AU2013217230B2

AU2013217230B2 - Oxidizer solution

Info

Publication number: AU2013217230B2
Application number: AU2013217230A
Authority: AU
Inventors: Leon Michael Zimmermann
Original assignee: Maxam Dantex South Africa Pty Ltd
Current assignee: Maxam Dantex South Africa Pty Ltd
Priority date: 2012-02-10
Filing date: 2013-02-11
Publication date: 2017-05-04
Anticipated expiration: 2033-02-11
Also published as: EP2812295A2; US20150000804A1; GB201202402D0; CL2014002115A1; BR112014019850B1; WO2013118103A2; EA027414B1; WO2013118103A3; AP2014007908A0; BR112014019850A2; BR112014019850A8; AP3822A; CA2864216C; ZA201406433B; PL2812295T3; CA2864216A1; AU2013217230A1; EA201400885A1; EP2812295B1

Abstract

According to this invention there is provided an aqueous oxidizer solution containing a mixture of dissolved oxidizing salts, for use in the preparation of explosives formulations, which a crystallization point as low as below 0°C. The solution has a water content of 25% by mass or less and contains ammonium nitrate and calcium nitrate wherein the ratio of the the molar concentration of ammonium nitrate to calcium nitrate is preferably approximately 1. When the water content of the solution is 24% by mass or less, the solution further contains monomethylammonium nitrate. This solution can be used for manufacturing watergel explosives, or emulsion explosives or ANE's (ammonium nitrate emulsion suspension or gel explosives). It can be easily transported underground in deep level mines through relatively small diameter pipelines, using existing access ways and shafts, to the working places at which point it can then be converted into a watergel or emulsion explosive or an ANE.

Description

WO 2013/118103 PCT/IB2013/051107 1

OXIDIZER SOLUTION

BACKGROUND OF THE INVENTION

In most countries where bulk explosives are used they fall in a category defined in the United Nations Handbook on the Transportation of Dangerous Goods as ammonium nitrate emulsions suspensions or gels (abbreviated ANE) and are transported and stored as oxidizers 5.1 with U.N. number 3375. As the name implies these are either in the form of emulsions or watergels (or slurries). Because they are not classified as explosives the regulations regarding transportation and storage are considerably less stringent than they would be if they were classified as explosives. These ANE’s are sensitized to become explosives as they are pumped into the blast hole ether by mechanical gas entrainment or by the addition of a chemical blowing agent during the pumping process.

One of the problems with existing bulk explosives formulations (whether they are of the watergel or emulsion type) are that they are extremely viscous fluids and are difficult to pump or transport in pipelines over long distances. This is not normally a problem in surface mining where vehicle access is simply a matter of driving to the hole to be charged and lowering the charging hose down the hole and then pumping the explosive into the hole. However when using bulk products in underground applications it would be very convenient if one could place the pumping unit at a point some distance from the working face to be charged and simply run a long length of hose to the hole to be charged. This is especially true in narrow reef stoping as encountered in many gold and platinum mines. A second problem is the problem of getting the explosive underground in the first place. Since this must be done by transporting it in containers using the same lifting equipment or access ways used for men, equipment and ore, this can seriously hamper production. Since they are non-explosive WO 2013/118103 PCT/IB2013/051107 2 until they are pumped into the shot hole it is at least theoretically possible to pump them through a long pipeline to the point where they are needed underground. Here again the viscosity is a problem as there is a finite limit on how far a viscous fluid can be pumped bearing in mind the energetic nature of the material being pumped and therefore the limitation on maximum pumping pressure to which it can be exposed.

