阅读说明：本技术 多孔卟啉聚合物以及使用其回收贵金属元素的方法 (Porous porphyrin polymer and method for recovering noble metal element using same ) 是由 C·亚维兹 洪荣兰 T·达米安 S·萨拉瓦南 于 2018-10-31 设计创作，主要内容包括：本发明涉及一种多孔卟啉聚合物以及一种使用其回收贵金属元素的方法,并且对贵金属元素具有高选择性和吸附性的化学式1的多孔卟啉聚合物可以应用于从电子产品废物的金属浸出液、河水或海水中回收贵金属元素。(The present invention relates to a porous porphyrin polymer and a method for recovering a noble metal element using the same, and the porous porphyrin polymer of chemical formula 1 having high selectivity and adsorbability for the noble metal element can be applied to recovery of the noble metal element from a metal leachate of electronic product waste, river water or sea water.)

1. A porphyrin polymer represented by formula 1:

[ formula 1]

Wherein n is an integer of 5,000 to 50,000, and m is an integer of 5,000 to 50,000.

2. The porphyrin polymer of claim 1, represented by formula 2:

[ formula 2]

Wherein n is an integer of 5,000 to 50,000, and m is an integer of 5,000 to 50,000.

3. The porphyrin polymer of claim 1, wherein the porphyrin polymer has a molecular weight of 300-²g^-1Specific surface area and pore size of 0-20 nm.

4. A method of making a porphyrin polymer of claim 1, comprising: polymerizing 5,10,15, 20-tetrakis (4-nitrophenyl) -21H, 23H-porphyrin monomer.

5. The method of preparing a porphyrin polymer of claim 4, wherein the 5,10,15, 20-tetrakis (4-nitrophenyl) -21H, 23H-porphyrin monomer is obtained by: 4-nitrobenzaldehyde is dissolved in propionic acid, and then acetic anhydride and pyrrole are added to the solution and reacted.

6. The method of preparing a porphyrin polymer of claim 4, comprising:

obtaining a reaction product by mixing and reacting the 5,10,15, 20-tetrakis (4-nitrophenyl) -21H, 23H-porphyrin monomer, paraphenylene diamine, and a base in anhydrous N, N-dimethylformamide; and

a precipitate is obtained by adding water to the reaction product, and the porphyrin polymer is obtained by filtering and drying the precipitate.

7. An adsorbent comprising the porphyrin polymer of claim 1.

8. A method of recovering a noble metal element from a solution containing the noble metal element, comprising:

a) adding the adsorbent according to claim 7 to the solution containing the noble metal element, and adsorbing the noble metal element onto the adsorbent; and

b) desorbing and recovering the noble metal element from the adsorbent having the noble metal element adsorbed thereon.

9. The method for recovering a noble metal element from a solution containing a noble metal element according to claim 8, wherein the solution containing a noble metal element is seawater or wastewater from a plating plant.

10. A method of recovering precious metal elements from waste electronic products, comprising:

a) removing the coating film from the sheet of the used electronic product;

b) immersing the plate from which the coating film is removed in an acidic solution, and filtering the solution;

c) adding an alkaline solution and deionized water to the filtered solution, and then adding the adsorbent according to claim 6 thereto, and adsorbing the noble metal element onto the adsorbent; and

d) desorbing and recovering the noble metal element from the adsorbent having the noble metal element adsorbed thereon.

11. The method for recovering a noble metal element from a solution containing a noble metal element according to claim 8 or 10, wherein the noble metal is selected from the group consisting of Au, Pt, Ag, Pd, Ru, Rh, Ir, Cu, and Re.

12. The method for recovering a noble metal element from a solution containing a noble metal element according to claim 8, wherein when the noble metal is gold (Au), the solution has a pH of 4 or less, and when the noble metal is platinum (Pt), the solution has a pH of 2 to 9.

13. The method for recovering a noble metal element from a solution containing a noble metal element according to claim 8, wherein step (b) comprises desorbing the noble metal element by adding the adsorbent adsorbing the noble metal element to an acidic solution.

14. The method of recovering precious metal elements from spent electronic products of claim 10, wherein step (d) comprises desorbing the precious metal elements by adding the adsorbent having the precious metal elements adsorbed thereto to an acidic solution.

