CN104060091B - Low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes - Google Patents

Abstract

The invention provides a kind of low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes, belong to hydrometallurgical processes technical field.Biomass adsorbent is joined the pickling liquor of low-grade valuable metals breeze or contains in the acid waste water of valuable metal by this technique, after stirring reaction, biomass adsorbent is filtered, obtain being enriched with the biomass adsorbent powder of trivalent metal iron ion and being rich in the filtrate of other valuable metals, biological adsorption agent powder is after water purification repetitive scrubbing, dry, put into tube furnace, through pyrolysis, obtain superfine metal iron powder; The mode of filtrate employing Extraction electrodeposition or biological adsorption-electrodeposition reclaims valuable metal wherein.Obtained superfine metal iron powder and hydrogen peroxide can be used for processing waste water under certain pH.This technique has the advantageous feature such as significant green, clean, efficient, resource is fully used, and has very much the prospect of application value and the existing hydrometallurgical processes of improvement.

Description

Low-grade ore valuable metal leaching-biosorption-electrowinning hydrometallurgical process

technical field

The invention relates to the technical field of hydrometallurgy technology, in particular to a leaching-biosorption-electrodeposition hydrometallurgy technology for valuable metals in low-grade ores.

Background technique

In recent years, after years of mining of non-ferrous metal rich ore, rich ore resources have become increasingly scarce, and some have even been exhausted. Therefore, the extraction of valuable metals from various low-grade tailings, miscellaneous ore and smelting slag has become a development trend of non-ferrous metallurgy. an important direction.

Hydrometallurgy is a very suitable technology choice for processing such low-grade mineral resources. For example, the bioleaching-extraction-electrodeposition technology developed for the smelting of low-grade copper ores has become a major copper smelting technology in the world. The wet copper extraction technology generally applicable to factories, similarly, the leaching-extraction-electrowinning process of low-grade zinc ore has also received a lot of research and exploration in recent years. From the comprehensive analysis of the effectiveness of the technology and the economics of the extraction cost, it can be judged that the leaching-extraction-electrodeposition technology will be an increasingly popular technology development direction in the field of industrial extraction of various low-grade non-ferrous metal ores. The successful development of the LIX series of special-effect copper extractants has led to the success of extensive practice in the industrialization of low-grade copper ore hydrometallurgy over the past few decades. As for the leaching of low-grade ore or slag, after years of development, more economical and feasible large-scale leaching technologies such as heap leaching and biological leaching have emerged, and the development of this technology is relatively mature. The extraction of low-grade ores, slags and their secondary resources of various valuable metals increasingly relies on the development of hydrometallurgical technology, and the optimization of the "leaching-extraction-electrodeposition" process as a key process will be directly related to Various technical and economic indicators of wet extraction, so various improvement measures around this key technical process have emerged in an endless stream.

The present invention discloses an improved new method aiming at the various troubles often encountered in the engineering site practice of the main process, and introduces biosorption technology into the above-mentioned traditional "leaching-extraction-electrodeposition (L-SX-EW )" process, an improved new hydrometallurgical extraction process is formed, that is, the present invention discloses two new hydrometallurgical process designs for low-grade non-ferrous metal ores, one is "leaching-biosorption-extraction-electrodeposition "New process, the other is a new process of "leaching-biosorption-electrodeposition".

