Nutrient Additive

Abstract

The invention related to a method of making a nutrient additive from electronic waste comprising the steps of: a) adding electronic waste to a reaction vessel; b) admixing the electronic waste and optionally one or more metal catalysts with one or more acids, wherein one or more metals in the electronic waste is dissolved by the acid to form a nutrient additive; and related products, such as fertilisers and soil improvers.

Claims

1. A method of making a nutrient additive from electronic waste comprising the steps of: a) adding electronic waste to a reaction vessel; b) admixing the electronic waste and optionally one or more metal catalysts with one or more acids, wherein one or more metals in the electronic waste is dissolved by the acid to form a nutrient additive.

2. The method according to claim 1, wherein the catalyst is any one or more metals that are lower than iron in the electrochemical series or compounds or alloys thereof.

3. The method according to claim 1, further comprising a separation step, after step b, wherein insoluble material, such as plastic is removed.

4. The method according to claim 1, further comprising a step, after step b, of adjusting the acidity by further additions of acids or alkalis.

5. The method according to claim 1, further comprising a step, after step b, of diluting the nutrient additive.

6. The method according to claim 1, further comprising a step, after step b, of concentrating the nutrient additive.

7. The method according to claim 1, further comprising a step, after step b, of adding further liquid ingredients to the nutrient additive.

8. The method according to claim 1, further comprising a step, after step b, of adding further liquid ingredients to the nutrient additive.

9. The method according to claim 1, further comprising a step, after step b, of adding one or more setting agents to set the nutrient additive so that it can be powdered or granulated.

10. The method according to claim 9 wherein the setting agent comprises or consist of one or more agents selected from: plaster of Paris (CaSO4 0.5H2O), chalk, dolomite or other metal carbonate compound, calcium hydroxide and calcium oxide.

11. The method according to claim 1, wherein the nutrient additive is added to a fertilizer, during manufacturing of the fertilizer, and the fertilizer is then set using plaster of Paris.

12. The method according to claim 1, wherein the catalyst is metallic lead, copper, gold, or sifter or compounds or alloys containing these metals.

13. (canceled)

14. A nutrient additive made by the method of claim 1.

15. A fertilizer or soil improver comprising a nutrient additive obtained or obtainable by the method of claim 1.

16. A method of fertilizing or improving soil comprising: I. making a nutrient additive from electronic waste comprising the steps of: a) adding electronic waste to a reaction vessel, said electronic waste comprising one or more metals; b) admixing said electronic waste with one or more acids, thereby dissolving said one or more metals by said one or more acids to form a nutrient additive; and II. adding said nutrient additive to soil, thereby fertilizing or improving the soil.

17. (canceled)

18. (canceled)

19. (canceled)

Description

[0067] The invention is now described with reference to the following specific embodiments and accompanying drawings in which:

[0068] FIG. 1: shows an example of a reaction vessel that the reaction to dissolve batteries in acid may take place in.

[0069] FIG. 2: shows examples of batteries that may be dissolved in the present invention,

[0070] FIG. 3: shows an example of a metal catalyst that may be used in the present method, in this case the metal catalyst is copper turnings, which are a waste product from industry,

[0071] FIG. 4: shows the liquid additive after the dissolving step and filtration to remove undissolved solids such as plastics. This may be used directly as a fertiliser and/or soil improver and/or additive solution,

[0072] FIG. 5: shows an example of the structure of a battery: top left shows an orthogonal view of the battery with some of the external plastic sleeve peeled back; Top right shows an exploded view of a battery showing the steel anode cap terminal, anode collector made of tinned brass, the insulator and the Nickel coated steel cathode collector; Bottom left shows an exploded view of a battery showing the metal separator, plastic grommet, anode and nickel coated steel cathode collector; Bottom right shows the separators from inside a battery.

[0073] FIG. 6: provides the contents of nutrient additive solution containing a range of metals and trace elements as obtained from batteries and added to slurry.

[0074] Dissolving batteries in acids with a metal catalyst produces a mineral rich solution for incorporation into fertilisers and soil improvers.