15. The method for recovering a noble metal element from a solution containing a noble metal element according to claim 8, further comprising a step of reintroducing the adsorbent having the noble metal element adsorbed thereto into step (a) after step (b).

16. The method for recovering noble metal elements from waste electronic products of claim 10, further comprising the step of re-inputting the adsorbent having the noble metal elements adsorbed thereto into step (a) after step (d).

17. The method for recovering a noble metal element from a solution containing a noble metal element according to claim 8, wherein step (a) comprises adsorbing the noble metal element onto the adsorbent while irradiating light.

18. The method for recovering a noble metal element from a waste electronic product according to claim 10, wherein the step (c) comprises adsorbing the noble metal element onto the adsorbent while irradiating light.

Technical Field

The present invention relates to a porous porphyrin polymer and a method for recovering a noble metal element using the same, and more particularly to a porous porphyrin polymer having high selectivity for a noble metal element and a method for recovering a noble metal element using the same.

Background

The noble metal elements generally include platinum group elements such as ruthenium, rhodium, palladium, iridium, and platinum; and coinage metal elements such as copper, silver, and gold. These metals are mainly used in various industries including the electronics industry, the automotive industry, chemical processes, the jewelry industry, and the pharmaceutical industry due to their excellent physical and chemical properties such as high stability, conductivity, ductility, malleability, gloss, and excellent catalytic properties.

These noble metal elements are used as important raw materials especially in the high-tech industry, and the demand for them is increasing with the high development of science and technology. However, the amount of valuable metals that can be extracted from natural ores is extremely small and is concentrated in some countries and regions. Results of studies on the amount of gold produced in natural mines in 2016 indicate that the first thirteen countries, including china, australia, russia, the united states, etc., account for greater than 70% of world gold production. Results of studies on the amount of platinum group metals produced from natural ores in the same year indicate that five countries including russia, south africa, canada, the united states and zimbabwe account for about 97% of the world platinum group metal production, indicating that resource maldistribution is more severe (U.S. geographic Survey, Mineral society summaries 2017).

Therefore, the source from which the noble metal elements are obtained should be broadened from a primary source such as natural ore to a secondary source such as industrial waste, wastewater, river, and ocean.

As a representative example, efforts have been made in many countries around the world to recover precious metal elements from waste electronic products. This idea derives from the concept of "urban mining" first proposed in 1986 by professor Michio Nanjo (Tohoku University, japan), and means to recover and recycle important metals accumulated in our lives, thus realizing innovation with limited resources. The waste electronic products contain various metals such as copper, iron, aluminum, tin, etc., and among these metals, noble metals such as gold, silver, and palladium account for less than 1% by weight of the waste electronic products. However, due to the high price of precious metals, the value of most waste electronic products is known from the recycling of precious metals (Hageluken, christian. electronics and the environment,2006.Proceedings of the 2006IEEE International Symposium on. IEEE, 2006).

Therefore, the recovery of precious metals from waste electronic products can be considered as an economically important technology for recovering high-value precious metals. Furthermore, the recovery of metals from waste electronic products is also important from an environmental point of view. With the development of the electronics industry, the huge amount of waste electronic products generated worldwide is enormous, and the amount of waste electronic products generated is increasing. The amount of waste electronic product produced is reported to reach 41.8MT in 2014 (Balde, C.P. et al, The global e-waste monitor-2014, United Nations University, IAS-SCYCLE, Bonn, Germany 2015). These waste electronic products generate heavy metals (such as mercury, cadmium, lead, and arsenic) and toxic gases during their disposal, resulting in increased water, air, and soil pollution. Therefore, there is a need to develop an environmentally friendly and efficient method for recovering metals from waste electronic products.

Current methods for recycling metals from waste electronic products include dry refining, wet refining, and biorefinery processes. In dry refining, pretreated waste electronic products are melted into molten slag in a furnace at a high temperature of 1,000 ℃ or higher. The slag and the metal components are separated by a difference in specific gravity, and the noble metal in solid solution is obtained in the captured metal. In the wet refining technique, metals from pretreated waste electronic products are dissolved in a solvent. For metal leaching, inorganic acids such as nitric acid and hydrochloric acid are generally used, and cyanide, halide, thiourea, thiosulfate, and the like are also used. Methods for recovering the precious metal ions present in the solution after leaching include ion exchange, solvent extraction, cementation, precipitation, and the like. Biorefinery is a process that uses algae, fungi or bacteria as an adsorbent to adsorb and separate precious metal elements. The bioadsorption of noble metal ions contained in a solution can be roughly classified into chemisorption and physisorption. Chemisorption mechanisms include complexation, chelation, micro-precipitation, and microbial reduction, and physisorption mechanisms are generally explained by electrostatic forces and ion exchange (Cui, Jirang et al, Journal of hazardous materials 158.2(2008): 228-.

