WO1997026796A1 - Recyclage et recuperation de l'agent de fumigation bromure de methyle - Google Patents

Recyclage et recuperation de l'agent de fumigation bromure de methyle Download PDF

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Publication number
WO1997026796A1
WO1997026796A1 PCT/IB1996/000212 IB9600212W WO9726796A1 WO 1997026796 A1 WO1997026796 A1 WO 1997026796A1 IB 9600212 W IB9600212 W IB 9600212W WO 9726796 A1 WO9726796 A1 WO 9726796A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl bromide
molecular sieve
enclosure
air
chamber
Prior art date
Application number
PCT/IB1996/000212
Other languages
English (en)
Inventor
Nagji Moez
Original Assignee
Halozone Technologies, Inc.
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 Halozone Technologies, Inc. filed Critical Halozone Technologies, Inc.
Priority to AU48407/96A priority Critical patent/AU4840796A/en
Priority to PCT/IB1996/000212 priority patent/WO1997026796A1/fr
Publication of WO1997026796A1 publication Critical patent/WO1997026796A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M13/00—Fumigators; Apparatus for distributing gases
    • A01M13/003—Enclosures for fumigation, e.g. containers, bags or housings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M17/00—Apparatus for the destruction of vermin in soil or in foodstuffs
    • A01M17/008—Destruction of vermin in foodstuffs
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B9/00—Preservation of edible seeds, e.g. cereals
    • A23B9/16—Preserving with chemicals
    • A23B9/18—Preserving with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor

