OA18010A - Heavy metal recycling process and material useful in such process. - Google Patents

Heavy metal recycling process and material useful in such process. Download PDF

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Publication number
OA18010A
OA18010A OA1201600353 OA18010A OA 18010 A OA18010 A OA 18010A OA 1201600353 OA1201600353 OA 1201600353 OA 18010 A OA18010 A OA 18010A
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OAPI
Prior art keywords
composite material
water
activated carbon
métal
filter
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OA1201600353
Inventor
Sreenath Bolisetty
Raffaele Mezzenga
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Eth Zurich
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Publication of OA18010A publication Critical patent/OA18010A/en

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Abstract

The present invention relates to the field of water treatment / metal recovery and to materials / devices useful in such processes. Specifically the invention provides for composite materials comprising amyloid fibrils; activated carbon; optionally a support material; whereby said amyloid fibrils and said activated carbon are in intimate contact. The invention further provides for the treatment of water using such composite materials.

Description

The présent invention relates to the field of water treatment / métal recovery and to materials / devices useful in such processes.
Treatment of water, particularly recovery of metals from aqueous compositions comprising métal ions, is important in view of both, environmental and commercial purposes. The same applies to purifying of water. Numerous methods and devices addressing these issues are known.
Acey (W02006/045103) describes devices and methods for removing heavy metals from contaminated samples with membranes comprising purified metallothionein proteins. The process disclosed therein is considered disadvantageous as it requires obtaining metallothionein proteins by biotechnological methods (isolation, amplification and expression in transgenic tobacco), making the required devices difficult to produce and expensive. Further, recovery of metals from these sensitive devices is difficult.
Drobot (Us4257807) describes process for recovering precious metals from aqueous media by contacting with blood meal. The process disclosed therein is considered disadvantageous as it requires long contacting times of blood meal and contaminated water and a further requires a multi-step treatment.
In conséquence, the prior art either (i) suggests the use of very advanced materials, providing good séparation results but difficulties in recovery and applicability of the process or (ii) suggests the use of simple materials, providing poor séparation results and requiring multi-step processes.
Thus, it is an object of the présent invention to mitigate at least some of these drawbacks of the state of the art In particular, it is an aim of the présent invention to provide processes for treatment of water and for recovery of metals form aqueous compositions, as well as materials and devices useful in such processes.
These objectives are achieved by the material as defined in claim 1 and a method as defined in claim 10. Further aspects of the invention are disclosed in the spécification and
-2independent daims, preferred embodiments are disdosed in the spedfication and the dépendent daims.
The présent invention will be described in more detail below, referring to the first and second aspect of the invention. The first aspect is directed to new materials, devices, their manufacturing and their uses. The second aspect is directed to methods for the treatment of water using such materials and devices. It is understood that the various embodiments, preferences and ranges as provided / disdosed in this spécification may be combined at will. Further, depending of the spécifie embodiment, selected définitions, embodiments or ranges may not apply.
Unless otherwise stated, the following définitions shall apply in this spécification:
As used herein, the term “a,” an,” “the” and similar terms used in the context of the présent invention (especially in the context of the daims) are to be construed to cover both the singular and plural unless otherwise indicated herein or clearly contradicted by the context.
As used herein, the terms including, containing and comprising are used herein in their open, non-limiting sense.
The présent invention will be better understood by référencé to the figures; wherein fig. 1 shows an AFM image of gold nanoparticles produced according to the ex. 1, and their clusters dispersed in the fibril solution and fig. 2 shows optical microscopy image of Au single crystals formed after heating @ 60°C, according to ex. 1.
In more general terms, in a first aspect, the invention provides for a composite material comprising (a) amyloid fibrils; (b) activated carbon; (c) optionally a support material; whereby said amyloid fibrils and said activated carbon are in intimate contact. This aspect ofthe invention shall be explained in further detail below:
It was surprisingly found that constituents (a) and (b) synergistically interact when treating waste water. The ratio of both constituents may vary over a broad range, depending on the spécifie material, the intended use and the device containing the composite material.