[0075] Method

[0076] Batteries are added to the reaction vessel with premixed copper catalyst

[0077] Acid is added to the batteries in a reaction vessel

[0078] Additional minerals are added if required

[0079] Finishing of the Product

[0080] The nutrient additive may be neutralised by a suitable neutralising medium before application to soil

EXAMPLE 1

[0081] 500 g Batteries were mixed with 3000 ml of 50% nitric acid with 2-5% of the battery mass of copper catalyst (10-25 g copper metal). These can be mixed in any order. The mixtures was left for 120 mins without stirring. The mixture may be stirred to increase the reaction rate. Insoluble plastics and paper impurities were separated by filtration. The resulting liquid containing metals dissolved in nitric acid was bottled.

[0082] The resulting liquid is very acidic and high in metal ions. Liquid was used directly as a fertiliser or soil improver by adding to the soil and by adding to slurry.

EXAMPLE 2

[0083] The liquid from example 1 was added to sulfuric acid to make a slurry additive. Sulfuric acid is a cheap additive that was used to bulk out the liquid to produce a slurry additive that was very acidic but had a lower concentration of metals than the liquid produced in example 1.

EXAMPLE 3

[0084] The liquid from example 1 was neutralised to about pH 6 by adding hydrogen peroxide pellets before applying to soil as a soil improver or fertiliser. The solution may also be neutralised by chalk or lime. The neutralised solution may be advantageous because it is less damaging if it directly touches plants than the acidic solution. It is also easier to handle because it is less acidic.

EXAMPLE 4

[0085] The liquid from example I was diluted 1000 fold and 10000 by adding it to fertiliser to enrich the fertiliser.

EXAMPLE 5

[0086] The method of example 1 was carried out using circuit boards and electronic scrap instead of batteries. This is advantageous because circuit boards and other electronic scrap contain different minerals and metals from those contained in batteries. It would also be possible to mix the liquids made by dissolving different types of electronic waste in order to produce a fertiliser or soil additive with a wider range of minerals, metals or trace elements or a particular balance of minerals, metals or trace elements for a particular indication.

EXAMPLE 5

[0087] Additional compounds or metals could be added during the step of dissolving in acid to increase and make bio-available by dissolving elements such as selenium, boron, cobalt etc.

EXAMPLE 6

[0088] ##STR00001##

EXAMPLE 7

[0089] Battery Trial

[0090] 14/10/16

[0091] 3 litres 50% Nitric Acid

[0092] 20 Duracell alkaline AA batteries 25.42 g20=508.4 g

[0093] 10 g Cu for electrochemical displacement of Fe in battery shells

[0094] Warm to commence then self-sustaining.

[0095] 2.9 litres solution containing a range of metals and trace elements. This solution was analysed and is described in table 3.

[0096] 7 g plastic remaining (1.4% waste)

[0097] Research Paper Composition of Batteries

[0098] Second batch (White top bottles) also contain magnesium, selenium, boron, zinc, cobalt.

TABLE-US-00001 TABLE 1 Analysis of batteries Average dry weight.sup.b Moisture content.sup.b Ash content.sup.b Higher heating value.sup.b Lower heating value Components Base Material (g per battery) (%, dry basis) (%, dry basis) (kJ kg.sup.1, dry basis) (kJ kg.sup.1, dry basis) Anode cap Steel 0.288 0.003 Insulator Cardboard 0.060 0.002 6.4 0.1 9.3 0.5 23.8 10.sup.3 0.4 10.sup.3 22,675 Plastic grommet Polyamide (PA) 0.215 0.005 1.4 0.2 1.0 0.3 35 10.sup.3 2 10.sup.3 33,041 Metal separator Steel 0.377 0.005 Anode collector Tin-plated brass 0.438 0.004 Anode Zn + ZnO + KOH 3.86 0.05 1.8-28.7 99 1 6.1 10.sup.3 0.7 10.sup.3 6142 Separator Paper 0.107 0.009 5 1 2.4 0.2 26 10.sup.3 2 10.sup.3 25,008 Cellophane 0.045 0.003 10 1 5.26 0.06 22.09 10.sup.3 0.7 10.sup.3 20,857 Cathode MnO.sub.2 + C + KOH 11.9 0.9 8 2 88.3 0.4 6.8 10.sup.3 0.8 10.sup.3 6799 Cathode collector Steel 4.01 0.05 Plastic sleeve Polyvinylchloride (PVC) 0.23 0.01 1.7 0.2 5.8 0.08 20.4 10.sup.3 0.9 10.sup.3 19,455 Entire batteries 23.5.sup.a 0.4.sup. 98.1 0.2 , not determinded. .sup.aAs collected. .sup.b95% confidence interval.