The physical nature of the ANE’s is another limitation as to the distance that it can be transported in a pipeline. In the case of a watergel or a slurry type ANE the product is in the form of a saturated solution of oxidizer salts and soluble fuels thickened with a thickener of some sort (normally guar gum) into which is mixed further quantities of oxidizer salts and (possibly) insoluble fuels. When pumping such a suspension through a very long line one runs the risk of the solids blocking the line entirely and stopping the pumping process entirely. If one were considering dropping or pumping such a suspension through a long vertical (or inclined) pipe in order to get it underground the risk of the pipeline blocking would be so great as to make this a foolhardy exercise indeed. In the case of an emulsion type ANE these are made by preparing a solution of oxidizer salts in water at an elevated temperature and then emulsifying this solution into a fuel phase consisting of oil and emulsifier and then allowing the emulsion to cool down to ambient temperature. Due to the very small size of the emulsion micelles the salts are incapable of recrystallizing. It must be remembered that the fuel phase of the emulsion only makes up about 6% or 7% of the product and that this is the continuous phase. The oxidizer salt solution makes up in excess of 90% of the emulsion and this is the disperse phase. This means that the cell walls around the oxidizer solution droplets is extremely thin and stretched and that if these cell walls should fail for any reason the oxidizer solution droplets would agglomerate together and once the micelles get big enough the salts will then start crystallizing out of solution. When this happens the growing crystals start piercing further micelle walls and the emulsion rapidly breaks down and the salts crystallize because they are so far below their crystallization temperature. When this happens the entire mass solidifies and ceases to be a pumpable fluid. If one is contemplating -3a - 2013217230 06 Apr 2017 transporting the emulsion from surface to underground through a long pipeline the risk of the emulsion breaking down during transportation must be considered and if this happens the pipeline would block completely with severe economic and production consequences.

Theft is also a major problem both of packaged explosive and of bulk explosives used in the mining industry. Stolen explosives can find their way into the hands of criminals or terrorists and are a major threat to the public.

It is an object of this invention to address these problems.

Throughout the specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

SUMMARY OF THE INVENTION

According to the present invention there is provided an aqueous oxidizer solution consisting essentially of a mixture of dissolved oxidizing nitrate salts with less than 25% by mass water, for use in the preparation of explosives formulations, which has a crystallization point of 10eC or less, as low as 5eC or less, even as low 0eC or less, said solution containing: ammonium nitrate; and calcium nitrate or mixture of calcium nitrate and magnesium nitrate, preferably calcium nitrate; wherein the molar concentration of ammonium nitrate to calcium nitrate or mixture of calcium nitrate and magnesium nitrate is between 0.5:1 and 1.5:1, more preferably between 0.75:1 and 1.25:1 and most preferably approximately 1; and an alkylamine nitrate or monoethanolamine nitrate present in an amount of 1 % to 20% by mass.

By “crystallization point" is meant the temperature at which one or more of 2013217230 06 Apr 2017 -3b- the dissolved oxidizing salt/s begin to precipitate from the oxidizer solution.

When the solution comprises a mixture of calcium nitrate and magnesium nitrate, the ratio of the molar concentrations of the calcium nitrate to the magnesium nitrate should not be less than about 4:1 and preferably not less WO 2013/118103 PCT/IB2013/051107 4 than about 4.5:1.

Typically, the oxidizer solution has a water content of between 10% and 25%, between 12% and 24%, preferably between 17% and 22%, by mass.

When the water content of the solution is 24% by mass or less, the solution preferably further contains alkylamine nitrate.

The alkylamine nitrate may be present in an amount of 1% to 20% by mass, typically in an amount of 10% to 18% by mass, or from 12% to 17% by mass.

For every 1% reduction in the water content below 24%, the solution preferably contains at least an additional 1.67% alkylamine nitrate in order to retain a low crystallization point for the solution. Put in another way, the alkylamine nitrate is preferably present in at least a quantity to satisfy the equation: M > 5(24-W)/3 (where W = the percentage water in the solution and M = the percentage alkylamine nitrate in the solution).

The alkylamine nitrate may be methylamine nitrate (also called monomethylammonium nitrate), monoethanolamine nitrate, dimethylamine nitrate or trimethylamine nitrate, preferably methylamine nitrate.

This solution can be used for the manufacture of either a watergel or an emulsion explosives or an ANE. Other nitrates, such as magnesium nitrate, sodium nitrate and potassium nitrate can be introduced but these must be at molar concentrations significantly lower than the calcium nitrate.

The invention also covers a method of manufacturing an explosives formulation by mixing the oxidizer solution described above with a fuel.

The invention further covers an explosives formulation comprising a mixture of the oxidizer solution described above with a fuel. -5a- 2013217230 06 Apr 2017

The fuel may be a hydrocarbon fuel such as diesel fuel, paraffin, oil etc, a water soluble alcohol or polyol (e.g. monoethylene glycol, glycerol, ethanol, methanol, propanol) a water soluble carbohydrate such as sugar. In general if one were making a watergel type ANE one might well choose a water soluble fuel, however immiscible fuels can also be used with great success to make a watergel. If one were making an emulsion type ANE then the choice would be for one of the hydrocarbon fuels mentioned above or even recovered lubricating or other oil such as vegetable oil.