-3Particularly good results are obtained, in case the ratio (a) / (b) is in the range of 1 /1 to 1 /100 (w/w).
Composite material: According to the invention constituents (a) and (b) are in intimate contact. The individual constituents remain separate and distinct within the finished structure but are thoroughly and randomly mixed. This is ensured by the manufacturing process. The material exhibits properties of both, amyloid fibrils and activated carbon, and is therefore also termed hybrid material. The support material may be a separate layer, e.g. in case of a filter membrane.
Amyloid fibrils: The term “amyloid fibrils” is generally known in the field and particularly describes fibrils made by proteins or peptides prevalently found in beta-sheet secondary structure. Accordingly, the term amyloid fibrils excludes native proteins.
Advantageously, the amyloid fibrils hâve high aspect ratio, preferably with 2 10 nm in diameterand s 1pm in length.
Advantageously, the amyloid fibrils hâve a highly charged surface. The term highly charged surfaces is generally known in the field and particularly describes surfaces showing electrophoretic mobilities of the order 2 pm-cm/V-s at pH 4.
Activated carbon: The term is known in the field and includes ail commercial grades thereof. Suitable activated carbon may be produced from produced from carbonaceous source materials such as renewable sources (including nutshells, coconut husk, peat, wood, coir) but also conventional sources (including lignite, coal, and petroleum pitch). Suitable activated carbon may be produced by chemical activation or physical (gas) activation.
Support material: Support materials may or may not be présent in the inventive composite material. For many applications, such support materials are preferred and may be selected from a broad range of known materials. The choice of support material dépends on its intended use. Suitable are, for example porous support materials. In certain applications, it is advantageous the support material being a carbonaceous material that readily oxidizes in a furnace, such as cellulose membranes.
In one advantageous embodiment, the invention relates to a composite material as described herein in the form of a filter membrane, said filter membrane comprising
-4constituents (a), (b) and (c). Accordingly, the invention also provides for a filter device, comprising such composite material. Such filter may be any type of filter known in the field, typically surface filters including pressure- and vacuum- surface filters. In such filters, constituents (a) (b) are arranged upstream, while support material (c) is arranged downstream.
In one alternative embodiment, the invention relates to a composite material as described herein in the form of a particulate material. Typically the particle size of such material is in the range of 1 micromètre to 5 millimétrés. Such particulate material comprises constituents (a) and (b), and may or may not comprise constituent (c); typically no supporting material (c). Such materials may be used in depth filters. Accordingly, the invention also provides for a filter device, comprising such composite material, typically depth filters.
Manufacturing: The inventive composites are simple in manufacturing, using starting materials readily available. This is considered a great advantage, as it allows for single use. The invention thus provides for a method for manufacturing a composite material as described herein, said method comprising the steps of (a) combining water, amyloid fibrils and activated carbon to obtain a suspension; and (b) filtering said suspension through a porous support material. The manufacturing may take place at room température, or at slightly elevated températures. Typically, an aqueous suspension of amyloid fibrils is provided first, activated carbon is added as a solid material while stirring. For certain application the thus obtained composite material may be directly used. Alternatively, the obtained composite material is filtered through a support material to obtain a composite material of constituents (a), (b) and (c).
The synthesis of amyloid fibrils is a known technology. Suitable is in particular protein hydrolysis followed by /3-sheets driven fibrillation, as described e.g. in Jung et al. (Biomacromolecules. 2008, 9, 2477-2486). Suitable starting materials are food-grade proteins, which are structural stable, wide accessible and inexpensive. Such starting materials allow préparation of amyloid fibrils, such as /3-lactoglobulin. Suitable proteins may be selected from the group consisting of /3-lactoglobulin, lysozyme, ovalbumin, and sérum albumines. The self-assembly process is facile and controllable. Typical process parameters include incubating protein solution (e.g. 2 wt.% /3-lactoglobulin) for a prolonged period of time (e.g. 5 h) under acidic conditions (e.g. pH ~ 2), low ionic strength (e.g. I < 20 mM), high température (e.g. T ~ 90 °C).