These two new hydrometallurgical processes are mainly aimed at two problems often encountered in the enrichment of valuable metal ions from leaching solutions: first, the problem of iron interference. In the process of hydrometallurgy, iron is one of the most common impurity elements in various non-ferrous metal ores. It appears in the leaching solution, which is almost a very common thing. The most troublesome place is: iron ions are present in almost all wet In the method of extraction, the extraction will take place prior to the valuable metal ions such as copper, zinc, nickel, cobalt, bismuth, indium, etc. If the precipitation method is used to extract the valuable metal ions in the immersion solution, then the iron ions will be preferentially precipitated , typical precipitation methods include jarosite method, goethite method, and hematite method, but these precipitation methods are complicated to operate, consume a large amount of chemical reagents, produce a large amount of slag, and the iron element is difficult to be effectively used and discarded The direct neutralization and precipitation will only result in colloidal ferric hydroxide, which will lead to more valuable metal ions being entrapped, co-adsorbed and co-precipitated. Therefore, the precipitation method is also inseparable from the interference of iron. In order to solve the above shortcomings of iron removal by crystal precipitation, people have carried out various explorations and researches, expecting to develop a better iron removal method. Iron removal by extraction method is one of the most researched, based on the fact that ferric ions are easily extracted and enriched by most extractants, such as P204, P507, Cyanex272, 3,5-diisopropylsalicylic acid, tertiary amine etc., but the extracted Fe(III) ions are difficult to back-extract, and the Fe(III) ions have certain oxidative degradation properties to the organic extractant and are easily hydrolyzed to cause emulsification during the extraction process, plus the price of the extractant Due to the high cost and low value of iron, the extraction method for iron removal is rarely widely used in the actual industry. Therefore, the extraction agent iron removal method also failed to solve many problems existing in the traditional crystallization precipitation method iron removal. Obviously, the iron interference problem has become a common and challenging problem in the field of hydrometallurgy. Second, the problem of low extraction efficiency. For example, for low-grade copper ore resources, leaching-extraction-electrowinning is the most effective and widely applicable metallurgical process. Although this method has been widely used in industry, some outstanding shortcomings still need to be overcome, such as the extraction agent is expensive, easy to emulsify, the viscosity of the extraction system is high in low-temperature regions or in low-temperature weather, and for low-grade copper ore The low concentration of copper ions in the leaching solution affects the extraction and enrichment effect, etc., which are common problems encountered in the extraction process. Therefore, the above two problems have also brought new opportunities and challenges to the development of the traditional "leaching-extraction-electrowinning" process. If we can try to improve the two problems of iron interference and low extraction agent efficiency to a certain extent Even if it is solved, it is expected to make more promotions for the development of the hydrometallurgical industry.

Among them, one of the main goals proposed by the first "leaching-biosorption-extraction-electrodeposition" new process is designed for "iron interference". The role of biosorption is to remove iron, and its basic principle is to use biosorption The phenomenon of preferential adsorption of trivalent iron ions by common reagents is used to remove iron impurities in the leaching solution of various valuable metals, so as to eliminate the interference of iron for the subsequent extraction process, thereby improving the efficiency of the existing extraction process; Another main goal proposed by the process is to use biosorption to remove iron, continue to add biosorption to pre-enrich and concentrate the valuable metal ions in the low-concentration leaching solution, and then supply the next process for extraction and enrichment. The higher concentration of the valuable metal ion solution after the pre-enrichment of the biosorption is beneficial to the enhancement and improvement of the extraction efficiency, so it will also be a beneficial promotion to the existing extraction process.

The second design of the new process of "leaching-biosorption-electrodeposition" is specially designed for the enrichment and extraction of valuable metal ions in some low-concentration leaching solutions. The extraction efficiency is very low when using extraction technology, which is close to extraction. When the lower limit is reached, biosorption technology can be considered to achieve economical and efficient extraction of low-concentration valuable metal ions. In specific practice, it can be considered to use biosorption to remove the iron ions in the leaching solution first, and then add biosorbent to extract and enrich the valuable metal ions in the leaching solution. The concentrated valuable metal ion solution is obtained, and then recovered through electrode deposition technology.

This process makes the biosorbent material that has absorbed iron into functional powder materials, which are used as raw materials in the fields of environmental purification, soil remediation, etc., so as to realize the rational collocation and use of resources in different disciplines and fields, thus realizing the whole process Thoroughly clean, friendly and green process.

