FERTILIZER COMPOSITIONS AND METHODS OF MAKING AND USING THE SAME

Abstract

Generally, the instant disclosure relates to fertilizer compositions and methods of making and using the same. More specifically, the instant disclosure relates to blast suppressant and/or blast resistant ammonium nitrate fertilizer compositions, as well as methods of making and using the same.

Claims

1. A fertilizer composition, comprising: an ammonium nitrate material; and an effective amount of a stabilizer material to result in. a specific impulse of not greater than 13.5 kPa*ms/kg when measured in accordance with a blast propagation test; wherein the stabilizer material comprises an aluminum production byproduct, wherein the stabilizer material is at least 12.5 wt. % of the total fertilizer composition.

2. The composition of claim 1, wherein the aluminum production byproduct comprises: a layered double hydroxide.

3. The composition of claim 1, wherein the stabilizer material comprises hydrocalumite.

4. The composition of claim 1, wherein the stabilizer material comprises hydrotalcite.

5. The composition of claim 1, wherein the stabilizer material comprises hydroxyapatite.

6. In some embodiments, the stabilizer material comprises an additive.

7. A fertilizer composition, comprising: an ammonium nitrate material; and an effective amount of a stabilizer material to result in a specific impulse of not greater than 13.5 kPa*ms/kg when measured in accordance with a blast propagation test; wherein the stabilizer material is selected from the group consisting of: layered double hydroxide, apatite, and combinations thereof; wherein the stabilizer material is at least 12.5 wt. % of the total fertilizer composition.

8. The fertilizer of claim 7, further comprising a filler material.

9. The fertilizer of claim 8, wherein the filler material is selected from the group consisting of: bauxite residue, fire day, red lime, and combinations thereof.

10. A fertilizer composition, comprising: an ammonium nitrate material; and an effective amount of a stabilizer material to result in a specific impulse of not greater than 13.5 kPa*ms/kg when measured in accordance with a blast propagation test; wherein the stabilizer material comprises hydrotalcite, wherein the stabilizer material is at least 12.5 wt. % to not greater than 20 wt. % of the total fertilizer composition.

11. A fertilizer composition, comprising: an ammonium nitrate material; and an effective amount of a stabilizer material to result in a specific impulse of not greater than 13.5 kPa*ms/kg when measured in accordance with a blast propagation test; wherein the stabilizer material comprises hydrotalcite, wherein the stabilizer material is at least 12.5 wt. % to not greater than 20 wt. % of the total fertilizer composition.

12. A fertilizer composition, comprising: an ammonium nitrate material; and an effective amount of a stabilizer material to result in a specific impulse of not greater than 115 kPa*ms/kg when measured in accordance with a blast propagation test; wherein the stabilizer material comprises hydrocalumite, wherein the stabilizer material is at least 12.5 wt. % to not greater than 20 wt. % of the total fertilizer composition.

13. A fertilizer composition, comprising: an ammonium nitrate material; and an effective amount of a stabilizer material to result in a specific impulse of not greater than 13.5 kPa*ms/kg when measured in accordance with a blast propagation test; wherein the stabilizer material comprises apatite, wherein the stabilizer material is at least 12.5 wt. % to not greater than 20 wt. % of the total fertilizer composition.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0153] FIG. 1 depicts a schematic of an embodiment of a blast test article in accordance with the instant disclosure.

[0154] FIG. 2 depicts a schematic cut-away side view of the blast test article of FIG. 1, depicting the booster and fertilizer composition to he tested.

[0155] FIG. 3 is a chart depicting the relative specific impulse of prilled fertilizer compositions, with the specific impulse from each overpressure sensor, For prilled samples, referring to FIG. 3, blast tests were completed and specific impulse values were calculated for multiple test articles including: two test articles with commercially available AN fertilizer from vendor1 (Control 1); three test articles with commercially available AN fertilizer from vendor 2 (Control 2); one test article with a commercially available blast resistant AN fertilizer; two test articles of AN fertilizer from vendor 1 coated with bauxite residue (having 15 wt. % phosphate from a neutralization step with phosphoric acid), and one test article of AN fertilizer from vendor 2 coated with bauxite residue (having 15 wt. % phosphate). As depicted in FIG. 3, BR coated prills performed better than any of the commercially available AN prills, with two test articles of BR coated prills out-performing the commercially available blast resistant fertilizer,

[0156] FIG. 4 is a chart depicting the relative Specific Impulse of ground fertilizer compositions, with the specific impulse from each overpressure sensor (two sensors for each blast test), Fertilizer compositions were prepared in accordance with the Examples. Blast tests were conducted in accordance with Examples. Referring to FIG. 4, blast tests were completed and specific impulse values were calculated for multiple test articles including: two test articles with commercially available AN fertilizer from vendor1 (Control 1); three test articles with commercially available AN fertilizer from vendor 2 (Control 2); one test article with a commercially available blast resistant AN fertilizer (in ground form); two test articles of AN fertilizer from vendor 1 blended with bauxite residue (having 15 wt. % nitrate, present via addition of aluminum hydroxide and anthropogenic exposure to atmospheric carbon dioxide), and two test articles of AN fertilizer from vendor 2 blended with 25 weight percent of bauxite residue (having 15 wt. % phosphate),

[0157] As depicted in FIG. 4, the fertilizer compositions of BR and ammonium nitrate outperformed the commercially available AN, The commercially available blast resistant BR. coated prills performed slightly better than ammonium nitrate from vendor 1 blended with bauxite residue having nitrate therein. Mean. specific impulse values are provided in the table in the corresponding Examples section, Based on the results from this set of experiments, further blast testing was completed using only ground materials in the test articles, since any reduction in specific impulse realized in the ground form would translate to the milled or pelletized form.

[0158] FIG. 5 is a chart depicting booster size (in grams) as a function of charge diameter (in inches) for a fertilizer composition of 25 wt. % hydrotalcites where solid circles indicate detonation while an x indicates no detonation. The plotted line depicts detonation versus non detonation region at a sensitivity of +50 g increase in booster size.

[0159] FIG. 6 is a chart depicting booster size (in grams) as a function of charge diameter (in inches) for a fertilizer composition of 22.5 wt. % hydrotalcites where solid circles indicate detonation while an x indicates no detonation. The plotted line depicts detonation versus non detonation region at a sensitivity of +50 g increase in booster size,

[0160] FIG. 7 is a graph is a chart depicting booster size (in grams) as a function of charge diameter (in inches) for a fertilizer composition of 20 wt. % hydrotalcites where solid circles indicate detonation while an x indicates no detonation. The plotted line depicts detonation versus non detonation region at a sensitivity of +50 g increase in booster size,

[0161] FIG. 8 is a graph is a chart depicting booster size (in grams) as a function of charge diameter (in inches) for a fertilizer composition of 20; 22.5 and 25 wt. % HTC-PO4. The plotted line depicts detonation versus non detonation region at a sensitivity of +50g increase in booster size.

[0162] FIG. 9 is a graph depicting the specific impulse for test articles that resulted in a non-perforation of the witness plate, where x refers to 25 wt. % HTC, diamond depicts 22.5 wt. % and dashes depict 20 wt. %.

[0163] FIG. 10 is a graph depicting specific impulse at different booster sizes , where x refers to the standard fuel oil content (i.e. 6%, as compared to AN content); diamond refers to 50% more stoichiometric fuel oil (i.e. 9% as compared to the AN content); and where dash refers to 100% fuel oil (i.e. 12 wt. % as compared to AN content).

[0164] FIG. 11 is a graph depicting the specific impulse at different booster sizes for 20 wt. % HTC in a 5 diameter tube (test article).

[0165] FIG. 12 is a graph that illustrates the specific impulse of HTC at 22.5% (square) and 25% (diamonds) concentration at an 8 diameter with booster size ranging from 300-600 g.

[0166] FIG. 13 is a graph that depicts the global cliff of all the stabilizer materials. The graph is plotted as number of sample against specific impulse. This data represents all data analyzed in the Blast Suppression and Desensitization Example and shows the distinction between non perforation and perforation. The data consists of HTC-PO.sub.4, Apatite and HTC PO.sub.4-15%/BR 10% mixture.