Definitions

  • This invention relates to the field of fumigation of products with .methyl bromide, and more particularly to a fumigation method in which methyl bromide is recycled and recovered for repeated use.
  • Methyl bromide is widely used for fumigating fruits, vegetables, grains, soil, lumber and enclosures requiring a sterilized atmosphere.
  • ODP ozone depleting substance
  • CFCs chlorofluorocarbons
  • the current method of fumigating fruits and vegetables or other produce with methyl bromide is to fill a chamber defining an enclosed space of, e.g. 1000 ft 3 to over 100,000 ft 3 with the produce. Pure methyl bromide is added to the chamber at a concentration of 10,000 to 20,000 ppm and maintained for several hours to ensure proper fumigation. For example, when fumigating cherries, 65 g/m 3 of methyl bromide is added to the chamber and maintained for 2 hours. 2
  • the chamber is purged with huge amounts of fresh air and all the remaining methyl bromide is vented to the atmosphere.
  • the methyl bromide is diluted with sufficient fresh air to attain a 500 ppm concentration in the effluent. In any event, no matter what the concentration, all of the unused methyl bromide must eventually be vented to the atmosphere.
  • One purpose of the present invention is to prevent pollution of the atmosphere with methyl bromide during fumigation of a product.
  • Another purpose of the invention is to shorten the time between fumigation cycles.
  • a still further purpose of the invention is to recycle unused methyl bromide to the fumigation process.
  • the method may additionally include the steps of:
  • the effluent may be cooled sufficiently to recover liquid methyl bromide to use for other purposes.
  • the method may terminate at step (7) .
  • a 50,000 ft 3 chamber is filled with boxes of cherries. It is assumed that about 60% to 80% of the chamber is void volume so that 30,000 ft 3 to 40,000 ft 3 of air is present in the chamber. After the chamber is sealed, from about 175 to 233 lbs. (depending upon the temperature of the cherries) of 100% methyl bromide is introduced into the chamber to provide the required amount of methyl bromide to ensure proper fumigation. The methyl bromide is allowed to remain in contact with the cherries for about 2 hours. Then the chamber is purged. Four fans moving 5,000. to 10,000 SCFM are switched on. Air from the chamber can be vented directly to the atmosphere or it may be mixed with o ⁇ tside air and purged through a 25 ft stack.
  • an analyzer controls the air flow from the chamber to ensure that the air outlet is closed if the concentration of methyl bromide in the effluent exceeds 500 ppm.
  • the chamber is purged until the methyl bromide concentration in the chamber is about 5 ppm. At this point, the purging is stopped and the cherries are removed, ready to be exported.
  • the fumigation unit comprises a fumigation enclosed space defined by a chamber (1) having a sealable entry (2), a supply intake (3) for methyl bromide, a fan (4) for circulating the gaseous atmosphere in the chamber (1) through a molecular sieve adsorber unit (5) containing at least one molecular sieve bed (6) having an outlet (7) to the chamber, an optional hot air supply (8) , a cooler (9) , a vent (10) to the outside atmosphere, a heat exchanger (14) and a fresh air supply (11) .
  • Check valves 15-24 are used to open or close appropriate feed lines or pipes for carrying out the process of the present invention.
  • An air analyzer unit (12) analyzes the methyl bromide content of the chamber atmosphere and the outlet air from the cooler (9) during regeneration.
  • the gaseous atmosphere in the chamber is circulated by fan (4) over the molecular sieve bed (6) in the adsorption unit (5) .
  • the methyl bromide is adsorbed by the molecular sieve bed and the effluent is recycled back to the chamber through outlet (7) .
  • the air/methyl bromide effluent from the adsorption unit may be cooled to atmospheric temperature e.g. between 70-105*F before it is recirculated back to the chamber. It is generally accepted that an amount of air equivalent to 3 to 6 void volumes of the chamber are needed to purge the chamber.
  • the moleculer sieve adsorption unit (5) can be designed to provide outlet specifications of well under 500 ppm, before the air is exhausted to the atmosphere through vent (10) .
  • the adsorption unit (5) is then blocked off, the fumigated cherries are removed and a new load of cherries to be fumigated is brought in.
  • the entry (2) to the chamber is sealed and the regeneration of the adsorber unit is started.
  • Regeneration may occur in a closed cycle by drawing air from the chamber (11) through a heat exchanger (14) so that heated air will be introduced into the adsorption unit (5) from within the chamber (1) to desorb the methyl bromide and to simultaneously provide a sterilizing atmosphere for the new load of product.
  • hot air may be supplied to the adsorption unit (5) from an optional hot air supply (8) which may be internally or externally generated without introducing external air. Regeneration of unit (5) is preferably stopped when the air in the chamber (1) and the air effluent (7) exiting the molecular sieve bed are within 200 ppm, as determined by the air analyzer (12) .
  • the adsorption unit (5) may also be flushed with some fresh air from the fresh air supply (11) to purge any remaining methyl bromide in the voids of the molecular sieve bed and for cooling off the molecular sieve bed although, as explained hereafter, no cooling of the bed is necessary.
  • the methyl bromide concentration in the chamber is adjusted to the required fumigation level by adding fresh methyl bromide from the methyl bromide supply (3) . The steps following fumigation are then repeated as necessary. It should be apparent that the fumigation operation may be used for fumigating other fruits as well as cut flowers, grains, nuts, timber, etc. , and may be applicable to any enclosure including a greenhouse, ship hold, etc.
  • a single bed adsorption unit provides a reservoir to capture the methyl bromide during the purging step in its gaseous state and as a source of methyl bromide for repeated fumigation.
  • the methyl bromide is desorbed and recycled for reuse in one fumigation cycle, thereby not only protecting the environment but conserving methyl bromide. This adds to the economic advantage of a shortened fumigation cycle.
  • the preferred molecular sieve used in the process according to the invention includes the commercially available S-115 Silicalite, sold by Union Carbide Corporation and ZSM5 zeolite.
  • the silicalite is not strictly speaking a zeolite because it has no ion-exchange capacity. It is a hydrophobic material containing more than 99% Si02, having a pore volume of 0.19 cc/gm and a pore size approximately ⁇ angstroms in diameter.
  • the ZSM5 is an organophilic, hydrophobic Y-type zeolite as disclosed in U.S.
  • This zeolite has a pore size of about 6 angstroms and a Si:Al ratio of 15 up to 1000. Volatile hydrocarbons emitted by fruit are not adsorbed by the silicalite or the zeolite in the presence of methyl bromide.
  • the adsorption unit In a conventional adsorption system, the adsorption unit needs to be cooled after heating. In the system according to the invention, no cooling of the bed is necessary since the methyl bromide is recirculated into the chamber. During the next adsorption step, the bed gets cooled and starts re-adsorbing. In a conventional system, this cannot be done as during the adsorption/cooling step, the contaminant would slip through. If it is a closed loop, the desorbed methyl bromide will be recirculated while heating the molecular sieve bed. At the end of the heating step, the ppm level of methyl bromide in the chamber is close to the ppm level at the start of the adsorption.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • General Chemical & Material Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Environmental Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Soil Sciences (AREA)
  • Treating Waste Gases (AREA)