As in the aforementioned new hydrometallurgical process, the biomass adsorption method is used to selectively remove iron, so that the iron can be recovered in a relatively high-purity manner; the iron obtained by adsorption or concentrated by desorption can be used as reagent iron, or Iron powder is made directly through in-situ thermal reduction without desorption for water purification. In the present invention, it is particularly recommended that the prepared ultrafine zero-valent iron powder be provided to the water purification treatment industry, such as as an adsorption purification material, and can also be used as an iron source for the Fenton oxidation reaction, thereby being used in various Fenton reactions. Applications, such as degradation and non-toxic treatment of organic wastewater, oxidative sterilization and disinfection treatment, and many other aspects.

Because the biological adsorbent adopted in the technical secret disclosed by the present invention has a wide range of sources, is cheap, has low production cost, and has comprehensive advantages such as good adsorption effect (strong selectivity, high adsorption capacity, and fast adsorption speed) to iron ions, making the biosorbent to be treated The leaching solution of various valuable metals can quickly and conveniently remove the iron in it, and the loss of other valuable metal ions that coexist can also be effectively suppressed by the co-adsorption, so the obtained iron purity Higher, it is expected to have better reuse value, and the adsorbent particles are larger, the settling property is good, and it is easy to realize solid-liquid separation. In this way, the huge amount of iron-rich leaching solution produced by the existing hydrometallurgical industry can be transformed into a rich iron source, supplying a large amount of ultra-fine iron powder required by the water purification industry as an adsorbent material, As well as the iron source materials used in the widely used Fenton reagent, thereby greatly reducing the cost of adsorbent water purification materials and the reagent cost of Fenton reaction, it has found a broad field for these iron resources that are regarded as waste by traditional iron removal methods It provides an economically acceptable and technically feasible simple technology. The iron powder prepared by this method has fine and dispersed particle size, high reactivity, low price, wide and abundant sources, and can be compared with traditional iron powder adsorbent preparation and ferrous ion chemical reagents used in Fenton reaction. The excess iron source can be conveniently separated and recovered by solid-liquid separation, so that it will not remain in the treated aqueous solution to cause excess reagents and pollute the purified water. If the biosorbent uses those agricultural wastes as raw materials, it will find a good high-value utilization method for these agricultural waste biomass resources, so as to realize the circular economic growth mode in the agricultural field and a new type of Utilizing the method is expected to provide a new practical technical method and a broad application field for the development of new agriculture. It is a good technical method that benefits many parties and kills three birds with one stone.

Therefore, due to the wide range of sources of biosorbent materials, cheap and easy to obtain, and the preparation process is simple, convenient, green and clean, based on this feature of biosorbents, compared with the existing hydrometallurgical "metal-extraction-electrodeposition" process Combined with the advantages of low cost, high efficiency, and environmental friendliness that biological waste raw materials have as adsorbents, a new high-efficiency hydrometallurgical new process can be constructed.

Contents of the invention

The technical problem to be solved by the present invention is to provide a low-grade ore valuable metal leaching-biosorption-electrodeposition hydrometallurgical process.

The process steps are as follows:

First, take the valuable metal ore powder pickling solution containing iron and valuable metals Zn, Cu, Ni, Co, In, Bi whose grade is lower than 1%, or contain Fe and valuable metals Zn, Cu, Ni, Co, For the acid wastewater of In and Bi, by adding the same metal ore powder, the pH value of the acid leaching solution or acid wastewater is adjusted to 2-3, and the biomass adsorbent material is added. The amount of the biomass adsorbent material added is Add 0.1-300g of liquid or waste water, stir and react for 100-300min, and filter to obtain biomass adsorbent powder enriched with trivalent metal iron ions and filtrate rich in other valuable metals;

