EP4056544A1 - Emulsion-type explosives of the water-in-oil type - Google Patents

Emulsion-type explosives of the water-in-oil type Download PDF

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Publication number
EP4056544A1
EP4056544A1 EP21161190.0A EP21161190A EP4056544A1 EP 4056544 A1 EP4056544 A1 EP 4056544A1 EP 21161190 A EP21161190 A EP 21161190A EP 4056544 A1 EP4056544 A1 EP 4056544A1
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EP
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Prior art keywords
composition
total weight
view
oil
phase
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP21161190.0A
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German (de)
French (fr)
Inventor
Francois Ledoux
Petr CHLADEK
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Yara International ASA
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Yara International ASA
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Priority to EP21161190.0A priority Critical patent/EP4056544A1/en
Priority to CA3207404A priority patent/CA3207404A1/en
Priority to US18/280,526 priority patent/US20240076247A1/en
Priority to PCT/EP2022/055786 priority patent/WO2022189372A1/en
Priority to EP22711939.3A priority patent/EP4305008A1/en
Priority to AU2022235178A priority patent/AU2022235178A1/en
Priority to BR112023017284A priority patent/BR112023017284A2/en
Publication of EP4056544A1 publication Critical patent/EP4056544A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
    • C06B31/285—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with fuel oil, e.g. ANFO-compositions

