EP4056545A1 - Explosifs à émulsion de type eau dans huile - Google Patents

Explosifs à émulsion de type eau dans huile Download PDF

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Publication number
EP4056545A1
EP4056545A1 EP21161191.8A EP21161191A EP4056545A1 EP 4056545 A1 EP4056545 A1 EP 4056545A1 EP 21161191 A EP21161191 A EP 21161191A EP 4056545 A1 EP4056545 A1 EP 4056545A1
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EP
European Patent Office
Prior art keywords
composition
total weight
view
organic phase
oil
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.)
Withdrawn
Application number
EP21161191.8A
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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
Original Assignee
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 EP21161191.8A priority Critical patent/EP4056545A1/fr
Priority to AU2022233004A priority patent/AU2022233004A1/en
Priority to BR112023017507A priority patent/BR112023017507A2/pt
Priority to EP22711522.7A priority patent/EP4305007A1/fr
Priority to CA3207422A priority patent/CA3207422A1/fr
Priority to PCT/EP2022/055797 priority patent/WO2022189381A1/fr
Publication of EP4056545A1 publication Critical patent/EP4056545A1/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Withdrawn legal-status Critical Current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

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.
  • the organic phase thus forms a thin film around the droplets of the oxidizer phase.
  • Typical examples of commonly used 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
  • Patent documents often mention the use of vegetable oil as a trivial raw material to be used in explosive emulsions.
  • a renewable oil such as vegetable oil
  • This observation may be attributed to the different chemistry and properties of the non-renewable oils compared to renewable oils.
  • the inventors have observed that monosalt emulsions with ammonium nitrate in the oxidizer phase and a fuel comprising vegetable oil in the organic phase does not form a stable emulsion.
  • stable explosive emulsions comprising renewable oils, such as vegetable oil, as fuel can be obtained by adding a suitable amount of one or more secondary salts.
  • stable explosive emulsions with viscosities similar to explosive emulsions based on non-renewable fuel oils were also obtained with a fuel comprising both a bio-fuel, such as a hydrotreated vegetable oil (HVO), and a straight vegetable oil, when using a higher amount of one or more secondary salts in the oxidizer phase.
  • a bio-fuel such as a hydrotreated vegetable oil (HVO)
  • HVO hydrotreated vegetable oil
  • an explosive emulsion composition of the water-in-oil type comprising
  • the explosive emulsion 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 consists of between 0 wt.% and 30 wt.% of one or more non-renewable oils and between 70 wt.% and 100 wt.% of one or more renewable oils in view of the total weight of the fuel composition.
  • the fuel more in particular consists of 100 wt.% of one or more 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 10 wt.% and 50 wt.% of calcium nitrate (CN), in particular between 15 wt.% and 40 wt.% CN, and optionally one or more other secondary nitrate salts, all in view of the total weight of the oxidizer phase composition.
  • AN ammonium nitrate
  • CN calcium 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 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 total emulsion composition.
  • the one or more emulsifiers are added to prevent separation of the different phases and thus to obtain a stable emulsion.
  • the one or more emulsifiers are from a renewable source.
  • a fully green explosive emulsion is obtained.
  • the one or more renewable oils in the explosive composition according to the present disclosure may be chosen from
  • the straight vegetable oil may be chosen from chosen from soybean oil, palm oil, rapeseed oil, maize oil, corn oil, sunflower oil, ricin oil, coconut oil, jojoba oil, j atropha oil or a mixture thereof.
  • the explosive emulsion composition 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.
  • the present disclosure provides stable, green explosive emulsions in which most or even all of the non-renewable oil in the organic phase as used in traditional explosive emulsions is replaced by one or more renewable oils.
  • the viscosity of the explosive emulsions according to the present disclosure can be adapted to be used in different applications.
  • the explosive emulsion composition of the present disclosure generally 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.% of an oxidizer phase and between 5 wt.% and 15 wt.% of an organic phase in view of the total weight of the emulsion composition.
  • the organic phase of the explosive emulsion composition according to the present disclosure generally comprises between 1 wt.% and 8 wt.%, more in particular between 2 wt.% and 5 wt.%, even more in particular between 3 wt.% and 4.5 wt.% of a fuel composition, based on the total weight of the emulsion composition.
  • the fuel composition as envisaged herein consists of between 0 wt.% and 50 wt.% of one or more non-renewable oils (meaning a single non-renewable oil or a mixture of different non-renewable oils), and between 50 wt.% and 100 wt.% of one or more renewable oils (meaning a single renewable oil or a mixture of different renewable oils), in view of the total weight of the fuel composition.
  • non-renewable oils meaning a single non-renewable oil or a mixture of different non-renewable oils
  • renewable oils meaning a single renewable oil or a mixture of different renewable oils
  • the fuel composition consists of between 0 wt.% and 40 wt.%, between 0 wt.% and 30 wt.%, between 0 wt.% and between 20 wt.% or between 0 wt.% and 10 wt.% of one or more non-renewable oils and between 60 wt.% and 100 wt.%, between 70 wt.% and 100 wt.%, between 80°wt.% and 100 wt.% or between 90 wt.% and 100 wt.% (respectively, of one or more renewable oils, in view of the total weight of the fuel composition. It is understood that the total weight% of the different oils needs to be equal to 100.
  • the non-renewable oil is diesel.
  • the fuel composition consists of 100 wt.% of one or more renewable oils in view of the total weight of the fuel composition. More in particular, the fuel composition consists of 0 wt.% and 100 wt.% of one or more biofuels, more in particular one or more hydrotreated renewable oils (HVO), and between 0 wt.% and 100 wt.% of one or more straight vegetable oils (SVO).
  • HVO hydrotreated renewable oils
  • SVO straight vegetable oils
  • 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 biofuels, 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 biofuels, in particular HVO, and the one or more SVO equals 100.
  • HVO hydrotreated renewable oils