Among them, the biomass adsorbent material is prepared according to the method disclosed in Patent No. ZL: 201210019530.1, that is, the washed biomass containing active functional groups such as -COOH, -SH, -NH ₂ , -(phenol)OH, such as garlic residue , mangosteen residues, seaweed, distiller's grains, orange residues, apple peels, grapefruit peels, etc., are stirred and mixed with alkali and water according to the mass ratio of 1:0.05-0.2:0.5-2, stirred for 12 to 24 hours, and filtered to obtain a solid product , wherein the alkali is lithium, sodium, potassium, calcium, magnesium oxide, hydroxide, carbonate, bicarbonate or ammonium carbonate, ammonium bicarbonate, urea, one or more than two in ammonia Mixing; washing the above solid product with water until neutral, sending it into a vacuum oven, drying at a temperature of 60-120°C, crushing and sieving the dried product, and collecting particles below 40 mesh to obtain a biomass adsorbent material.

Then, the filtrate rich in valuable metals is contacted with the extractant P ₂₀₄ to extract the valuable metal ions therein, after washing and stripping to obtain a solution containing valuable metals, which is supplied to the electrowinning process to recover the valuable metals in the lifting industry, or The filtrate rich in valuable metals reacts with the biomass adsorbent to absorb the valuable metal ions in it, and then washes and desorbs to obtain a solution containing valuable metals, which is supplied to the electrowinning process to recover the valuable metals;

Finally, the biomass adsorbent powder enriched with trivalent metal iron ions was repeatedly washed with distilled water for 2 to 3 times, then placed in an oven at 60 to 80°C for 6 to 8 hours with hot air, and the obtained dry adsorbent powder was spread on the In a porcelain boat, put it into a tube furnace, under the condition of vacuum, protective gas (hydrogen, argon, nitrogen, carbon dioxide) or active gas (air), it is heated and decomposed at a temperature of 400-600 ° C to produce The metal iron powder is obtained, and then through grinding, sieving, and classification, ultrafine metal iron powder with a particle size below 200 meshes is obtained.

According to the mass volume ratio of the prepared superfine metal iron powder: 1 g: 0.1-10 ml hydrogen peroxide, adjust the pH of the solution in the range of 1-6, carry out stirring reaction, and prepare Fenton with strong oxidizing ability The reaction system is used for the treatment and purification of industrial wastewater.

The beneficial effects of above-mentioned technical scheme of the present invention are as follows:

In the above scheme, an effective technical scheme is provided for the problems of iron interference and low extraction efficiency encountered in the existing leaching-extraction-electrodeposition process, and at the same time, the high-value utilization of the absorbed iron ion resources It provides a novel technical approach that is economically acceptable and technically feasible, and is expected to realize the efficient resource utilization of iron resources in hydrometallurgical industrial wastewater, and provide ultra-fine zero-valent iron powder for water treatment and Fenton oxidation reaction. It is a new type of iron source material that is cheap, abundant in sources, high in activity, and has few iron reagent residues. At the same time, it can also absorb and remove heavy metal ions that may be contained in industrial wastewater, so as to realize various types of iron in the field of hydrometallurgy. Comprehensive treatment of metal ion wastewater.

Description of drawings

Fig. 1 is the schematic diagram of the leaching-adsorption iron removal-extraction enrichment of valuable metals-electrowinning process taking copper as an example of the present invention;

Fig. 2 is a schematic diagram of the leaching-adsorption iron removal-adsorption enrichment of valuable metals-electrowinning process taking copper as an example in the present invention.

detailed description

In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following will describe in detail with reference to the drawings and specific embodiments.

The invention aims at the shortcomings of the existing low-grade metal ore "leaching-extraction-electrodeposition" process, and provides a low-grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical process.