Definitions

  • the present disclosure relates to emulsion-type explosives of the water-in-oil type.
  • Emulsion-type explosives have become increasingly more important in the civil explosives industry.
  • an emulsion explosive of the water-in-oil type for the explosives industry two immiscible phases are mixed, i.e., an (aqueous) oxidizer phase which is the discontinuous phase and an organic (oil) phase which is the continuous phase.
  • the discontinuous phase or oxidizer phase consists of an usually supersatured solution of one or more oxidizing salts such as amongst others ammonium nitrate (AN). Other chemicals such as additives, pH-modifier, urea, etc, can also be present in the oxidizer phase.
  • the continuous phase or organic phase consists of one or more fuels and one or more emulsifiers.
  • the discontinuous (oxidizer) phase consists of droplets that are finely dispersed in the continuous (organic) phase.
  • Typical examples of fuels include diesel, paraffin wax, paraffin oil, slack wax and the like.
  • an emulsifier is added, which acts at the interface between the two phases to stabilize the emulsion. Due to its organic nature, the emulsifier is included in the stoichiometry of the explosion. Due to supersaturation and the immiscibility of the two phases that are mixed, an emulsion explosive is a metastable system. The emulsion is said to "break" when the organic phase and the oxidizer phase separate and / or some oxidizer crystallizes out of the oxidizer phase.
  • Ammonium nitrate (AN) emulsions used for mining applications normally use a non-renewable mineral fuel, typically diesel, as the main fuel.
  • AN Non-renewable mineral fuel
  • diesel typically diesel
  • a "greener” solution more environmentally friendly
  • renewable oils have by nature a totally different chemistry and behavior than diesel or other non-renewable oils, which affect the viscosity and stability of the emulsion composition. There thus remains a need to identify new fuel sources and formulate stable emulsion compositions based on these.
  • an explosive emulsion composition of the water-in-oil type comprising
  • Chemically processed renewable oils are renewable oils of which the chemistry has been adapted, often to mimic the diesel characteristics, especially for engines' applications and compatibility.
  • a "greener” explosive emulsion is obtained.
  • using chemically processed renewable oils destabilizes the emulsion or it hampers the emulsification process through which no emulsion is formed, particularly for mono-nitrate salts explosive emulsion compositions.
  • one or more secondary nitrate salts a single secondary salt or a mix of different secondary salts
  • the chemically processed renewable oil is chosen from bio-diesel, recycled heat-treated vegetable oil, recycled heat-treated animal fat, hydrotreated renewable oil, or a mixture of two or more of these.
  • the explosive emulsion composition comprises between 85 wt.% and 95 wt.% oxidizer phase and between 5 wt.% and 15 wt.% organic phase, both in view of the total weight of the emulsion composition.
  • the fuel composition consists of between 0 wt.% and 80 wt.% of one or more straight vegetable oils, more in particular between 20 wt.% and 80 wt.% of one or more straight vegetable oils, and between 20 wt.% and 100 wt.% of one or more chemically processed renewable oils, more in particular between 20 and 80 wt.% of one or more chemically processed renewable oils, all in view of the total weight of the fuel composition.
  • the fuel consists of 100 wt.% of one or more chemically processed renewable oils in view of the total weight of the fuel composition.
  • the oxidizer phase comprises between 40 wt.% and 80 wt.% of ammonium nitrate (AN) and between 5 wt.% and 50 wt.% of calcium nitrate (CN) or sodium nitrate (SN) or a mixture thereof, more in particular between 10 wt.% and 40 wt.% CN, SN or a mixture thereof or between 10 wt.% and 40 wt.% CN, all in view of the total weight of the oxidizer phase composition.
  • AN ammonium nitrate
  • CN calcium nitrate
  • SN sodium nitrate
  • the oxidizer phase comprises between 5 wt.% and 25 wt.% of water in view of the total weight of the oxidizer phase composition.
  • the emulsifier is present in an amount of between 0.5 wt.% and 5.0 wt.%, more in particular between 1.0 wt.% and 2.5 wt. %, in view of the total weight of the emulsion composition.
  • the emulsifier is from a renewable source.
  • a fully green explosive emulsion is obtained.
  • the SVO is chosen from soybean oil, palm oil, rapeseed oil, canola oil, maize oil, corn oil, sunflower oil, ricin oil, coconut oil, jojoba oil, jatropha oil or a mixture thereof.
  • the explosive emulsion comprises
  • the explosive emulsion comprises
  • the composition has a viscosity of between 10 000 and 200 000 cP measured with a Brookfield viscometer with spindle size 7 at a frequency of 20 rpm.
  • the present disclosure relates to water-in-oil type emulsion explosives comprising an (aqueous) oxidizer (discontinuous) phase and an organic (continuous) phase, wherein the organic phase comprises renewable fuel oils.
  • the explosive emulsion composition typically comprises between 80 wt.% and 95 wt.% of an oxidizer phase and between 5 wt.% and 20 wt.% of an organic phase, both in view of the total weight of the emulsion composition. More in particular, the explosive emulsion composition comprises between 85 wt.% and 95 wt.% oxidizer phase and between 5 wt.% and 15 wt.% organic phase, both in view of the total weight of the emulsion composition.
  • the organic phase typically comprises between 12 wt.% and 50 wt.% of one emulsifier or a mixture of different emulsifiers, and between 50 wt.% and 88 wt.% of a fuel composition, both in view of the total weight of the organic phase composition.
  • the fuel composition consists of between 5 wt.% and 100 wt.% of a single chemically processed renewable oil or a mixture of different chemically processed renewable oils, and between 0 wt.% and 95 wt.% of a single straight vegetable oil (SVO) or a mixture of different straight vegetable oils, in view of the total weight of the fuel composition.
  • SVO straight vegetable oil
  • up to 50 wt % of a single non-renewable oil or a mixture of different non-renewable oils, in particular diesel oil, in view of the total weight of the fuel composition can be present in the fuel composition.
  • the fuel composition consists of between 10 wt.% and 90 wt.%, between 20 wt.% and 80 wt.%, between 30 wt.% and 70 wt.% or between 40 wt.% and 60 wt.%, of one or more chemically processed renewable oils, more in particular one or more hydrotreated renewable oils (HVO), and between 10 wt.% and 90 wt.%, between 20 wt.% and 80 wt.%, between 30 wt.% and 70 wt.% or between 40 wt.% and 60 wt.%, of one or more straight vegetable oils (SVO), wherein the total weight% of the one or more chemically processed renewable oils and the SVOs equals 100, all in view of the total weight of the fuel composition.
  • HVO hydrotreated renewable oils
  • the fuel consists of 100 wt.% of a single chemically processed renewable oil or a mixture of chemically processed renewable oils, in view of the total weight of the fuel composition.
  • renewable oils By chemically processed renewable oils is meant renewable oils of which the chemistry has been changed. Typical chemical processes are transesterification, hydrogenation, heat treatment, etc.
  • Bio-fuels are any type of transportation fuel that is derived from biomass including plant or algae material or animal waste.
  • the bio-fuels comprise bio-diesel as well as other types of chemically processed oils which have a chemistry which has been adapted to mimic the diesel characteristics, especially for engines.
  • These oils comprise hydrotreated (also called hydrogenated) vegetable oils, recycled vegetable oils or recycled animal fats, waste from wood processing, etc..
  • hydrotreated also called hydrogenated
  • These type of oils produce lower greenhouse emissions by 40 - 90 %, they often have higher energy per content yields than petroleum-based diesels, and better cold-flow properties to work in colder climates.
  • There are many different suppliers of such chemically processed renewable oils are many different suppliers of such chemically processed renewable oils.
  • Biodiesel is a form of diesel fuel derived from plants or animals and consisting of long-chain fatty acid esters. It is typically made by chemically reacting lipids such as animal fat (tallow), soybean oil or other vegetable oils with an alcohol, producing methyl, ethyl or propyl ester (the chemical process being called esterification). Biodiesel has a lower boiling point and viscosity than SVO. Pure biodiesel is marketed as B100 at the gasoline stations.
  • Chemically processed renewable oils can be produced in small scale in a modular plant. This is especially interesting in remote locations. It is typically applicable to produce bio-diesel. Such a modular plant can be combined with a modular fast-deploy emulsion plant. When bio-diesel would be combined with a straight vegetable oil, the renewable oil feedstock can be split into two flows, i.e. an untreated straight vegetable oil flow which goes directly to the emulsion plant and a flow of a bio-diesel produced in a transesterification modular unit.
  • Recycled vegetable oil or recycled animal fat originates from cooking such as frying or other industrial processes without intermediate processing. These recycled oils and fat could also be further chemically processed.
  • Hydrotreated renewable oils are paraffinic bio-based liquid oils originating from many kinds of vegetable oils, such as rapeseed, sunflower, soybean, algae, and palm oil, as well as animal fats or rests from wood processing.
  • hydrotreated renewable or vegetable oils are obtained by subjecting fatty acid containing oils, such as vegetable oils or waste fats to a hydro-processing treatment or a hydrotreatment, wherein hydrogen is used to make paraffin and cycloalkanes out of the unsaturated compounds in the oils, which typically further undergo hydrocracking or isomerization.
  • the term "hydrotreated vegetable oil” or “HVO” also refers to recycled vegetable oil, animal fats or waste fats, that have been subject to the hydrotreatment process.
  • the organic phase can next to chemically processed renewable oils also comprise one or more straight vegetable oils.
  • a straight vegetable oil is defined as any of a group of oils that are esters of fatty acids and glycerol and are obtained from plants and which are non-chemically processed.
  • the straight vegetable oil is chosen from soybean oil, palm oil, rapeseed oil, canola oil, maize oil, corn oil, sunflower oil or a mixture thereof.
  • SVO's which are economically less attractive but which are also suitable are groundnut oil, kernel oil, virgin olive oil, oil of olive residues, karite nuts butter, castor bean oil, hydrogenated castor oil, tung nuts oil, safflower seed oil, sesame seed oil, mustard seed oil, poppy seed oil, vegetable tallow, stillingia oil, kapok oil, cottonseed oil linseed oil, hempseed oil, algae oil, rice bran oil, linseed oil, peanut oil and safflower oil or a mixture thereof.
  • the straight animal fat can be cattle fat, buffalo fat, sheep fat, goats fat, pigs fat, poultry fat, camels fat, fat from other camelids, ghee fat or whale fat (blubber), fish oil or a mixture thereof. Animal fats tend to have more free fatty acids than vegetable oils do.
  • the organic phase can next to chemically processed renewable oils also comprise one or more non-renewable oils.
  • non-renewable oils include diesel, paraffin wax, paraffin oil, slack wax and the like.
  • the organic phase of the explosive emulsion composition according to the present disclosure furthermore comprises an emulsifier which is added to prevent separation of the different phases and thus to obtain a stable emulsion.
  • the emulsifier may be chosen from the wide range of emulsifiers known in the art to be suitable for the preparation of explosive emulsion compositions.
  • Particularly suitable emulsifiers include PIB (polyisobutylene) derivatives such as PIBSA (polyisobutylene succinic anhydrides), sorbitan ester emulsifiers such as SMO (sorbitan monooleate) and mixtures thereof.
  • the emulsifier can be bio-sourced, i.e. produced from renewable resources. When the fuel is also completely from a renewable origin, providing an emulsifier which is bio-sourced provides a fully green solution of an explosive emulsion. Typically, between 12 wt.% and 50 wt.% of a single emulsifier or a mixture of different emulsifiers in view of the total weight of the organic phase composition is present.
  • Typical amounts of such emulsifiers in view of the total weight of the emulsion composition are between 0.5 and 5 wt.%, more in particular between 1.0 wt.% and 2.5 wt.%. In this context, it is understood that the skilled person is able to select a suitable emulsifier and its concentration without any inventive skill.
  • the oxidizer phase comprises next to ammonium nitrate as an oxidizer salt also a secondary nitrate salt.
  • a secondary nitrate salt refers particularly to an alkali nitrate salt, an alkaline earth nitrate salt, or a mixture thereof.
  • Particularly preferred secondary nitrate salts include calcium nitrate (CN), sodium nitrate (SN) or a mixture thereof.
  • AN typically is present in an amount between 40 wt.% and up to 80 wt.% and the secondary nitrate salt is present in an amount of at least 5 wt.%, in view of the total weight of the oxidizer phase composition.
  • the oxidizer phase comprises between 40 wt.% to 80 wt.% AN and between 5 wt.% and 50 wt.% of calcium nitrate and/or sodium nitrate, in particular between 10 wt.% and 40 wt.% of CN and/or SN, more in particular between 10 wt.% and 35 wt.% CN and/or SN, even more in particular between 15 wt.% and 35 wt.% CN and/or SN, between 10 wt.% and 30 wt.% CN and/or SN, or between 15 wt.% and 30 wt.% CN and/or SN, in view of the total weight of the oxidizer phase composition.
  • any combination of different chemically processed renewable oils or a combination of one or more different chemically processed renewable oils with an SVO or a non-renewable oil is possible, this depending on the viscosity necessary for the application.
  • the viscosity depends on the amount of oil present in the fuel phase, which is related to the amount of secondary salt present in the oxidizer phase, particularly the amount of calcium nitrate in the oxidizer phase. Bulk applications require a lower viscosity while for packaged emulsion (cartridge) applications, a high viscosity is acceptable.
  • the oxidizer phase further typically comprises between 5 wt.% and 25 wt.% of (de-ionized) water in view of the total weight of the oxidizer composition.
  • the water content of the oxidizer phase is between 10 wt.% and 20 wt.%, more in particular between 12 wt.% and 17 wt.%, such as about 15 wt.%, in view of the weight of the oxidizer composition.
  • the explosive emulsion composition according to the present disclosure comprises
  • the explosive emulsion composition according to the present disclosure comprises
  • the explosive emulsion comprises
  • the explosive emulsion composition typically has a viscosity of between 10 000 30 and 200 000 cP, as measured with a Brookfield viscometer with spindle size 7 and frequency of 20 rpm, particularly as measured at a temperature between 20°C and 80°C. More in particular, the explosive emulsion composition according to the present disclosure has a viscosity of between 20 000 and 120 000 cP, as measured with a Brookfield viscometer with spindle size 7 and frequency of 20 rpm at a temperature of 30°C and/or has a viscosity of between 20 000 and 80 000 cP, as measured with a Brookfield viscometer with spindle size 7 and frequency of 20 rpm at a temperature of 70°C.
  • the viscosity as mentioned in Table 4 below of the different tested samples as mentioned in Table 1 was measured using the following measurement method: a spindle of a Brookfield viscometer with spindle size 7 at a frequency of 20 rpm is rotated for 30s (this time being an optional choice in the viscometer settings). The viscosity of the following emulsions is measured as:

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  • Engineering & Computer Science (AREA)
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Abstract

The present disclosure relates to a water-in-oil emulsion explosive composition, comprising an organic phase and an oxidizer phase at least comprising ammonium nitrate, wherein at least 50 wt.%, or even 100 wt.% of the normally used non-renewable oil in the organic phase is replaced with one or more chemically processed renewable oils and/or straight vegetable oils or straight animal fats. The present disclosure relates to an explosive emulsion composition of the water-in-oil type is disclosed, comprising- between 5 wt.% and 20 wt.% of an organic phase in view of the total weight of the emulsion composition, the organic phase comprising• between 12 wt.% and 50 wt.% of one or more emulsifiers,• between 50 wt.% and 88 wt.% of a fuel composition,in view of the total weight of the organic phase composition,in which the fuel composition consists of• between 5 wt.% and 100 wt.% one or more chemically processed renewable oils,• between 0 wt.% and 95 wt.% of one or more straight vegetable oils (SVO) or one or more straight animal fats, and• between 0 wt.% and 50 wt.% one or more non-renewable oils,in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and- between 80 wt.% and 95 wt.% of an oxidizer phase in view of the total weight of the emulsion composition, comprising• at least 40 wt. and up to 80 wt.% of ammonium nitrate (AN), and• at least 5 wt.% of one or more secondary nitrate salts,in view of the total weight of the oxidizer phase composition.