[0167] FIG. 14 is a graph that depicts the trends of specific impulse reduction in relation to concentration in percent. Listed in the graph are HTC-PO.sub.4-22.5% (diamond), HTC-PO.sub.4-20% (X), HTC-PO.sub.4-15% (square), HTC-PO.sub.4-10% (triangle) and AN (circle)

[0168] FIG. 15 is a graph that illustrates the percent reduction of specific impulse when compared to concentration of 10, 15, 17.5, 20, 22.5 and 25%.

[0169] FIG. 16 is a graph depicts the specific impulse of stabilizer materials that showed non perforation at different booster levels at different concentration. X=HTC-PO.sub.4-25%; Triangle =Apatite; Dash-HTC-PO.sub.4415%/BR 10%,

[0170] FIG. 17 is a graph that depicts perforating versus non-perforating of stabilizer materials at different booster charge and percent stabilizer material at 5 diameter with a 100% accuracy. Solids symbols indicate perforation; open symbols depicts non perforation. Circle=HTC PO.sub.4-25%; Diamond=Apatite-25%; Square HTC PO.sub.4-15%/BR 10%

[0171] FIG. 18 is a graph that depicts perforating versus non-perforating of stabilizer materials at different booster charge and percent stabilizer material at 6 diameter. Solids symbols indicate perforation; open symbols depicts non perforation.

[0172] FIG. 19 is a graph that depicts perforating versus non-perforating of stabilizer materials at different booster charge and percent stabilizer material at 8 diameter. Solids symbols indicate perforation; open symbols depicts non perforation.

[0173] FIG. 20 is a graph that depicts specific impulse at different booster charge for HTC PO.sub.4 at different concentration; X=25%; dash=20%; diamond=22.5%. The graph also illustrates the specific impulse of alternate product (ALT PRDT) at 13.25 kPa*ms/kg and control-AN at 15.5 kPa*ms/kg .

DETAILED DESCRIPTION

Example: Thermodynamic Calculations

[0174] A series of isenthalpic equilibrium calculations were performed on mixtures of different materials in combination with ammonium nitrate, In this method, a mixture is put into a box that retains all of the energy of the system. The equilibrium chemical composition of the mixture was calculated via a computer model and the energy released causes the system temperature to rise.

[0175] In completing the computer model and. performing the calculation in this way, pure ammonium nitrate decomposes into N.sub.2, H.sub.2, and H.sub.2O (all lower energy than AN) and the energy that is released increase the gas temperature (i.e. in the box) to 970 C. Addition of other components to the system can now be explored to see their effect on the final system temperature. For example, a 1:1 mixture of AN and SiO2 will result in the final composition of N.sub.2, H.sub.2, H.sub.2O and SiO.sub.2 at 604 C. The lower temperature is due to the presence of the SiO.sub.2 as an inert material that absorbs some of the energy released from AN decomposition. The energy absorption can be enhanced if the stabilizer material itself is not inert, but can react to change state (and/or degrade to form other compounds). For example, a 1:1 mixture of AN with chalk (CaCO3) gives a final. composition N.sub.2, H.sub.2, H.sub.2O, CaO, and CO.sub.2 at a temperature of 585 C. Some of the AN decomposition energy is used to convert chalk to lime (CaO) and CO.sub.2 via the endothermic reaction CaCO.sub.3.fwdarw.CaO+CO.sub.2.

[0176] In some embodiments, bauxite residue (BR.) is a mixture of inert materials (SiO.sub.2, TiO.sub.2, Fe.sub.2O.sub.3, etc.) and components which may act as energy absorbers (Al(OH).sub.3, AlOOH, Fe.sub.2O.sub.3, H.sub.2O, etc.) the final system temperature for a 1:1 mixture of AN+BR is 711 C. in addition to BR, a number of other materials were evaluated as energy absorbers. The best performer (i.e. at a 1:1 mix) is Bayer process hydrate (Al(OH).sub.3) with a final system temperature of 233 C. Some other attractive materials could be hydrated lime (Ca(OH).sub.2) and gypsum (CaSO.sub.4*2H.sub.2O). The results of the energy absorption performance calculations are summarized in the following table below, where the lower the final temperature, the better the performance,

TABLE-US-00001 Final Temp % Material* ( C. ) Reduction AN Control (NH.sub.4NO.sub.3) 970 NIAControl Bauxite Residue 711 27% (mixed metal oxides, as above) Bayer Process Hydrate 233 76% (Al(OH).sub.3) Silicon Dioxide 601 38% (SiO.sub.2) Calcium Carbonate 585 40% (CaCO.sub.3) Calcium Sulfate Hydrate 369 62% (CaSO.sub.4*2H.sub.2O) Calcium Hydroxide 497 51% (Ca(OH).sub.2) *Control was 100% AN, all other Materials modeled were in a 1:1 concentration with AN

[0177] All additions to AN performed better (resulted in lower equilibrium temperatures) as compared to the pure AN and some additions to AN performed better than others. Percent reductions in equilibrium temperature were computed for the isenthalpic models, and the percent reduction values ranged from a 27% reduction (bauxite residue) to a 76% reduction (aluminum hydroxide). The general trends observed from the computer modeling of isenthalpic equilibrium of various AN data were used to down-select constituents as stabilizer materials to AN fertilizer. Without being bound by a particular mechanism or theory, it is believed that if a constituent of a material lowered the isenthalpic equilibrium temperature, then the resulting material would also potentially prevent the combustion of ammonium nitrate (and thus, potentially provides a blast suppression and/or desensitization mechanism to ammonium nitrate fertilizer(s)). For example, constituents having metal oxides, hydrates, carbonates, and hydroxides were explored as fertilizer compositions (i.e. experiments performed include blast tests to explore potential of blast suppression and/or desensitization of stabilizer materials in AN fertilizer).

Example: Standard Operating Procedure for Blast Tests

[0178] Test articles refer to the container (PVC pipe), a mild steel plate (called a witness plate), fertilizer composition (stabilizer material and AN mixed with 6 wt. % fuel oil of AN), and a booster (includes C4 explosive in a plastic storage cup). A schematic of a test article is depicted in FIG. 1, while the innards of each test article, including the detonator, booster, and fertilizer composition are shown in FIG. 2.

Sample Preparation:

[0179] To make a fertilizer composition for the test article, ammonium nitrate fertilizer prills were dry ground using a ball mill to make a less than 20 mesh (<800 micrometers). Then, the AN powder was dry blended with the stabilizer material powder.

[0180] Samples containing iHTC with phosphate had a 15 wt. % phosphate. Bauxite residue samples had either phosphate (Le. 5-10% wt. %) or nitrate (i.e. 5-10 wt %) Sample mixtures were dry weighed, and fuel oil was added (6 wt. %) in accordance with the AN content. For all tests, the contents of each article included a ratio of 6% fuel oil to 94% ammonium nitrate (based on mass). The resulting fertilizer/fuel oil composition was mixed/blended for at least 30 minutes and checked for caking with visual observation.

[0181] Each test article was weighed empty using a scale with an accuracy of +/0.2 grams. The resulting mixture was added to each container (PVC with glued end cap) to within 25 mm of top edge, Each filled test article (ammonium nitrate and stabilizer material, mixed with fuel oil) was weighed on a scale having an accuracy of +/0.1 ounce.

[0182] Each test article was left to stand for at least 12 hours prior to testing with a covering (e.g. plastic bag) applied to prevent ambient moisture from entering the test article. Just prior to testing, the booster (C4 in a plastic cup) was inserted flush with the top of the pipe, with the detonator wire attached to the booster.

[0183] Boosters for each test article were prepared in small plastic storage cups. A predetermined amount of C4 was measured into each cup. A C4 booster was added to a 5 diameter tube with blast material to be tested. The total weight of the tube was approximately eight kg (including the blast material),

[0184] Each test article included a 0.25 inch thick mild steel plate (called a witness plate), with a PVC Pipe, base/end cap. However, the base caps were domed and would not sit vertically on the witness plate. An additional section of 6 PVC pipe, 3 in length was cut (split) and slipped over the outer surface of the test article. This piece provided good stability to the test article for filling and testing. The test article was placed onto a 4 stack thick piece of foam (12 inches12 inches) on a level sand pit.

[0185] Filled test articles were placed onto witness plates and positioned and centered on the witness plate. Cable (Cat6 cable) was routed from the shelter to Over Pressure probes.

