• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method for biological recovery of metals in electrical and electronic waste, comprises a) introducing a series of iron-oxidizing microorganisms and a mineral medium in a reactor (10); b) carrying out a first stage of biological oxidation of iron II ions present in said mineral medium to iron III ions; c) separating the iron-oxidant microorganisms present in suspension within the reactor (10), providing a solid phase comprising the iron-oxidizing microorganisms and a liquid phase comprising the iron III ions; d) continuously irrigating the liquid phase inside a column (30) configured to house one or more printed circuit boards of an electronic waste or electrical material from which the metals are to be recovered, resulting in a reduction of the iron ions III oxidizing the metals, to iron II, and separating the metals from their solubilization; and e) extracting said metals from the solution. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2707353A1
    申请号:ES201830406
    申请日:2018-04-25
    公开日:2019-04-03
    发明作者:Antonio David Dorado；Xavier Gamisans；Sole Montserrat；Lao Concepcion；Eva Benzal
    申请人:Universitat Politecnica de Catalunya UPC；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003] Field of technique
    [0004]
    [0005] The present invention relates in general to methods for the recycling of electrical and electronic waste. In particular, the invention concerns a method for biological recovery of metals in electrical and electronic waste from printed circuit boards (PCBs), for example from mobile phones, among others.
    [0006]
    [0007] BACKGROUND OF THE INVENTION
    [0008]
    [0009] Printed circuit boards (PCBs) are common components in most electrical and electronic equipment. Electrical and electronic waste, which consists of computers, televisions, mobile phones, stereo equipment and other discarded electronic equipment, has become a major problem throughout the world. Rapid technological advances make electrical and electronic products obsolete in a short time. This, together with the explosive sales in consumer electronics, means that more products are being disposed of, even if they still work. One of the main problems with this type of electrical and electronic waste is that they are full of toxic chemicals - arsenic, lead, mercury, polychromatic flame retardants, among others. On the other hand, electrical and electronic waste also contains a significant portion of valuable metals such as copper, silver or gold, which could be recovered for reuse.
    [0010]
    [0011] In general, chemical methods are used to recover these metals from the mineral matrix (minerals) or from the plastic matrix (electronic waste). Lately, bioleaching has been proven as an alternative to chemical processes, showing important advantages such as low cost, high efficiency and friendliness with the environment.
    [0012]
    [0013] Bioleaching is based on the release of metals from metal concentrates, such as electrical and electronic waste, using the activity of microorganisms.
    [0014]
    [0015] Some patents or patent applications are known in this sector.
    [0016]
    [0017] For example, document CN105734284A discloses a bioleaching treatment of electronic waste of PCBs, promoted by the use of biocarbon. According to the method, through oxidation-reduction radicals in the biocarbon, the copper metal in the PCB is biolixed by Fe <2+> microorganisms. The oxidation-reduction capacity of Biocarbon and bioleaching are combined, so that Fe <2+> is oxidized to obtain Fe <3+>, and the leaching rate of the copper metal is increased.
    [0018]
    [0019] The documents CN103898550, CN102091711 and CN202519343 are based on the use of acidophilic Acidithiobacillus bacteria for the leaching of copper. Patent CN104328280 shows a method and equipment for bioleaching with Acidithiobacillus ferrooxidans to extract copper, gold and nickel from PCBs. In CN patent 104862475 the bioleaching with Acidithiobacillus ferrooxidans has been improved by the proliferation of the bacteria in conditions of low dissolved oxygen level to maximize its growth, and then increasing the concentration of oxygen when the PCBs are added to maximize the leaching of the copper . The patent application CN105039704 is based on the bioleaching with Thiobacillus acidophilus (reclassified as Acidiphilium acidophilum) for the extraction of copper.
    [0020]
    [0021] Exhibition of the invention
    [0022]
    [0023] Exemplary embodiments of the present invention provide a method for biological recovery of metals in electrical and electronic waste, comprising first introducing a series of iron-oxidizing, aerobic microorganisms, and a mineral medium formed by different salts in solution in a and performing, in said reactor, a first stage of biological oxidation of iron II ions present in said mineral medium to iron III ions. The first stage is catalyzed by the metabolic activity of said iron-oxidizing microorganisms and is carried out within a pre-set temperature range, with constant mechanical agitation, controlling the pH of said mineral medium. Also, the first stage lasts at least two hours.