In one embodiment there is provided an aqueous oxidizer solution consisting of a mixture of dissolved oxidizing nitrate salts and water, for use in the preparation of explosives formulations, which has a crystallization point of 10eC or less; said solution consisting of: between 12% and 24% by mass water; an alkylamine nitrate or monoethanolamine nitrate in an amount of 10% to 18% by mass; and ammonium nitrate and calcium nitrate or mixture of calcium nitrate and magnesium nitrate; wherein the molar concentration of ammonium nitrate to calcium nitrate or mixture of calcium nitrate and magnesium nitrate is between 0.75:1 and 1.25:1.

DESCRIPTION OF PREFERRED EMBODIMENTS

This patent application claims priority from United Kingdom provisional patent application no. GB 1202402.2, the content of which is incorporated herein by reference. I have invented an aqueous oxidizer solution containing a mixture of dissolved oxidizing salts with less than 25% water that does not crystallize below 10eC, and even as low as 0eC or less (as low as -7eC), and that can be used to make a watergel or an emulsion explosive or an ANE (ammonium nitrate emulsion suspension or gel) provided that it meets the following criteria: 2013217230 06 Apr 2017 - 5b- 1) The solution contains less than 25% water; 2) The solution contains ammonium nitrate (NH4N03) and calcium nitrate (Ca(N03)2) in a molar ratio of ammonium nitrate to calcium nitrate of between 0.5:1 and 1.5:1 and preferably between 0.75:1 and 1.25:1 and most preferably as close to 1:1 as possible; and 3) When the water content of the solution drops below 24%, for every 1% of water removed from the solution one adds at least 1.67% of monomethylammonium nitrate (CH3NH3N03, also known as methylamine nitrate). Put differently, the content of monomethylammonium nitrate should satisfy the equation: M > 5(24-W)/3 (where W = the percentage water in the solution and M = the percentage monomethylammonium nitrate in the solution). WO 2013/118103 PCT/IB2013/051107 6

Since the molecular mass of ammonium nitrate is 80.043 and the molecular mass of calcium nitrate is 164.086, condition 2) can be restated as (for example): The solution contains ammonium nitrate and calcium nitrate in a percentage ratio of calcium nitrate to ammonium nitrate of between 8.2:1 and 1:1 and preferably between 4.1:1 and 1.37:1 and preferably between 2.73:1 and 1.64:1 and ideally as close to 2.05:1 as possible.

If it is desired one can replace some of the calcium nitrate with magnesium nitrate (i.e. have a calcium nitrate/magnesium nitrate mixture), provided that the ratio of the molar concentration of ammonium nitrate to the sum of the molar concentrations of the calcium nitrate and the magnesium nitrate should be between 0.25:1 and 2:1, preferably between 0.5:1 and 1.5:1 and preferably between 0.75:1 and 1.25:1 and most preferably as close to 1:1 as possible. Furthermore the ratio of the molar concentrations of the calcium nitrate to the magnesium nitrate should not be less than about 4:1 and preferably not less than about 4.5:1. Sodium nitrate and/or potassium nitrate can be introduced as well but in this case, in order to obtain a subzero crystallization point, the controlling factor is the ratio of molar concentrations of the ammonium nitrate and the calcium nitrate as well as the relative water and monomethylammonium nitrate percentages and the quantity of sodium or potassium nitrate that can be introduced is determined mainly by their solubility in the available water.

This solution can then be used for manufacturing (among other things) watergel or emulsion explosives or ANE’s. It can be most advantageously easily transported underground in deep level mines through relatively small diameter pipelines, using existing access ways and shafts, to the working places at which point it can then be converted into a watergel or emulsion explosive or an ANE.