[0186] The detonator was placed into the booster, the charge was armed, and the booster was detonated. For each test article, the detonator was Exploding Bridge Wire (EBW) Type RP-83.

[0187] Blast suppression was measured via two blast pressure probes (PCB model), positioned at a distance of 7 m from the test article, Coaxial cable ran from each probe (2-channel, 12 bit, IEPE, 100 kHz) to a computer, Steel rods were positioned between the probes and the target (i.e. test article) to deflect any possible shrapnel.

[0188] For each test, two blast pressure probes were used to measure the pressure versus time of each explosion (kPa*ms). The resulting pressure readings were used to compute the specific impulse of the fertilizer composition for each test article. Blast overpressure (i.e. impulse pressure) was collected for each test article.

[0189] This data was then integrated by standard means and then. divided by the amount of ammonium nitrate present to generate a specific impulse (i.e. maximum pressure reading for each blast test impulse). These were then measured against a reference specific impulse of ANFO itself or ammonium nitrate combined with other fuels.

[0190] Without being bound by a particular mechanism or theory, stabilizer materials with a specific impulse at approximately the same level as the baseline (AN controls) are considered inert, in that it is believed that these materials affect the impulse at the same levels as the concentration dictates (i.e. operate by a mechanical filler mechanism).

[0191] Without being bound by a particular mechanism or theory, measurements below the baseline results are considered suppressants, in that it is believed that these materials affect the impulse by a chemical reaction or mechanism independent, or in combination. with, a dilution factor.

Example: Blast TestGround vs. Coated Prilled Ammonium Nitrate

[0192] It is noted that test articles which had materials that were powdered (ground to a fine texture) produced higher specific impulse values than materials that were produced with prills.

TABLE-US-00002 Average Specific Prill Specific Specific Impulse Test Articles Impulse A Impulse B (kPa .Math. mg/kg) AN V2, BR2 0.81 0.92 0.86 AN V1, BR2 0.95 1.00 0.98 ALT PRDT 1.23 1.34 1.29 AN V1, BR2 1.34 1.37 1.36 CRTL-V1 2.26 2.32 2.29 CRTL-V1 2.70 2.66 2.68 CRTL-V2 2.85 2.89 2.87 CRTL-V2 3.01 3.02 3.01 CRTL-V2 3.21 3.79 3.25

TABLE-US-00003 Average Specific Ground Specific Specific Impulse Test Articles Impulse A Impulse B (kPa .Math. mg/kg) AN V1, BR1 12.67 12.60 12.64 ALT PRDT 12.02 12.47 12.75 AN V1, BR1 13.31 13.32 13.31 AN V2, BR2 14.50 14.49 14.49 AN V2, BR2 14.63 14.79 14.71 CTRL-V2 14.79 15.51 15.24 CTRL-V1 15.29 15.27 15.28 CTRL-V1 N/A* 15.49 15.49 CTRL-V2 15.52 15.65 15.58 CTRL-V2 15.80 15.67 15.74 N/A* = probe was disconnected - no reading was obtained

Example: Blast TestDiffer Stabilizer Materials

[0193] In order to identify stabilizer materials with blast suppression and/or desensitization characteristics, various stabilizer materials were tested (each at 25 wt. %), in a 5 diameter tube with 200 g booster. The specific impulse was calculated for each test article and is presented in the table below, which also provides the mean impulse (obtained as an average of the overpressure sensor measurements from each detonation) and the visual observation of the state of the witness plate (perforated, non-perforated).

TABLE-US-00004 Mean Impulse Impulse Stabilizer Sp. Imp. Impulse Witness 1 2 # materials kPa*ms/kg kPa*ms Plate (kPa*ms) (kPa*ms) 1 AN 14.7 110.9 perf 108.7 113.1 2 AN 14.7 111.5 perf 109.6 113.3 3 AN 14.2 108.8 perf 107.5 110.1 4 AN 14.3 110.9 perf 108.8 113.1 5 Bauxite 12.1 84.2 perf 83.1 85.1 6 Bauxite 13.2 86.5 perf 85.3 87.8 7 Bauxite 13.3 87.0 perf 85.1 88.8 8 Bauxite 12.2 83.5 perf 81.6 85.5 9 BR1(NO3) 15.1 90.4 perf 87.9 92.8 10 BR1(NO3) 14.4 86.7 perf 85.9 87.4 11 BR1(NO3) n/a n/a no perf n/a n/a 12 BR1(NO3) 15.3 90.5 perf 88.9 92.0 13 BR1(PO4) 12.7 86.1 perf 85.2 87.1 14 BR2(PO4) 11.9 83.7 perf 82.0 85.4 15 BR2(PO4) n/a n/a no perf n/a n/a 16 BR2(PO4) 12.4 85.1 perf 83.3 86.9 17 HTC-CO3 0.0 19.3 no perf 18.9 19.7 18 HTC-CO3 0.2 18.3 no perf 18.2 18.4 19 HTC-CO3 0.0 19.3 no perf 18.7 19.8 20 HTC-PO4 0.9 23.2 no perf 22.9 23.5 21 HTC-PO4 0.6 22.2 no perf 21.9 22.6 22 HTC-PO4 1.2 24.6 no perf 24.2 25.1 23 HTC-PO4 1.0 23.9 no perf 23.9 n/a 24 Hydrate 13.5 83.7 perf 82.7 84.8 25 Hydrate 13.4 83.2 perf 81.8 84.7 26 Hydrate 13.3 81.8 perf 79.7 83.9 27 Hydrate 13.2 80.2 perf 78.4 81.9 28 Oxalate 13.5 81.6 perf 80.3 83.0 29 Oxalate 12.9 80.8 perf 79.4 82.2 30 Oxalate 13.4 81.3 perf 79.9 82.7 31 Oxalate 13.4 83.1 perf 80.3 85.9 32 Sand 14.5 91.6 perf 90.0 93.2 33 Sand 14.4 91.2 perf 89.7 92.7 34 Sand 13.8 90.7 perf 88.9 92.4 35 Sand 13.3 87.6 perf 85.9 89.4 36 SGA 10.8 74.0 perf 73.3 74.7 37 SGA 9.7 71.9 perf 70.8 73.0 38 SGA 9.8 71.2 perf 69.2 73.1 39 SGA 10.7 73.3 perf 72.1 74.6

[0194] It is noted that for runs 11 and 15, the booster (C4) did not detonate, which resulted in no perforation of the witness plate.

[0195] In order to account for the booster shot in the specific impulse calculation, multiple booster shots (6) were completed at various amounts of booster. The results were linear as the amount of booster increased, so too did the resulting specific impulse.

EXAMPLE: BLAST TESTBLAST SUPPRESSION AND DESENSITIZATION

[0196] In order to identify blast suppression and desensitization parameters, three variables were tested under this set of experiments, including:

(1) fertilizer composition (i.e. AN+(a) stabilizer material 1 (HTC at different wt. %), (2) stabilizer material 2 (apatite), and (3) stabilizer material 3 (combined 15 HTC/10 BR);
(2) booster size/quantity (e.g. 200 g, 300 g, 400 g, 600 g, 800 g); and
(3) tube diameter of the test article (i.e. 5 inch, 6 inch, or 8 inch diameter).