Example 1

Using the process principle of "leaching-adsorption iron removal-extraction and enrichment of valuable metals-electrodeposition" as shown in Figure 1, take 2 kilograms of low-grade zinc ore powder (sieved 100 mesh) from a certain real estate, and the solid-liquid ratio is Add 0.5M sulfuric acid at 1:10 for stirring and leaching, and heat to 90 degrees Celsius, keep stirring and leaching for 3 hours, filter, take out 18 liters of the obtained filtrate, add new zinc ore powder to make the pH of the solution 2.3, and filter to obtain The filtrate is ready for use;

Record iron 4.6g/L in the filtrate, zinc 6.3g/L, drop into 500 grams of garlic waste granule adsorbent, after stirring and reacting for 120 minutes, the adsorbent is filtered, and the iron concentration recorded in the filtrate is 0.4g/L , zinc 6.2g/L, and then use the extractant P ₂₀₄ to contact the solution to react, extract the zinc ions in it, and get a zinc solution with a concentration of 43.2g/L through water washing and back extraction, and further supply the electrodeposition process to recover the zinc in it. Metal.

The adsorbent that has adsorbed iron was washed with distilled water for 3 times, and then put into an oven at 60°C for hot air drying for 6 hours; the obtained dry adsorbent was spread out in a porcelain boat, placed in a tube furnace, and nitrogen gas was introduced. The gas flow rate is 1 liter per minute, and it is heated and decomposed at 400°C to obtain metallic iron powder. After further grinding, sieving, and classification, ultrafine metallic iron powder products with a particle size below 200 mesh can be obtained.

Take 0.5 g of the obtained metal iron powder, mix it with 500 ml of 10PPM concentration dye methylene blue wastewater, add dropwise 10 ml of hydrogen peroxide, and dropwise add 5 ml of 0.5M sulfuric acid solution, stir for 20 minutes and filter to obtain a clear and colorless solution.

Example 2

Using the process principle of "leaching-adsorption iron removal-extraction and enrichment of valuable metals-electrodeposition" as shown in Figure 1, a certain low-grade copper ore powder (sieved to 80 mesh) is taken, and the calcined sand after high-temperature roasting is used. Take 1 kg and mix it with 10 liters of 0.2M dilute sulfuric acid, heat it to 80 degrees Celsius, keep stirring and leaching for 1 hour, adjust the pH of the solution to about 2.3 with calcined sand, and then filter to obtain a clear filtrate, which contains 3.5g/L iron About 0.6g/L copper.

Get this clarification infusion, drop into 200 grams of garlic dregs adsorbents, after stirring and reacting for 100 minutes, filter and collect the filtrate, record the residual iron concentration in the filtrate to be 0.11g/L, copper 0.58g/L, this filtrate uses extraction agent again P ₂₀₄ contacts and reacts with the solution, extracts the copper ions in it, washes with water and back-extracts to obtain a copper solution with a concentration of 17.8g/L. The deposition process recovers the copper metal therein.

After the adsorbent that has adsorbed iron was washed with distilled water for 3 times, it was put into an oven at 60°C and baked with hot air for 6 hours; the obtained dried adsorbent was spread out in a porcelain boat, and placed in a tube furnace to maintain a vacuum degree of 100 Pa, heated and decomposed at 400°C to obtain metallic iron powder, further grinding, sieving, and grading to obtain ultrafine metallic iron powder products with a particle size below 200 mesh.

Take 5.5 grams of the obtained metal iron powder, mix it with 500 milliliters of cadmium-containing heavy metal aqueous solution with a concentration of 10PPM artificially prepared, stir for 4 hours and then filter, the residual cadmium ion concentration in the filtrate is 0.1PPM.

Example 3

Using the process principle of "leaching-adsorption iron removal-extraction and enrichment of valuable metals-electrodeposition" as shown in Figure 1, the acidic wastewater from a mining field is taken, which contains about 1g/L iron and 0.15g/L copper Around, the pH is 2.5.

Get 1 liter of this soaking liquid, drop into 100 grams of garlic dregs adsorbents, after stirring and reacting for 120 minutes, filter, the filtrate collected by filtering records that the residual iron concentration is 0.05g/L, copper 0.15g/L, and this solution is then The extractant P ₂₀₄ is used to contact the solution to extract the copper ions, and after water washing and back extraction, a copper solution with a concentration of 28g/L can be obtained, which can be used for the electrodeposition process to recover the copper metal therein.