Abstract

Selon l'invention, du bromure de méthyle non utilisé provenant d'un cycle de fumigation est piégé par adsorption sur un tamis moléculaire et recyclé pour être réutilisé ou récupéré par désorption avec du gaz chaud sans qu'il soit nécessaire de purger la chambre de fumigation au moyen de l'air extérieur. La perte de bromure de méthyle dans l'atmosphère est minimale.
PCT/IB1996/000212 1996-01-24 1996-01-24 Recyclage et recuperation de l'agent de fumigation bromure de methyle WO1997026796A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU48407/96A AU4840796A (en) 1996-01-24 1996-01-24 Recycling and recovery of methyl bromide fumigant
PCT/IB1996/000212 WO1997026796A1 (fr) 1996-01-24 1996-01-24 Recyclage et recuperation de l'agent de fumigation bromure de methyle

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB1996/000212 WO1997026796A1 (fr) 1996-01-24 1996-01-24 Recyclage et recuperation de l'agent de fumigation bromure de methyle

Publications (1)

Publication Number Publication Date
WO1997026796A1 true WO1997026796A1 (fr) 1997-07-31

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ID=11004411

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB1996/000212 WO1997026796A1 (fr) 1996-01-24 1996-01-24 Recyclage et recuperation de l'agent de fumigation bromure de methyle

Country Status (2)

Country Link
AU (1) AU4840796A (fr)
WO (1) WO1997026796A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006099696A1 (fr) * 2005-03-24 2006-09-28 Desclean Belgie, Naamloze Vennootschap Procede et dispositif de fumigation de produits dans un espace clos
CN102114382A (zh) * 2011-01-14 2011-07-06 浙江诚信医化设备有限公司 一种熏蒸药剂的分离回收方法
WO2014051441A1 (fr) * 2012-09-29 2014-04-03 Lance Allen Dear Recyclage de gaz toxiques

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3206275A (en) * 1961-12-15 1965-09-14 Griffith Laboratories Pulsation process of gas treatment for fumigation and the like
JPS52116403A (en) * 1976-03-26 1977-09-29 Masakata Suwauchi Recovering method of methyl bromide
JPS5448701A (en) * 1977-09-24 1979-04-17 Masakata Suwauchi Method of recovering methyl bromide
US4322394A (en) * 1977-10-31 1982-03-30 Battelle Memorial Institute Adsorbent regeneration and gas separation utilizing microwave heating
EP0068724A2 (fr) * 1981-06-18 1983-01-05 The New Zealand Apple And Pear Marketing Board Méthode et appareil de fumigation de denrées
JPS5824319A (ja) * 1981-08-05 1983-02-14 Hitachi Plant Eng & Constr Co Ltd くん蒸排ガスの処理装置
SU1113071A1 (ru) * 1982-08-02 1984-09-15 Львовский Сельскохозяйственный Институт Установка дл фумигации грузов бромистым метилом в контейнерах без их вскрыти
US4748013A (en) * 1985-04-17 1988-05-31 Toyo Soda Manufacturing Co., Ltd. Adsorbent for recovery of bromine and bromine-recovering process using same
US4966755A (en) * 1987-07-09 1990-10-30 Rentokil Limited Method and apparatus for fumigation of materials
EP0467668A1 (fr) * 1990-07-19 1992-01-22 The BOC Group plc Magasinage et transport de marchandises sous l'atmosphère controlée
DE4030102A1 (de) * 1990-09-22 1992-03-26 Hermann Prof Dipl In Schreiner Verfahren fuer emissionsfreie insekten-raumbegasung
US5187131A (en) * 1990-01-16 1993-02-16 Tigg Corporation Method for regenerating particulate adsorbents
US5259853A (en) * 1992-12-10 1993-11-09 Uop Vent gas processing scheme with vacuum swing adsorption