    [0024]
    [0025] Once the first stage has been carried out, the iron-oxidizing microorganisms present in suspension inside the reactor are separated, outside the reactor, providing a solid phase comprising the iron-oxidizing microorganisms and a liquid phase comprising the iron III ions.
    [0026]
    [0027] Subsequently, said liquid phase is continuously irrigated into a column with dimensions suitable for housing one or more printed circuit boards of an electronic waste or electrical material from which the metals are to be recovered, occurring in contact with said phase liquid a reduction of the iron III ions by oxidizing the metals, to iron II, and the metals of interest are separated from their solubilization. The aforesaid printed circuit board or plates are in contact with the phase liquid inside the column for at least one hour. Finally, the metals of interest are extracted from the solution.
    [0028]
    [0029] The solid phase with the iron-oxidizing microorganisms is preferably returned back to the reactor.
    [0030]
    [0031] To improve the contact between the electronic waste or electrical material and iron III, and ensure that all incoming iron III ions react with the metals, you can also recirculate said iron III ions from a lower part of the column to a part superior of it.
    [0032]
    [0033] Preferably, the different steps of the proposed method are carried out continuously.
    [0034] In other embodiments, the first step instead of, or additionally, performing within a predetermined temperature range can also be performed with redox and / or oxygen control.
    [0035]
    [0036] Said pre-set temperature range can be comprised between 25 and 35 ° C, preferably 30 ° C, and constant mechanical agitation is preferably maintained at a speed of 200 rpm.
    [0037]
    [0038] In an exemplary embodiment, when the metals of interest have been extracted from the solution, they are reduced from their soluble state to a metallic state by a cementing process which provides a spontaneous reaction between a soluble copper II extracted from the plate or printed circuit boards or electrical material and metallic iron. In said spontaneous reaction soluble copper II is reduced to copper metal and metallic iron is oxidized to soluble iron II. The cementing process in this embodiment is carried out in a mechanically stirred tank at a speed comprised in a range of 120 to 140 rpm at room temperature.
    [0039]
    [0040] Alternatively, in another embodiment, the reduction of the extracted metals of interest to their metallic state is carried out by electrolysis or by a precipitation technique.
    [0041]
    [0042] In an exemplary embodiment, when the metals of interest have been extracted from the solution, the soluble iron II obtained at the first stage of biological oxidation is recirculated to reduce the amount of iron necessary therein.
    [0043] In an example of embodiment, the different salts of the mineral medium include an iron salt II and salts that provide nitrogen, sulfur, phosphorus, magnesium, potassium and calcium. Preferably, the composition of the mineral medium introduced into the reactor comprises: 30 g / L of FeSO 4 ■ 7 H 2 O, 3 g / L of (NH 4) 2 SO 4; 0.5 g / L of MgSO4 ■ 7 H2O, 0.5 g / L of K2 HPO4, 0.10 g / L of KCl and 0.01 g / L of Ca (NO3) 2 • 4 H2O. Also, the pH of the mineral medium is controlled in a range between 1.7 and 1.8 by the addition of an acid or a base. For example, by the addition of sulfuric acid at a concentration of 10%.
    [0044]
    [0045] In an exemplary embodiment, a monitoring of the activity of the iron-oxidizing microorganisms in the reactor is also carried out, for example by:
    [0046] - preparation of a solution with the same composition of the mineral medium but without the iron salt FeSO4 • 7 H2O;
    [0047] - extraction of a certain amount of reactor sample, preferably 2 ml, and centrifugation for about 10 minutes at 5000 rpm;
    [0048] - elimination of the excess and addition / addition of another certain quantity, preferably 2 ml, of the mineral medium but without the iron salt FeSO4 • 7 H2O;
    [0049] - stabilization of the temperature by placing the sample in a thermostatic bath at 30 ° C; - addition / addition of another certain quantity, preferably 2 ml, of the mineral medium with the iron salt FeSO4 • 7 H2O and homogenization;
    [0050] - extraction of a certain amount, preferably 1 ml, of the mineral medium and introduction into a vessel that is brought back into said thermostatic bath with magnetic stirring;
    [0051] - introduction of an oxygen microprobe into said container until it is in contact with the sample; Y
    [0052] - recording by means of said microprobe of the evolution of the concentration of oxygen and from the slope of time evolution obtained determination of the biological activity of the sample.