When using the oxidizer solutions according to the present invention for making emulsion explosives, it is possible to transport the oxidizer solution and the fuel/emulsifier mixture separately and create the emulsion at the WO 2013/118103 PCT/IB2013/051107 7 point of use in such a way that if the explosive is left without being used for more than a few days (for example) then the emulsion would separate and render it non-explosive due to the inherently unstable nature of any emulsion. This new system can provide a major step forward in the fight against criminal activity and terrorism, since it makes the theft of the explosives unattractive due to the extremely short shelf life of the final explosive. Obviously, since the two components of the emulsion are liquids, there is no practical limit to how far they can be transported in a pipeline and what is more the pipeline could be of a very small diameter and therefore of very low cost which is not the case with a normal emulsion type ANE.

If one were making a watergel type ANE then the solution could be thickened with a suitable thickener, such as guar gum and in this case one could use any one of the previously mentioned water soluble fuels or one of the hydrocarbon fuels. When using a hydrocarbon fuel one might want to add a surfactant of some kind to assist in keeping the hydrocarbon in suspension. Clearly one could simply thicken the oxidizer solution before transport to the point of use and then add the hydrocarbon fuel (or alcohol or polyol) as the product is pumped into the hole. Whichever method of manufacture is followed the fact that the watergel has no suspended solid means that it would be perfectly safe to drop it down a vertical pipe of virtually any length in order to get it from surface to underground. In addition the free flowing characteristics of this product is such that pumping through a long hose presents no difficulties whatsoever. In a narrow reef mining situation one could place the pumping unit in a safe location and run a hose from there to the working face. Once the charging up is complete the miner would wind the hose up and the next day, once the face has been cleaned he would unreel the hose to the new working face and charge up once more. It would probably not be necessary to move the pumping unit more than once per month making a huge saving in time and manpower.

The Invention will be described in more detail with reference to the WO 2013/118103 PCT/IB2013/051107 8 following non-limiting Examples.

In the Examples described below the solutions were made from 80% monomethylammonium nitrate solution and either solid ammonium nitrate or 88% ammonium nitrate solution as well as agricultural calcium nitrate manufactured by South African company OMNIA Fertilizer Ltd and sold under the trade name OMNICAL™ which contains about 80% calcium nitrate and about 15% water with the balance being ammonium nitrate. The reason for using this and not chemically pure material is that the standard chemically pure calcium nitrate contains 30.5% water in the form of water of crystallization and by using the agricultural material I was able to prepare solutions containing high levels of calcium nitrate while still maintaining relatively low levels of water. The mixture was then heated to prepare a clear solution which was then cooled while stirring and the crystallization point was measured and reported as being the point at which the first crystals appeared.

The invention will now be demonstrated by means of some examples shown in Table 1 below:

Table 1:

Mix number A1 A2 A3 A4 A5 A6 A7 A8 Ammonium nitrate (AN) (%) 6.6 12.0 16.3 20.0 23.1 25.8 28.1 30.1 Calcium nitrate (CN) (%) 54.4 49.0 44.7 41.0 37.9 35.2 32.9 30.9 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 Water (%) 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 Monomethylammonium nitrate (%) 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 Crystallization point (°C) 16 4 -7 -6 3 6 11 14 Mix number B1 B2 B3 B4 B5 B6 B7 B8 Ammonium nitrate (AN) (%) 7.0 12.5 17.1 21.0 24.2 27.0 29.5 31.6 Calcium nitrate (CN) (%) 57.0 51.5 46.9 43.0 39.8 37.0 34.5 32.4 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 Water (%) 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 Monomethylammonium nitrate (%) 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 6 3 -4 -4 3 8 13 17 WO 2013/118103 PCT/IB2013/051107 9

Mix number C1 C2 C3 C4 C5 C6 C7 C8 Ammonium nitrate (AN) (%) 7.3 13.1 17.9 22.0 25.4 28.3 30.9 33.1 Calcium nitrate (CN) (%) 59.7 53.9 49.1 45.0 41.6 38.7 36.1 33.9 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 Water (%) 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 Monomethylammonium nitrate (%) 11.0 11.0 11.0 11.0 11.0 11.0 11.0 11.0 Crystallization point (°C) 38.8 20.5 -6 -5 3 9 15 18

These results demonstrate that at constant quantities of water, even when the water content is relatively high (22%) the crystallization point is well above 0°C when the molar ratio of ammonium nitrate to calcium nitrate is outside the range 0.5:1 to 1.5:1 and is always below 0°C when the molar ratio of ammonium nitrate to calcium nitrate is 1:1.

