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WO2003061384A1 - Formulation de fumigant - Google Patents

Formulation de fumigant Download PDF

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Publication number
WO2003061384A1
WO2003061384A1 PCT/AU2003/000087 AU0300087W WO03061384A1 WO 2003061384 A1 WO2003061384 A1 WO 2003061384A1 AU 0300087 W AU0300087 W AU 0300087W WO 03061384 A1 WO03061384 A1 WO 03061384A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethyl formate
fumigant
diluent
efficacy
flammable
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.)
Ceased
Application number
PCT/AU2003/000087
Other languages
English (en)
Inventor
Robert Francis Ryan
Simon Robert Bishop
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.)
BOC Ltd Australia
Original Assignee
BOC Gases Australia Ltd
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 BOC Gases Australia Ltd filed Critical BOC Gases Australia Ltd
Priority to AU2003201533A priority Critical patent/AU2003201533B2/en
Priority to NZ534903A priority patent/NZ534903A/en
Publication of WO2003061384A1 publication Critical patent/WO2003061384A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof

Definitions

  • the present invention relates to a non-flammable fumigant formulation comprising ethyl formate as the active ingredient.
  • Ethyl formate [EtF: C 3 H 6 O 2 ] is used as a flavour essence and is a low risk GRAS (Generally Regarded As Safe) food additive. It is used as a flavour in lemonade and essences for the manufacture of rum and arrac.
  • Ethyl formate is made by reacting ethanol with formic acid. Ethyl formate is hydrolysed/metabolised back to these naturally occurring chemicals when used to fumigate commodities and accordingly, would not persist in the environment. "Formic acid and ethanol are widely distributed in the plant and animal kingdom. These two hydrolysis products of ethyl formate are present in the atmosphere in very large amounts, and ethyl formate is also present in some samples. It is therefore difficult to see the use of ethyl formate as a fumigant contributing to global atmosphere problems" (PostHarvest News and Information 1999 Vol.10, No 1, pp 7N-12).
  • ethyl formate is viewed as a real alternative to the well-known fumigant methyl bromide, now listed on the Montreal Protocol as an ozone depletory and is currently being phased out. Methyl bromide will not be available after 2005 in developed countries and 2015 in developing countries.
  • Ethyl formate has also been investigated by various parties as an insecticide. Ethyl formate has been used in the protection of tobacco, cereals and dried fruits and is currently used in large volumes in the treatment of dried grapes.
  • ethyl formate works quickly and is therefore useful for rapid disinfestation in grain storage applications and fruit and vegetable treatment.
  • the naturally occurring ethyl formate achieves a residue-free status since it decomposes on or is easily aerated from the treated product.
  • Ethyl formate is quite volatile having a boiling point of 54°C, a vapour pressure of 194 mm Hg and a low flash point. Moreover, ethyl formate is a highly flammable liquid in its natural state, posing a dangerous fire and explosion risk. Due to these flammability and associated handling issues the potential for ethyl formate as a commonly used fumigant has not yet been realised.
  • the present invention provides a fumigant comprising ethyl formate combined with a diluent in a quantity sufficient to render the fumigant nonflammable while at least retaining the efficacy of the ethyl formate.
  • the diluent is present in a quantity sufficient to render the fumigant non-flammable while retaining the efficacy of the ethyl formate. In another embodiment, the diluent is present in a quantity sufficient to render the fumigant non- flammable while synergistically enhancing the efficacy of the ethyl formate.
  • a diluent would decrease the efficacy of an active ingredient, such as ethyl formate, in a fumigant.
  • a particularly preferred diluent is carbon dioxide. Hydrofluorcarbons could also fill this role however they are much more expensive than liquid CO .
  • the CO can act as a diluent, solvent and propellant.
  • a nonflammable fumigant can be provided for safe use on so called 'organic' produce.
  • the fumigant can be distributed as an aerosol or vapour/fog over the material to be treated.