Description

    Technical field
  • The present disclosure relates to emulsion-type explosives of the water-in-oil type.
    • Background
  • Emulsion-type explosives have become increasingly more important in the civil explosives industry. In an emulsion explosive of the water-in-oil type for the explosives industry, two immiscible phases are mixed, i.e., an (aqueous) oxidizer phase which is the discontinuous phase and an organic (oil) phase which is the continuous phase. The discontinuous phase or oxidizer phase consists of an usually supersatured solution of one or more oxidizing salts such as amongst others ammonium nitrate (AN). Other chemicals such as additives, pH-modifier, urea, etc, can also be present in the oxidizer phase. The continuous phase or organic phase consists of one or more fuels and one or more emulsifiers. The discontinuous (oxidizer) phase consists of droplets that are finely dispersed in the continuous (organic) phase. Typical examples of fuels include diesel, paraffin wax, paraffin oil, slack wax and the like. In the organic phase, an emulsifier is added, which acts at the interface between the two phases to stabilize the emulsion. Due to its organic nature, the emulsifier is included in the stoichiometry of the explosion. Due to supersaturation and the immiscibility of the two phases that are mixed, an emulsion explosive is a metastable system. The emulsion is said to "break" when the organic phase and the oxidizer phase separate and / or some oxidizer crystallizes out of the oxidizer phase.
  • Ammonium nitrate (AN) emulsions used for mining applications normally use a non-renewable mineral fuel, typically diesel, as the main fuel. However, there is a demand for a "greener" solution (more environmentally friendly) and a more sustainable solution in view of the raw materials used in the explosive emulsion. However, renewable oils have by nature a totally different chemistry and behavior than diesel or other non-renewable oils, which affect the viscosity and stability of the emulsion composition. There thus remains a need to identify new fuel sources and formulate stable emulsion compositions based on these.
    • Summary
  • According to a first aspect of the present disclosure, an explosive emulsion composition of the water-in-oil type is disclosed, comprising
    • between 5 wt.% and 20 wt.% of an organic phase in view of the total weight of the emulsion composition, the organic phase comprising
      • between 12 wt.% and 50 wt.% of one or more emulsifiers,
      • between 50 wt.% and 88 wt.% of a fuel composition,
      in view of the total weight of the organic phase composition,
      in which the fuel composition consists of
      • between 5 wt.% and 100 wt.% one or more chemically processed renewable oils,
      • between 0 wt.% and 95 wt.% of one or more straight vegetable oils (SVO) or one or more straight animal fats, and
      • between 0 wt.% and 50 wt.% one or more non-renewable oils,
      in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and
    • between 80 wt.% and 95 wt.% of an oxidizer phase in view of the total weight of the emulsion composition, comprising
      • between 40 wt.% and up to 80 wt.% of ammonium nitrate (AN), and
      • at least 5 wt.% of one or more secondary nitrate salts,
      in view of the total weight of the oxidizer phase composition,
  • Chemically processed renewable oils are renewable oils of which the chemistry has been adapted, often to mimic the diesel characteristics, especially for engines' applications and compatibility. By replacing at least 50 wt.% in view of the total weight of the organic phase composition of the explosive emulsion of the normally used non-renewable oil with either a single chemically processed renewable oil or a mixture of different chemically processed renewable oils, or a combination of one or more chemically processed renewable oils with one or more straight vegetable oils, a "greener" explosive emulsion is obtained. However, using chemically processed renewable oils destabilizes the emulsion or it hampers the emulsification process through which no emulsion is formed, particularly for mono-nitrate salts explosive emulsion compositions. Reformulating the composition of the emulsion with at least 5 wt.% of one or more secondary nitrate salts (a single secondary salt or a mix of different secondary salts), such as at least 10 wt.% of one or more secondary nitrate salts, in view of the total weight of the oxidizer phase composition added to the already present ammonium nitrate in the oxidizer phase surprisingly allows to produce stable emulsions.
  • In a particular embodiment of a composition according to the present disclosure, the chemically processed renewable oil is chosen from bio-diesel, recycled heat-treated vegetable oil, recycled heat-treated animal fat, hydrotreated renewable oil, or a mixture of two or more of these.
  • In a specific embodiment of a composition according to the present disclosure, the explosive emulsion composition comprises between 85 wt.% and 95 wt.% oxidizer phase and between 5 wt.% and 15 wt.% organic phase, both in view of the total weight of the emulsion composition.
  • In a particular embodiment of a composition according to the present disclosure, the fuel composition consists of between 0 wt.% and 80 wt.% of one or more straight vegetable oils, more in particular between 20 wt.% and 80 wt.% of one or more straight vegetable oils, and between 20 wt.% and 100 wt.% of one or more chemically processed renewable oils, more in particular between 20 and 80 wt.% of one or more chemically processed renewable oils, all in view of the total weight of the fuel composition.
  • In a possible embodiment of a composition according to the present disclosure, the fuel consists of 100 wt.% of one or more chemically processed renewable oils in view of the total weight of the fuel composition.
  • In an optional embodiment of a composition according to the present disclosure, the oxidizer phase comprises between 40 wt.% and 80 wt.% of ammonium nitrate (AN) and between 5 wt.% and 50 wt.% of calcium nitrate (CN) or sodium nitrate (SN) or a mixture thereof, more in particular between 10 wt.% and 40 wt.% CN, SN or a mixture thereof or between 10 wt.% and 40 wt.% CN, all in view of the total weight of the oxidizer phase composition.
  • In an embodiment of a composition according to the present disclosure, the oxidizer phase comprises between 5 wt.% and 25 wt.% of water in view of the total weight of the oxidizer phase composition.
  • In a possible embodiment of a composition according to the present disclosure, the emulsifier is present in an amount of between 0.5 wt.% and 5.0 wt.%, more in particular between 1.0 wt.% and 2.5 wt. %, in view of the total weight of the emulsion composition.
  • In a particular embodiment of a composition according to the present disclosure, the emulsifier is from a renewable source. In combination with 100 wt.% of a renewable oil in view of the total weight of the fuel composition, a fully green explosive emulsion is obtained.
  • In a possible embodiment of a composition according to the present disclosure, the SVO is chosen from soybean oil, palm oil, rapeseed oil, canola oil, maize oil, corn oil, sunflower oil, ricin oil, coconut oil, jojoba oil, jatropha oil or a mixture thereof.
  • In an embodiment of a composition according to the present disclosure, the explosive emulsion comprises
    • between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
      • between 12 wt.% and 50 wt.% of one or more emulsifiers,
      • between 50 wt.% and 88 wt.% of a fuel composition,
      in view of total weight of the organic phase composition,
      in which the fuel composition consists of
      • between 5 wt.% and 100 wt.% of one or more chemically processed renewable oils, particularly between 20 wt. and 80 wt.% of one or more chemically processed renewable oils, and
      • between 0 wt.% and 95 wt.% of one or more SVO's, particularly between 20 wt.% and 80 wt% of one or more SVO's,
        in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and
    • between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
      • between 40 wt.% and 80 wt.% AN,
      • between 5 wt.% and 50 wt.% CN and/or SN, in particular between 15 wt.% and 35 wt.% CN and/or SN or between 15 wt.% and 35 wt.% CN,
      • between 5 wt.% and 25 wt.% water,
      in view of the total weight of the oxidizer composition.
  • In a possible embodiment of a composition according to the present disclosure, the explosive emulsion comprises
    • between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
      • between 12 wt.% and 50 wt.% of one or more emulsifiers,
      • between 50 wt.% and 88 wt.% of a fuel composition,
        in view of total weight of the organic phase composition,
        in which the fuel composition consists of 100 wt.% of one or more chemically processed renewable oils in view of the total weight of the fuel composition.
    • between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
      • between 40 wt.% and 80 wt.% AN,
      • between 5 wt.% and 50 wt.% CN and/or SN, in particular between 15 wt.% and 35 wt.% CN and/or SN or between 15 wt.% and 35 wt.% CN,
      • between 7 wt.% and 25 wt.% water,
      in view of the total weight of the oxidizer composition.
  • In an embodiment of a composition according to the present disclosure, the composition has a viscosity of between 10 000 and 200 000 cP measured with a Brookfield viscometer with spindle size 7 at a frequency of 20 rpm.
    • Detailed description
  • The present disclosure relates to water-in-oil type emulsion explosives comprising an (aqueous) oxidizer (discontinuous) phase and an organic (continuous) phase, wherein the organic phase comprises renewable fuel oils.