  • the one or more renewable oils can be chosen from a straight vegetable oil (SVO), a straight animal fat, a biofuel comprising bio-diesel, recycled vegetable oil, recycled animal fat or a hydrotreated renewable oil. Also a mixture of two of these can be applied.
  • SVO straight vegetable oil
  • a straight animal fat a biofuel comprising bio-diesel
  • recycled vegetable oil recycled animal fat or a hydrotreated renewable oil.
  • a mixture of two of these can be applied.
  • 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.
  • 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, rice bran oil, linseed oil, algae 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.
  • Bio-fuels are any type of transportation fuel that is derived from biomass including plant or algae material or animal waste. Bio-fuels are renewable.
  • 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 by a chemical process called esterification. Biodiesel has a lower boiling point and viscosity than SVO. Pure biodiesel is marketed as B100 at the gasoline stations.
  • Recycled vegetable oil or recycled animal fat originates from cooking such as frying or other industrial processes without intermediate processing.
  • Hydrotreated renewable oils also referred to as hydrotreated vegetable oils or HVO
  • hydrotreated renewable or vegetable oils are paraffinic bio-based liquid oils originating from many kinds of vegetable oils, such as rapeseed, sunflower, soybean, 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 oxidizer phase of the explosive emulsion composition of the present invention comprises next to ammonium nitrate (AN) as an oxidizer salt also a suitable amount of one or more of a secondary nitrate salt such as an alkaline earth metal nitrate salt, in particular calcium nitrate (CN), and/or an alkali metal nitrate salt, in particular sodium nitrate (SN).
  • AN ammonium nitrate
  • CN calcium nitrate
  • SN alkali metal nitrate salt
  • the oxidizer phase of the explosive emulsion composition according to the present disclosure generally comprises at least 40 wt.% of AN, particularly between 40 wt% and 80 wt% AN, in view of the total weight of the oxidizer phase composition.
  • the oxidizer phase comprises at least 40 wt.% of AN, particularly between 40 wt% and 80 wt.% of AN, and at least 10 wt.%, particularly at least 15 wt% of CN, and, optionally, one or more other secondary nitrate salts, with wt.% in view of the total weight of the oxidizer phase composition.
  • the oxidizer phase can comprise between 40 wt.% to 80 wt.% AN or between 40 wt.% and 75 wt.% AN and between 10 wt.% and 50 wt.%, particularly between 15 wt.% and 50 wt.%, more particularly between 15 wt.% and 40 wt.% of calcium nitrate, and, optionally, one or more other secondary nitrate salts, such as sodium nitrate, with wt.% in view of the total weight of the oxidizer phase composition.
  • the use of calcium nitrate as secondary nitrate salt in combination with a fuel composition comprising a vegetable oil allows to obtain stable explosive emulsion compositions with a suitable viscosity range for multiple applications.
  • the oxidizer phase comprises at least 40 wt.% of AN, particularly between 40 wt% and 75 wt.% of AN, and at least 20 wt.% CN, SN, or a mixture thereof, particularly between 20 wt% and 50 wt.% CN, SN, or a mixture thereof, more particularly between 20 wt% and 40 wt.% CN, SN, or a mixture thereof, even more particularly between 20 wt.% and 35°wt.% or between 25 wt.% and 35 wt.% CN, SN or a mixture thereof, with wt/% in view of the total weight of the oxidizer phase composition.
  • an explosive emulsion composition according to the present disclosure comprising SN is suitable for use in packaged emulsion (cartridge) applications.
  • the oxidizer phase of the explosive emulsion composition according to the present disclosure further typically comprises between 5 wt.% and 25 wt.% or between 7 wt.% and 25 wt.% of (de-ionized) water in view of the total weight of the oxidizer composition. More in particular, the amount of water present in the oxidizer phase is between 10 wt.% and 20 wt.%, such as between 12 wt.% and 17 wt.% or about 15 wt.%.
  • 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.
  • emulsifiers include, but are not limited to 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 may be chosen from the wide range of emulsifiers known in the art to be suitable for the preparation of explosive emulsion compositions.
  • 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.
  • emulsifiers meaning a single emulsifier or a mixture of different emulsifiers
  • 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.%.
  • the explosive emulsion composition according to the present disclosure comprises
  • the explosive emulsion according to the present disclosure comprises
  • the explosive emulsion composition according to the present disclosure comprises
  • the explosive emulsion composition according to the present disclosure comprises
  • the explosive emulsion composition according to the present disclosure comprises
  • the explosive emulsion composition according to the present disclosure comprises
  • Adding a biofuel such as a hydrotreated renewable oil lowers the viscosity of the composition.
  • the viscosity of the composition can be adjusted. This is particular the case when using CN as secondary nitrate salt.
  • the explosive emulsion composition typically has a viscosity of between 10 000 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.
  • samples 1 to 10 are samples not according to the present disclosure, while samples 11 to 19 are samples according to the present disclosure.
  • Table 1 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 80.8 0.0 0.0 14.3 Soybean 3.7 Anfomul 1.2 Sample 2 80.9 0.0 0.0 14.2 Soybean 3.7 Lubrizol 1.2 Sample 3 80.9 0.0 0.0 14.2 Soybean 3.7 C615 1.2 Sample 4 80.7 0.0 0.0 14.3 Rapeseed 3.8 Anfomul 1.2 Sample 5 80.9 0.0 0.0 14.3 Rapeseed 3.6 Lubrizol 1.2 Sample 6 80.8 0.0 0.0 14.3 Rapeseed 3.7 C615 1.2 Sample 7 77.1 0.0 0.0 18.1 Soybean + diesel 50/50 3.6 Lubrizol 1.2 Sample 8 75.3 0.0
  • the viscosity as mentioned in Table 3 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:
EP21161191.8A 2021-03-08 2021-03-08 Explosifs à émulsion de type eau dans huile Withdrawn EP4056545A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP21161191.8A EP4056545A1 (fr) 2021-03-08 2021-03-08 Explosifs à émulsion de type eau dans huile
AU2022233004A AU2022233004A1 (en) 2021-03-08 2022-03-08 Emulsion-type explosives of the water-in-oil type
BR112023017507A BR112023017507A2 (pt) 2021-03-08 2022-03-08 Explosivos do tipo emulsão do tipo água em óleo
EP22711522.7A EP4305007A1 (fr) 2021-03-08 2022-03-08 Explosifs à émulsion du type eau dans huile
CA3207422A CA3207422A1 (fr) 2021-03-08 2022-03-08 Explosifs a emulsion du type eau dans huile
PCT/EP2022/055797 WO2022189381A1 (fr) 2021-03-08 2022-03-08 Explosifs à émulsion du type eau dans huile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21161191.8A EP4056545A1 (fr) 2021-03-08 2021-03-08 Explosifs à émulsion de type eau dans huile

