EP4056544A1 - Explosifs de type émulsion du type eau dans l'huile - Google Patents

Explosifs de type émulsion du type eau dans l'huile 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
European Patent Office
Prior art keywords
composition
total weight
view
oil
phase
Prior art date
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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Application number
EP21161190.0A
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German (de)
English (en)
Inventor
Francois Ledoux
Petr CHLADEK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yara International ASA
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Yara International ASA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yara International ASA filed Critical Yara International ASA
Priority to EP21161190.0A priority Critical patent/EP4056544A1/fr
Priority to PCT/EP2022/055786 priority patent/WO2022189372A1/fr
Priority to BR112023017284A priority patent/BR112023017284A2/pt
Priority to US18/280,526 priority patent/US20240076247A1/en
Priority to AU2022235178A priority patent/AU2022235178A1/en
Priority to EP22711939.3A priority patent/EP4305008A1/fr
Priority to CA3207404A priority patent/CA3207404A1/fr
Publication of EP4056544A1 publication Critical patent/EP4056544A1/fr
Withdrawn legal-status Critical Current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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Colloid Chemistry (AREA)
  • Edible Oils And Fats (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP21161190.0A 2021-03-08 2021-03-08 Explosifs de type émulsion du type eau dans l'huile Withdrawn EP4056544A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP21161190.0A EP4056544A1 (fr) 2021-03-08 2021-03-08 Explosifs de type émulsion du type eau dans l'huile
PCT/EP2022/055786 WO2022189372A1 (fr) 2021-03-08 2022-03-08 Explosifs de type émulsion du type eau dans huile
BR112023017284A BR112023017284A2 (pt) 2021-03-08 2022-03-08 Explosivos do tipo emulsão do tipo água em óleo
US18/280,526 US20240076247A1 (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
EP22711939.3A EP4305008A1 (fr) 2021-03-08 2022-03-08 Explosifs de type émulsion du type eau dans huile
CA3207404A CA3207404A1 (fr) 2021-03-08 2022-03-08 Explosifs de type emulsion du type eau dans huile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21161190.0A EP4056544A1 (fr) 2021-03-08 2021-03-08 Explosifs de type émulsion du type eau dans l'huile

Publications (1)

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EP4056544A1 true EP4056544A1 (fr) 2022-09-14

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EP21161190.0A Withdrawn EP4056544A1 (fr) 2021-03-08 2021-03-08 Explosifs de type émulsion du type eau dans l'huile
EP22711939.3A Pending EP4305008A1 (fr) 2021-03-08 2022-03-08 Explosifs de type émulsion du type eau dans huile

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EP22711939.3A Pending EP4305008A1 (fr) 2021-03-08 2022-03-08 Explosifs de type émulsion du type eau dans huile

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US (1) US20240076247A1 (fr)
EP (2) EP4056544A1 (fr)
AU (1) AU2022235178A1 (fr)
BR (1) BR112023017284A2 (fr)
CA (1) CA3207404A1 (fr)
WO (1) WO2022189372A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023326A1 (fr) * 1999-09-28 2001-04-05 Bulk Mining Explosives (Pty.) Ltd. Cartouches explosives
DE10208317A1 (de) * 2001-02-27 2002-09-05 Dynaenergetics Gmbh & Co Kg Biologisch abbaubarer Emulsionssprengstoff
US20040055678A1 (en) * 2002-09-23 2004-03-25 Dyno Nobel Inc. Emulsion phase having improved stability
WO2010071946A1 (fr) * 2008-12-24 2010-07-01 Orica Explosives Technology Pty Ltd ÉMULSIONS EXPLOSIVES ÉPAISSIES PAR UN COMPOSÉ CARBONYLE α,β-INSATURÉ AYANT RÉAGI AVEC UNE AMINE
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR241896A1 (es) * 1982-05-12 1993-01-29 Union Explosivos Rio Tinto Composicion y procedimiento para la obtencion de explosivos en emulsion.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023326A1 (fr) * 1999-09-28 2001-04-05 Bulk Mining Explosives (Pty.) Ltd. Cartouches explosives
DE10208317A1 (de) * 2001-02-27 2002-09-05 Dynaenergetics Gmbh & Co Kg Biologisch abbaubarer Emulsionssprengstoff
US20040055678A1 (en) * 2002-09-23 2004-03-25 Dyno Nobel Inc. Emulsion phase having improved stability
WO2010071946A1 (fr) * 2008-12-24 2010-07-01 Orica Explosives Technology Pty Ltd ÉMULSIONS EXPLOSIVES ÉPAISSIES PAR UN COMPOSÉ CARBONYLE α,β-INSATURÉ AYANT RÉAGI AVEC UNE AMINE
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

Also Published As

Publication number Publication date
CA3207404A1 (fr) 2022-09-15
BR112023017284A2 (pt) 2023-09-26
EP4305008A1 (fr) 2024-01-17
WO2022189372A1 (fr) 2022-09-15
US20240076247A1 (en) 2024-03-07
AU2022235178A1 (en) 2023-09-07

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