  • The explosive emulsion composition typically comprises between 80 wt.% and 95 wt.% of an oxidizer phase and between 5 wt.% and 20 wt.% of an organic phase, both in view of the total weight of the emulsion composition. More in particular, the explosive emulsion composition comprises between 85 wt.% and 95 wt.% oxidizer phase and between 5 wt.% and 15 wt.% organic phase, both in view of the total weight of the emulsion composition.
  • The organic phase typically comprises between 12 wt.% and 50 wt.% of one emulsifier or a mixture of different emulsifiers, and between 50 wt.% and 88 wt.% of a fuel composition, both in view of the total weight of the organic phase composition.
  • The fuel composition consists of between 5 wt.% and 100 wt.% of a single chemically processed renewable oil or a mixture of different chemically processed renewable oils, and between 0 wt.% and 95 wt.% of a single straight vegetable oil (SVO) or a mixture of different straight vegetable oils, in view of the total weight of the fuel composition. Optionally, up to 50 wt % of a single non-renewable oil or a mixture of different non-renewable oils, in particular diesel oil, in view of the total weight of the fuel composition, can be present in the fuel composition. More in particular, the fuel composition consists of between 10 wt.% and 90 wt.%, between 20 wt.% and 80 wt.%, between 30 wt.% and 70 wt.% or between 40 wt.% and 60 wt.%, of one or more chemically processed renewable oils, more in particular one or more hydrotreated renewable oils (HVO), and between 10 wt.% and 90 wt.%, between 20 wt.% and 80 wt.%, between 30 wt.% and 70 wt.% or between 40 wt.% and 60 wt.%, of one or more straight vegetable oils (SVO), wherein the total weight% of the one or more chemically processed renewable oils and the SVOs equals 100, all in view of the total weight of the fuel composition. With one or more is meant a single oil or a mixture of different oils. It is also possible that the fuel consists of 100 wt.% of a single chemically processed renewable oil or a mixture of chemically processed renewable oils, in view of the total weight of the fuel composition.
  • By chemically processed renewable oils is meant renewable oils of which the chemistry has been changed. Typical chemical processes are transesterification, hydrogenation, heat treatment, etc.
  • Bio-fuels are any type of transportation fuel that is derived from biomass including plant or algae material or animal waste. The bio-fuels comprise bio-diesel as well as other types of chemically processed oils which have a chemistry which has been adapted to mimic the diesel characteristics, especially for engines. These oils comprise hydrotreated (also called hydrogenated) vegetable oils, recycled vegetable oils or recycled animal fats, waste from wood processing, etc.. These type of oils produce lower greenhouse emissions by 40 - 90 %, they often have higher energy per content yields than petroleum-based diesels, and better cold-flow properties to work in colder climates. There are many different suppliers of such chemically processed renewable oils.
  • Biodiesel is a form of diesel fuel derived from plants or animals and consisting of long-chain fatty acid esters. It is typically made by chemically reacting lipids such as animal fat (tallow), soybean oil or other vegetable oils with an alcohol, producing methyl, ethyl or propyl ester (the chemical process being called esterification). Biodiesel has a lower boiling point and viscosity than SVO. Pure biodiesel is marketed as B100 at the gasoline stations.
  • Chemically processed renewable oils can be produced in small scale in a modular plant. This is especially interesting in remote locations. It is typically applicable to produce bio-diesel. Such a modular plant can be combined with a modular fast-deploy emulsion plant. When bio-diesel would be combined with a straight vegetable oil, the renewable oil feedstock can be split into two flows, i.e. an untreated straight vegetable oil flow which goes directly to the emulsion plant and a flow of a bio-diesel produced in a transesterification modular unit.
  • Recycled vegetable oil or recycled animal fat originates from cooking such as frying or other industrial processes without intermediate processing. These recycled oils and fat could also be further chemically processed.
  • Hydrotreated renewable oils are paraffinic bio-based liquid oils originating from many kinds of vegetable oils, such as rapeseed, sunflower, soybean, algae, and palm oil, as well as animal fats or rests from wood processing. As well understood by the skilled person, hydrotreated renewable or vegetable oils are obtained by subjecting fatty acid containing oils, such as vegetable oils or waste fats to a hydro-processing treatment or a hydrotreatment, wherein hydrogen is used to make paraffin and cycloalkanes out of the unsaturated compounds in the oils, which typically further undergo hydrocracking or isomerization. The term "hydrotreated vegetable oil" or "HVO" also refers to recycled vegetable oil, animal fats or waste fats, that have been subject to the hydrotreatment process.
  • The organic phase can next to chemically processed renewable oils also comprise one or more straight vegetable oils. A straight vegetable oil is defined as any of a group of oils that are esters of fatty acids and glycerol and are obtained from plants and which are non-chemically processed. The straight vegetable oil is chosen from soybean oil, palm oil, rapeseed oil, canola oil, maize oil, corn oil, sunflower oil or a mixture thereof. Less preferred SVO's which are economically less attractive but which are also suitable are groundnut oil, kernel oil, virgin olive oil, oil of olive residues, karite nuts butter, castor bean oil, hydrogenated castor oil, tung nuts oil, safflower seed oil, sesame seed oil, mustard seed oil, poppy seed oil, vegetable tallow, stillingia oil, kapok oil, cottonseed oil linseed oil, hempseed oil, algae oil, rice bran oil, linseed oil, peanut oil and safflower oil or a mixture thereof.
  • The straight animal fat can be cattle fat, buffalo fat, sheep fat, goats fat, pigs fat, poultry fat, camels fat, fat from other camelids, ghee fat or whale fat (blubber), fish oil or a mixture thereof. Animal fats tend to have more free fatty acids than vegetable oils do.
  • Furthermore, the organic phase can next to chemically processed renewable oils also comprise one or more non-renewable oils. Typical examples of commonly used non-renewable oils include diesel, paraffin wax, paraffin oil, slack wax and the like.
  • The organic phase of the explosive emulsion composition according to the present disclosure furthermore comprises an emulsifier which is added to prevent separation of the different phases and thus to obtain a stable emulsion. In this context, the emulsifier may be chosen from the wide range of emulsifiers known in the art to be suitable for the preparation of explosive emulsion compositions. Particularly suitable emulsifiers include PIB (polyisobutylene) derivatives such as PIBSA (polyisobutylene succinic anhydrides), sorbitan ester emulsifiers such as SMO (sorbitan monooleate) and mixtures thereof. It is however remarked that other types of emulsifiers, leading also to highly stable emulsions, could be used. The emulsifier can be bio-sourced, i.e. produced from renewable resources. When the fuel is also completely from a renewable origin, providing an emulsifier which is bio-sourced provides a fully green solution of an explosive emulsion. Typically, between 12 wt.% and 50 wt.% of a single emulsifier or a mixture of different emulsifiers in view of the total weight of the organic phase composition is present. Typical amounts of such emulsifiers in view of the total weight of the emulsion composition are between 0.5 and 5 wt.%, more in particular between 1.0 wt.% and 2.5 wt.%. In this context, it is understood that the skilled person is able to select a suitable emulsifier and its concentration without any inventive skill.
  • Since a mixture of a chemically processed renewable oil with straight ammonium nitrate (AN) as the sole oxidizer salt, and a commonly used emulsifier does either not form an emulsion, or if an emulsion is formed, the emulsion is not stable at all, in the context of the present disclosure, the oxidizer phase comprises next to ammonium nitrate as an oxidizer salt also a secondary nitrate salt. In the context of the present disclosure, a secondary nitrate salt refers particularly to an alkali nitrate salt, an alkaline earth nitrate salt, or a mixture thereof. Particularly preferred secondary nitrate salts include calcium nitrate (CN), sodium nitrate (SN) or a mixture thereof.
  • AN typically is present in an amount between 40 wt.% and up to 80 wt.% and the secondary nitrate salt is present in an amount of at least 5 wt.%, in view of the total weight of the oxidizer phase composition. In certain embodiments, the oxidizer phase comprises between 40 wt.% to 80 wt.% AN and between 5 wt.% and 50 wt.% of calcium nitrate and/or sodium nitrate, in particular between 10 wt.% and 40 wt.% of CN and/or SN, more in particular between 10 wt.% and 35 wt.% CN and/or SN, even more in particular between 15 wt.% and 35 wt.% CN and/or SN, between 10 wt.% and 30 wt.% CN and/or SN, or between 15 wt.% and 30 wt.% CN and/or SN, in view of the total weight of the oxidizer phase composition. Calcium nitrate as secondary nitrate was found to be particularly effective in obtaining stable explosive emulsions with customized viscosity, particularly when using a fuel composition consisting of 100% of one or more renewable oils.