In the case of dry refining, the pretreatment of waste electronic products is relatively simple and convenient, but the equipment cost is very high, and high-temperature use consumes a large amount of energy. In addition, there are limitations in that the combustion of plastic causes air pollution and some metals such as aluminum are not recovered, and there are disadvantages in that the recovery rate of precious metals is low due to the use of slag. In the case of wet refining, the equipment cost is lower than that of wet refining and the separation of metals is easy, but there are disadvantages in that valuable metals are recovered through several steps using various solvents or materials and toxic waste water is generated in the recovery process. In the current korean valuable metal recovery company, the kinds of metals to be recovered are limited to copper and the like, and the level of the preparation technology and method design for recovering valuable metals is low, and therefore, successful commercialization results are insufficient, and the commercialization rate is lower than the research results. Biological based techniques have limitations because, despite their theoretically unlimited possibilities, they can only be used in very limited situations due to the difficulty of controlling microbial behaviour.

Other examples of sources from which precious metal elements may be recovered include rivers or oceans. Seawater is known to contain high value metals such as copper, silver, gold, palladium and platinum. Although the concentration of these metal ions is very low (in the order of a few ppt or less), the amount of metals in seawater is also very large when considering the enormous amount of seawater in the world. For example, about 1430 million tons of gold (http:// amscieria. blogspot. kr/2012/04/gold-from-seawater. html) are known to be present in seawater.

Although the concentration of such metal ions has been variously reported according to literature and measurement methods, it is generally known that the concentration is very low (several ppt or less in order of magnitude). However, when it is considered that more than 70% of the earth's surface is covered with seawater, it can be seen that the amount of the main metals contained in seawater is quite large (Lodeiro, Pablo et al, Marine Chemistry152(2013):11-19., Terada, Kikuo et al, analytical Chimica Acta 116.1(1980): 127-.

The presence of gold in seawater was first reported in 1872, and attempts to extract gold from seawater were a well-known case by Fritz Haber in the twentieth century. However, successful extraction of gold from valuable metals of seawater has not been reported because the concentration of metal ions in seawater is very low and conditions including seawater depth and temperature are difficult to control (Falkner, K.Kenison et al, Earth and Planet Science Letters 98.2(1990): 208-.

Accordingly, the present inventors have made a great effort to solve the above-described problems, and as a result, have found that the porous porphyrin polymer represented by formula 1 has high selectivity for noble metal elements and thus can be applied to the recovery of noble metal elements from a metal leachate from waste electronic products or from river water or seawater, thereby completing the present invention.

Disclosure of Invention

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a porous porphyrin polymer having high selectivity for a noble metal element.

It is another object of the present invention to provide a method in which a noble metal element in a noble metal-containing solution is selectively adsorbed using a porous porphyrin polymer, and the adsorbed noble metal element and polymer adsorbent are recovered again.

The above object of the present invention can be achieved by the present invention as specified below.

In order to achieve the above object, the present invention provides a porphyrin polymer represented by the following formula 1:

[ formula 1]

Wherein n is an integer of 5,000 to 50,000, and m is an integer of 5,000 to 50,000.

The present invention also provides a method for preparing the porphyrin polymer, which comprises: a step of polymerizing 5,10,15, 20-tetrakis (4-nitrophenyl) -21H, 23H-porphyrin monomer.

The invention also provides an adsorbent which comprises the porphyrin polymer.

The present invention also provides a method for recovering a noble metal element from a solution containing the noble metal element, the method comprising the steps of:

(a) adding an adsorbent comprising a porphyrin polymer of formula 1 to the noble metal element-containing solution, and adsorbing the noble metal element onto the adsorbent; and

(b) desorbing and recovering the noble metal element from the adsorbent having the noble metal element adsorbed thereon.