TABLE-US-00002 TABLE 2 Table 4 Concentration of heavy metals in battery components of dry , except for Hg and As, expressed as . Total Metals (mg per components As Cd Co Cs Cu Hg Mn Ni Pb Sb Si Tl V Zn battery) Anode cap 4.7 < 11 .11 0.96 2.1 14.3 0.16 <DL <DL <DL 0.009 3.3 6.3 7 .12 1.1 <DL 2.3 16.4 0.18 0.30 Insulator <DL <DL <DL <0.082 <DL < <0.11 0.22 <DL <DL <DL <0.022 0.065 0.11 1.4 0.44 0.40 Plastic <DL <DL <DL 0.028 <DL <0.029 0.079 <DL <DL <DL 0.051 0.19 grommet 0.035 1.1 Metal 3.7 0.087 2.4 0.072 2.2 0.19 0.15 <DL <DL <DL 0.005 2.1 separator 7.1 12 0.12 2.6 .14 0.23 0.17 0.045 Anode <DL <DL <DL <0.052 589 <DL <0.015 0.046 <DL <DL <DL 317 428 collector 0.022 692 0.069 365 Anode 6.633 <DL <DL <DL <DL <DL 0.011 <DL 0.047 <DL <DL <DL 792 3154 0.11 0.025 0.049 830 Separator <DL <DL <DL , <DL 0.73 <DL 0.14 <DL <DL <DL 13.6 2.4 paper 0.30 2.87 0.63 35.8 Cellophane <DL <DL <DL <0.14 <DL 6.16 <DL <0.26 <DL <DL <DL 13.8 2.0 0.44 8.37 0.83 Cathode 0.065 <DL 0.027 <DL <0.11 453 0.018 <0.011 <DL. 0.084 <DL 9. 5487 0.11 0.029 0.008 0.43 0.030 0.0052 0.097 10. Cathode 2.8 2. 0.065 2 13.9 0.0087 0.095 < 0.076 <DL 0.034 80 collector 5.0 0.015 0.12 2.1 16.2 0.0094 0.12 0.41 0.093 0.073 Plastic <DL <DL <DL < < < <0.10 <DL <DL <DL <0.013 0.19 sleeve 0.40 #,899; 0.18 0.12 0.47 Battery 0.021 0.060 9.5 281 0.0038 5382 66 1.2 0.44 1.4 9163 total amount (mg per battery) <DL, below detection limit. , not determined. Determined by M. E. et al.: Waste Management indicates data missing or illegible when filed