  • the fumigant allows for disinfestations of food and other commodities and provides for suitable insecticide/pesticide treatment of 'organic' produce without affecting its 'organic' status.
  • efficacy refers to efficacy of the fumigant as would be understood by persons skilled in the relevant art and includes biocidal, insecticidal and fungicidal efficacy.
  • the invention may be used in a wide variety of environments including quarantine disinfestations of imported produce, horticulture, treatment of domestic food commodities, grain storage etc.
  • the ethyl formate and the diluent are provided separately.
  • each of the components of the fumigant formulation of the present invention may be provided to the area being fumigated separately.
  • the area may first be filled with the gaseous diluent with the ethyl formate being added later.
  • the ethyl formate and the diluent are provided in a premixed form.
  • the fumigant is prepared and packaged off site and later transported to the area requiring fumigation.
  • the proportion of ethyl formate vapour in carbon dioxide gas is up to about 25.0 % v/v, more preferably up to about 15.0 % v/v, more preferably up to about 12.5 % v/v. Most preferably, the proportion is about 10.8 % v/v.
  • the present invention provide a packaged fumigant product comprising a pressurised vessel containing a fumigant formulation of ethyl formate combined with a diluent in a quantity sufficient to render the fumigant non-flammable upon release from the pressurised vessel while at least retaining the efficacy of the ethyl formate.
  • the diluent is carbon dioxide.
  • the formulation comprises up to about 22 wt %, more preferably between about 10.0 wt % to about 20.0 wt % of ethyl formate in liquid carbon dioxide. Most preferably, the formulation comprises about 16.7 wt % of ethyl formate in liquid carbon dioxide.
  • the vessels used to package the fumigant formulation of the present invention may be any suitable shape and size.
  • the vessel could be a relatively small gas cylinder suitable for domestic use or alternatively, a larger pressurised vessel for industrial applications.
  • the present invention provides a method of producing a fumigant comprising the step of combining ethyl formate and a diluent wherein the amount of ethyl formate and diluent are selected to render the fumigant non-flammable while at least retaining the efficacy of the ethyl formate.
  • the present invention provides a method of fumigating a volume in need thereof comprising filling the volume with a non-flammable fumigant comprising ethyl formate combined with a diluent in a quantity sufficient to render the fumigant non-flammable while at least retaining the efficacy of the ethyl formate.
  • the volume may be an enclosed space containing for example a stored commodity, or alternatively a domestic area.
  • the present invention provides a method of rendering an ethyl formate fumigant non-flammable comprising the step of combining the ethyl formate with a diluent in a quantity sufficient to render the fumigant non-flammable while at least retaining the efficacy of the ethyl formate.
  • the present invention provides a method of enhancing the efficacy of ethyl formate comprising combining the ethyl formate with a synergistically effective amount of diluent.
  • the diluent is added in a quantity sufficient to render the resultant fumigant non-flammable.
  • the amount of fumigant that is provided to the volume being fumigated varies depending on the level of infestation and the types of species present.
  • the amount of fumigant required is then calculated using a combination of fumigant concentration and exposure time. In general a lower concentration requires an increased duration and a higher concentration is suitable for shorter durations. Concentrations of ethyl formate may range from a few g/m 3 up to over 90 g/m 3 .
  • Figure 1 Schematic representation of the test developed for assessing the flammability of ethyl formate.
  • Figure 2. Graph showing the theoretical vapour concentrations of ethyl formate vs measured vapour concentrations of ethyl formate for the flammability test shown in Figure 1.
  • Figure 3. Calibration plot for the flammability test of Figure 1.
  • Figure 4 A plot of the limits of flammability for ethyl formate in carbon dioxide/air mixtures.
  • Figure 5 The efficacy of a fumigant comprising ethyl formate alone with respect to three insect species.
  • Figure 6. Bar graph showing the effect of varying amounts of carbon dioxide on the toxicity of ethyl formate.