The invention also provides a method for recovering precious metal elements from waste electronic products, which comprises the following steps:

(a) removing the coating from the substrate of the used electronic product;

(b) immersing the substrate from which the coating is removed in an acidic solution, and filtering the solution;

(c) adding an alkaline solution and deionized water to the filtered solution, and then adding thereto an adsorbent comprising the porphyrin polymer of formula 1, and adsorbing the noble metal element onto the adsorbent; and

(d) desorbing and recovering the noble metal element from the adsorbent having the noble metal element adsorbed thereon.

Drawings

Fig. 1 is a graph showing FT-IR spectra of porphyrin monomer TNPPH2 and the synthesized porphyrin polymer.

Fig. 2 is a graph showing nitrogen adsorption/desorption curves at 77K for the synthesized porphyrin polymer.

Fig. 3 is a graph showing the pore characteristics of a porous porphyrin polymer.

Fig. 4 is a graph showing an XRD pattern of the porous porphyrin polymer.

Fig. 5 is a graph showing the change in weight of the porous polymer with an increase in temperature under each of an air atmosphere and a nitrogen atmosphere, and illustrates the thermal durability of the polymer.

Fig. 6 is a graph showing the results of a metal ion adsorption experiment in the standard solution (1) using a porous porphyrin polymer, and shows the metal ion selectivity of the porous porphyrin polymer.

Fig. 7 is a graph showing the results of a metal ion adsorption experiment in the standard solution (2) using a porous porphyrin polymer, and shows the metal ion selectivity of the porous porphyrin polymer.

Fig. 8 is a graph showing the results of a metal ion adsorption experiment performed with a porous porphyrin polymer in a mixture solution of the standard solution (1) and the standard solution (2), and shows the metal ion selectivity of the porous porphyrin polymer.

Fig. 9 is a graph showing the results of a metal ion adsorption experiment in the standard solution (3) with a porous porphyrin polymer, and shows the metal ion selectivity of the porous porphyrin polymer.

Fig. 10 is a graph showing the results of a metal ion adsorption experiment in the standard solution (4) with a porous porphyrin polymer, and shows the metal ion selectivity of the porous porphyrin polymer.

Fig. 11 is a graph showing the concentration-dependent change in gold ion adsorption, and shows the results of experiments performed under natural light and under light-shielding conditions and under light irradiation.

Fig. 12 is a graph showing concentration-dependent changes in platinum ion adsorption, and shows the results of performing a natural light experiment.

Figure 13 shows the time dependent adsorption of gold ions at different pH conditions.

Figure 14 shows the time-dependent adsorption of platinum ions at different pH conditions.

Fig. 15 is a graph showing the efficiency of time-dependent desorption of gold ions adsorbed on a porous porphyrin polymer at 80 ℃ under different acidic conditions.

Fig. 16 is a graph showing the efficiency of time-dependent desorption of platinum ions adsorbed on a porous porphyrin polymer at 80 ℃ under different acidic conditions.

Fig. 17 is a graph showing the efficiency of time-dependent desorption of silver ions adsorbed on a porous porphyrin polymer at 80 ℃ under different acidic conditions.

Fig. 18 is a graph showing the efficiency of time-dependent desorption of palladium ions adsorbed on a porous porphyrin polymer at 80 ℃ under different acidic conditions.

Fig. 19 shows the change in gold ion adsorption efficiency of the porous porphyrin polymer when adsorption and desorption are repeated for a total of three cycles.

Fig. 20 is a photo album of a used electronic product used in an experiment for recovery of gold contained in the used electronic product, and shows before and after metal leaching.

Fig. 21 shows the results of an experiment for recovery of gold contained in waste electronic products, and shows the kinds of metal ions contained in waste electronic products and the adsorption efficiency of porous porphyrin polymer.

Fig. 22 is a schematic diagram of an experiment performed to recover platinum from seawater.

Fig. 23 is a schematic diagram showing an experiment performed to confirm that adsorption of gold ions is increased by light irradiation according to an embodiment of the present invention.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature used herein and the laboratory procedures described below are those well known and commonly employed in the art.

In the present invention, it has been found that the porous porphyrin polymer represented by formula 1 has high selectivity for the noble metal element, and thus can be applied to the recovery of the noble metal element from a metal leachate from waste electronic products or from river water or seawater.

Accordingly, in one aspect, the present invention relates to a porphyrin polymer represented by the following formula 1:

[ formula 1]

Wherein n is an integer of 5,000 to 50,000, and m is an integer of 5,000 to 50,000.