Wash the dry adsorbent obtained by adsorbing iron with distilled water for 3 times, put it into an oven at 60°C and dry it with hot air for 6 hours; put the obtained dry adsorbent into a porcelain boat, spread it out flat, put it into a tube furnace, and pass in nitrogen, The nitrogen flow rate is 0.1 liter per minute, and the metal iron powder can be obtained by heating and decomposing at 500°C. After further grinding, sieving, and classification, the ultrafine metal iron powder product with a particle size below 200 mesh can be obtained.

Take 1 gram of the obtained metal iron powder, mix it with 500 ml of 10PPM dye methyl orange wastewater, add 10 ml of hydrogen peroxide dropwise, and add 5 ml of 0.5M sulfuric acid solution dropwise, stir for 30 minutes and filter to obtain a clear and colorless solution.

Example 4

Using the process principle of "leaching-adsorption iron removal-extraction enrichment of valuable metals-electrodeposition" as shown in Figure 1, take a low-grade nickel ore powder (screened 150 mesh), take 1 kg and 8 liters of 0.2M mixed dilute sulfuric acid, and heated to 80 degrees Celsius, kept stirring and leaching for 1 hour, adjusted the pH of the solution to about 2.3 with mineral powder, and then filtered to obtain a clear filtrate, which contained about 5.5g/L of iron and about 1.3g/L of nickel. L.

Get this clarification infusion, drop into 350 grams of garlic dregs adsorbents, after stirring and reacting for 300 minutes, filter and collect the filtrate, record the residual iron concentration in the filtrate to be 0.2g/L, nickel 1.25g/L, this filtrate is used again P ₂₀₄ Contact and react with the solution to extract the nickel ions, wash with water and back-extract to obtain a nickel solution with a concentration of 10.8g/L, which can be supplied to the electrodeposition process to recover the nickel metal therein.

The adsorbent that has adsorbed iron was washed with distilled water for 3 times, and then put into an oven at 60°C for hot air drying for 6 hours; put the obtained dry adsorbent into a porcelain boat, spread it out, put it into a tube furnace, and pass it with argon. Protected, heated and decomposed at 400°C to obtain metallic iron powder, further grinding, sieving, and grading to obtain ultrafine metallic iron powder products with a particle size below 200 mesh.

5 grams of the obtained metal iron powder was mixed with 500 milliliters of artificially prepared copper-containing heavy metal aqueous solution with a concentration of 10 PPM. After stirring for 4 hours, the residual copper ion concentration in the solution was 0.3 PPM.

Example 5

Using the process principle of "leaching-adsorption iron removal-adsorption enrichment of valuable metals-electrodeposition" as shown in Figure 1, take a low-grade cobalt-containing smelting slag (screened 100 mesh), take 1 kg and 10 liters of 0.3 M mixed with dilute sulfuric acid, heated to 80 degrees Celsius, kept stirring and leaching for 1 hour, adjusted the pH of the solution to about 2.3 with smelting slag powder, and then filtered to obtain a clear filtrate, which contained about 5.5g/L iron and about 0.3 cobalt g/L.

Get this clarification infusion, drop into 450 grams of garlic dregs adsorbents, after stirring and reacting for 300 minutes, filter and collect the filtrate, record the residual iron concentration in the filtrate to be 0.2g/L, cobalt 0.25g/L, this filtrate is used again 300 grams The mangosteen slag reacts with the solution to adsorb and extract the cobalt ions, and after washing and desorbing, a cobalt solution with a concentration of 3.8g/L can be obtained, which can be used for the electrodeposition process to recover the cobalt metal.

The adsorbent that has adsorbed iron was washed with distilled water for 3 times, and then put into an oven at 60°C for hot air drying for 6 hours; Heat and decompose at 400°C to obtain metallic iron powder, and further grind, sieve, and classify to obtain ultrafine metallic iron powder products with a particle size below 200 mesh.