    [0053]
    [0054] Likewise, the activity of the sample can be related to the concentration of iron-oxidizing microorganisms (ie, biomass) by a previous calibration, for example, by determining the biological activity of various known concentrations of biomass and correlating them with said parameters of activity and concentration
    [0055] In an exemplary embodiment, a calibration of the oxygen microprobe is also carried out in an oxygen-free aqueous medium and under saturation conditions at a constant temperature.
    [0056] In an exemplary embodiment, said irrigation step is carried out at room temperature and at a pH lower than 1.8.
    [0057]
    [0058] BRIEF DESCRIPTION OF THE DRAWINGS
    [0059]
    [0060] The foregoing and other features and advantages will be more fully understood from the following detailed description of exemplary embodiments, merely illustrative and not limiting, with reference to the accompanying drawings, in which:
    [0061]
    [0062] Fig. 1 is a flow chart illustrating a method for biological recovery of metals in electrical and electronic waste according to the present invention.
    [0063]
    [0064] Fig. 2 illustrates schematically a bioleaching plant for implementation of the proposed method.
    [0065]
    [0066] Detailed description of some examples of embodiment
    [0067]
    [0068] With reference to Fig. 1, there is shown an example of embodiment of the proposed method for biological recovery of metals in electrical and electronic waste. As seen in the first figure, step 101, a series of iron-oxidizing, aerobic microorganisms are introduced, and a mineral medium formed by different salts in solution in a reactor 10 (see Fig. 2) such as a reactor. Jacketed, among others. Then, step 102, a first stage of biological oxidation of iron II ions present in said mineral medium to iron III ions is carried out in said reactor 10. This first stage is catalyzed by the metabolic activity of the aforementioned iron-oxidizing microorganisms and is carried out within a pre-set temperature range between 25 and 35 ° C, preferably 30 ° C, with constant mechanical agitation at a speed of about 200 rpm, controlling the pH of the mineral medium. The first stage lasts at least two hours to ensure good contact between the microorganisms and the iron II solution. Then, step 103, the iron-oxidizing microorganisms present in suspension are separated within the reactor 10 outside thereof, thereby providing a solid phase comprising the iron-oxidizing microorganisms and a liquid phase comprising the iron III ions. , and step 104, continuously irrigates the liquid phase inside a column 30 arranged to house one or more printed circuit boards of electronic waste or electrical material, producing a reduction of iron III ions by oxidizing metals , to iron II, and the metals of interest are separated from their solubilization. Finally, step 105, the metals of interest are extracted from the solution.
    [0069] Referring now to Fig. 2, there is shown an embodiment of the bioleaching plant used to carry out the present invention. As can be seen in the figure, according to this embodiment, the plant consists of 4 stages, a first stage where the biological oxidation of iron II is carried out, a second one of sedimentation, a third of leaching of the waste and a fourth of cementing. The different reactions that intervene in each phase are:
    [0070]
    [0071] " A c t i v i d a B i o lo q i c a
    [0072] 1st stage: 4 Fe 2 + 4 H + + 0 2 -----------> 4 Fe 3 + 2 H20 (Eq 1) 3rd stage: Cu + 2Fe 3 ^ Cu 2 + 2Fe 2 (Eq. . two)
    [0073] 4th stage: Fe 0 + Cu 2 ^ Fe 2 + Cu 0 (Eq 3)
    [0074] The objective of the first stage is the oxidation of the iron II ion to an iron III ion catalyzed by the metabolic activity of the iron-oxidizing microorganisms that obtain their energy from the oxidation of iron. During this step, which takes place in said reactor 10, preferably at a temperature of 30 ° C, with constant mechanical agitation, the pH is controlled between 1.7 and 1.8 by the addition of an acid or a base. In an exemplary embodiment, said control is carried out by the addition of 10% sulfuric acid. The agitation used in this system is of the mechanical type and is maintained at a speed of about 200 rpm. The material of the agitator is Teflon since this material is not chemically attacked nor reacts with any of the compounds found in the reactor 10. Since the iron-oxidizing microorganisms used are aerobic, the reactor 10 is aerated with network air with a flow rate of about 30 L / h. The correct functioning of the method is guaranteed with the continuous monitoring of the pH (optionally or additionally it is also possible to carry out an oxygen and / or redox control) that allows knowing the degree of oxidation achieved at each moment (approximately 600 mV in regime).