TABLE-US-00005 Diluent Booster Tube Witness Sp. Imp. # Sample (%) (g) (in) Plate (kPa .Math. ms/kg) 1 HTC 10 200 5 Perf 13.68 2 HTC 15 400 5 Perf 12.66 3 HTC 15 200 5 Perf 10.61 4 HTC 15 200 5 Perf 13.61 5 HTC 17.5 200 5 Perf 12.92 6 HTC 20 200 6 Perf 11.48 7 HTC 20 200 6 Perf 12.44 8 HTC 20 500 5 Perf 12.40 9 HTC 20 400 5 Perf 12.08 10 HTC 20 400 5 Perf 9.29 11 HTC 22.5 400 6 Perf 11.41 12 HTC 22.5 400 8 Perf 9.64 13 HTC 22.5 350 8 Perf 10.30 14 HTC 25 600 8 Perf 9.43 15 HTC 25 500 8 Perf 8.11 16 HTC 20 200 5 No perf 3.53 17 HTC 20 300 5 No perf 3.57 18 HTC 22.5 400 5 No perf 3.99 19 HTC 22.5 600 5 No perf 4.52 20 HTC 22.5 700 5 No perf 4.86 21 HTC 22.5 300 6 No perf 2.66 22 HTC 22.5 300 8 No perf 4.02 23 HTC 25 200 5 No perf 1.56 24 HTC 25 300 5 No perf 1.76 25 HTC 25 400 5 No perf 2.10 26 HTC 25 500 5 No perf 2.60 27 HTC 25 600 5 No perf 4.59 28 HTC 25 700 5 No perf 5.15 29 HTC 25 400 6 No perf 2.79 30 HTC 25 600 6 No perf 2.50 31 HTC 25 400 8 No perf 4.12 32 HTC 25 450 8 No perf 4.25 33 HTC 25 400 5 No perf 2.86 34 HTC 25 600 5 No perf 3.48 35 HTC 25 400 5 No perf 2.01 36 HTC 25 600 5 No perf 2.49 37 HTC 25 800 5 No perf 4.17 38 Apatite 25 200 5 No perf 1.74 39 Apatite 25 400 5 No perf 2.19 40 15HTC/10BR 25 200 5 No perf 1.41 41 15HTC/10BR 25 400 5 No perf 2.32

[0197] In order to account for the booster shot in the specific impulse calculation, multiple booster shots (16) were completed at various amounts of booster. The results were linear as the amount of booster increased, so too did the resulting specific impulse.

[0198] It is noted that the BR in runs 40 and 41 had a phosphate content of 5-15 wt. %.

[0199] It is noted that runs 33-36 had increased fuel oil in the fertilizer composition. Run 33 and 34 were 50% fuel oil (i.e. 9 wt % fuel oil compared to AN content) and rims 35 and 36 were 100% fuel oil 12 wt. % fuel oil, as compared to AN content).

Data Comparison:

[0200] The below table illustrates all stabilizer materials in ground coma at the standard operating procedure of 5 diameter and 200 g booster size; with the exception of HTC-P04-22.5%. This sample was a 5 tube with booster sizes of 300, 400, 600, and 700.

TABLE-US-00006 Stabilizer Sp. Avg. Sp. St material Imp. Imp. Dev. BR1-(PO.sub.4) 12.64 12.98 0.48 13.31 Bauxite-25% 12.1 12.7 0.6 12.2 13.2 13.3 Oxalate-25% 12.9 13.3 0.3 13.4 13.4 13.5 Apatite-25% 1.7 1.7 HTC-PO.sub.4-15%/ 1.4 1.4 BR-10% BR2 14.49 14.60 0.15 14.71 BR1-(NO.sub.3) 14.4 14.9 0.4 15.1 15.3 BR2-PO.sub.4 11.9 12.3 0.4 12.4 12.7 SGA-25% 9.7 10.2 0.6 9.8 10.7 10.8 Hydrate-25% 13.2 13.3 0.1 13.3 13.4 13.5 Sand-23% 13.3 14.0 0.5 13.8 14.4 14.5 HTC-CO.sub.3- 0.2 0.0 0.1 25% 0.0 0.0 HTC-PO.sub.4- 2.7 6.4 3.4 22.5% 4.0 4.0 1.5 4.9 9.6 10.3 11.4 HTC-PO.sub.4- 12.9 12.9 17.5% HTC-PO.sub.4- 0.6 1.2 0.4 25% 0.9 1.0 1.2 1.6 1.8 HTC-PO.sub.4- 13.7 13.7 10% HTC-PO.sub.4- 10.6 12.3 1.5 15% 12.7 13.6 HTC-PO.sub.4- 3.5 9.3 4.4 20% 3.6 11.5

[0201] For the following three sets of blast data, we note the hydrotalcite, hydrocalumite, red lime, and hydroxyapatite materials were obtained from an alumina refining process, unless otherwise indicated (i.e. synthetic refers to materials obtained via a commercial vendor).

[0202] As these materials were obtained via an alumina refining process, analytical data was compiled in order to better understand the characteristics of the aluminum byproduct material (e.g. as compared to commercially available alternatives with high purity and low to no unavoidable minor components). Below, the analytical data is set forth for the materials obtained via the alumina refining process, with minor variations depicted for different batches of the same material.

[0203] Two batches of hydrotalcite were utilized in the following three blast tests. For the first batch of hydrotalcite: the density was measured at 2.1135 g/cc, while the surface area was 30.8 m2/g. The average particle size was measured at 12.98 microns. The x-ray diffraction noted the following components: Major: Mg4Al2 (OH)14.Math.3H2O, Magnesium Aluminum Hydroxide Hydrate, Meixnerite and/or Mg4Al2 (OH)12CO3.Math.3H2O, Magnesium Aluminum Hydroxy Carbonate Hydrate and/or Mg6Al2CO3 (OH)16.Math.4H2O, Hydrotalcite, Trace possible: Ca3Al2 (OH)12.

[0204] For the second batch of hydrotalcite: the density was measured at 2.0941 g/cc, while the surface area was 29 m2/g. The average particle size was measured at 12.31 microns. The x-ray diffraction noted the following components: Major: Mg6Al2(CO3)(OH)16.Math.4(H2O), Hydrotalcite and/or Mg6Al2 (OH)18.Math.4.5H2O, Magnesium Aluminum Hydroxide Hydrate, Trace possible: Ca3AlFe (SiO4) (OH)8, Calcium Aluminum Iron Silicate Hydroxide.

[0205] For the bauxite residue material, the density was measured at 3.3441 g/cc, while the surface area was 42.3 m2/g. The average particle size was measured. at 4.892 microns. The x-ray diffraction noted the following components: Major: Fe2O3, Hematite; CaCO3, Calcium Carbonate; Minor: TiO2, Titanium Oxide, Rutile; Fe O (OH), Goethite; Al(OH)3, Baverite; AlO (OH), Boehmite; Trace possible: Al(OH)3, Gibbsite; Na8Si6Al6O24 (OH)2 (H2O)2, Sodium Silicon Aluminate.

[0206] For the apatite, two batches were utilized. For the first batch of apatite material, the density was measured at 2.6645 g/cc, while the surface area was 76 m2/g. The average particle size was measured at 5.518 microns. The x-ray diffraction noted the following components: Major: Ca10(PO4)3 (CO3)3 (OH)2, Calcium Carbonate Phosphate Hydroxide; Mg6Al2(CO3)(OH)16.Math.4(H2O), Hydrotalcite and/or Mg6Al2 (OH)18.Math.4.5H2O, Magnesium Aluminum Hydroxide hydrate, with Minor possible: CaCO3, Calcium Carbonate.

[0207] For the second batch of apatite material, the density was measured at 2.6443 glee, while the surface area was 89 m2/g. The average particle size was measured at 5.367 microns. The x-ray diffraction noted the following components: Major: Ca10(PO4)3 (CO3)3 (OH)2, Calcium Carbonate Phosphate Hydroxide; Mg6Al2(CO3)(OH)16.Math.4(H2O), Hydrotalcite and/or Mg6Al2 (OH)18.Math.4.5H2O Magnesium Aluminum Hydroxide Hydrate, Minor possible: CaCO3, Calcium Carbonate.

[0208] For the red lime, two batches were utilized.

[0209] For the first batch of red lime material, the density was measured at 2.5621 g/cc, while the surface area was 4.1 m2/g. The average particle size was measured at 20.62 microns, The x-ray diffraction noted the following components: Major: CaCO3, Calcium Carbonate. Minor: Ca3AlFe (SiO4) (OH)8, Calcium Aluminum Iron Silicate Hydroxide. Very Small: Ca(OH)2, Calcium Hydroxide. Trace: Mg6Al2(CO3)(OH)16.Math.4(H2O), Hydrotalcite and/or Mg6Al2 (OH)18.Math.4.5H2O, Magnesium Aluminum Hydroxide.

[0210] For the second batch of red lime material, the density was measured at 2.5658 Wee, while the surface area was 4.7 m2/g. The average particle size was measured at 12.43 microns, The x-ray diffraction noted the following components: Major: CaCO3, Calcium Carbonate. Minor: Ca3AlFe (SiO4) (OH)8, Calcium Aluminum Iron Silicate Hydroxide. Very Small: Ca(OH)2, Calcium Hydroxide. Trace: Mg6Al2(CO3)(OH)16.4(H2O), Hydrotalcite and/or Mg6Al2 (OH)18.Math.4.5H2O, Magnesium Aluminum Hydroxide.