TABLE-US-00003 TABLE 3 BATCH 290 MB/RD NITRIC ACID SOLUTIONS FOR TRACE METAL ANALYSES SAMPLES RUN ON 26.10.16. DATA RECORDED IN LN 7007 RESULTS ARE REPORTED AS PPM IN SOLUTION (CORRECTED FOR 100X DILUTION) Al As Ca Cd Co Cr Cu Fe K Mg 396.153 188.979 315.887 228.802 228.616 267.716 327.393 238.204 766.490 279.077 290/1 3.585 8.437 7.505 0.095 111.709 1.960 2260.336 3223.445 541.408 15.651 290/2 2.820 8.515 7.747 0.114 112.529 1.984 2292.923 3308.522 551.593 16.831 290/3 3.528 8.997 7.378 0.132 113.666 1.979 2308.214 3287.549 549.631 17.020 CORRECTED FURTHER FOR 10X DILUTION Raw Al As Ca Cd Co Cr Cu Fe K Mg Solution 396.153 188.979 315.887 228.802 228.616 267.716 327.393 238.204 766.490 279.077 290/1 35.9 84.4 75.0 0.9 1117.1 19.6 22603.4 32234.5 5414.1 156.5 290/2 28.2 85.1 77.5 1.1 1125.3 19.8 22929.2 33085.2 5515.9 168.3 290/3 35.3 90.0 73.8 1.3 1136.7 19.8 23082.1 32875.5 5496.3 170.2 Mean PPM 33.1 86.5 75.4 1.1 1126.3 19.7 22871.6 32731.7 5475.4 165.0 % 0.003 0.009 0.008 0.000 0.113 0.002 2.287 3.273 0.548 0.017 Prepared Dilluted 10x by further adding to 50% sulfuric acid(1.41 sg) by elementral Digest Solution 290/1 3.59 8.44 7.50 0.09 111.71 1.96 2260.34 3223.45 541.41 15.65 290/2 2.82 8.51 7.75 0.11 112.53 1.98 2292.92 3308.52 551.59 16.83 290/3 3.53 9.00 7.38 0.13 113.67 1.98 2308.21 3287.55 549.63 17.02 Mean PPM 3.31 8.65 7.54 0.11 112.63 1.97 2287.16 3273.17 547.54 16.50 Then Dilluted *1000 when added at 1 kg per tonne slurry Al As Ca Cd Co Cr Cu Fe K Mg 290/1 0.004 0.008 0.008 0.000 0.112 0.002 2.260 3.223 0.541 0.016 290/2 0.003 0.009 0.008 0.000 0.113 0.002 2.293 3.309 0.552 0.017 290/3 0.004 0.009 0.007 0.000 0.114 0.002 2.308 3.288 0.550 0.017 Mean PPM 0.003 0.009 0.008 0.000 0.113 0.002 2.287 3.273 0.548 0.017 % Mn Mo Na Ni P Pb S Se Ti Zn 257.610 202.031 589.592 231.604 213.617 220.353 181.975 196.026 334.940 206.200 290/1 2741.747 0.492 9.053 842.017 60.927 1.739 12.029 2.090 0.158 2862.354 290/2 2811.855 0.503 1.564 860.193 71.359 1.595 12.044 0.670 0.123 2968.696 290/3 2824.696 0.422 2.885 865.315 70.256 1.816 12.634 2.635 0.170 2948.690 Raw Mn Mo Na Ni P Pb S Se Ti Zn Solution 257.610 202.031 589.592 231.604 213.617 220.353 181.975 196.026 334.940 206.200 290/1 27417.5 4.9 90.5 8420.2 609.3 17.4 120.3 20.9 1.6 28623.5 290/2 28118.5 5.0 15.6 8601.9 713.6 15.9 120.4 6.7 1.2 29687.0 290/3 28247.0 4.2 28.8 8653.1 702.6 18.2 126.3 26.3 1.7 29486.9 Mean PPM 27927.7 4.7 25.8 8558.4 675.1 17.2 122.4 18.0 1.5 29265.8 % 2.793 0.000 0.003 0.856 0.068 0.002 0.012 0.002 0.000 2.927 Prepared Solution 290/1 2741.75 0.49 9.05 842.02 60.93 1.74 207195.70 2.09 0.16 2862.35 290/2 2811.85 0.50 1.56 860.19 71.36 1.59 146950.82 0.67 0.12 2968.70 290/3 2824.70 0.42 2.88 865.31 70.26 1.82 146951.41 2.63 0.17 2948.69 Mean PPM 2792.77 0.47 2.58 855.84 67.51 1.72 167032.64 1.80 0.15 2926.58 Mn Mo Na Ni P Pb S Se Ti Zn 290/1 2.742 0.000 0.009 0.842 0.061 0.002 207.196 0.002 0.000 2.862 290/2 2.812 0.001 0.002 0.860 0.071 0.002 146.951 0.001 0.000 2.969 290/3 2.825 0.000 0.003 0.865 0.070 0.002 146.951 0.003 0.000 2.949 Mean PPM 2.793 0.000 0.003 0.856 0.068 0.002 167.033 0.002 0.000 2.927 %