    [0075]
    [0076] Preferably, the reactor 10 is fed continuously with a mineral medium with the following composition: 30 g / L of FeSO 4 • 7 H 2 O, 3 g / L of (NH 4 ) 2 SO 4; 0.5 g / L of MgSO 4 • 7 H 2 O, 0.5 g / L of K 2 HPO 4 , 0.10 g / L of KCl and 0.01 g / L of Ca (NO 3 ) 2 ■ 4 H 2 O. It should be noted that other mineral media or different compositions could also be used.
    [0077]
    [0078] To prepare the mineral medium (approximately 1 liter), all salts (except the iron salt) are dissolved in 700 ml of deionized water and the pH of this solution is adjusted to 1.75, for example with 10% sulfuric acid. Then the iron salt is dissolved in 300ml of deionized water and the pH of this solution is adjusted to 1.75, also with 10% sulfuric acid. Finally, the two solutions are combined and the resulting pH is checked and, if necessary, readjusted again to a pH of 1.75 with 10% sulfuric acid.
    [0079] The monitoring of the activity of the iron-oxidizing microorganisms in the reactor 10 can be carried out by microrespirometric techniques (oxygen consumption), for example by preparing a solution with the same composition of the mineral medium but without the iron salt FeSO4 • 7 H2O; extracting a certain amount of sample from reactor 10, preferably 2 ml (non-limiting since other amounts could be extracted) and centrifuged for about 10 minutes at 5000 rpm; removing the excess and adding another certain amount, preferably also 2 ml, of the mineral medium but without the iron salt FeSO4 • 7 H2O; stabilizing the temperature by placing the sample in a thermostatic bath at about 30 ° C; adding another certain amount, preferably 2 ml, of the mineral medium with the iron salt FeSO4 • 7 H2O and homogenizing it; extracting a certain amount, preferably 1 ml, from the mineral medium and introducing it into a vessel that is brought back into the thermostatic bath with magnetic stirring; introducing an oxygen microprobe into the container until it is in contact with the sample; and recording through the microprobe the evolution of the concentration of oxygen and from the slope of time evolution obtained by determining the biological activity of the sample.
    [0080]
    [0081] The above process allows detecting the activity of iron-oxidizing microorganisms with very small sample volumes, less than 2 mL of sample.
    [0082]
    [0083] The oxygen microprobe is calibrated in an oxygen-free aqueous medium (displacement with nitrogen) and under saturation conditions (oxygen by means of a diffuser until a stable signal is obtained) at a constant temperature.
    [0084]
    [0085] The objective of the second stage is to separate the iron-oxidizing microorganisms that are in suspension inside the reactor 10. This step is carried out guaranteeing a resting time of the solution of at least two hours to sediment the iron-oxidizing microorganisms. The solid phase in the bottom of the settler 20 with the iron-oxidizing microorganisms is preferably returned back to the reactor 10. The supernatant with the iron III solution is driven to the next stage at the same rate as the mineral medium has been introduced in the reactor 10. Periodically a part of the sediment is purged from the system to maintain the continuity of the process.
    [0086]
    [0087] The objective of the third stage is the oxidation of metals in the metallic state contained in the printed circuit boards of the electrical and electronic equipment to be recovered. The chemical element responsible for the oxidation of metals is iron III, which when chemically attacking the metal is reduced to iron II and allows the metals of interest to be extracted from the solid-liquid system after their solubilization.