-5Use: As outlined above, the composite materials are useful in the treatment of water. The invention thus provides for the use of a composite material or a filter as described herein, for the treatment of water (such as, for example réduction of métal content in said water), particularly for purification of water and / or for the recovery of metals from aqueous solutions. The composite materials are useful for treatment of both, municipal waste water and industrial waste water. It will be appreciated by the skilled person, and further outlined below, that the term “filtering” and “filtration” are used in a broad sense, particularly including removal of dissolved impurities from water or aqueous compositions. Such impurities include dissolved compounds of Au, Pd, Pt, Rh, Ru, Ir, Hg, as well as complex compounds such as Au(CN)4·. Typically, the réduction of impurities, such as dissolved metals is in the range of 95 % or more.
In a second aspect, the invention relates to a method for the treatment of water (such as wastewater), said method comprising the step of contacting said water with a composite material comprising amyloid fibrils and activated carbon and separating the treated water from said amyloid fibrils. This aspect of the invention shall be explained in further detail below:
The term wastewater is known in the field and relates to water containing impurities. Accordingly, the term “treated water” relates to water containing a lower amount of said impurities. Wastewaters includes municipal waste water and industrial waste water. Industrial waste waters typically occur during manufacturing as a by-product and typically contain well-known impurities.
The term impurities, more generally unwanted materials, is known in the field, and particularly include metals. Metals may be présent in oxidation +/-0 (i.e. elemental form, colloid) or in positive oxidation state (ie. in sait form or complexed with ligands). The method described herein is suitable for transition metals, lanthanoids, actinoids, metals of the 3rd, 4th, 5th main group. The method described herein is particular suitable for metals having a positive standard potential, such as Cu, Ag, Au, Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Cd, Hg; Pb particularly good results are obtained for Au, Pd, Pt, Hg, Pb.
Treatment of water particularly includes removal of impurities from wastewater and isolation of desired materials from aqueous compositions (solutions, suspensions,
-6emulsions). By the inventive process, it is possible to remove (recycle) more than 95% of impurities by one single treatment cycle. The method as described herein has an extremely broad application spectrum and includes industrial water purification, métal mining, heavy métal recovery, pollution control and métal recycling. Impurities are significantly reduced by the présent method, typically 200 fold, often more.
In one embodiment, the invention provides for the treatment of water, said method comprising the step of (a) providing a composite material according as defined herein and waste water; (b) contacting said waste water with said composite material, thereby obtaining purified water and loaded composite material; (c) separating the purified water from the loaded composite material.
In one further embodiment, the invention provides for method for recovering metals from an aqueous solution, said method comprising the steps of (a) providing a composite material as defined herein and an aqueous solution containing métal ions; (b) contacting said aqueous solution with the composite material thereby obtaining purified water and loaded composite material; (c) separating the purified water from the loaded composite material; and (d) oxidizing the loaded composite material in an high température environment to obtain elemental metals and ash; (e) separating the elemental métal from the ash.
The individual steps noted above are entirely conventional in the field - but not yet applied using the composite material as described herein and not yet applied to the wastewaters as discussed above. Advantageous embodiments of the above steps shall be further elucidated below.
In one embodiment, the composite material may be provided in the form of a filter and the waste water may be provided continuously. Step (b) and (c) may be performed simultaneously by filtering said waste water through said filter. As noted above, filtering also includes removal of dissolved impurities.
In one alternative embodiment, the composite material may be provided in the form of particulate material in step (a). In step (b) waste water and said composite material are contacted for a prolonged period, e.g. 20 sec -24 hrs., optionally with stirring. Optionally, the température is controlled, e.g. in a range from 5 - 95°C. In step (c) the obtained
-7materials are separated by known methods, e.g. by filtering, centrifuging or settling. In this embodiment, steps (b) and (c) are optionally repeated.
In step (d) the oxidation may take place in a furnace, at températures suitable to allow oxidation of the fibrils, the support material (if présent) and the réduction of the métal impurities. Suitable are températures in the range of 600-1200°C, such as 700 °C. Suitable reaction times are in the range of 0.1-12 hrs., such as 3 hrs.
In step (e) the removed impurities may be separated from the impurities isolated. Any method suitable in this field, particularly methods for separating solid materials of different density and / or wettability, may be employed. In one embodiment, séparation in step (e) is performed by floatation, optionally with the aid of ultrasound. In one alternative embodiment, séparation in step (e) is performed by air floating, optionally with the aid of ultrasound.