  • It is remarked that any combination of different chemically processed renewable oils or a combination of one or more different chemically processed renewable oils with an SVO or a non-renewable oil, within the ranges claimed and as mentioned above, is possible, this depending on the viscosity necessary for the application. The viscosity depends on the amount of oil present in the fuel phase, which is related to the amount of secondary salt present in the oxidizer phase, particularly the amount of calcium nitrate in the oxidizer phase. Bulk applications require a lower viscosity while for packaged emulsion (cartridge) applications, a high viscosity is acceptable.
  • The oxidizer phase further typically comprises between 5 wt.% and 25 wt.% of (de-ionized) water in view of the total weight of the oxidizer composition. In certain embodiments, the water content of the oxidizer phase is between 10 wt.% and 20 wt.%, more in particular between 12 wt.% and 17 wt.%, such as about 15 wt.%, in view of the weight of the oxidizer composition.
  • In certain embodiments, the explosive emulsion composition according to the present disclosure comprises
    • between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
      • between 12 wt.% and 50 wt.% of one or more emulsifiers,
      • between 50 wt.% and 88 wt.% of a fuel composition,
      in view of total weight of the organic phase composition,
      in which the fuel composition consists of
      • between 5 wt.% and 100 wt.% of one or more chemically processed renewable oils, particularly between 20 wt.% and 80 wt.% of one or more chemically processed renewable oils, more in particular between 20 wt.% and 60 wt.% of one or more chemically processed renewable oils, and
      • between 0 wt.% and 95 wt.% of one or more SVO's, particularly between 20 wt.% and 80 wt% of one or more SVOs, more in particular between 40 wt.% and 80 wt.% of one or more SVOs,
        in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and
    • between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
      • between 40 wt.% and 80 wt.% AN,
      • between 5 wt.% and 50 wt.% CN and/or SN, in particular between 10 wt.% and 40 wt.% CN and/or SN, more in particular between 15 wt.% and 35 wt.% CN and/or SN,
      • between 5 wt.% and 25 wt.% water,
      in view of the total weight of the oxidizer composition.
  • In particular embodiments, the explosive emulsion composition according to the present disclosure comprises
    • between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
      • between 12 wt.% and 50 wt.% of one or more emulsifiers,
      • between 50 wt.% and 88 wt.% of a fuel composition,
      in view of total weight of the organic phase composition,
      in which the fuel composition consists of
      • between 20 wt.% and 50 wt.% of one or more chemically processed renewable oils, such as HVO, particularly between 20 wt.% and 40 wt.% of one or more chemically processed oils; and
      • between 50 wt.% and 80 wt% of one or more SVOs, particularly between 60 wt.% and 80 wt.% of one or more SVOs,
        in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and
    • between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
      • between 40 wt.% and 75 wt.% AN,
      • between 10 wt.% and 50 wt.% CN and/or SN, particularly between 10 wt.% and 40 wt.% CN and/or SN, particularly between 10 wt.% and 40 wt.% CN, more in particular between 15 wt.% and 35 wt.% CN and/or SN, even more in particular between 15 wt.% and 35 wt.% CN, and
      • between 10 wt.% and 25 wt.% water,
      in view of the total weight of the oxidizer composition.
    Advantageously, by combining the use of calcium nitrate, particularly at levels of between 10 wt.% and 50 wt.% of the oxidizer phase, such at a levels between 15 wt.% and 40 wt.% or between 15 wt.% and 35 wt.%, with a fuel composition consisting of SVOs and chemically processed renewable oil, such as HVO, wherein the SVOs make up at least 30 wt.%, 40 wt.% or at least 50% of the fuel composition, a green and stable explosive emulsion composition is obtained with customizable viscosity, with viscosity as further discussed herein.
  • In certain embodiments of an explosive composition according to the present disclosure, the explosive emulsion comprises
    • between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
      • between 12 wt.% and 50 wt.% of one or more emulsifiers,
      • between 50 wt.% and 88 wt.% of a fuel,
      in view of total weight of the organic phase composition,
      in which the fuel consists of 100 wt.% of one or more chemically processed renewable oils in view of the total weight of the fuel composition.
    • between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
      • between 40 wt.% and 80 wt.% AN,
      • between 5 wt.% and 50 wt.% CN and/or SN, in particular between 10 wt.% and 40 wt.% CN and/or SN, more in particular between 15 wt.% and 35 wt.% CN and/or SN,
      • between 5 wt.% and 25 wt.% water, in particular between 10 wt.% and 20 wt.% water
      in view of the total weight of the oxidizer composition.
  • The explosive emulsion composition typically has a viscosity of between 10 000 30 and 200 000 cP, as measured with a Brookfield viscometer with spindle size 7 and frequency of 20 rpm, particularly as measured at a temperature between 20°C and 80°C. More in particular, the explosive emulsion composition according to the present disclosure has a viscosity of between 20 000 and 120 000 cP, as measured with a Brookfield viscometer with spindle size 7 and frequency of 20 rpm at a temperature of 30°C and/or has a viscosity of between 20 000 and 80 000 cP, as measured with a Brookfield viscometer with spindle size 7 and frequency of 20 rpm at a temperature of 70°C.
    • Example
  • In Table 1 below, an overview is given of the tested samples of explosive emulsions, produced by the following procedure:
    • weighing solid AN, CN and/or SN into a beaker and adding water,
    • heating and stirring this mixture forming a heated aqueous oxidizer solution of between 50°C to 90°C, typically between 70°C and 80°C,
    • pre-mixing by gradual addition of this heated oxidizer solution to a heated mixture of oil and emulsifier while stirring at 800 rpm,
    • refining at 2000 rpm for 1.5 min.
    It is remarked that the steps, times and rpm used depend obviously on the equipment used, protocol developed, etc, and are not essential parts of this disclosure and can consequently be varied.
  • The following materials are used:
    • crystalline grade ammonium nitrate (NH4NO3 or AN),
    • calcium nitrate (Ca(NO3)2 or CN) using granules containing double salt calcium nitrate and with the overall composition: 79 wt.% Ca(NO3)2, 6 wt.% NH4NO3, 15 wt.% H2O,
    • guaranteed reagent (GR) grade for analysis sodium nitrate (NaNO3 or SN),
    • de-ionized (DI) water,
    • food grade rapeseed oil (Rema1000, originating from Germany),
    • BioLife 58 from Total, which is a type of hydrotreated vegetable oil,
    • 2G Polar from DrivEnergy (Norway) (in Table 1 called "2G Polar DE") and 2G Polar from Eco-1 Bioenergi AS (Norway) (in Table 1 called "2G Polar ECO1"), which both are types of 2nd generation renewable biofuels,
    • milesBIO® HVO100 (in Table 1 called "HVO100") from CircleK (Norway), which is a type of renewable diesel,
    • B100 from Shell (Sweden), which is a type of biodiesel.
    In Table 1 below, the physical properties of the different fuels as mentioned above are shown. Table 1: physical properties of different fuels present in tested samples of Table 2
    Fuel
    Property Unit B100 2G Polar HYO100
    Density (15°C) kg/m3 883 780 780
    Viscosity (40°C) mm2/s 4.4 2.95 3.09
    Flash point °C 160 78.5 99
  • The following emulsifiers were used in the tests as shown in Table 2:
    • Lubrizol 2810 (referred to in Table 1 as "Lubrizol") from Lubrizol which is an emulsifier in which the dominant component is PIBSA,
    • Anfomul 2500 (referred to in Table 1 as "Anfomul") from Croda which is a PIB-lactone base polymeric emulsifier,
    • C615 from Experse which is an emulsifier in which the dominant component is PIBSA, and
    • SPAN®80 (referred to in Table 1 as "SPAN") from Croda which is a type of SMO emulsifier.
  • The following samples as produced by the procedure as described above were tested:
    • The reference which is a common emulsion with solely ammonium nitrate in the oxidizer phase, diesel as the fuel and a PIBSA emulsifier in the organic phase,
    • Samples 1 to 6 which are monosalt-emulsions with ammonium nitrate in the oxidizer phase, different types of chemically processed renewable oils and a 50 / 50 combination of a chemically processed renewable oil and diesel as fuel and a PIBSA emulsifier in the organic phase.
    • Samples 7 to 10 which are monosalt-emulsions with ammonium nitrate in the oxidizer phase, a hydrotreated vegetable oil as the fuel and different types of emulsifiers in the organic phase.
    • Sample 11 in which about 2.5 wt.% of CN is added to AN in the oxidizer phase, with a hydrotreated vegetable oil as the fuel in the organic phase.
    • Samples 12 and 13 in which an amount of 5 wt.% of a secondary salt, i.e. SN or CN, in view of the total emulsion composition, is added to AN, with a hydrotreated vegetable oil as fuel and a Lubrizol emulsifier in the organic phase.
    • Samples 14 to 20 in which a higher amount of CN or SN as a secondary salt, i.e. 10.0 wt.%, 14.1 wt.% or 27.9 wt.% versus the total weight of the emulsion composition, is added to AN in the oxidizer phase, in combination with a hydrotreated vegetable oil as the fuel and different types of PIB derivatives emulsifiers in the organic phase.
    • Samples 21 to 25 in which a higher amount of CN as a secondary salt, i.e. 14.9 wt.% / 14.1 wt.% versus the total weight of the emulsion composition, is added to AN in the oxidizer phase, in combination with other hydrotreated vegetable oils in view of samples 16 to 20, biodiesel and a blend with diesel as the fuel and a PIBSA emulsifier in the organic phase.