[0211] Two batches of hydrocalumite were utilized.

[0212] For the first batch of hydrocalumite material, the density was measured at 2.2296 glee. while the surface area was 10.4 m2/g. The average particle size was measured at 12.21 microns. The x-ray diffraction noted the following components: Major: Ca(OH)2, Calcium Hydroxide; CaCO3, Calcium Carbonate; Ca4Al2 (OH)12 (CO3) (H2O)5, Calcium Aluminum Hydroxide Carbonate Hydrate; Ca4Al2 06 C12 (H2O)10, Hydrocalumite, Minor possible: Mg6Al2(CO3)(OH)16.4(H20), Hydrotalcite and/or Mg.

[0213] For the second batch of hydrocalumite material, the density was measured at 2.2561 g/cc, while the surface area was 11.71 m2/g. The average particle size was measured at 16.31 micorns. The x-ray diffraction noted. the following components: Major: Ca(OH)2, Calcium Hydroxide; CaCO3, Calcium Carbonate; Ca4Al2 (OH)12 (CO3) (H2O)5, Calcium Aluminum Hydroxide Carbonate :Hydrate; Ca4Al2 O6 Cl2 (H2O)10, Hydrocalumite, Minor possible: Mg6Al2(CO3)(OH)16.Math.4(H2O), Hydrotalcite and/or Mg.

Example: Blast TestBlast Suppression and Desensitization

[0214] The below table illustrates experimental results from blast tests completed on a control (AN) as compared to two stabilizer materials: hydrotalcite and hydroxyapatite in various forms (e.g. recovered from an alumina production process, s),Tithetic, etc) and at different weight percent.

[0215] For this blast test, the fuel was fuel oil for all materials, though the booster size varied (as indicated) and a few of the runs included larger diameter tubes (e.g. 8 inches) as compared to the standard size (5) utilized for many of the runs, The blast test components were prepared as previously indicated, according to the standard operating procedure. The specific impulse readings are provided below, along with a comparative view of the Reduction in Blast, measured as a percentage according to various SI baselines (e.g. 13.5, 10.0, and 8.0). When a blast test did not result in a reduction in specific impulse, the reduction percentage is indicated as N/A.

TABLE-US-00007 Sp. Reduction Reduction Reduction Imp. vs. 13.5 vs. 10.0 vs. 8.0 Booster Dia. (kPa .Math. Baseline Baseline Baseline Material (g) (in.) ms/kg) (%) (%) (%) Ammonium Nitrate (control) 10 5 15.38 N/A N/A N/A Ammonium Nitrate (control) 10 5 15.37 N/A N/A N/A Ammonium Nitrate (control) 25 5 15.24 N/A N/A N/A Ammonium Nitrate (control) 100 5 15.25 N/A N/A N/A Hydrotalcite 17.5 wt.% 200 5 1.01 92.5 89.9 87.3 Hydrotalcite 17.5 wt % 300 5 7.92 41.3 20.8 1 Hydrotalcite 17.5 wt % 400 5 10.91 19.2 N/A N/A Hydrotaicite 17.5 wt % 400 5 3.16 76.6 68.4 60.5 Hydrotalcite 25 wt. % 400 5 1.76 87 82.4 78 Hydrotaleite 25 wt. % 600 5 1.88 86.1 81.2 76.5 Synthetic Hydrotalcite 17.5 wt % 200 5 0.92 93.2 90.8 88.5 Synthetic Hydrotalcite 17.5 wt % 400 5 1.57 88.4 84.3 80.4 Synthetic Hydrotalcite 17.5 wt % 400 8 2.05 84.8 79.5 74.3 Synthetic Hydrotalcite 17.5 wt % 600 8 3.02 77.6 69.8 62.2 Synthetic Hydrotalcite 17.5 wt.% 600 8 2.87 78.7 71.3 64.1 Synthetic Hydrotalcite 17.5 wt % 600 5 2.21 83.6 77.9 72.3 Synthetic Hydrotalcite, 400 5 2.9 78.5 71 63.8 cooked 25 wt % Rehydrated Synthetic Hydrotalcite 200 5 14.62 N/A N/A N/A Reground 17.5 wt. % Rehydrated Synthetic Hydrotalcite 200 5 14.35 N/A N/A N/A Reground 17.5 wt, % Rehydrated Synthetic Hydrotalcite 400 5 13.75 N/A N/A N/A Prill 17.5 wt. % Rehydrated Synthetic Hydrotalcite 200 5 14.9 N/A N/A N/A Prill 17.5 wt. % Rehydrated Synthetic Hydrotalcite 200 5 13.28 1.6 N/A N/A Prill 17.5 wt. % Hydrotalcite + phosphate 20 wt. % 200 5 11.29 16.4 N/A N/A Hydrotalcite + phosphate 20 wt. % 200 5 12.32 8.7 N/A N/A Hydrotalcite + phosphate 20 wt. % 400 5 11.99 11.2 N/A N/A Hydroxyapatite 10 wt % 200 5 13.25 1.9 N/A N/A Hydroxyapatite 10 wt % 200 5 13.13 2.8 N/A N/A Hydroxyapatite 15 wt. % 400 5 5.52 59.1 44.8 30.9 Hydroxyapatite 15 wt. % 600 5 9.38 30.5 6.2 N/A Hydroxyapatite 20 wt. % 400 5 3.16 76.6 68.4 60.5 Hydroxyapatite 20 wt. % 600 5 3.8 71.8 62 52.5 Hydroxyapatite 25 wt. % 200 5 2.12 84.3 78.8 73.5 Hydroxyapatite 25 wt. % 400 8 2.13 84.2 78.7 73.3 Hydroxyapatite 25 wt. % 600 5 2.68 80.1 73.2 66.5 Hydroxyapatite 25 wt. % 700 5 2.82 79.1 71.8 64.7 Hydroxyapatite 25 wt. % 700 5 2.43 82 75.7 69.6 Hydroxyapatite 25 wt. % 600 8 0.24 98.2 97.6 97 Hydroxyapatite 25 wt. % 700 8 5.13 62 48.7 35.9 Hydroxyapatite 25 wt. % 700 8 4.44 67.1 55.6 44.4

Example: Blast TestBlast Suppression and Desensitization

[0216] The below table illustrates experimental results from blast tests completed on various materials, in which stabilizer and combinations of stabilizers and fillers were evaluated against a control SI baseline (ammonium nitrate), Materials evaluated for this blast test included: red lime (individually and in combination with bauxite residue at different weight percentages), hydrocalumite (individually and in combination with bauxite residue at different weight percentages), hydroxyapatite (individually and in combination with bauxite residue at different weight percentages), hydrotalcite (individually and in combination with bauxite residue at different weight percentages), a combination of hydrotalcite and hydroxyapatite (individually and in combination with bauxite residue at different weight percentages).

[0217] For this blast test, the hydrotalcite and hydroxyapatite were recovered from an alumina production process, The standard operating procedure was followed to prepare the blast components and complete the blast tests, while other variables were modified: i.e. the diameter of the tube (8 vs. 12), the amount of booster (200 g, 400 g, 450 g), and the type of fuel (i.e. fuel oil (FO), AL (aluminum)).

[0218] The specific impulse readings are provided below, along with a comparative view of the Reduction in Blast, measured as a percentage according to various SI baselines (e.g. 13.5, 10.0, and 8.0). When a blast test did not result in a reduction in specific impulse, the reduction percentage is indicated as N/A.