The skilled person will appreciate that the method described herein provides significant advantages over the prior art: First, the method is economical, simple, safe robust and fast. Second, a scale-up is simple. Finally, the method may be fine-tuned by using several cycles, by adapting the composite material used and other parameters.
To further illustrate the invention, the following examples are provided. These examples are provided with no intend to limitthe scope of the invention.
example 1: recovery of Au from Au(CN)4 solution:
1.1 Préparation of composite material
0.5 g act. carbon are mixed with 0.5 ml of 2 wt% beta-lactoglobulin pH2 protein fibrils solution (see PCT/CH2014/000014) at room température. This solution is vacuum filtered using 0.22 micromètre cellulose filter membrane. Protein fibrils remarkable adhesiveness and stiffness enable the assembly of act. carbon into the fibrils. The thus obtained coated cellulose filter is used in the next step.
1.2 Contacting and Separating (“Filtering” Au(CN)T) ml industrial waste water, containing 30mg/l Au (présent as Au(CN)4’, determined by AAS) was filtered through the filter of step 1.1 using vacuum filtration. The purified water
-8now contains, after a single passage through the filter, 0.105mg/l Au (determined by the same AAS method). This corresponds to a réduction of 99.65% and shows the extremely high absorption rate ofthe inventive composite material.
1.3 Oxidizing of loaded composite material
The loaded composite material is placed in a furnace for 3 hrs. @ 750°C. After cooling to room température, the sample colour changed from black to red. This indicates formation of nanoparticulate material. Activated carbon converted to ash.
1.4 Separating elemental gold
The material obtained from the previous step is mixed with distilled water and sonicated @ 100Hz /15 min. Gold particles sédiment on the bottom and the ash floated. The ash is removed and the sonicaton - removal cycle is repeated. The obtained particles contain elemental gold, as confirmed by AAS, and are virtually non-toxic and may be used for further applications.
1.5 Préparation of conductive gold crystals
The material obtained from the previous step is combined with 0.2wt% beta-lactoglobulin fibril solution, fig. 1 shows an AFM image thereof. This material is combined with 0.01 M chloroauric acid and heated to 60°C /12 hrs. to produce conductive gold single crystals. The thus obtained gold crystals hâve hexagonal, triangle and polyhedral structures, see fig. 2.
example 2: recovery of toxic heavy métal pollutants:
2.1 Préparation of composite material
Hybrid composite filter membranes are prepared to absorb the toxic heavy métal pollutants. Initially, 5ml of 10 wt% activated carbon solution mixed with the 0.5 ml of 2 wt% β- lactoglobulin (pH 2) protein fibrils solution. 1 ml of above solution is vacuum filtered using 0.22 pm cellulose filter. Protein fibril’s extreme adhesiveness and stiffness behavior enable the assembly of activated carbon into homogeneous composite filtration membrane. These filtration membranes are very useful to absorb heavy métal ion pollutants as well as recovery of the expensive heavy metals from the environmental pollutants.
2.2 Contacting and separating
After preparing this composite filter membrane having the protein fibrils and activated carbon, the 50 ml of toxic heavy métal ion solution is passed through this composite membrane using vacuum filtration method.
The concentrations of the environmental pollutants were estimated before and after filtration to détermine the absorption of toxic heavy métal ions inside the filter membrane.
The details of filtration and absorption efficiency of various toxic environmental pollutants within these hybrid filter membrane is discussed below
2.3 Results:
Mercury chloride solution (pH 4) was filtered. The AAS measurements estimated that the mercury atom concentration is reduced from initial 84 ppm to < 0.4 ppm after filtration.
Lead acetate solution (pH 3.7) was also filtered and the concentration of the lead is calculated by AAS, before and after the filtration process. Since the concentration of lead solution before filtration is above than our available AAS calibration curve, the initial unfiltered solution is diluted 20 times for the measurement. The concentrations of lead atoms are reduced from 65 ppm to < 0.02 ppm after filtration. A change of the solution color before and after filtration is observed. The solution became completely colorless because of absorption of lead atoms inside the filter membrane.
Disodium tetrachloro palladate was also filtered to show the generality of this filtration approach to prove the filtration of the heavy métal pollutant. The concentrations of the solutions are measured by UV-Vis absorption spectroscopy. The concentrations reduced from the 12.2 ppm to <0.16 ppm after filtration process.
Based on the above data, it was realized that the inventive method is generally applicable. Particularly, different types of heavy métal pollutants are filtered using the inventive composite material. Accordingly, the inventive method is suitable to absorb several heavy métal toxic environmental pollutants. Especially, potassium gold cyanide [KAu(CN)2], mercuric chloride [HgCI2], lead acetate [Pb(C2H3O2)4], disodium tetrachloro palladate [Na2PdCI4] may be efficiently removed and recovered.