Publications (1)

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EP4056545A1 true EP4056545A1 (fr) 2022-09-14

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EP21161191.8A Withdrawn EP4056545A1 (fr) 2021-03-08 2021-03-08 Explosifs à émulsion de type eau dans huile
EP22711522.7A Pending EP4305007A1 (fr) 2021-03-08 2022-03-08 Explosifs à émulsion du type eau dans huile

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EP22711522.7A Pending EP4305007A1 (fr) 2021-03-08 2022-03-08 Explosifs à émulsion du type eau dans huile

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EP (2) EP4056545A1 (fr)
AU (1) AU2022233004A1 (fr)
BR (1) BR112023017507A2 (fr)
CA (1) CA3207422A1 (fr)
WO (1) WO2022189381A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931110A (en) * 1989-03-03 1990-06-05 Ireco Incorporated Emulsion explosives containing a polymeric emulsifier
US5322576A (en) * 1991-08-21 1994-06-21 Ici Canada Inc. Vegetable oil modified explosive
DE10208317A1 (de) * 2001-02-27 2002-09-05 Dynaenergetics Gmbh & Co Kg Biologisch abbaubarer Emulsionssprengstoff
US20040020573A1 (en) * 2000-10-04 2004-02-05 Palmer Anthony Martin Emulsion explosive

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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931110A (en) * 1989-03-03 1990-06-05 Ireco Incorporated Emulsion explosives containing a polymeric emulsifier
US5322576A (en) * 1991-08-21 1994-06-21 Ici Canada Inc. Vegetable oil modified explosive
US20040020573A1 (en) * 2000-10-04 2004-02-05 Palmer Anthony Martin Emulsion explosive
DE10208317A1 (de) * 2001-02-27 2002-09-05 Dynaenergetics Gmbh & Co Kg Biologisch abbaubarer Emulsionssprengstoff

Also Published As

Publication number Publication date
EP4305007A1 (fr) 2024-01-17
CA3207422A1 (fr) 2022-09-15
WO2022189381A1 (fr) 2022-09-15
BR112023017507A2 (pt) 2023-10-10
AU2022233004A1 (en) 2023-09-07

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