5 grams of the obtained metal iron powder was mixed with 500 milliliters of 1PPM mercury-containing heavy metal aqueous solution, and after stirring for 4 hours, the residual mercury ion concentration in the solution was 0.003PPM.

The above description is a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvements and modifications It should also be regarded as the protection scope of the present invention.

Claims (6)

1. Low-grade ore valuable metal leaching-biosorption-electrodeposition hydrometallurgy process, characterized in that: the process steps are as follows: First, take low-grade valuable metal ore powder acid leaching solution containing iron and valuable metals Zn, Cu, Ni, Co, In, Bi or For acidic wastewater, adjust the pH value of the pickling solution or acidic wastewater to 2-3 by adding the same metal ore powder, and add biomass adsorbent materials. 0.1-300g, stirring and reacting for 100-300min, and filtering to obtain biomass adsorbent powder enriched with trivalent metal iron ions and filtrate rich in other valuable metals; Then, the filtrate rich in valuable metals is contacted with the extractant P204, and the valuable metal ions are extracted, washed with water and back-extracted to obtain a solution containing valuable metals, which is supplied to the electrowinning process to recover the valuable metals; or rich in The filtrate of the valuable metal is contacted with the biomass adsorbent to react, absorb the valuable metal ions in it, wash and desorb to obtain a solution containing the valuable metal, and supply the valuable metal in the electrowinning process to recover it; Finally, the biomass adsorbent powder enriched with trivalent metal iron ions was repeatedly washed with distilled water for 2 to 3 times, then placed in an oven at 60 to 80°C for 6 to 8 hours with hot air, and the obtained dry adsorbent powder was spread on the Put it into a tube furnace in a porcelain boat, heat and decompose it at a temperature of 400-600°C under the conditions of vacuum, protective gas or active gas, and obtain metallic iron powder, which is then ground, sieved, and classified , to obtain ultra-fine metal iron powder with a particle size below 200 mesh. 2. The low-grade ore valuable metal leaching-biosorption-electrodeposition hydrometallurgical process according to claim 1 is characterized in that: the prepared ultrafine metal iron powder is 1 gram according to the mass-volume ratio: 0.1- 10 milliliters of hydrogen peroxide, adjust the pH of the solution in the range of 1 to 6, carry out stirring reaction, and prepare a Fenton reaction system with strong oxidizing ability, which is used for the treatment and purification of industrial wastewater. 3. The low-grade ore valuable metal leaching-biosorption-electrowinning hydrometallurgical process according to claim 1, characterized in that the grade of the low-grade valuable metal is below 1%. 4. The low-grade ore valuable metal leaching-biosorption-electrodeposition hydrometallurgical process according to claim 1, characterized in that: the protective gas introduced into the tube furnace is hydrogen, argon, nitrogen, carbon dioxide , the active gas is air. 5. The low-grade ore valuable metal leaching-biosorption-electrowinning hydrometallurgical process according to claim 1, characterized in that: the preparation method of the biomass adsorbent material is as follows: washing with -COOH , -SH, -NH ₂ , -(phenol)OH active functional group biomass, alkali, and water are stirred and mixed according to the mass ratio of 1:0.05-0.2:0.5-2, stirred for 12 to 24 hours, filtered, and obtained Solid product, wherein, the alkali is lithium, sodium, potassium, calcium, magnesium oxide, hydroxide, carbonate, bicarbonate or one or both of ammonium carbonate, ammonium bicarbonate, urea, and ammonia Mix the above; wash the above solid product with water until neutral, send it to a vacuum oven, dry it at a temperature of 60-120°C, crush and sieve the dried product, and collect particles below 40 mesh to obtain a biomass adsorbent material. 6. The low-grade ore valuable metal leaching-biosorption-electrowinning hydrometallurgical process according to claim 1 or 5, characterized in that: the biomass is garlic residue, mangosteen residue, seaweed, distiller's grains, orange residue , apple peel, grapefruit peel.