    • Samples 26 and 27 in which in view of sample 16, part of the hydrotreated vegetable oil is replaced by a straight vegetable oil (rapeseed oil), in sample 26 in an equal amount and in sample 27 the amount of straight vegetable oil being double in view of the hydrotreated vegetable oil.
    • Samples 28 to 30 in which different amounts of CN as a secondary salt are added to AN in the oxidizer phase, i.e. 10.0 wt.%, 14.1 wt.% and 27.9 wt.% in view of the total weight of the emulsion composition, in combination with a hydrotreated vegetable oil as the fuel and an SMO emulsifier in the organic phase.
    It is remarked that samples 1 to 11 are samples not according to the present disclosure, while samples 14 to 27 are samples according to the present disclosure. Table 2: Overview of the tested samples with their composition expressed in weight% in view of the total emulsion composition
    Sample AN CN SN DI water Fuel oil Emulsifier
    Type Amount Type Amount
    Reference 80.8 0.0 0.0 14.3 Diesel 3.7 Lubrizol 1.2
    Sample 1 80.9 0.0 0.0 14.3 BioLife 3.8 Lubrizol 1.0
    Sample 2 80.9 0.0 0.0 14.3 2G Polar DE 3.8 Lubrizol 1.0
    Sample 3 80.9 0.0 0.0 14.3 2G Polar ECO1 3.8 Lubrizol 1.0
    Sample 4 80.9 0.0 0.0 14.3 HVO100 3.8 Lubrizol 0.95
    Sample 5 80.9 0.0 0.0 14.3 B100 3.8 Lubrizol 0.95
    Sample 6 80.9 0.0 0.0 14.2 Biolife / Diesel 50/50 3.6 Lubrizol 1.2
    Sample 7 80.9 0.0 0.0 14.3 BioLife 3.8 Lubrizol 1.0
    Sample 8 81.0 0.0 0.0 14.2 BioLife 3.6 C615 1.2
    Sample 9 81.0 0.0 0.0 14.2 BioLife 3.6 Anfomul 1.2
    Sample 10 80.9 0.0 0.0 14.2 BioLife 3.6 SPAN80 1.2
    Sample 11 77.8 2.5 0.0 14.7 BioLife 3.7 Lubrizol 1.3
    Sample 12 74.8 4.9 0.0 15.2 BioLife 4.1 Lubrizol 1.0
    Sample 13 75.6 0.0 5.0 14.2 BioLife 4.1 Lubrizol 1.0
    Sample 14 68.4 10 0.0 16.1 BioLife 4.4 Lubrizol 1.1
    Sample 15 65.8 14.1 0.0 14.1 BioLife 4.8 Lubrizol 1.2
    Sample 16 51.1 27.9 0.0 13.9 BioLife 5.9 Lubrizol 1.2
    Sample 17 70.3 0.0 10.0 14.1 Biolife 4.5 Lubrizol 1.1
    Sample 18 51.1 0.0 27.9 13.9 Biolife 5.9 Lubrizol 1.2
    Sample 19 51.1 27.9 0.0 13.9 BioLife 5.9 C615 1.2
    Sample 20 51.1 27.9 0.0 13.9 BioLife 5.9 Anfomul 1.2
    Sample 21 62.3 14.9 0.0 16.9 2G Polar DE 4.4 Lubrizol 1.5
    Sample 22 62.3 14.9 0.0 16.9 2G Polar ECO1 4.4 Lubrizol 1.5
    Sample 23 65.8 14.1 0.0 14.1 HVO100 4.5 Lubrizol 1.5
    Sample 24 65.8 14.1 0.0 14.1 B100 4.5 Lubrizol 1.5
    Sample 25 65.8 14.1 0.0 14.1 BioLife / Diesel 50/50 4.8 Lubrizol 1.5
    Sample 26 51.1 27.9 0.0 13.9 Rapeseed / BioLife 50/50 5.9 Lubrizol 1.2
    Sample 27 51.1 27.9 0.0 13.9 Rapeseed / BioLife 67/33 5.9 Lubrizol 1.2
    Sample 28 68.4 10.0 0.0 16.1 BioLife 4.4 SPAN 1.1
    Sample 29 65.8 14.1 0.0 14.1 BioLife 4.5 SPAN 1.5
    Sample 30 51.1 27.9 0.0 13.9 BioLife 5.3 SPAN 1.8
    Table 3: Overview of the tested samples with their composition expressed in weight%
    Sample Oxidiser phase (wt.% in view of total emulsion composition ) Fuel oil phase (wt.% in view of total emulsion composition ) Oxidiser phase composition (wt.% in view of oxidizer phase composition) Fuel oil phase composition (wt.% in view of the fuel oil phase composition)
    AN CN SN DI water Fuel oil Emulsifier
    Reference 95.10 4.90 85.00 0.00 0.00 15.00 75.3 24.7
    Sample 1 95.21 4.79 85.00 0.00 0.00 15.00 80.12 19.88
    Sample 2 95.21 4.79 85.00 0.00 0.00 15.00 80.12 19.88
    Sample 3 95.21 4.79 85.00 0.00 0.00 15.00 80.12 19.88
    Sample 4 95.21 4.79 85.00 0.00 0.00 15.00 80.12 19.88
    Sample 5 95.21 4.79 85.00 0.00 0.00 15.00 80.12 19.88
    Sample 6 95.18 4.82 85.03 0.00 0.00 14.97 74.94 25.06
    Sample 7 95.21 4.79 85.00 0.00 0.00 15.00 80.12 19.88
    Sample 8 95.20 4.80 85.07 0.00 0.00 14.93 75.00 25.00
    Sample 9 95.20 4.80 85.07 0.00 0.00 14.93 75.00 25.00
    Sample 10 95.18 4.82 85.03 0.00 0.00 14.97 74.94 25.06
    Sample 11 95.01 4.99 81.91 2.58 0.00 15.51 74.90 25.10
    Sample 12 94.86 5.14 78.83 5.196 0.00 15.99 79.99 20.01
    Sample 13 94.81 5.19 79.76 0.00 5.28 14.96 79.95 20.05
    Sample 14 94.50 5.50 72.44 10.56 0.00 17.00 80.01 19.99
    Sample 15 94.00 6.00 69.97 15.04 0.00 14.98 80.00 20.00
    Sample 16 92.90 7.10 55.01 30.03 0.00 14.96 83.02 16.98
    Sample 17 94.43 5.57 74.4 0.00 10.62 14.98 79.97 20.03
    Sample 18 92.90 7.10 55.02 0.00 30.04 14.94 83.06 16.94
    Sample 19 92.90 7.10 55.02 30.02 0.00 14.96 83.10 16.90
    Sample 20 92.90 7.10 55.02 30.02 0.00 14.96 83.10 16.90
    Sample 21 94.13 5.87 66.20 15.80 0.00 18.00 75.00 25.00
    Sample 22 94.13 5.87 66.20 15.80 0.00 18.00 75.00 25.00
    Sample 23 94.03 5.97 70.02 15.00 0.00 14.98 74.92 25.08
    Sample 24 94.03 5.97 69.99 15.00 0.00 15.00 75.00 25.00
    Sample 25 94.03 5.97 69.93 15.05 0.00 15.03 75.00 25.00
    Sample 26 92.90 7.10 55.02 30.02 0.00 14.96 83.10 16.90
    Sample 27 92.90 7.10 55.02 30.02 0.00 14.96 83.10 16.90
    Sample 28 94.50 5.50 72.44 10.56 0.00 17.00 80.01 19.99
    Sample 29 94.03 5.97 69.93 15.05 0.00 15.03 75.00 25.00
    Sample 30 92.91 7.09 54.98 30.01 0.00 15.01 74.96 25.04
    Stability
  • The shear stress stability as mentioned in Table 4 below of the different tested samples as mentioned in Table 1 was measured by the following method:
    • cooling the explosive emulsion to room temperature (20°C),
    • mixing the cooled explosive emulsion in a kitchen mixer and stressing it for 30 minutes,
    • revealing the number and the size of the formed crystals by means of a polarized light microscope analysis,
    • multiplying the crystal size and the crystal number resulting in a stability score between 0 and 20, where 0 corresponds to a separated emulsion and 20 to a perfect emulsion with nearly no crystals. In industry, according to the applicant's experience, emulsions having a stability score between 18 and 20 are considered stable.
    Viscosity
  • The viscosity as mentioned in Table 4 below of the different tested samples as mentioned in Table 1 was measured using the following measurement method: a spindle of a Brookfield viscometer with spindle size 7 at a frequency of 20 rpm is rotated for 30s (this time being an optional choice in the viscometer settings). The viscosity of the following emulsions is measured as:
    • freshly made emulsion (temperature may typically vary from between 50°C and 85°C depending on the salt concentration - higher salt content requires higher temperature for dissolution)
    • at a temperature of 70°C;
    • cooled emulsion (1 hour at 5°C), which gives emulsion temperatures of ∼ 30°C.
    The viscosity is measured in mPa∗s = cP and a typical value for a commercial emulsion is between 35 000 and 50 000 cP. Based on our experience and equipment, the measured viscosity is well reproducible and has an and has an accuracy of ± 2000 cP. Table 4: The viscosity of the samples which are freshly made, at a temperature of 70°C and at a temperature of 30°C, and the stability of the tested samples as listed in Table 1
    Sample Viscosity (mPa*s) Stability
    Fresh 70°C 30°C (LSST)
    Reference 41800 51600 65600 20
    Sample 1 Did not emulsify
    Sample 2 Did not emulsify
    Sample 3 Did not emulsify
    Sample 4 Did not emulsify
    Sample 5 Did not emulsify
    Sample 6 Did not emulsify
    Sample 7 Did not emulsify
    Sample 8 Did not emulsify
    Sample 9 Did not emulsify
    Sample 10 Did not emulsify
    Sample 11 Did not emulsify
    Sample 12 25600 30800 37200 20.0
    Sample 13 29000 33400 35600 19.7
    Sample 14 24800 27600 32000 19.9
    Sample 15 26200 24000 32400 19.9
    Sample 16 25600 30000 33600 20.0
    Sample 17 17400 16600 19600 19.6
    Sample 18 14200 12400 18200 19.9
    Sample 19 13200 12800 20200 20.0
    Sample 20 13200 14800 16800 20.0
    Sample 21 33200 Not measured 37800 20.0
    Sample 22 32600 Not measured 36200 19.9
    Sample 23 29800 30000 34800 19.7
    Sample 24 50600 53400 60400 19.9
    Sample 25 32400 32400 38000 19.9
    Sample 26 35600 30600 38400 20.0
    Sample 27 48400 46200 54200 20.0
    Sample 28 34200 36400 43200 19.9
    Sample 29 35000 38000 45200 20.0
    Sample 30 26800 26600 30400 20.0
  • Out of results as shown in Table 4, it can be concluded that:
    • Monosalt emulsions with ammonium nitrate in the oxidizer phase and a hydrotreated vegetable oil or a blend of a hydrotreated vegetable oil and diesel as a fuel in the organic phase do not form an emulsion regardless of the type of hydrotreated vegetable oil or the type of emulsifier used.
    • Addition of a low amount of a secondary salt (less than 2.5 wt.% in view of the composition of the oxidizer phase) and a hydrotreated vegetable oil as a fuel in the organic phase does not form an emulsion.
    • Addition of a higher amount of a secondary salt (at least about 5 wt.% or 10 wt. % CN or SN in view of the composition of the oxidizer phase) surprisingly stabilizes the emulsion. This was observed for different types of hydrotreated vegetable oils and for a blend of a hydrotreated vegetable with diesel.
    • Addition of higher amounts of a secondary salt (around 10 wt.%, 15 wt.% and 30 wt.% CN or SN in view of the composition of the oxidizer phase) lowers the viscosity. Furthermore, addition of higher amounts of a secondary salt also allows the possibility to reduce the water content which provides more power in the explosion.
    • By replacing part of the hydrotreated vegetable oil in the organic phase by a straight vegetable oil (SVO) and adding a higher amount of a secondary salt (for instance about 30 wt.% in view of the composition of the oxidizer phase) allows tailoring of the viscosity. The higher the amount of SVO added, the higher the viscosity. The higher the amount of secondary salt, the lower the viscosity.
    • The type of emulsifier (SMO or PIBSA or other) seems to have no significant impact on the viscosity and the shear stress stability of the explosive emulsion.