Claims (10)

Claims:
1 pm in length and /or showing electrophoretic mobilities of the order 2 μΐτι-cm/V-s at pH 4; and /or (b) the activated carbon is selected from activated carbon obtained by chemical and / or physical activation; and / or (c) the support material, if présent, is selected from porous support materials.
1. A composite material comprising (a) amyloid fibrils;
(b) activated carbon;
(c) optionally a support material;
whereby said amyloid fibrils and said activated carbon are in intimate contact.
2. The composite material according to claim 1 where (a) the amyloid fibrils are selected from fibrils being < 10 nm in diameter and >
3. The composite material according to claim 1 or 2, selected from a filter membrane, comprising constituents (a), (b) and (c); or a particulate material, comprising constituents (a) and (b), but no supporting material (c).
4. The composite material according to any of the preceding daims, where the ratio (a) / (b) is in the range of 1 /1 to 1 /100 (w/w).
5 5 - 95°C; and / or in step (c) the obtained materials are separated, by filtering, centrifuging or settling; and whereby steps (b) and (c) are optionally repeated.
5. A filter, comprising a composite material according to any of the previous daims.
6. A method for manufacturing a composite material according to any of daims 1-4, said method comprising the steps of (a) combining water, amyloid fibrils and activated carbon to obtain a suspension; and (b) filtering said suspension through a porous support material.
7. Use of a composite material according to any of daims 1 - 4, or a filter according to claim 5, for the treatment of water and / or for the recovery of metals.
8. The use of claim 7, wherein said treatment of water comprises réduction of métal content in said water; and / or said water being municipal waste water or industrial waste water.
9. The use of claim 7, wherein said métal is selected from Au, Pd, Pt, Rh, Ru, Ir; and / or said métal is selected from Au, Pd, Pt, Hg, Pb; and / or said réduction is 95 % or more.
10. A method for the treatment of water, said method comprising the step of (a) providing a composite material according to claim 1-4 and waste water;
(b) contacting said waste water with said composite material, thereby obtaining purified water and loaded composite material;
(c) separating the purified water from the loaded composite material.
11. A method for recovering metals from an aqueous solution, said method comprising the steps of (a) providing a composite material according to claim 1-4 and an aqueous solution containing métal ions;
(b) contacting said aqueous solution with the composite material thereby obtaining purified water and loaded composite material;
(c) separating the purified water from the loaded composite material; and (d) oxidizing the loaded composite material in an high température environment to obtain elemental metals and ash;
(e) separating the elemental métal from the ash.
12. The method according to claim 10 or 11, wherein in step (a) the composite material is provided in the form of a filter; and steps b and c are performed by filtering said waste water through said filter.
13. The method according to claim 10 or 11, wherein in step (a) the composite material is provided in the form of particulate material; and / or in step (b)said waste water and said composite material are contacted for a period of 20 sec - 24 hrs., optionally with stirring, at a température range from
10 14. The method according to claim 11, wherein in step (d) the oxidation takes place in a furnace, at températures in the range of 600-1200°C;
in step (e), séparation is performed by floatation or air floating, optionally with the aid of ultrasound.
OA1201600353 2014-03-17 2015-03-13 Heavy metal recycling process and material useful in such process. OA18010A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14000983.8 2014-03-17
EP14168815.0 2014-05-19

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OA18010A true OA18010A (en) 2018-03-23

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