KR101328154B1 - The recycling method of the high purity valuable metal in the organic waste containing the valuable metal - Google Patents

Abstract

The present invention relates to a production method of high purity metal oxide from organic waste containing valuable metal, more specifically the production method of the high purity metal oxide which comprises the following steps: diluting the organic waste containing the valuable metal with an organic solvent to obtain a diluted solution; adding an acidic aqueous solution containing a phosphorus based extraction agent into the diluted solution, and stirring the mixture for the extraction reaction; inserting the aqueous solution after the extraction reaction into a high temperature reactor, and adding an alkaline solvent before stirring to obtain valuable metal hydroxide; and adding an amine based negative ion extraction agent to the valuable metal hydroxide for extracting, and washing and filtering the result before drying and calcinating. The production method of the high purity metal oxide by the present invention does not use a combustion method for remarkably reducing the discharge amount of contaminants causing air pollution, and reducing the energy costs for the combustion method to improve economic feasibility. [Reference numerals] (AA) Diluting using an organic solvent;(BB) Acidic aqueous solution producing;(CC) Phosphorus based extraction agent addition;(DD) Mixing;(EE,JJ) Injection;(FF) Acid deposition reaction;(GG) Fluid separation;(HH) Soluble solution;(II) Alkali solvent;(KK) Organic metal oxide;(LL) Anion extractor extraction;(MM) Washing, filtering, drying;(NN) High purity metal oxide

Description

The recycling method of the high purity valuable metal in the organic waste containing the valuable metal}

The present invention relates to a method for producing a high-purity metal oxide from organic wastes containing valuable metals. More specifically, after extraction of valuable metals using an acidic aqueous solution and a phosphorus extractant, alkali leaching is carried out at a high temperature and an amine The present invention relates to a method for producing a high purity metal oxide by removing impurities using a system anion extractant.

Molybdenum products used to maximize the wear resistance of lubrication products used in machinery operation and gears, automobiles, ships, etc. contain molybdenum as little as 5% to as high as 20%. If the content is less than 5% organic molybdenum, if the content exceeds 5% molybdenum particles are generally mixed with lubricating oil or grease by using a grinding device such as a jet mill and dispersion equipment. Molybdenum is one of the domestic resources currently in existence in the United States and China, and its domestic production is poor, so it depends on imports. In particular, the domestic molybdenum reserves are about 5 million tons, and the mining year considering the domestic demand is only 2.3 years. As the resources are depleted in the future, the United States and China are more likely to weaponize molybdenum, a rare metal, and there is a necessity to establish a network capable of recycling resources by recycling molybdenum-containing wastes.

In addition, the catalysts introduced in the petrochemical process are generated as organic waste catalysts, and in particular, organic tin catalysts are frequently used to synthesize urethane or polyol. For example, tin catalysts used in the synthesis of urethanes frequently use butyltin or octyltin catalysts. Desulfurization catalysts to remove sulfur contained in crude oil use vanadium, molybdenum and nickel, which are stearic or oleic vanadium and molybdenum catalysts. That is, by synthesizing various organic substances to metals to increase the solubility of the catalyst in crude oil, recycling of valuable metals is quite difficult unlike recycling of valuable metals contained in waste such as dust, scrap, and waste water. Moreover, since these organic wastes are hazardous wastes, safe and eco-friendly recovery of valuable metals is urgently required.

In general, in the case of organic wastes containing valuable metals, primary metals are prepared by incineration using an oxidation furnace or by recovering valuable metals by reducing the coke with a coke in a reduction furnace. In this regard, after roasting in the Patent Publication Nos. 10-2008-0026448, 10-2009-0132462, or 10-1998-0021919, the molybdenum is recovered by using ammonia water and residual nickel vanadium is recovered. The recovery process is disclosed. In other words, the organic material is removed through a roasting process to obtain a low-purity metal or low-purity oxide form, and then a high-purity oxide is produced by purification. However, this method has a problem of generating environmental pollution by emitting a large amount of air pollutants such as sulfur oxides, nitrogen oxides, CO ₂ .

Accordingly, in the present invention, in order to solve the above problems, in the method for producing a metal oxide from organic waste such as waste lubricating oil, organic waste catalyst, etc., wet method using a phosphorus-based extractant that is not a valuable metal recovery method by incineration in an electric furnace Extracting the valuable metal by the method, to provide a method for producing a high purity metal oxide by removing impurities using an amine-based extractant.