    [0088] The third stage is carried out in a column 30 inside which one or more printed circuit boards are placed. During the operation of the plant, the column 30 is constantly irrigated with the iron III solution so that the plates come into contact with the solution and the chemical reaction is produced which allows the extraction of the metals of interest. To improve the contact between the residue and the iron III, and ensure that all the iron III reacts with the metals, preferably part of the leachate obtained in the lower part of the column 30 is recirculated back to the top of the column 30. For guaranteeing efficient leaching of the metals contained in the printed circuit board (s) requires a contact time inside column 30 of at least one hour.
    [0089]
    [0090] The process takes place at room temperature and at a pH below 1.8. It is important to keep the pH below this value to avoid the precipitation of iron III, a fact that would diminish the effectiveness of the process and therefore, the effectiveness of the extraction of the metals. To carry out this pH adjustment, a pH control can be performed on the liquid that is recirculated to the column 30.
    [0091]
    [0092] The objective of the fourth stage is to reduce the metal extracted from the printed circuit board (s) from its soluble state to its metallic state so that it can be used again as a raw material. In this embodiment, the process used to obtain the metal in the metallic state is cementation. This process consists of the spontaneous reaction between soluble copper II and metallic iron, in which copper is reduced to metallic copper and iron is oxidized to soluble iron II. To achieve a higher purity, an electrorefining can additionally be carried out.
    [0093]
    [0094] The cementation in this case takes place in a stirred tank 40 with mechanical agitation at a speed between 120 and 140 rpm and at room temperature. The contact time between the two metals to ensure the complete reaction is at least one hour. After this time, through a filtration 41, the metallic copper is obtained in the form of a powder, while in the liquid the iron II and other soluble elements that may have leached in the previous stage remain.
    [0095]
    [0096] The iron II solution resulting from this fourth stage can be recirculated to the first stage to decrease the iron requirement of the biological process.
    [0097]
    [0098] The scope of the present invention is defined in the appended claims.
    权利要求:
    Claims (15)
    [1]
    1. Method for biological recovery of metals in electrical and electronic waste, comprising:
    a) introducing a series of iron-oxidizing, aerobic microorganisms, and a mineral medium formed by different salts in solution in a reactor (10);
    b) performing, in said reactor (10), a first stage of biological oxidation of iron II ions present in said mineral medium to iron III ions, wherein said first stage is catalyzed by the metabolic activity of said iron oxidizing microorganisms and it is carried out within a pre-set temperature range, with constant mechanical agitation, controlling the pH of said mineral medium, and wherein said first stage has a duration of at least two hours;
    c) separating the iron-oxidant microorganisms present in suspension inside the reactor (10), outside said reactor (10), providing a solid phase comprising the iron-oxidizing microorganisms and a liquid phase comprising the iron III ions ;
    d) continuously irrigating the liquid phase inside a column (30) configured to house one or more printed circuit boards of an electronic waste or electrical material from which the metals are to be recovered, resulting in a reduction of the iron ions III oxidizing the metals, to iron II, and separating the metals of interest from their solubilization, wherein the printed circuit board or plates are in contact with the liquid phase inside the column (30) for at least one hour; Y
    e) extracting said metals of interest from the solution.
    [2]
    The method according to claim 1, wherein said step e) comprises reducing said metals of interest extracted from their soluble state to a metallic state by means of a cementing process that provides a spontaneous reaction between a soluble copper II extracted from the plate or plates of printed circuit or electrical material and metallic iron, where in said spontaneous reaction soluble copper II is reduced to copper metal and metallic iron is oxidized to soluble iron II.
    [3]
    The method according to claim 1 or 2, further comprising recirculating the soluble iron II obtained in step e) to said first stage of biological oxidation to decrease the amount of iron needed in said first step.
    [4]
    Method according to any one of the preceding claims, wherein said steps a) to e) are carried out continuously.
    [5]
    The method according to claim 1, wherein the different salts of the mineral medium include an iron salt II and salts that provide nitrogen, sulfur, phosphorus, magnesium, potassium and calcium.
    [6]
    The method according to claim 5, wherein said mineral medium comprises the following composition: 30 g / L of FeSO 4 • 7 H 2 O, 3 g / L of (NH 4 ) 2 SO 4 ; 0.5 g / L of MgSO 4 • 7 H 2 O, 0.5 g / L of K 2 HPO 4 , 0.10 g / L of KCl and 0.01 g / L of Ca (NO 3 ) 2 ■ 4 H 2 O.