TABLE-US-00008 Sp. Reduction Reduction Reduction Imp. vs. 13.5 vs. 10.0 vs. 8.0 Booster Dia. (kPa .Math. Baseline Baseline Baseline Material (g) (in.) Fuel ms/kg) (%) (%) (%) Ammonium Nitrate 450 12 AL 13.98 N/A N/A N/A Hydrocalumite 20 wt % 450 12 AL 5.13 62.0 48.7 35.9 Hydrocalumite 20 wt. % 200 8 FO 1.61 88.1 83.9 79.9 Hydrocalumite 20 wt. % 200 8 FO 1.99 85.2 80.1 75.1 Hydrocalumite 20 wt. % 200 8 FO 1.34 90.1 86.6 83.3 Hydrocalumite 15 wt. % 200 8 FO 3.78 72.0 62.2 52.8 Hydrocalumite 15 wt. % 200 8 FO 4.17 69.1 58.3 47.9 Hydrocalumite 15 wt % 400 8 FO 7.84 41.9 21.6 2.0 Hydrocalumite 15 wt % + 450 12 FO 8.68 35.7 13.2 N/A bauxite residue 5 wt % Hydrocalumite 2.5 wt. % + 450 12 AL 14.78 N/A N/A N/A bauxite residue 17.5 wt % Red Lime 20 wt. % 200 8 FO 3.68 72.7 63.2 53.9 Red Lime 20 wt. % 200 8 FO 5.39 60.1 46.1 32.7 Red Lime 20 wt. % 400 8 FO 12.45 7.8 N/A N/A Red Lime 15 wt. % 200 8 FO 15.21 N/A N/A N/A Red Lime 15 wt. % 200 8 FO 13.40 0.7 N/A N/A Red Lime 15 wt. % + 200 8 FO 9.21 31.8 7.9 N/A bauxite residue 5 wt % Red Lime 15 wt. % + 200 8 FO 5.26 61.0 47.4 34.2 bauxite residue 5 wt % Red Lime 15 wt. % + 200 8 FO 4.64 65.7 53.6 42.0 bauxite residue 5 wt % Hydroxyapatite 17.5 wt. % 200 8 AL 6.21 54.0 37.9 22.3 Hydroxyapatite 15 wt % 200 8 AL 10.36 23.3 N/A N/A Hydroxyapatite 12.5 wt % 200 8 FO 5.45 59.6 45.5 31.9 Hydroxyapatite 12.5 wt % 200 8 FO 5.57 58.7 44.3 30.3 Hydroxyapatite 15 wt. % + 200 8 AL 8.88 34.3 11.2 N/A bauxite residue 5 wt % Hydroxyapatite 15 wt. % + 450 12 AL 8.63 36.1 13.7 N/A bauxite residue 5 wt. % Hydroxyapatite 10 wt. % + 200 8 FO 4.17 69.1 58.3 47.8 bauxite residue 10 wt. % Hydroxyapatite 10 wt. % + 200 8 FO 5.34 60.5 46.6 33.3 bauxite residue 10 wt. % Hydroxyapatite 10 wt. % + 200 8 FO 11.38 15.7 N/A N/A bauxite residue 10 wt. % Hydroxyapatite 10 wt. % + 200 8 FO 7.16 47.0 28.4 10.5 bauxite residue 10 wt. % Hydroxyapatite 5 wt. % + 200 8 FO 4.82 64.3 51.8 39.8 bauxite residue 15 wt. % Hydroxyapatite 5 wt. % + 200 8 FO 4.93 63.5 50.7 38.4 bauxite residue 15 wt. % Hydroxyapatite 2.5 wt % + 200 8 FO 14.17 N/A N/A N/A bauxite residue 17.5 wt % Hydroxyapatite 2.5 wt % + 200 8 FO 13.64 N/A N/A N/A bauxite residue 17.5 wt % Hydroxyapatite 2.5 wt % + 200 8 FO 4.59 66.0 54.1 42.7 bauxite residue 17.5 wt % Hydrotalcite 17.5 wt. % + 200 8 AL 5.03 62.8 49.7 37.2 bauxite residue 5 wt. % Hydrotalcite 15 wt. % + 200 8 AL 8.86 34.3 11.4 N/A bauxite residue 5 wt. % Hydrotalcite 15 wt. % + 450 12 AL 12.31 8.8 N/A N/A bauxite residue 5 wt. % Hydrotalcite 10 wt. % + 200 8 FO 13.79 N/A N/A N/A bauxite residue 10 wt % Hydrotalcite 10 wt. % + 200 8 FO 4.44 67.1 55.6 44.5 bauxite residue 10 wt % Hydrotalcite 10 wt. % + 200 8 FO 13.45 0.4 N/A N/A bauxite residue 10 wt % Hydrotalcite 10 wt. % + 200 8 FO 14.05 N/A N/A N/A bauxite residue 5 wt % Hydrotalcite 10 wt. % + 200 8 FO 12.75 5.6 N/A N/A bauxite residue 5 wt. % Hydrotalcite 5 wt % + 200 8 FO 5.86 56.6 41.4 26.8 bauxite residue 15 wt % Hydrotalcite 5 wt % + 200 8 FO 14.05 N/A N/A N/A bauxite residue 15 wt % Hydrotalcite 5 wt % + 200 8 FO 10.48 22.3 N/A N/A bauxite residue 15 wt % Hydrotalcite 2.5 wt. % + 200 8 FO 15.18 N/A N/A N/A bauxite residue 17.5 wt % Hydrotalcite 2.5 wt. % + 200 8 FO 15.61 N/A N/A N/A bauxite residue 17.5 wt % Hydrotalcite 2.5 wt. % + 200 8 FO 14.82 N/A N/A N/A bauxite residue 17.5 wt % Hydrotalcite 10 wt. % + 200 8 AL 19.81 N/A N/A N/A Hydroxyapatite 5 wt % Hydroxyapatite 10 wt. % + 450 12 AL 4.52 66.5 54.8 43.5 Hydrotalcite 5 wt % + bauxite residue 5 wt % Hydrotalcite 10 wt. % + 450 12 AL 7.84 42.0 21.6 2.1 hydroxyapatite 5 wt % bauxite residue 5 wt. %

Example: Blast TestBlast Suppression and Desensitization

[0219] The below table illustrates experimental results from blast tests completed on various materials, in which stabilizer and combinations of stabilizers and filters were evaluated against a control SI baseline (ammonium nitrate). Materials evaluated for this blast test included: fire clay (individually and in combination with bauxite residue at different weight percentages), hydroxyapatite (individually and in combination with bauxite residue at different weight percentages), and hydrotalcite (individually and in combination with bauxite residue at different weight percentages).

[0220] It is noted that fire day was utilized as a diluents (in lieu of bauxite residue). The fire clay was obtained from a commercial vendor, and fire clay refers to a calcined commercial clay product that is an inert alumino-silicate material (e.g. applications in mortar/ceramic bricks, and refractory lining for furnaces and chimneys).

[0221] It is noted that EG AN refers to explosive grade ammonium nitrate, which is a low density AN made for improved explosive performance (e.g. as compared to the high density AN optimized for Fertilizer Grade FG.)

[0222] For this blast test, the hydrotalcite and hydroxyapatite were recovered from an alumina production process. The standard operating procedure was followed to prepare the blast components and complete the blast tests, though the diameter of the blast components was set at a standard 8. Other variables were modified, including the amount of booster (200 g, 400 g), and the type of fuel (i.e. fuel oil (FO), AL (aluminum), and PS (powdered sugar)).

[0223] The specific impulse readings are provided below, along with a comparative view of the Reduction in Blast, measured as a percentage according to various SI baselines (e.g. 13.5, 10.0, and 8.0). When a blast test did not result in a reduction in specific impulse, the reduction percentage is indicated as N/A.