Table 2:

Mix number G1 G2 G3 G4 G5 G6 G7 G8 Ammonium nitrate (AN) (%) 7.3 13.3 18.2 22.3 25.8 28.7 31.3 33.6 Calcium nitrate (CN) (%) 59.5 54.7 49.8 45.7 42.2 39.3 36.7 34.4 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 Water (%) 15.6 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Monomethylammonium nitrate (%) 17.6 17.0 17.0 17.0 17.0 17.0 17.0 17.0 Crystallization point (°C) 27 18 -4 -4 8 19 22 28 Mix number H1 H2 H3 H4 H5 H6 H7 H8 Ammonium nitrate (AN) (%) 7.6 13.9 19.0 23.3 26.9 30.0 32.7 35.1 Calcium nitrate (CN) (%) 62.7 57.1 52.0 47.7 44.1 41.0 38.3 35.9 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 Water (%) 15.4 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Monomethylammonium nitrate (%) 14.3 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 54.5 37.5 17.6 4 10 18 25 28 Mix number J1 J2 J3 J4 J5 J6 J7 J8 Ammonium nitrate (AN) (%) 8.0 14.5 19.8 24.3 28.0 31.3 34.1 36.5 Calcium nitrate (CN) (%) 65.8 59.5 54.2 49.7 46.0 42.7 39.9 37.5 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 Water (%) 15.1 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Monomethylammonium nitrate (%) 11.1 11.0 11.0 11.0 11.0 11.0 11.0 11.0 WO 2013/118103 PCT/IB2013/051107 10

Crystallization point (°C) 53 48 25 17 9 17 27 32

These results show that with solutions having a low water content if the content of monomethylammonium nitrate drops below a certain level the solution, while still having a minimum crystallization point when the molar ratio of ammonium nitrate to calcium nitrate is in the range 0.75:1 to 1.25:1, this minimum is no longer below 0°C. While a sub-zero crystallization point is almost certainly not needed for handling and use underground it is certainly of great benefit during transport to the mine as well as for storage both at the point of manufacture and at the mine. The point is that what has been discovered is a method of minimizing the crystallization point of an oxidizer solution while maintaining relatively low water levels which in turn allows one to produce an explosive at the point of end use which has sufficient energy to perform well when breaking rock.

Table 3:

Mix number Z1 Z2 Z3 Ammonium nitrate (AN) (%) 26.2 25.6 24.9 Calcium nitrate (CN) (%) 53.8 52.4 51.1 Moles AN/Moles CN 1.00 1.00 1.00 Water (%) 20.0 22.0 24.0 Monomethylammonium nitrate (%) 0 0 0 Crystallization point (°C) 18 11 -3

Here the results show that when the molar ratio of ammonium nitrate to calcium nitrate is 1:1, if the water content of the solution is 24% or higher no monomethylammonium nitrate is needed in order to achieve a sub-zero crystallization point.

Table 4:

Mix number G4 G4A G4B H4 Ammonium nitrate (AN) (%) 22.3 22.6 23.0 23.3 Calcium nitrate (CN) (%) 45.7 46.4 47.0 47.7 WO 2013/118103 PCT/IB2013/051107 11

Moles AN/Moles CN 1.00 1.00 1.00 1.00 Water (%) 15.0 15.0 15.0 15.0 Monomethylammonium nitrate (%) 17.0 16.0 15.0 14.0 Crystallization point (°C) -4 -4 -1 18

These results indicate that at a water content of 15% if the monomethylammonium nitrate content is 15% then one can still achieve a sub-zero crystallization point provided that the molar ratio of ammonium nitrate to calcium nitrate is 1:1.

Table 5 below looks at a series of results for solutions where the molar ratio of ammonium nitrate (AN) to calcium nitrate (CN) was held at 1:1 while the water content was reduced in 1% steps from 24% to 14% while the monomethylammonium nitrate (MMAN) content was increased from 0 to 16.67% in steps of 1.67%. In every single case the crystallization point remained below 0°C.