According to an aspect of the present invention,

Diluting an organic waste containing valuable metals with an organic solvent to prepare a diluent; An acid leaching step of adding and stirring an acidic aqueous solution containing a phosphorus extractant to the diluent to perform a leaching reaction; Adding an aqueous solution of the acid leaching reaction to a high temperature reactor, and adding and stirring an alkali solvent to prepare a valuable metal hydroxide; And extracting a solvent by adding an amine anion extractant to the valuable metal hydroxide, followed by washing, filtration, drying, and calcining thereof, to a method of manufacturing a high purity metal oxide from an organic waste containing a valuable metal. .

In the present invention, preferably, the phosphorus extractant is a water-soluble phosphorus extractant having the following formula. Provided that R, R ₁ and R ₂ are aliphatic hydrocarbons having 1 to 30 carbon atoms.

More preferably the phosphorus extractant is 4-[(4-hydroxy-butyl) -pentyl-phosphinoyl] -butan-1-ol, (4-hydroxy-butyl) -pentyl-phosphonic acid, and It is characterized by one or more selected from 4-hydroxy-butyl-pentyl-phosphonic acid.

Also preferably, it is a water-soluble polyphosphorus extractant having the following formula. (Wherein R, R ₁ and R ₂ are aliphatic hydrocarbons having 1 to 30 carbon atoms and n is an integer from 1 to 100).

In addition, in the present invention, it is preferable that the oil-water separator is further included in the acidic aqueous solution containing the phosphorus-based extractant. At this time, the oil-and-water separator is selected from at least one of nonyl phenol ethoxy resin, isobutyl phenol ethoxy resin, octyl phenol ethoxy resin, dodecyl benzene sulfonic acid resin, decane benzene sulfonic acid resin, paranonyl zylene ethoxy resin. More preferred.

In the present invention, an aqueous hydrochloric acid, sulfuric acid or phosphoric acid may be used as the acidic aqueous solution.

In the present invention, the production process of the valuable metal hydroxide is characterized in that the acid leaching solution is added to a high temperature reactor of 110 ~ 130 ℃, an alkali solvent is added and stirred to produce a valuable metal hydroxide. .

In the present invention, the amine-based anion extractor is characterized by using TIOA (Tri-iso-octyl amine) or triethylamine.

In the present invention, the alkali solvent is characterized in that sodium hydroxide, potassium hydroxide or ammonium.

In the present invention, the metal oxide is at least one selected from molybdenum oxide, tin oxide, nickel oxide, vanadium oxide, cobalt oxide, lead oxide, manganese oxide and copper oxide.

As described above, the present invention relates to a method for producing high-purity metal oxides from organic wastes containing valuable metals such as waste lubricating oil and organic waste catalyst by a wet method, and does not use an incineration method. Can significantly reduce the energy cost for incineration can be produced environmentally and economically metal oxides. In particular, according to the method of the present invention, while using the wet extraction reaction by using a water-soluble phosphorus extractant rather than a useful extractant has an effect of greatly improving the efficiency of the reaction, it is easy to recover valuable metal components, alkali at high temperature After reacting with a solvent to form a hydroxide, the solvent is extracted using an amine anion extractant to remove impurities, thereby producing a high purity metal oxide.

1 shows a high purity metal oxide manufacturing process according to the present invention.

The present invention recovers valuable metals by a wet method using an acidic aqueous solution and a phosphorus extractant from an organic waste, makes hydroxide with an alkali solvent at high temperature, and then removes impurities by solvent extraction using an amine extractant to remove high purity metal oxides. It relates to a manufacturing method.

Hereinafter, the present invention will be described in detail by dividing the process with reference to FIG. 1.

The first step is a step of mixing and diluting an organic solvent in an organic waste containing valuable metals. In general, organic waste or commercial organic compounds including waste lubricants, waste grease and the like have high viscosity and are in poor condition so that the organic solvent is diluted using an organic solvent to allow a smooth extraction reaction. At this time, an organic solvent can be used without a restriction | limiting in the range. For example, aliphatic compounds, such as normal hexane, aliphatic hydrocarbons, such as heptane, octane, and decane, aromatic compounds, such as benzene toluene and xylene, etc. can be selected. In one embodiment of the present invention used normal hexane.