TABLE-US-00009 Sp. Reduction Reduction Reduction Imp. vs. 13.5 vs. 10.0 vs. 8.0 Booster (kPa .Math. Baseline Baseline Baseline Material (g) Fuel ms/kg) (%) (%) (%) Ammonium Nitrate (control) 200 PS 11.28 16.5 N/A N/A Ammonium Nitrate (control) 200 PS 11.06 18.0 N/A N/A Ammonium Nitrate (control) 200 AL 15.39 N/A N/A N/A Fire Clay 25 wt % 200 FO 6.39 52.7 36.1 20.2 Fire Clay 25 wt % 200 FO 11.17 17.2 N/A N/A Hydroxyapatite 17.5 wt % 200 FO 2.66 80.3 73.4 66.8 Hydroxyapatite 17.5 wt % 200 FO 2.71 79.9 77.9 66.2 Hydroxyapatite 17.5 wt. % 200 FO 4.70 65.2 53.0 41.2 Hydroxyapatite 17.5 wt % 200 AL 4.97 63.2 50.3 17.8 Hydroxyapatite 15 wt. % 400 FO 5.97 55.8 40.3 25.4 Hydroxyapatite 15 wt. % 200 FO 4.69 65.2 53.1 41.4 Hydroxyapatite 15 wt. % 200 FO 5.67 58.4 43.8 29.7 Hydroxyapatite 15 wt % 200 FO 12.94 4.1 N/A N/A Hydroxyapatite 15 wt % 200 AL 8.98 33.5 10.2 N/A Hydroxyapatite 12.5 wt. % 400 FO 10.39 23.0 N/A N/A Hydroxyapatite 12.5 wt. % 200 FO 4.87 64.0 51.3 39.2 Hydroxyapatite 12.5 wt. % 200 FO 9.58 29.1 4.2 N/A Hydroxyapatite 12.5 wt. % 200 FO 1.95 85.6 80.5 75.7 Hvdroxyapatite 10 wt. % 200 FO 11.93 11.6 N/A N/A Hydroxyapatite 10 wt. % 200 FO 11.70 13.3 N/A N/A Hydroxyapatite 15 wt % 200 PS 2.41 82.2 75.9 69.9 bauxite residue 2.5 wt % Hydroxyapatite 15 wt. % + 200 FO 4.39 67.5 56.1 45.1 bauxite residue 5 wt. % Hydroxyapatite 15 wt. % + 200 FO 2.13 84.2 78.7 73.4 bauxite residue 5 wt. % Hydroxyapatite 15 wt. % + 200 FO 3.88 71.3 61.2 51.5 bauxite residue 5 wt. % Hydroxyapatite 12.5 wt % + 200 FO 10.58 21.6 N/A N/A bauxite residue 2.5 wt % Hydroxyapatite 12.5 wt, % + 200 FO 5.30 60.8 47.0 33.8 bauxite residue 2.5 wt % Hydroxyapatite 12.5 wt. % + 200 FO 4.11 69.6 58.9 48.6 bauxite residue 2.5 wt % Hydroxyapatite 12.5 wt. % + 200 FO 3.33 75.3 66.7 58.4 bauxite residue 5 wt % Hydroxyapatite 12.5 wt. % 200 FO 4.00 70.4 60.0 50.0 bauxite residue 5 wt % Hydroxyapatite 12.5 wt. % + 400 FO 6.27 53.6 37.3 21.6 bauxite resume 7.5 wt % Hydroxyapatite 12.5 wt. % + 200 FO 3.94 70.8 60.6 50.7 bauxite resume 7.5 wt. % Hydroxyapatite 12.5 wt. % + 200 FO 3.75 72.2 62.5 53.2 bauxite resume 7.5 wt % Hydroxyapatite 10 wt. % + EG 400 FO 13.18 2.4 N/A N/A AN Hydroxyapatite 10 wt. % + EG 400 FO 12.34 8.6 N/A N/A AN Hydrotalcite 26 wt % 200 AL 2.42 82.0 75.8 69.7 Hydrotalcite 15 wt. % 200 FO 5.71 57.7 42.9 28.6 Hydrotalcite 12.5 wt. % 200 FO 9.21 31.8 7.9 N/A Hydrotalcite 17.5 wt. % + bauxite 200 FO 1.68 87.5 83.2 79.0 residue 2.5 wt. % Hydrotalcite 17.5 wt. % + bauxite 200 FO 1.01 92.5 89.9 87.4 residue 2.5 wt. % Hydrotalcite 17.5 wt. % + bauxite 200 FO 1.21 91.0 87.9 84.8 residue 2.5 wt. % Hydrotalcite 17.5 wt % + bauxite 200 AL 3.71 72.5 62.9 53.6 residue 2.5 wt % Hydrotalcite 15 wt. % + bauxite 400 FO 2.78 79.4 72.2 65.2 residue 2.5 wt. % Hydrotalcite 15 wt. % + bauxite 400 FO 1.38 89.8 86.2 82.8 residue 2.5 wt. % Hydrotalcite 15 wt. % + bauxite 200 FO 1.50 88.9 85.0 81.3 residue 2.5 wt. % Hydrotalcite 15 wt. % + bauxite 200 FO 2.84 79.0 71.6 64.5 residue 2.5 wt. % Hydrotalcite 15 wt. % + bauxite 200 FO 3.31 75.5 66.9 58.7 residue 2.5 wt % Hydrotalcite 15 wt % + bauxite 200 FO 5.04 62.6 49.6 37.0 residue 2.5 wt % Hydrotalcite 15 wt. % + bauxite 200 FO 3.80 71.9 62.0 52.5 residue 5 wt% Hydrotalcite 15 wt. % + bauxite 200 FO 2.47 81.7 75.3 69.2 residue 5 wt % Hydrotalcite 15 wt. % + bauxite 200 FO 9.95 26.3 0.5 N/A residue 5 wt % Hydrotalcite 15 wt. % + bauxite 200 AL 4.93 63.5 50.7 38.4 residue 5% hydrotalcite 15 wt % + bauxite 200 PS 3.47 74.3 65.3 56.7 residue 2.5 wt % Hydrotalcite 12.5 wt % + bauxite 200 FO 4.22 68.8 57.8 47.3 residue 2.5 wt % Hydrotalcite 12.5 wt % + bauxite 400 FO 5.17 61.7 48.3 35.3 residue 2.5 wt % Hydrotalcite 12.5 wt % + bauxite 200 FO 8.55 36.7 14.5 N/A residue 2.5 wt % Hydrotalcite 12.5 wt % + bauxite 200 FO 3.39 74.9 66.1 57.7 residue 5 wt % Hydrotalcite 12.5 wt % + bauxite 200 FO 9.66 28.4 3.4 N/A residue 5 wt % hydrotalcite 12.5 wt % + bauxite 2.00 FO 3.71 72.5 62.9 53.7 residue 5 wt % Hydrotalcite 12.5 wt % + bauxite 400 FO 3.74 72.3 62.6 53.2 residue 7.5 wt % Hydrotalcite 12.5 wt % + bauxite 200 FO 3.41 74.8 65.9 57.4 residue 7.5 wt % Hydrotalcite 12.5 wt. % + bauxite 200 FO 10.54 21.9 N/A N/A residue 7.5 wt. % Hydrotalcite 10 wt. % + bauxite 200 FO 12.84 4.9 N/A N/A residue 2.5 wt. % Hydrotalcite 10 wt. % + bauxite 200 FO 11.83 12.4 N/A N/A residue 2.5 wt .% Hydrotalcite 10 wt. % + bauxite 400 FO 3.63 73.1 63.7 54.6 residue 5 wt. % Hydrotalcite 10 wt. % + bauxite 200 FO 3.78 72.0 62.2 52.8 residue 5 wt. % Hydrotalcite 10 wt. % + bauxite 200 FO 10.26 24.0 N/A N/A residue 7.5 wt. % Hydrotalcite 10 wt. % + bauxite 400 FO 10.07 25.4 N/A N/A residue 7.5 wt % Hydrotalcite 10 wt. % + bauxite 200 FO 11.66 13.7 N/A N/A residue 10 wt. % Hydrotalcite 10 wt. % + bauxite 200 FO 11.55 14.4 N/A N/A residue 10 wt. %

Example: Intercalation of Hydrotalcite

[0224] In order to intercalate hydrotalcites, the following procedure was performed, were anion substitution is completed by thermal activation followed by rehydration.

[0225] For thermal activation, 4.25 kg of HTC powder is placed in a ceramic bowl (to a depth of 1) and heated to a temperature of 450 C. for one hour, followed, by cooling below 100 C. in a furnace or in an external holding unit (drying cabinet, desiccators).

[0226] For rehydration, approximately 12 L of water (DI or distilled) is stirred in a container, followed by phosphate addition (using diammonium phosphate (DAP) add 1.6 kg (12 moles) to the 1.2 L of water) and mix until phosphate salt is dissolved (20-30 minutes). Slowly, activated HTC powder was added and the resulting mixture is stirred for a minimum of 12 hours. The wet slurry was placed in pans of to 1 depth and put into a drying oven and dried at 125 C. until dry solids are obtained. The resulting intercalated HTC is screened to <20 mesh and stored for use in the blast tests.

Example: Bauxite Residue Preparation as Stabilizer Material

[0227] In order to neutralize bauxite residue, phosphoric acid (85%) was added to a BR slurry, while being mixed by an agitator. The pH of the bauxite residue was lowered to less than 8.0. The bauxite residue was permitted to settle and the resulting liquid was poured from the top of the mixture and the resulting mixture was poured to inch thick pans, and oven dried (100 C.). The resulting bauxite residue is believed to have a phosphate content of from 5 wt. % to not greater than about 10 wt. % based on the phosphoric acid neutralization.