  • Figure 7. Bar graph showing the effect of the fumigant according to a first embodiment on a single insect species at different stages in its life cycle.
  • Figure 8 A Diagrammatic representation of the set up of Room #1 (tested with ethyl formate alone)
  • Figure 8B Diagrammatic representation of the set up of Room #5 (tested with combination of ethyl formate and carbon dioxide)
  • Figure 9 Table showing the varying concentrations of ethyl formate at the sample sites in Room # 1.
  • Figure 10. Table showing the varying concentrations of ethyl formate at the sample sites in Room # 5.
  • Figure 11. Table showing the insects counts in Rooms #1 and #5 in the week after fumigation.
  • Figure 12. Table showing the mortality rates per week after fumigation for Room #1.
  • Figure 13. Table showing the mortality rates per week after fumigation for Room #5.
  • Flammability of Ethyl Formate/Diluent Fumigant As may be known to those skilled in the art, fuel vapours and gases are only flammable or explosable at concentrations between their Lower (LEL) and Upper (UEL) Explosability Limits. These limits are normally determined by mixing known proportions of a fuel with fresh air, containing approximately 21% v/v oxygen. The mixtures are then tested for propagation of flame after exposure to a suitable ignition source.
  • Ethyl formate flammability test set up A test set up was developed as shown in Figure 1. The set up allows continuous metering and mixing of known proportions of ethyl formate vapour, carbon dioxide and air. The set up comprises sources of compressed air 1 and carbon dioxide 2.
  • Wosthoff positive displacement gas mixing pump 3 provides a convenient method of proportioning the carbon dioxide with air and pumping the resulting mixture through the test set up.
  • a liquid syringe pump 4 is provided downstream of the pump 3. Liquid ethyl formate is dispensed via this syringe at a constant flow rate.
  • a heat exchanger 5 is provided downstream of the liquid syringe pump.
  • the heat exchanger is a coiled length of aluminium tubing 6 placed in a water bath at a temperature approximately 10°C above the boiling point of the ethyl formate. This produces ethyl formate vapour.
  • the unmixed ethyl formate vapour and CO /air mixture then passes to a static mixer 7.
  • the resultant mixed fumigant leaves the static mixture 7 and is diverted via valve 8 to a paramagnetic oxygen analyser 9 and an ignition tube 10.
  • a spark is provided by an ignition source 11 and the fumigant gas passed across this spark to determine the flammability/flame propagation.
  • ERANOLTM is the ORICA Chemnet veteran insecticide currently registered by the Australian National Registration Authority - Approval No: 48346/1 and containing 98 w/w % ethyl formate.
  • Flammability tests were then conducted by introduction of a known flow of ethyl formate vapour into the known flow of the Wosthoff pump 3. At least 7 minutes were allowed to elapse for each adjustment of the syringe pump flow and any ignition tests to ensure constant concentrations.
  • the known LEL and UEL of ethyl formate is 2.8 and 16% v/v respectively. After establishing that the test set up could be used reliably for concentrations up to 20% ethyl formate v/v, tests where conducted to find the flammability limits. The lower flammability limit determined by the test is between 3.1 and 3.6% v/v.
  • the literature value is around 3.0 % v/v.
  • the upper flammability limit as determined experimentally was between 15.0 and 15.7% v/v.
  • the literature value being 16% v/v. While the test set up over estimated the LEL and under estimated the UEL, it is believed this is due to the small size of the flow ignition tube or amount of ignition energy. In any case, the differences are not great.
  • a non-flammable fumigant may be produced by combining the usually flammable active chemical ethyl formate with a diluent such as carbon dioxide.
  • a diluent such as carbon dioxide.
  • carbon dioxide may enhance the toxicity of ethyl formate to insects, particularly adult insects.
  • carbon dioxide has been shown to improve the distribution and penetration of the ethyl formate.
  • Example 1 Efficacy of ethyl formate in three insect species of stored product pest.
  • Example 2 The effect of CO? on ethyl formate toxicity in three species of stored product pest.