The second step is a step of extracting valuable metals by acid leaching using an acidic solution containing a phosphorus-based extractant prepared by adding and stirring a phosphorus-based extractant to an acidic aqueous solution. By adding and stirring the acidic aqueous solution containing the phosphorus extractant to the dilution liquid of the organic waste prepared above, the organic metal contained in the organic waste becomes unstable by the acidic aqueous solution, and the organic metal in the phosphorus extractant As the metal is bonded to break the organic metal bond, the valuable metal to be extracted is extracted in an acidic aqueous solution, and oil and water separation occurs.

In this case, preferably, when the oil and water separator is further added, the organic waste from which the valuable metal is removed and the oil and water separator of the aqueous solution serve as a reaction aid to increase the oil and water separation efficiency. The oil-and-water separator may be selected from at least one of nonyl phenol ethoxy resin, isobutyl phenol ethoxy resin, octyl phenol ethoxy resin, dodecyl benzene sulfonic acid resin, decane benzene sulfonic acid resin, and paranonyl zylene ethoxy resin. Can be.

At this time, the acidic aqueous solution may use hydrochloric acid, sulfuric acid, phosphoric acid and the like, preferably in the range of 0.0001N to 0.1N. However, when the concentration is increased, the acid concentration may be increased since the reaction time may be reduced and the recovery of valuable metals may be increased. The reaction efficiency can be improved. In one embodiment of the present invention to prepare a phosphate solution of 1 normal concentration so that the pH is 0 or less.

At this time, the phosphorus-based extractant is an oil-soluble extractant having an aliphatic compound in the terminal group, but in the present invention, a water-soluble phosphorus extractant is used. That is, an aliphatic compound is attached on one side to facilitate the action with organic wastes, and on the other side, an alcohol is attached to the water-soluble phosphorus extractant in the form of R-PO-R ₁ OH-R ₂ OH as shown in the above formula. Is characterized in that R, R ₁ and R ₂ are aliphatic hydrocarbons having 1 to 30 carbon atoms.

As an example of such a water-soluble phosphorus extractant, one or more kinds of the following extractants having a pentyl group as the aliphatic compound may be selected and used.

In addition, since the water-soluble phosphorus extracting agent having the form of R-PO-R ₁ OH-R ₂ OH has the characteristic that the phosphorus can be polymerized, various forms of polymerized polyphosphorus extraction while opening a double bond of the ketone It is possible to prepare the agent. Such polyphosphorus extractant may improve the extraction efficiency of the valuable metals by increasing the reaction efficiency. Therefore, preferably in the present invention, the phosphorus-based extractant is characterized in that it is a water-soluble polyphosphorus extractant having the following formula (wherein R, R ₁ and R ₂ are aliphatic hydrocarbons having 1 to 30 carbon atoms, and n is Is an integer from 1 to 100).

The third step is a step of preparing a valuable metal hydroxide by adding an acidic aqueous solution in which the extraction of the valuable metal is completed into a high temperature reactor, and adding and stirring an alkali solvent. At this time, the alkali solvent is preferably sodium hydroxide, potassium hydroxide or ammonium, especially when the reaction at a high temperature of 110 ~ 130 ℃ acidic and basic amphoteric reaction of the valuable metal is active to prevent leaching of the valuable metal It can be remarkably improved. In this case, hydrogen peroxide may be added as needed to promote oxidation of the metal sulfide.

In the fourth step, the amine anion extractant is added to the valuable metal hydroxide to extract a solvent, followed by washing, filtration, drying and calcining to produce a high purity metal oxide. It is possible to produce a high purity metal oxide. At this time, the amine-based anion extractor is preferably TIOA (Tri-iso-octyl amine) or triethylamine. By using such an amine anion extractor, it is possible to separate molybdenum oxide having a high purity of 99% or more regardless of solubilized impurities. In the embodiment of the present invention was filtered and washed using a paper filter vacuum filter, the number of washing was the most suitable three times, and finally dried and calcined to form MoO ₃ .

< Example  1>

First, 100 g of waste lubricating oil and 100 g of normal hexane were added and stirred for 1 hour.

In addition, in order to make 1N aqueous solution of phosphoric acid, 6.8 g of phosphoric acid was dissolved in water to prepare a total of 200 g, and 0.12 g of (4-hydroxy-butyl) -phentyl-phosphinic acid as a phosphorus extractant was added thereto and stirred.