Example: Preparation of Bauxite Samples

[0228] Raw Bauxite ore was reduced down to +/20mesh by feeding the ore through a plate crusher, a roll crusher with serrated rolls (Sturtevant roll crusher), and a ball mill (with ceramic balls to further reduce the particles to usable fractions. The resulting 20 mesh fraction was blended with ammonium nitrate material and blast tests were conducted in accordance with the above-referenced. Example.

Example: Apatite Preparation from Bayer Liquor

[0229] Apatite tested in accordance with the aforementioned example was made with precursor materials phosphoric acid, slaked lime and Bayer liquor, as per the following process. A mixture of phosphoric acid, carbon dioxide, and refinery spent Bayer liquor was heated to 70C. (In some embodiments, add additional carbonate or phosphate to increase yield. In some embodiments, an alternative phosphorous source is crandalite.) Next, slaked lime was added and stirred for 15-30 minutes. The resulting mixture was filtered, washed and oven dried. After preparation, entrained liquor was removed via an additional filtration and washing step.

[0230] The resulting material tested in accordance with the aforementioned Example had the following phases: carbonate hydroxyl apatite (major), hydroxyl apatite (trace), and possible trace quantities of CaCO.sub.3 & hydrotalcite (e.g. formed via impurities in the slaked lime or formed during the apatite production process).

[0231] The apaptite tested in accordance with aforementioned Examples is a Bayer carbonate hydroxyapatite of the following formula (Ca.sub.7Na.sub.2(PO.sub.4).sub.3(CO.sub.3).sub.3(H.sub.2O).sub.3OH) with major element as follows: 12-22 wt % CO.sub.2; 44-49 wt % CaO; 19-26 wt. % P.sub.2O.sub.5; 7-12 wt. % Na.sub.2O; and 1-3 wt. % Al.sub.2O.sub.3.

Example: Methods for Making Fertilizer Composition

[0232] Ammonium nitrate is manufactured in three steps, including: (1) neutralizing nitric acid with ammonia to produce a concentrated solution; (2) evaporating to provide a melt; and (3) processing by prilling or granulation to provide the commercial solid ammonium nitrate product. Frilling is the formation of a rounded, granular solid by allowing molten. droplets to fall through a fluid cooling medium. In one embodiment, prilling of AN involves spraying the concentrated solution (i.e. 96-99.sup.+%) solution into the top of a large tower. Then, the descending droplets are cooled by an upward flow of air, solidifying into spherical prills that are collected at the bottom of the tower.

[0233] In one embodiment, fertilizer compositions of the instant disclosure are made by spraying the concentrated AN solution (i.e. 96-99%) while simultaneously spraying a concentrated solution of the stabilizer materials) (e.g. suspended or in solution in a solvent) and co-prilling the resulting fertilizer composition.

[0234] In one embodiment, fertilizer compositions of the instant disclosure are made by adding the stabilizer material(s) to the concentrated ammonium nitrate solution prior to prilling.

[0235] In one embodiment, fertilizer compositions of the instant disclosure are made by coating the stabilizer material(s) onto the prill after the AN prill is formed. In some embodiments, a drum roller is used (e.g. with optional solvents and/or binders) to adhere and/or coat the stabilizer material(s) onto the AN prill.

[0236] In some embodiments, the stabilizer material(s) are mixed into the ammonium nitrate solution (with optional solvents) and the resulting fertilizer composition is recrystallized from solution or suspension.

[0237] In some embodiments, AN prills are ground with stabilizer material(s) in a milling press and utilized in a powder form. In some embodiments, the powder is mixed with binder(s) and rolled into agglomerated forms, In some embodiments, the blended powder is mixed with a binder and formed (e.g. pressed) into pellets or plates (e.g. with a disk-press or pelletization process),

[0238] In some embodiments, the solution (or suspension) of ammonium nitrate with stabilizer materials (e.g. optionally with solvents to reduce viscosity) are spray dried.

[0239] In some embodiments, the solution (or suspension) of ammonium nitrate with stabilizer material(s) is agglomerated (e.g. pan agglomeration), followed by a pelletization process.

Example: Method of Making Fertilizer

[0240] The following procedure was utilized to form ammonium nitrate coated in hydrotalcite, Subsequently, this coated fertilizer was utilized in the crop studies (crop study #1).

[0241] As received ammonium nitrate fertilizer (AN) was added to an electric cement mixer, ceramic balls were added, and the AN was mixed for 2.5 hours. The material was then screened to separate the AN (deagglomerated AN) from the ceramic balls.

[0242] A composition of 80% ammonium nitrate: 20% hydrotalcite was screened together to mix the materials, and processed in the ceramic mixer for 30 minutes to blend the materials. The blended material was slowly added to a drum roller (pelletizing machine/fertilizer granulator), which was operated at a pre-set angle and speed, while binder (water) was slowly added in a fine mist to the blended mixture, As the water was added, the blended mixture formed pellets. In alternating fashion, blended fertilizer material and water were sequentially added to the drum roller and were formed into pellets, As the pellets rolled through the drum roller and increased in size and density, the pellets reached a suitable weight to roll out of the drum roller into a collection area.

Example: Crop Studies

[0243] Two crop studies were completed utilizing fertilizer compositions in accordance with one or more embodiments of the instant disclosure, in order to evaluate bow fertilizer compositions including stabilizer materials performed in comparison to commercially available fertilizers.

[0244] Statistical analysis was performed on the crop yields, with the basic analysis procedure as follows: test whether the variability differs across the treatments; test whether the averages differ across the treatments (e.g. using the appropriate method determined by whether (1) is true or false); and if at least two averages can be shown to be different, identify which treatments differ. The statistical evaluation yielded that

[0245] The first crop study consisted of 1 fertilizer composition treatment (pelletized HTC with AN, (26-0-0)) and 5 Controls (no treatment (N/A), AN fertilizer (34-0-0), Urea fertilizer (46-0-0), UAN (liquid) fertilizer (30-0-0), and ESN fertilizer (44-0-0) (a commercially available polymer coated urea fertilizer)). Each treatment was applied with an equivalent Nitrogen delivery of 100 and 140 (lbs N/Acre), Two responses were measured: Ears/Acre, and Weight/Acre. In comparing the two responses, it was determined that there are no statistically significant differences between the fertilizer composition (HTC+AN) compared to the commercially available fertilizer controls and no fertilizer addition. For the first crop study, there were no observable differences (in Ears/Acre or Weight/Acre) between the fertilizer composition, nitrogen-baring controls, or non-nitrogen control, nor between low and high nitrogen levels of the same product.

[0246] The second crop study consisted of 3 fertilizer composition treatments and 5 Controls. Controls included: ammonium nitrate fertilizer, urea fertilizer, UAN fertilizer (liquid application), no fertilizer application, and ESN fertilizer (commercially available polymer coated urea product). Three fertilizer compositions included: fertilizer #1: AN having by weight, 5% bauxite residue, and 15% hydrotalcite; fertilizer #2: AN having by weight, 5% bauxite residue and 15% apatite; and fertilizer #3: AN having by weight, 5% bauxite residue, 10% hydrotalcite, and 5% apatite. Each Treatment was applied with 120 Lbs N/Acre and the Alcoa and AN Treatments were also applied at 261 Lbs Product/Acre. One response was measured: Yield @15.5% Moisture (Bushels/Acre).

[0247] In viewing the response, all products show higher yield (bushels/acre) than the non-nitrogen control. In completing the statistical analysis on the response, it was determined that there are no statistically significant differences between the fertilizer compositions compared to the commercially available fertilizer controls and no fertilizer addition (i.e. it is possible to distinguish some of the high N treatments from some of the low N treatments, but it is not possible to distinguish among the high N or among the low N treatments).

[0248] Various ones of the inventive aspects noted herein above may be combined to yield fertilizer compositions and methods of making and using the same to fertilize soil, while preventing, reducing, or eliminating the fertilizer (AN fertilizer) from being used in explosives and/or improvised explosive devices.

[0249] While various embodiments of the instant disclosure have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the instant disclosure.