the highly oxidizing acid is 5 to 40%. a method for recovering metal in a tungsten-containing waste catalyst according to claim 1 or 2 or 7, wherein the tungsten-containing waste catalyst contains tungsten, molybdenum, nickel and aluminum, or tungsten, molybdenum and aluminum, or Tungsten, nickel and aluminum. The method for recovering metal in a tungsten-containing waste catalyst according to claim 2 or 7, wherein the calcination and refining step has a calcination temperature of 300 to 800 °C.