Next, the diluted waste lubricant was slowly added to the aqueous phosphoric acid solution containing the phosphorus extractant and stirred. And temperature was advanced at 40 degreeC in order to make reaction smooth. At this time, normal hexane can be easily volatilized and refluxed using a countercurrent cooler. The reaction time was 1 hour. After the reaction was carried out, 0.02 g of nonyl phenol ethoxylate resin was added thereto, followed by stirring for 10 minutes and allowed to stand. When the stirrer was settled, the acidic aqueous solution from which the valuable metals were extracted and the waste oil from which the valuable metals were removed were separated. After layer separation, the acidic aqueous solution of the separated lower layer was added to a high-temperature pressure reactor to make a valuable metal oxide, 12 g of sodium hydroxide was added, and the reaction mixture was heated at 120% at a mineral concentration of 30% and stirred at 360 rpm for 4 hours. For the purpose of removing impurities, 4 g of TIOA (Tri-iso-octyl amine) was added as an amine-based anion extractor, and mixed at 400 rpm or more for about 1 hour to increase efficiency, and allowed to stand for 4 hours for reliable separation. After solid-liquid separation, Mo (OH) ₆ was washed and filtered three times, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. for 2 hours to prepare MoO ₃ , and then analyzed the content of Mo by ICP analysis.

< Example  2>

Prepared in the same manner as in Example 1, 3.6g of triethylamine instead of TIOA was added to prepare a high purity metal oxide MoO ₃ and analyzed the content of Mo by ICP analysis.

< Comparative Example  1>

First, 100 g of waste lubricating oil and 100 g of normal hexane were added and stirred for 1 hour.

In addition, in order to make 1N aqueous solution of phosphoric acid, 6.8 g of phosphoric acid was dissolved in water to prepare a total of 200 g, and 0.12 g of (4-hydroxy-butyl) -phentyl-phosphinic acid as a phosphorus extractant was added thereto and stirred.

Next, the diluted waste lubricant was slowly added to the aqueous phosphoric acid solution containing the phosphorus extractant and stirred. And temperature was advanced at 40 degreeC in order to make reaction smooth. At this time, normal hexane can be easily volatilized and refluxed using a countercurrent cooler. The reaction time was 1 hour. After the reaction was carried out, 0.02 g of nonyl phenol ethoxylate resin was added thereto, followed by stirring for 10 minutes and allowed to stand. When the stirrer was settled, the acidic aqueous solution from which the valuable metals were extracted and the waste oil from which the valuable metals were removed were separated. After layer separation, 12 g of sodium hydroxide was added to the separation solution to make a valuable metal oxide, and the mixture was reacted at 360 rpm for 4 hours at room temperature. For the purpose of removing impurities, 4 g of TIOA was added and mixed for about 1 hour at 400 rpm or more to increase the efficiency, and allowed to stand for 4 hours for reliable separation. After solid-liquid separation, Mo (OH) ₆ was washed and filtered three times, dried at 120 ° C. for 12 hours, and calcined at 500 ° C. for 2 hours to prepare MoO ₃ , and then analyzed the content of Mo by ICP analysis.

<Result>

ICP analysis results according to Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below. As shown in Table 1, the molybdenum content was higher in the high-purity metal oxide where the extraction reaction was completed and the impurities were significantly higher than the extraction at room temperature when the basic solvent extractant was extracted in the valuable metal oxide state at high temperature. It was confirmed that the decrease. It is confirmed that the acidic and basic amphoteric functions of Mo become more smooth when the back extraction with a basic solvent in a high temperature reaction enables extraction of a large amount of molybdenum, and at least 99% of high purity molybdenum oxide can be obtained using an amine anion extractant. Could.