Table 5:

Mix number K1 K2 K3 K4 K5 K6 K8 K9 K10 K11 K12 % AN 24.9 24.7 24.5 24.3 24.0 23.8 23.6 23.4 23.2 23.0 22.7 % CN 51.9 50.6 50.2 49.7 49.3 48.8 48.4 47.9 47.5 47.0 46.6 Moles AN/Moles CN 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 % Water 24.0 23.0 22.0 21.0 20.0 19.0 18.0 17.0 16.0 15.0 14.0 % MMAN 0.00 1.67 3.33 5.00 6.67 8.33 10.00 11.67 13.33 15.00 16.6 7 Crystallization point (°C) -3 -3 -4 -4 -2 -5 -3 -2 -2 -1 -5

Table 6 below looks at a series of results for solutions where the molar ratio of ammonium nitrate (AN) to calcium nitrate (CN) was once more held at 1:1 while the water content was again reduced in 1% steps from 24% to 14% while the monomethylammonium nitrate (MMAN) content was increased from 0 to 20% in steps of 2%. In every single case the crystallization point remained below 0°C. WO 2013/118103 PCT/IB2013/051107 12

Table 6:

Mix number L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11 % AN 24.9 24.6 24.3 23.9 23.6 23.3 23.0 22.6 22.3 22.0 21.6 % CN 51.1 50.4 49.7 49.1 48.4 47.7 47.0 46.4 45.7 45.0 44.4 Moles AN/Moles CN 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 % Water 24.0 23.0 22.0 21.0 20.0 19.0 18.0 17.0 16.0 15.0 14.0 % MMAN 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 Crystallization point (°C) -6 -6 -5 -7 -6 -6 -5 -6 -6 -5 -4

The above two sets of results show that maintaining these constant proportions yields remarkably consistent crystallization points.

One can introduce magnesium nitrate into the solution and still maintain a sub-zero crystallization point provided that the molar ratio of calcium nitrate to magnesium nitrate does not drop below about 4.0:1 and preferably that this ratio does not drop below about 4.25:1 and most preferably that this ratio does not drop below 4.5:1 in addition the ratio of the molar concentration of ammonium nitrate to the sum of the molar concentrations of calcium nitrate and magnesium nitrate must be as close to 1:1 as possible.

This is demonstrated in the results shown in Table 7 below where MN refers to magnesium nitrate:

Table 7:

Mix number N1 N2 N3 N4 N5 N6 N7 N8 N9 % AN 13.5 18.3 22.4 25.8 28.8 18 22.5 25.9 22.5 % CN 45 41.0 37.6 34.7 32.2 39 35.5 32.8 32.9 % MN 9 8.2 7.5 6.9 6.4 10.5 9.6 8.8 12.1 Moles CN/Moles MN 4.5 4.5 4.5 4.5 4.5 3.4 3.4 3.4 2.46 Moles AN/(Moles CN + Moles MN) 0.50 0.75 1.00 1.25 1.50 0.73 1.00 1.25 1.00 Moles AN/Moles CN 0.61 0.92 1.22 1.53 1.83 0.95 1.30 1.62 1.40 % Water 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 WO 2013/118103 PCT/IB2013/051107 13 % MMAN 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 6 1 -2 11 20 11.5 7 9 11

In Table 8 below we show results for solutions made with identical quantities of water and MMAN but without the presence on magnesium nitrate.

Table 8:

Mix number E1 E2 E3 E4 E5 E6 E7 E8 % AN 7.3 13.2 18.1 22.1 25.6 28.5 31.1 33.3 % CN 60.2 54.3 49.4 45.4 41.9 39.0 36.4 34.2 Moles AN/Moles CN 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 % Water 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 % MMAN 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 6 4 -3 -7 7 14 18 22

This demonstrates that with relatively low concentrations of magnesium nitrate, at a molar ratio of calcium nitrate to magnesium nitrate of about 4.5:1 or greater, one can still achieve a sub-zero crystallization point provided that the molar ratio of ammonium nitrate to the sum of calcium and magnesium nitrate is about 1:1. It is clear that where there is magnesium nitrate present the molar ratio is between ammonium nitrate and the sum of calcium and magnesium nitrate and not between ammonium nitrate and calcium nitrate alone.