  • the effect of carbon dioxide on ethyl formate toxicity was investigated in three species of stored product pest: the flour beetle (Tribolium castaneum), rice weevil (Sitophilus oryzae) and the lesser grain borer (Rhyzopertha dominica).
  • the mortality in T. castaneum due to ethyl formate increased from 3 to 99% in the presence of fumigant and 5% carbon dioxide, as shown in Table 1.
  • the toxicity of the fumigant mixture was also investigated in immature stages of T. castaneum.
  • the addition of 5% carbon dioxide to ethyl formate enhanced the toxicity in immature insects but not as significantly as the enhancement of toxicity in adult insects as shown below in Table 2.
  • Example 5 The effect of CO? on ethyl formate toxicity on mixed stage cultures of
  • a further test was conducted in order to more fully investigate the potential for enhanced activity of a fumigant comprising a mixture of ethyl formate and carbon dioxide as opposed to ethyl formate alone.
  • the activity of a fumigant comprising ethyl formate and 5% CO 2 was assessed against mixed stage cultures of the most tolerant insect species, usually Sitophilus oryzae. While adult T. castaneum were the most tolerant of the three species towards ethyl formate (as shown in Table 1), juvenile stages of the internally developing
  • S. oryzae have been shown in related research to be the most tolerant overall. Therefore, S. oryzae was used to determine the effect of carbon dioxide on ethyl formate toxicity in mixed age cultures.
  • a mixed age S. oryzae culture was fumigated with ethyl formate or a mixture of ethyl formate and 5% carbon dioxide, and the number of adults emerging from the grain over a 6 week period after treatment were removed and counted.
  • the concentration of ethyl formate selected for the fumigation was 33 g m "3 .
  • the number of adults emerging from the treated grain was compared with the number from untreated mixed age cultures or 5% carbon dioxide treated.
  • Figure 7 shows the mean number of Sitophilus oryzae adult insects emerging after treatment of mixed age cultures with 33 g m "3 ethyl formate (EF) or EF plus 5% carbon dioxide for 24 h compared with control or 5% carbon dioxide treatment. The results are the mean emergence of duplicate samples.
  • EF ethyl formate
  • Example 6 Fumigation trials using a fumigant according to the present invention and in comparison to liquid ethyl formate. Experiments were conducted in order to compare the distribution and efficacy of a fumigant comprising ethyl formate alone and a fumigant comprising ethyl formate in combination with carbon dioxide.
  • Sample sites 1, 2, 3 and 4 are in room samples; sample sites 5 and 6 are in "buckets" or wire bins filled with bags of samples; and sample site 7 is in the middle of a bag of sorghum.
  • ERANOLTM 11 litres of ERANOLTM is equivalent to 9.922 kg of ethyl formate. This equates to 0.902 kg EtF/L
  • the concentration of ethyl formate at each sample site in each room was measured over the various time frames as shown in Figures 9 and 10.
  • the average concentration measured in Room #1 was 9.19g/m and the average concentration measured in Room #5 was 19.92 g/m 3 . Accordingly, the concentration of ethyl formate at all sample sites was more than double using a fumigant according to the invention.
  • insects tested in the seed rooms is shown below in Table 3.
  • the fumigant, packaged fumigant product, methods of producing a fumigant and methods of fumigation may be embodied in other forms without departing from the spirit or scope of the present invention.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Agronomy & Crop Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un fumigant comprenant du formiate d'éthyle comme agent actif combiné à un diluant en quantité suffisante de façon à rendre ledit fumigant ininflammable et, parallèlement, à au moins conserver l'efficacité de l'agent actif. L'invention concerne également des produits fumigant emballés, des procédés de production de fumigants et des procédés de fumigation.
PCT/AU2003/000087 2002-01-25 2003-01-28 Formulation de fumigant Ceased WO2003061384A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003201533A AU2003201533B2 (en) 2002-01-25 2003-01-28 Fumigant formulation
NZ534903A NZ534903A (en) 2002-01-25 2003-01-28 Non-flammable fumigant formulation of ethyl formate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPS0158A AUPS015802A0 (en) 2002-01-25 2002-01-25 Fumigant formulation
AUPS0158 2002-01-25