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3206275A (en) * 1961-12-15 1965-09-14 Griffith Laboratories Pulsation process of gas treatment for fumigation and the like
JPS52116403A (en) * 1976-03-26 1977-09-29 Masakata Suwauchi Recovering method of methyl bromide
JPS5448701A (en) * 1977-09-24 1979-04-17 Masakata Suwauchi Method of recovering methyl bromide
US4322394A (en) * 1977-10-31 1982-03-30 Battelle Memorial Institute Adsorbent regeneration and gas separation utilizing microwave heating
EP0068724A2 (fr) * 1981-06-18 1983-01-05 The New Zealand Apple And Pear Marketing Board Méthode et appareil de fumigation de denrées
JPS5824319A (ja) * 1981-08-05 1983-02-14 Hitachi Plant Eng & Constr Co Ltd くん蒸排ガスの処理装置
SU1113071A1 (ru) * 1982-08-02 1984-09-15 Львовский Сельскохозяйственный Институт Установка дл фумигации грузов бромистым метилом в контейнерах без их вскрыти
US4748013A (en) * 1985-04-17 1988-05-31 Toyo Soda Manufacturing Co., Ltd. Adsorbent for recovery of bromine and bromine-recovering process using same
US4966755A (en) * 1987-07-09 1990-10-30 Rentokil Limited Method and apparatus for fumigation of materials
US5187131A (en) * 1990-01-16 1993-02-16 Tigg Corporation Method for regenerating particulate adsorbents
EP0467668A1 (fr) * 1990-07-19 1992-01-22 The BOC Group plc Magasinage et transport de marchandises sous l'atmosphère controlée
DE4030102A1 (de) * 1990-09-22 1992-03-26 Hermann Prof Dipl In Schreiner Verfahren fuer emissionsfreie insekten-raumbegasung
US5259853A (en) * 1992-12-10 1993-11-09 Uop Vent gas processing scheme with vacuum swing adsorption

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7745, Derwent World Patents Index; AN 77-80342y, XP002022609 *
DATABASE WPI Week 7921, Derwent World Patents Index; AN 79-39921b, XP002022610 *
DATABASE WPI Week 8513, Derwent World Patents Index; AN 85-080045, XP002022611 *
PATENT ABSTRACTS OF JAPAN vol. 7, no. 95 (C - 163) 23 August 1983 (1983-08-23) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006099696A1 (fr) * 2005-03-24 2006-09-28 Desclean Belgie, Naamloze Vennootschap Procede et dispositif de fumigation de produits dans un espace clos
CN102114382A (zh) * 2011-01-14 2011-07-06 浙江诚信医化设备有限公司 一种熏蒸药剂的分离回收方法
CN102114382B (zh) * 2011-01-14 2013-06-19 浙江诚信医化设备有限公司 一种熏蒸药剂的分离回收方法
WO2014051441A1 (fr) * 2012-09-29 2014-04-03 Lance Allen Dear Recyclage de gaz toxiques
AU2013324535B2 (en) * 2012-09-29 2015-05-28 Lance Allen Dear Recycling toxic gases

Also Published As

Publication number Publication date
AU4840796A (en) 1997-08-20

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