Solutions were then prepared with varying quantities of sodium nitrate (SN) together with the same quantities of monomethylammonium nitrate and water as those used in mixes A1 to A8 in Table 1 above but now without the calcium nitrate. The results are shown in Table 9 below:

Table 9:

Mix number SN1 SN2 SN3 SN4 SN5 SN6 SN7 SN8 SN9 SN10 % AN 61 59 57 55 53 51 49 47 45 43 % SN 0 2 4 6 8 10 12 14 16 18 Moles AN/Moles - 31.3 15.1 9.7 7.0 5.4 4.3 3.6 3.0 2.5 WO 2013/118103 PCT/IB2013/051107 14 SN % Water 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 22.0 % MMAN 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 Crystallization point (°C) 35 33 32 31 30 30 31 30 33 47

This shows clearly that while there is a slight crystallization point depressing effect with addition of sodium nitrate up to about 16% the effect is almost negligible when compared to the system containing only ammonium nitrate, monomethylammonium nitrate and water, unlike the system when calcium nitrate is used where the crystallization point depression is dramatic when the ratio of the molar concentration of ammonium nitrate to calcium nitrate is close to 1:1.

Solutions were prepared with sodium nitrate (SN) together with calcium nitrate, ammonium nitrate, monomethylammonium nitrate and water. The results are shown in table 10 below.

Table 10:

Mix number P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 % AN 14.6 20.0 24.6 28.4 31.7 14.2 19.4 23.8 27.5 30.7 %CN 44.9 39.5 34.9 31.1 27.8 47.8 42.6 38.2 34.5 31.3 % SN 8 8 8 8 8 5.5 5.5 5.5 5.5 5.5 Moles AN/Moles CN 0.67 1.04 1.44 1.87 2.34 0.61 0.93 1.28 1.63 2.01 % Water 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 % MMAN 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 25 19 16 18 20 6 5 -1 9 16

It is clear that in the presence of sodium nitrate as long as the ratio of the molar concentration of ammonium nitrate to calcium nitrate is in the range specified for the system without sodium nitrate then small amounts of sodium nitrate can be introduced, but even at these low levels it has the effect of raising the crystallization point. A similar effect is seen with WO 2013/118103 PCT/IB2013/051107 15 potassium nitrate as shown in the Table 11 a and Table 11 b below:

Table 11a:

Mix number KN1 KN2 KN3 KN4 KN5 KN6 KN7 KN8 KN9 KN10 % AN 14.4 15.5 19.6 24.1 27.8 31.0 14.0 16.4 19.2 23.5 %CN 43.6 42.5 38.4 33.9 30.2 27.0 47.0 44.6 41.8 37.5 % Potassium nitrate 9.5 9.5 9.5 9.5 9.5 9.5 6.5 6.5 6.5 6.5 Moles AN/Moles CN 0.68 0.75 1.05 1.46 1.89 2.35 0.61 0.75 0.94 1.28 % Water 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 % MMAN 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 0 <-6 -4 2 12 21 1 <-6 <-6 -3

Table 11b:

Mix number KN11 KN12 KN13 KN14 KN15 KN16 KN17 KN18 KN19 % AN 27.1 30.2 14.0 15.0 17.1 20.6 25.2 29.1 32.5 %CN 33.9 30.8 38.3 37.3 35.2 31.7 27.1 23.3 19.8 % Potassium nitrate 6.5 6.5 15.2 15.2 15.2 15.2 15.2 15.2 15.2 Moles AN/Moles CN 1.64 2.01 0.75 0.82 1.00 1.33 1.91 2.57 3.36 % Water 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 % MMAN 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Crystallization point (°C) 8 18 12.1 10.0 10.6 20.2 26.0 32.0 36.0

Emulsion products were then prepared from solutions B4 and K3 in order to investigate their effectiveness as an explosive. These two solutions were chosen since they both crystallized at -4°C and both contained the same quantity of water but differing quantities of monomethylammonium nitrate in order to check the effect of the monomethylammonium nitrate on the explosive properties of the resulting emulsion explosive. The final products had the following analyses.