The above formula 1 may preferably be the following formula 1-1:

[ formula 1-1]

Wherein n is an integer of 5,000 to 50,000, and m is an integer of 5,000 to 50,000, andcan be any chemical linking group that links the porphyrins. Preferably, the first and second electrodes are formed of a metal,may be selected from phenazine, azo, amide, benzamide, and triazine, each of which may be represented by the following formulae 3 to 7:

[ formula 3]

[ formula 4]

[ formula 5]

[ formula 6]

[ formula 7]

The porphyrin polymer according to the present invention may be represented by the following formula 2:

[ formula 2]

Wherein n is an integer of 5,000 to 50,000, and m is an integer of 5,000 to 50,000.

The porphyrin polymer according to the invention may have a molecular weight of 300-1000m²g^-1Specific surface area and pore size of 0-20 nm.

The porphyrin polymer according to the invention has been shown to be stable up to 330 ℃ under air and nitrogen atmosphere, indicating thermal durability.

In another aspect, the invention is a method of making the porphyrin polymer, comprising: a step of polymerizing 5,10,15, 20-tetrakis (4-nitrophenyl) -21H, 23H-porphyrin monomer.

The 5,10,15, 20-tetra (4-nitrophenyl) -21H, 23H-porphyrin monomer can be obtained by: 4-nitrobenzaldehyde is dissolved in propionic acid to obtain a solution, and then acetic anhydride and pyrrole are added to the solution and reacted.

The method for preparing a porphyrin polymer may comprise the steps of: mixing and reacting 5,10,15, 20-tetrakis (4-nitrophenyl) -21H, 23H-porphyrin monomer, paraphenylene diamine, and a base in anhydrous N, N-dimethylformamide to obtain a reaction product; and adding water to the reaction product to obtain a precipitate, and filtering and drying the precipitate, thereby obtaining the porphyrin polymer.

It has been found that the porphyrin polymer according to the present invention has high selectivity for gold or platinum metal ions in a solution containing a mixture of various metal ions and high adsorption efficiency at almost all pH, and thus when the porphyrin polymer is applied to a metal leachate from waste electronic products or seawater, it can adsorb and recover gold or platinum metal ions with high selectivity as compared with other metal ions.

In yet another aspect, the present invention relates to an adsorbent comprising a porphyrin polymer represented by the above formula.

In yet another aspect, the present invention relates to a method for recovering a noble metal element from a solution containing the noble metal element, the method comprising: (a) adding an adsorbent comprising a porphyrin polymer of formula 1 to the noble metal element-containing solution, and adsorbing the noble metal element onto the adsorbent; and (b) desorbing and recovering the noble metal element from the adsorbent having the noble metal element adsorbed thereon.

Step (b) may include desorbing the noble metal element by adding the adsorbent adsorbed with the noble metal element to an acidic solution.

The noble metal element-recovering method may further include a step of reintroducing the adsorbent having the noble metal element adsorbed thereto into step (a) after step (b).

The adsorption capacity of the noble metal element can be increased by performing the step (a) while irradiating light.

The solution containing the noble metal element may be seawater or wastewater from a plating plant.

In a further aspect, the invention relates to a method of recovering precious metal elements from spent electronic products, the method comprising the steps of: (a) removing the coating film from the sheet of the used electronic product; (b) immersing the plate from which the coating film is removed in an acidic solution, and filtering the solution; (c) adding an alkaline solution and deionized water to the filtered solution, and then adding thereto an adsorbent comprising the porphyrin polymer of formula 1, and adsorbing the noble metal element onto the adsorbent; and (d) desorbing and recovering the noble metal element from the adsorbent having the noble metal element adsorbed thereon.

The noble metal may be selected from Au, Pt, Ag, Pd, Ru, Rh, Ir, Cu, and Re.

When the noble metal is gold (Au), the solution preferably has a pH of 4 or less, and when the noble metal is platinum (Pt), the solution preferably has a pH of 2 to 9.

The adsorption capacity of the noble metal element can be increased by performing step (c) while irradiating light.

Step (d) may include desorbing the noble metal element by adding the adsorbent adsorbed with the noble metal element to an acidic solution.

The noble metal element-recovering method may further include a step of reintroducing the adsorbent having the noble metal element adsorbed thereto into step (a) after step (d).