Item

Example  One
Example  2
Comparative Example  One Si Not detected Not detected Not detected Cr 51.27 48.76 149.74 Fe 85.71 101.04 234.94 Sb 12.03 30.25 76.03 CD 29.88 35.65 35.65 Co Not detected 8.75 Not detected Ca 48.33 17.96 70.71 Mg Not detected Not detected Not detected Na Not detected Not detected 23.17 Zr Not detected Not detected Not detected Al Not detected Not detected Not detected Ni 46.02 58.78 134.88 Pb 34.29 61.12 101.85 Zn 7.74 6.96 49.74 Cu Not detected Not detected 24.96 Mn Not detected Not detected 6.54 K Not detected Not detected Not detected In Not detected Not detected Not detected W Not detected Not detected Not detected P Not detected Not detected Not detected Tl Not detected Not detected Not detected Ti Not detected Not detected Not detected Ag Not detected Not detected Not detected As Not detected Not detected Not detected
Mo  (%)

99.4672
99.3409
90.3920

According to the high purity metal oxide manufacturing method according to the present invention, not only recovers molybdenum from waste lubricating oil and tin from waste urethane, but also recovers valuable metals easily from petrochemical waste catalysts such as vanadium, molybdenum and nickel, which are desulfurization catalysts of crude oil. It is possible to obtain a high purity metal oxide using an amine anion extractant after extraction with a basic solvent in a high temperature state, the method of the present invention can be sufficiently applied to organic compounds including organic waste, industrial use It is expected to be very likely.

Claims (11)

Diluting an organic waste containing valuable metals with an organic solvent to prepare a diluent;
An acid leaching step of adding and stirring an acidic aqueous solution containing a phosphorus extractant to the diluent to perform a leaching reaction;
Adding an aqueous solution of the acid leaching reaction to a high temperature reactor, and adding and stirring an alkali solvent to prepare a valuable metal hydroxide; And
A method of producing a high purity metal oxide from an organic waste containing a valuable metal, comprising the step of adding a amine-based extractant to the valuable metal hydroxide, solvent extraction, washing, filtration, drying and calcining it. The method of claim 1,
The phosphorus extractant is a water-soluble phosphorus extractant having the following formula, characterized in that, to produce a high purity metal oxide from organic waste containing valuable metals.
(However, R, R ₁ , R ₂ are aliphatic hydrocarbons having 1 to 30 carbon atoms.)

3. The method of claim 2,
The phosphorus extractant is 4-[(4-hydroxy-butyl) -pentyl-phosphinoyl] -butan-1-ol, (4-hydroxy-butyl) -pentyl-phosphonic acid, and 4-hydroxy A method for producing a high purity metal oxide from organic wastes containing valuable metals, characterized in that at least one selected from -butyl-pentyl-phosphonic acid. The method of claim 1,
The phosphorus extract is a water-soluble polyphosphorus extract having the following formula, characterized in that, a high-purity metal oxide from the organic waste containing valuable metals.
(Wherein R, R ₁ and R ₂ are aliphatic hydrocarbons having 1 to 30 carbon atoms and n is an integer from 1 to 100).

The method of claim 1,
The acidic aqueous solution containing the phosphorus-based extractant is hydrochloric acid, sulfuric acid or a phosphoric acid aqueous solution, characterized in that a high-purity metal oxide from the organic waste containing valuable metals. The method of claim 1,
A method of producing a high purity metal oxide from an organic waste containing valuable metals, characterized in that the oil-water separator is further included in the acidic aqueous solution containing the phosphorus-based extractant. The method according to claim 6,
The oil-and-water separator is at least one resin selected from nonyl phenol ethoxy resin, isobutyl phenol ethoxy resin, octyl phenol ethoxy resin, dodecyl benzene sulfonic acid resin, decane benzene sulfonic acid resin, and paranonyl zylene ethoxy resin. A method for producing a high purity metal oxide from an organic waste containing valuable metals. The method of claim 1,
The manufacturing process of the valuable metal hydroxide, the valuable solution containing the valuable metal, characterized in that the aqueous leaching reaction is completed is put into a high temperature reactor of 110 ~ 130 ℃, an alkali solvent is added and stirred to produce a valuable metal hydroxide Process for producing high purity metal oxides from organic wastes. The method of claim 8,
The alkaline solvent is sodium hydroxide, potassium hydroxide or ammonium, characterized in that the production of high purity metal oxides from organic wastes containing valuable metals. The method of claim 1,
The amine extractant is TIOA (Tri-iso-octyl amine) or triethylamine, characterized in that a high-purity metal oxide from the organic waste containing valuable metals. 11. The method according to any one of claims 1 to 10,
The metal oxide is any one or more selected from molybdenum oxide, tin oxide, nickel oxide, vanadium oxide, cobalt oxide, lead oxide, manganese oxide and copper oxide, to produce a high purity metal oxide from organic waste containing valuable metals How to.

Images