Claims (15)

  1. An explosive emulsion composition of the water-in-oil type, comprising
    - between 5 wt.% and 20 wt.% of an organic phase in view of the total weight of the emulsion composition, the organic phase comprising
    • between 12 wt.% and 50 wt.% of one or more emulsifiers,
    • between 50 wt.% and 88 wt.% of a fuel composition,
    in view of the total weight of the organic phase composition,
    in which the fuel composition consists of
    • between 5 wt.% and 100 wt.% one or more chemically processed renewable oils,
    • between 0 wt.% and 95 wt.% of one or more straight vegetable oils (SVO) or one or more straight animal fats, and
    • between 0 wt.% and 50 wt.% one or more non-renewable oils,
    in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and
    - between 80 wt.% and 95 wt.% of an oxidizer phase in view of the total weight of the emulsion composition, comprising
    • between 40 wt.% and up to 80 wt.% of ammonium nitrate (AN), and
    • at least 5 wt.% of one or more secondary nitrate salts, in particular at least 10 wt. % of one or more secondary nitrate salts,
    in view of the total weight of the oxidizer phase composition,
  2. An explosive composition according to claim 1, wherein the chemically processed renewable oil is chosen from bio-diesel, recycled vegetable oil, recycled animal fat, a hydrotreated renewable oil, or a mixture of two or more of these.
  3. Explosive emulsion composition according to claim 1 or 2, wherein the explosive emulsion composition comprises between 85 wt.% and 95 wt.% oxidizer phase and between 5 wt.% and 15 wt.% organic phase, both in view of the total weight of the emulsion composition.
  4. Explosive composition according to any one of claims 1 to 3, wherein the fuel composition consists of
    - between 0 wt.% and 80 wt.% of one or more straight vegetable oils, and
    - between 20 wt.% and 100 wt.% of one or more chemically processed renewable oils,
    in view of the total weight of the fuel composition.
  5. Explosive composition according to any one of claims 1 to 4, wherein the fuel composition consists of
    - between 20 wt.% and 80 wt% of one or more straight vegetable oils, more in particular between 40 wt.% and 80°wt.% of one or more straight vegetable oils, and
    - between 20 wt.% and 80 wt.% of one or more chemically processed renewable oils, more in particular between 20 wt.% and 60 wt.% of one or more chemically processed renewable oils.
  6. Explosive composition according to any one of claims 1 to 4, wherein the fuel consists of 100 wt.% of one or more chemically processed renewable oils in view of the total weight of the fuel composition.
  7. Explosive composition according to any one of claims 1 to 6, wherein the oxidizer phase comprises between 40 wt.% and 80 wt.% of ammonium nitrate (AN) and between 5 wt.% and 50 wt.% of calcium nitrate (CN), sodium nitrate (SN) or a mixture thereof, particularly between 10 wt.% and 40 wt.% of CN, SN, or a mixture thereof, all in view of the total weight of the oxidizer phase composition.
  8. An explosive composition according to any one of claims 1 to 7, wherein the oxidizer phase comprises between 5 wt.% and 25 wt.% of water in view of the total weight of the oxidizer phase composition.
  9. An explosive composition according to any one of claims 1 to 8, wherein the one or more emulsifiers are present in an amount of between 0.5 wt.% and 5.0 wt.%, more in particular between 1.0 wt.% and 2.5 wt. %, in view of the total weight of the emulsion composition.
  10. An explosive composition according to any one of claims 1 to 9, wherein the one or more emulsifiers are from a renewable source.
  11. Explosive composition according to any one of claims 1 to 10, wherein the SVO is chosen from soybean oil, palm oil, rapeseed oil, canola oil, maize oil, corn oil, sunflower oil, ricin oil, coconut oil, jojoba oil, jatropha oil or a mixture thereof.
  12. Explosive emulsion composition according to any one claims 1 to 11, wherein the explosive emulsion comprises
    - between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
    • between 12 wt.% and 50 wt.% of one or more emulsifiers,
    • between 50 wt.% and 88 wt.% of a fuel composition,
    in view of total weight of the organic phase composition,
    in which the fuel composition consists of
    • between 5 wt.% and 100 wt.% of one or more chemically processed renewable oils, and
    • between 0 wt.% and 95 wt.% of one or more SVO's,
    in view of the total weight of the fuel composition, the total weight% of the different oils being 100, and
    - between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
    • between 40 wt.% and 80 wt.% AN, particularly between 40 wt.% and 70 wt.% AN,
    • between 5 wt.% and 50 wt.% CN and/or SN, in particular between 10 wt.% and 40 wt.% CN and/or SN, or between 10 wt.% and 40 wt.% CN, more in particular between 15 wt.% and 35 wt.% CN and/or SN or between 15 wt% and 35 wt% CN, and
    • between 5 wt.% and 25 wt.% water,
    in view of the total weight of the oxidizer composition.
  13. Explosive emulsion composition according to any one of claims 1 to 12, wherein the explosive emulsion comprises
    - between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
    • between 12 wt.% and 50 wt.% of one or more emulsifiers,
    • between 50 wt.% and 88 wt.% of a fuel composition,
    in view of total weight of the organic phase composition,
    in which the fuel composition consists of
    • between 20 wt.% and 80 wt.% of one or more chemically processed renewable oils, particularly between 20 wt.% and 60 wt.% of one or more chemically processed renewable oils and
    • between 20 wt.% and 80 wt.% of one or more SVOs, particularly between 40 wt.% and 80 wt.% of one or more SVOs
    in view of the total weight of the fuel composition, the total weight% of
    the different oils being 100, and
    - between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
    • between 40 wt.% and 75 wt.% AN, particularly between 40 wt.% and 70 wt.% AN,
    • between 15 wt.% and 50 wt.% CN and/or SN, in particular between 15 wt.% and 50 wt.% CN, more in particular between 20 wt.% and 40 wt.% CN and/or SN, more in particular between 20 wt.% and 40 wt.% of CN, and
    • between 5 wt.% and 25 wt.% water, particularly between 10 wt% and 20 wt.% water
    in view of the total weight of the oxidizer composition.
  14. Explosive emulsion composition according to any one of claims 1 to 12, wherein the explosive emulsion comprises
    - between 5 wt.% and 20 wt.% of an organic phase, more in particular between 5 wt.% and 15 wt.% of an organic phase, in view of the total weight of the emulsion composition, the organic phase comprising
    • between 12 wt.% and 50 wt.% of one or more emulsifiers,
    • between 50 wt.% and 88 wt.% of a fuel composition,
    in view of total weight of the organic phase composition,
    in which the fuel composition consists of 100 wt.% of one or more chemically processed renewable oils in view of the total weight of the fuel composition.
    - between 80 wt.% and 95 wt.% of an oxidizer phase, more in particular between 85 wt.% and 95 wt.% of an oxidizer phase, in view of the total weight of the emulsion composition, the aqueous oxidizer phase comprising
    • between 40 wt.% and 80 wt.% AN, in particular between 40 wt.% and 75 wt.% AN,
    • between 5 wt.% and 50 wt.% CN and/or SN, in particular between 10 wt.% and 40 wt.% CN and/or SN or between 10 wt.% and 40 wt.% CN, more in particular between 15 wt.% and 35 wt.% CN and/or SN or between 15 wt.% and 35 wt.% CN, and
    • between 5 wt.% and 25 wt.% water,
    in view of the total weight of the oxidizer composition.
  15. Explosive composition according to any one of the preceding claims, wherein the composition has a viscosity of between 10 000 and 200 000 cP measured with a Brookfield viscometer with spindle size 7 at a frequency of 20 rpm.
EP21161190.0A 2021-03-08 2021-03-08 Emulsion-type explosives of the water-in-oil type Withdrawn EP4056544A1 (en)