Table 12: WO 2013/118103 PCT/IB2013/051107 16

Mix number Emulsion B4 Emulsion K3 % AN 18.9% 21.6% % CN 38.8% 44.2% % MMAN 12.6% 2.9% % Water 19.8% 19.4% PIBSA Emulsifier 1.0% 1.0% Soya bean oil 5.8% 7.8% Glass microspheres* 3.1% 3.1% Oxygen balance -0.75% -0.04% Theoretical net explosive energy 2.874 MJ/kg 2.950 MJ/kg Product density 1.19 g/cm3 1.19 g/cm3 * K20 microspheres made by 3 M

The emulsions were each made into 50mm diameter cartridges, 600mm long, by loading into plastic lay-flat tubing (100 micron thick) and initiated with a 15g pentolite booster. Emulsion B4 initiated and detonated over its entire length at constant velocity as demonstrated by a witness pipe placed in contact with the cartridge which was flattened completely over the full length of the cartridge. Emulsion K3 failed to maintain detonation and most of the product was recovered. This trial indicates that the monomethylammonium nitrate not only improves the solubility of the salts at progressively lower water levels it also assists in the sensitivity of the final emulsion.

This invention opens the way to transporting the aqueous oxidizer solution, the oil and emulsifier mixture and the gassing reagent separately to the mine. And then transporting them from surface to the underground workings through relatively small diameter pipelines, over any desired length, directly to the face to be blasted and then only mixing the three liquids (oxidiser solution, oil/emulsifier solution and gassing reagent) to form an explosive emulsion as they are pumped into the hole. It might also be feasible to emulsify the gassing reagent into the oil/emulsifier mixture and in this way only transport two liquids underground for mixing at the blast face. The point is that throughout there would be no need to keep the WO 2013/118103 PCT/IB2013/051107 17 solution heated in heated storage vessels or heated and jacketed pipelines as would be needed with oxidizer solutions of the prior art.

Claims

1. An aqueous oxidizer solution consisting of a mixture of dissolved oxidizing nitrate salts and water, for use in the preparation of explosives formulations, which has a crystallization point of 10eC or less; said solution consisting of: between 12% and 24% by mass water; an alkylamine nitrate or monoethanolamine nitrate in an amount of 10% to 18% by mass; and ammonium nitrate and calcium nitrate or mixture of calcium nitrate and magnesium nitrate; wherein the molar concentration of ammonium nitrate to calcium nitrate or mixture of calcium nitrate and magnesium nitrate is between 0.75:1 and 1.25:1.

2. The aqueous oxidizer solution claimed in claim 1, wherein the crystallization point is 0eC or less.

3. The aqueous oxidizer solution claimed in claim 2, wherein the molar concentration of ammonium nitrate to calcium nitrate is approximately 1.

4. The aqueous oxidizer solution claimed in claim 2, wherein the molar concentration of ammonium nitrate to mixture of calcium nitrate and magnesium nitrate is approximately 1.

5. The aqueous oxidizer solution claimed in claim 4, wherein the ratio of the molar concentration of the calcium nitrate to the magnesium nitrate is not less than about 4:1.

6. The aqueous oxidizer solution claimed in claim 5, wherein the ratio of the molar concentration of the calcium nitrate to the magnesium nitrate is not less than about 4.5:1.

7. The aqueous oxidizer solution claimed in any one of the preceding claims, wherein the aqueous oxidizer solution has a water content of between 17% and 22%, by mass.

8. The aqueous oxidizer solution claimed in any one of the preceding claims, wherein the alkylamine nitrate or monoethanolamine nitrate is present in an amount of 12% to 17% by mass.

9. The aqueous oxidizer solution claimed in claim 8, wherein, for every 1% reduction in the water content below 24%, the solution contains at least an additional 1.67% alkylamine nitrate or monoethanolamine nitrate.

10. The aqueous oxidizer solution claimed in claim 8, wherein the alkylamine nitrate or monoethanolamine nitrate is present in the solution in at least a quantity to satisfy the equation: M > 5(24-W)/3 (where W = the percentage water in the solution and M = the percentage alkylamine nitrate or monoethanolamine nitrate in the solution).

11. The aqueous oxidizer solution claimed in any one of the preceding claims, wherein the alkylamine nitrate is monomethylamine nitrate, dimethylamine nitrate or trimethylamine nitrate.

12. The aqueous oxidizer solution claimed in claim 11, wherein the alkylamine nitrate is monomethylamine nitrate (CH3NH3N03).

13. A method of manufacturing an explosives formulation, the method including the step of mixing the aqueous oxidizer solution defined in any one of claims 1 to 12 with a fuel.

14. An explosives formulation comprising a mixture of the oxidizer solution defined in any one of claims 1 to 12 with a fuel.