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WO2003061384A1 true WO2003061384A1 (fr) 2003-07-31

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WO (1) WO2003061384A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006066308A1 (fr) 2004-12-24 2006-06-29 Commonwealth Scientific And Industrial Research Organisation Compositions et procedes pesticides
WO2008009315A1 (fr) * 2006-07-20 2008-01-24 Shivat Limited Méthode de régulation d'une population d'animaux nuisibles
WO2016197202A1 (fr) * 2015-06-12 2016-12-15 Innovative Biosecurity Pty Ltd Formulation de fumigation et appareil de vaporisation
WO2018197047A1 (fr) 2017-04-24 2018-11-01 Linde Aktiengesellschaft Formulation de fumigant
WO2018232468A1 (fr) * 2017-06-23 2018-12-27 Universal Biosecurity Limited Appareil de vaporisation
AU2017228596B2 (en) * 2007-02-23 2019-05-16 Boc Limited Improved disinfestation method
CN109907065A (zh) * 2019-04-02 2019-06-21 贵州大学 一种防治烟草粉螟的熏蒸剂及其使用方法
EP3777531A1 (fr) 2019-08-12 2021-02-17 Linde GmbH Procédé de fumigation, vaporisateur électrique et système de fumigation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618210A1 (de) * 1996-05-07 1997-11-13 Binker Materialschutz Gmbh Verfahren und Einrichtung zum Begasen von Räumen mit Ameisensäureester gegen Insekten
DE19706842A1 (de) * 1997-02-21 1998-08-27 Binker Materialschutz Gmbh Inertbegasung mit subletalem Zusatz

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618210A1 (de) * 1996-05-07 1997-11-13 Binker Materialschutz Gmbh Verfahren und Einrichtung zum Begasen von Räumen mit Ameisensäureester gegen Insekten
DE19706842A1 (de) * 1997-02-21 1998-08-27 Binker Materialschutz Gmbh Inertbegasung mit subletalem Zusatz

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
AHARONI Y. ET AL.: "Thrips mortality and strawberry quality after vacuum fumigation with acetaldehyde or ethyl formate", JOURNAL OF AMERICAN SOCIETY OF HORTICULTURAL SCIENCE, vol. 105, no. 6, 1980, pages 926 - 929 *
DATABASE CAPLUS [online] KHRAMOV V.V. ET AL., accession no. STN Database accession no. 1982:515255 *
DATABASE WPI Derwent World Patents Index; Class C03, AN 1997-551198/51 *
FISHER CHARLES D.: "Controlling storage insects by fumigation", FOOD INDUSTRIES (DRIED FRUIT ASSOCIATION OF CALIFORNIA), vol. 17, 1945, pages 1176 - 1178 *
JONES R.M.: "Reducing inflammability of fumigants with carbon dioxide", INDUSTRIAL AND ENGINEERING CHEMISTRY (AMERICAN CHEMICAL SOCIETY), vol. 25, 1933, pages 394 - 396 *
KHIMIKO-FARMATSEVTICHESKII ZHURNAL, vol. 16, no. 7, 1982, pages 860 - 865 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006066308A1 (fr) 2004-12-24 2006-06-29 Commonwealth Scientific And Industrial Research Organisation Compositions et procedes pesticides
RU2418411C2 (ru) * 2004-12-24 2011-05-20 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Композиции пестицидов и способ их получения и применения
US8278352B2 (en) 2004-12-24 2012-10-02 Commonwealth Scientific & Industrial Research Organisation Pesticide compositions and methods
WO2008009315A1 (fr) * 2006-07-20 2008-01-24 Shivat Limited Méthode de régulation d'une population d'animaux nuisibles
AU2017228596B2 (en) * 2007-02-23 2019-05-16 Boc Limited Improved disinfestation method
WO2016197202A1 (fr) * 2015-06-12 2016-12-15 Innovative Biosecurity Pty Ltd Formulation de fumigation et appareil de vaporisation
WO2018197047A1 (fr) 2017-04-24 2018-11-01 Linde Aktiengesellschaft Formulation de fumigant
WO2018232468A1 (fr) * 2017-06-23 2018-12-27 Universal Biosecurity Limited Appareil de vaporisation
CN109907065A (zh) * 2019-04-02 2019-06-21 贵州大学 一种防治烟草粉螟的熏蒸剂及其使用方法
EP3777531A1 (fr) 2019-08-12 2021-02-17 Linde GmbH Procédé de fumigation, vaporisateur électrique et système de fumigation

Also Published As

Publication number Publication date
AUPS015802A0 (en) 2002-02-14
NZ534903A (en) 2006-11-30
AU2003201533B2 (en) 2008-12-11

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