Priority Applications (7)

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EP21161190.0A EP4056544A1 (en) 2021-03-08 2021-03-08 Emulsion-type explosives of the water-in-oil type
CA3207404A CA3207404A1 (en) 2021-03-08 2022-03-08 Emulsion-type explosives of the water-in-oil type
US18/280,526 US20240076247A1 (en) 2021-03-08 2022-03-08 Emulsion-type explosives of the water-in-oil type
PCT/EP2022/055786 WO2022189372A1 (en) 2021-03-08 2022-03-08 Emulsion-type explosives of the water-in-oil type
EP22711939.3A EP4305008A1 (en) 2021-03-08 2022-03-08 Emulsion-type explosives of the water-in-oil type
AU2022235178A AU2022235178A1 (en) 2021-03-08 2022-03-08 Emulsion-type explosives of the water-in-oil type
BR112023017284A BR112023017284A2 (en) 2021-03-08 2022-03-08 Water-in-oil emulsion type explosives

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Citations (6)

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WO2001023326A1 (en) * 1999-09-28 2001-04-05 Bulk Mining Explosives (Pty.) Ltd. Blasting cartridges
DE10208317A1 (en) * 2001-02-27 2002-09-05 Dynaenergetics Gmbh & Co Kg Biodegradable emulsion explosive contains aqueous phase of organic oxidant and external phase of organic fuel, particularly plant oil
US20040055678A1 (en) * 2002-09-23 2004-03-25 Dyno Nobel Inc. Emulsion phase having improved stability
WO2010071946A1 (en) * 2008-12-24 2010-07-01 Orica Explosives Technology Pty Ltd Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsions
US9458066B2 (en) * 2010-08-13 2016-10-04 Orica International Pte Ltd Process for the production of intermediate emulsions for use in emulsion explosives
US10065898B1 (en) * 2017-09-21 2018-09-04 Exsa S.A. Bulk pumpable granulated explosive mix

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Publication number Priority date Publication date Assignee Title
AR241896A1 (en) * 1982-05-12 1993-01-29 Union Explosivos Rio Tinto A compound and procedure for obtaining explosives in emulsion.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023326A1 (en) * 1999-09-28 2001-04-05 Bulk Mining Explosives (Pty.) Ltd. Blasting cartridges
DE10208317A1 (en) * 2001-02-27 2002-09-05 Dynaenergetics Gmbh & Co Kg Biodegradable emulsion explosive contains aqueous phase of organic oxidant and external phase of organic fuel, particularly plant oil
US20040055678A1 (en) * 2002-09-23 2004-03-25 Dyno Nobel Inc. Emulsion phase having improved stability
WO2010071946A1 (en) * 2008-12-24 2010-07-01 Orica Explosives Technology Pty Ltd Amine reacted alpha, beta-unsaturated carbonyl compound thickened explosive emulsions
US9458066B2 (en) * 2010-08-13 2016-10-04 Orica International Pte Ltd Process for the production of intermediate emulsions for use in emulsion explosives
US10065898B1 (en) * 2017-09-21 2018-09-04 Exsa S.A. Bulk pumpable granulated explosive mix

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WO2022189372A1 (en) 2022-09-15
CA3207404A1 (en) 2022-09-15
US20240076247A1 (en) 2024-03-07
BR112023017284A2 (en) 2023-09-26
AU2022235178A1 (en) 2023-09-07

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