    [7]
    The method according to any one of the preceding claims, wherein the pH of said mineral medium of step b) is controlled in a range comprised between 1.7 and 1.8 by the addition of an acid or a base.
    [8]
    The method according to any one of the preceding claims, further comprising monitoring the activity of said iron-oxidizing microorganisms in the reactor (10) in said step b).
    [9]
    9. Method according to claim 8, wherein said monitoring is performed by the following steps:
    prepare a solution with the same composition of the mineral medium but without the iron salt FeSO 4 • 7 H 2 O;
    extract a certain amount of sample from the reactor (10), preferably 2 ml, and centrifuge it for about 10 minutes at 5000 rpm;
    remove the excess and add another quantity, preferably 2 ml, of the mineral medium but without the iron salt FeSO 4 • 7 H 2 O;
    stabilize the temperature by placing the sample in a thermostatic bath at 30 ° C;
    add another quantity, preferably 2 ml, of the mineral medium with the iron salt FeSO 4 • 7 H 2 O and homogenize;
    extracting a certain amount, preferably 1 ml, from the mineral medium and introducing it into a container that is brought back into said thermostatic bath with magnetic stirring;
    introducing an oxygen microprobe into said container until it is in contact with the sample; Y
    record through this microprobe the evolution of the concentration of oxygen and from the slope of time evolution obtained determine the biological activity of the sample.
    [10]
    The method according to claim 9, further comprising:
    to relate the activity of the sample with the concentration of iron oxidizing microorganisms by means of a previous calibration; I
    perform a calibration of the oxygen microprobe in an oxygen-free aqueous medium and under saturation conditions at a constant temperature.
    [11]
    The method of claim 1, wherein step d) further comprises recirculating iron III from a lower portion of said column (30) to an upper portion thereof.
    [12]
    12. Method according to claim 1 or 10, wherein step d) is carried out at room temperature and at a pH lower than 1.8.
    [13]
    The method according to claim 2, wherein the cementing process is carried out in a tank (40) mechanically agitated at a speed comprised in a range of 120 to 140 rpm at room temperature.
    [14]
    14. Method according to claim 1 or 13, wherein step e) has a duration of at least one hour.
    [15]
    The method according to claim 1, wherein said pre-set temperature range is between 25 and 35 ° C, preferably 30 ° C, and constant mechanical agitation is maintained at a speed of 200 rpm.
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    同族专利:
    公开号 | 公开日
    WO2019206755A1|2019-10-31|
    ES2707353B2|2019-11-26|
    引用文献:
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    WO2003006696A1|2001-07-13|2003-01-23|Teck Cominco Metals Ltd.|Heap bioleaching process for the extraction of zinc|
    CN103898550A|2014-04-14|2014-07-02|常州纺织服装职业技术学院|Recovery method of cupper in circuit board|
    CN104328280A|2014-10-15|2015-02-04|上海第二工业大学|Method and equipment for recycling all metal components in waste flexible circuit board|
    US5914441A|1996-06-12|1999-06-22|Yellowstone Environmental Science, Inc.|Biocatalyzed anaerobic oxidation of metal sulfides for recovery of metal values|
    CN103397195B|2013-08-09|2014-09-24|内蒙古科技大学|Recovery device and recovery method of metallic copper of waste printed circuit board|
    CN107746959B|2017-11-17|2019-01-11|中山大学|A kind of two step bioleaching process and device of total head recycling valuable metals in waste circuit board|CN112342384A|2020-09-27|2021-02-09|长春黄金研究院有限公司|Method for recycling waste circuit board and waste oxidizing solution in synergy manner|
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    ES201830406A|ES2707353B2|2018-04-25|2018-04-25|METHOD FOR BIOLOGICAL RECOVERY OF METALS IN ELECTRICAL AND ELECTRONIC WASTE|ES201830406A| ES2707353B2|2018-04-25|2018-04-25|METHOD FOR BIOLOGICAL RECOVERY OF METALS IN ELECTRICAL AND ELECTRONIC WASTE|
    PCT/EP2019/059886| WO2019206755A1|2018-04-25|2019-04-17|Method for the biological recovery of metals in electric and electronic waste|
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