JPH09291007A - Fumigation and fumigation system - Google Patents
Fumigation and fumigation systemInfo
- Publication number
- JPH09291007A JPH09291007A JP10701796A JP10701796A JPH09291007A JP H09291007 A JPH09291007 A JP H09291007A JP 10701796 A JP10701796 A JP 10701796A JP 10701796 A JP10701796 A JP 10701796A JP H09291007 A JPH09291007 A JP H09291007A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen phosphide
- phosphide
- fumigation
- containing gas
- hydrogen
- 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.)
- Granted
Links
- 238000003958 fumigation Methods 0.000 title claims description 143
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 275
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims abstract description 202
- 239000007789 gas Substances 0.000 claims abstract description 144
- 229940102396 methyl bromide Drugs 0.000 claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- PGYDGBCATBINCB-UHFFFAOYSA-N 4-diethoxyphosphoryl-n,n-dimethylaniline Chemical compound CCOP(=O)(OCC)C1=CC=C(N(C)C)C=C1 PGYDGBCATBINCB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006009 Calcium phosphide Substances 0.000 claims abstract description 9
- 239000006011 Zinc phosphide Substances 0.000 claims abstract description 9
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940048462 zinc phosphide Drugs 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 68
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- IHGSAQHSAGRWNI-UHFFFAOYSA-N 1-(4-bromophenyl)-2,2,2-trifluoroethanone Chemical compound FC(F)(F)C(=O)C1=CC=C(Br)C=C1 IHGSAQHSAGRWNI-UHFFFAOYSA-N 0.000 claims description 24
- 238000000746 purification Methods 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002023 wood Substances 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000005953 Magnesium phosphide Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims 1
- 208000019901 Anxiety disease Diseases 0.000 abstract 1
- 230000036506 anxiety Effects 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 239000007864 aqueous solution Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 235000013339 cereals Nutrition 0.000 description 12
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 10
- 238000010926 purge Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 241000233855 Orchidaceae Species 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 241000254171 Curculionidae Species 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 241000722921 Tulipa gesneriana Species 0.000 description 5
- 240000004507 Abelmoschus esculentus Species 0.000 description 4
- 240000000560 Citrus x paradisi Species 0.000 description 4
- 241000258937 Hemiptera Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 240000008790 Musa x paradisiaca Species 0.000 description 4
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001784 detoxification Methods 0.000 description 4
- 239000002316 fumigant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 244000298697 Actinidia deliciosa Species 0.000 description 2
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- 244000003416 Asparagus officinalis Species 0.000 description 2
- 235000005340 Asparagus officinalis Nutrition 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 2
- 240000005250 Chrysanthemum indicum Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 2
- 240000006497 Dianthus caryophyllus Species 0.000 description 2
- 235000009355 Dianthus caryophyllus Nutrition 0.000 description 2
- 241000245654 Gladiolus Species 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 240000008415 Lactuca sativa Species 0.000 description 2
- 235000003228 Lactuca sativa Nutrition 0.000 description 2
- 240000004658 Medicago sativa Species 0.000 description 2
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000003280 Pachira Nutrition 0.000 description 2
- 241000982311 Pachira Species 0.000 description 2
- 244000025272 Persea americana Species 0.000 description 2
- 235000008673 Persea americana Nutrition 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- 240000004713 Pisum sativum Species 0.000 description 2
- 235000010582 Pisum sativum Nutrition 0.000 description 2
- 241000985694 Polypodiopsida Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 244000098338 Triticum aestivum Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 210000000081 body of the sternum Anatomy 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 229940126639 Compound 33 Drugs 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000545593 Scolytinae Species 0.000 description 1
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
Landscapes
- Catching Or Destruction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は燻蒸方法および燻蒸
システムに関する。さらに詳しくは高濃度のリン化水素
を含有するガスにより短期間で生植物、穀物、木材また
は飼料を処理する燻蒸方法および特定の手段よりなる燻
蒸システムに関する。TECHNICAL FIELD The present invention relates to a fumigation method and a fumigation system. More specifically, it relates to a fumigation method and a fumigation system comprising specific means for treating a raw plant, grain, wood or feed in a short period of time with a gas containing a high concentration of hydrogen phosphide.
【０００２】[0002]
【従来の技術】従来、リン化水素は生植物、穀物、木材
または飼料の倉庫燻蒸、サイロ燻蒸、コンテナー燻蒸等
に使用されていることが知られている。しかしながら、
リン化水素は、低濃度（約１.５容量％）で自然発火す
る恐れがある極めて危険なガスである。リン化水素によ
る燻蒸は、通常リン化アルミニウムの錠剤を燻蒸室内に
配置し、リン化アルミニウムと空気中の湿分との反応に
よりリン化水素を発生させる方法が知られている。しか
しながら、リン化アルミニウムと空気中の湿分との反応
は時間がかかり、そのため長期間の燻蒸となり鮮度の要
求される短時間の燻蒸には使用できない欠点がある。2. Description of the Related Art It is known that hydrogen phosphide has been conventionally used for warehouse fumigation, silo fumigation, container fumigation, etc. of living plants, grains, wood or feed. However,
Hydrogen phosphide is a very dangerous gas that may spontaneously ignite at low concentrations (about 1.5% by volume). For fumigation with hydrogen phosphide, a method is generally known in which tablets of aluminum phosphide are placed in a fumigation chamber and hydrogen phosphide is generated by the reaction between aluminum phosphide and moisture in the air. However, the reaction between aluminum phosphide and the moisture in the air takes a long time, which results in a fumigation for a long period of time and cannot be used for a fumigation in a short time when freshness is required.
【０００３】また、特表平６−５００７６１号公報はリ
ン化水素の発生方法および装置を提案しており、ヨーロ
ッパ特許公開第０３１８０４０号明細書もリン化水素の
発生装置を提案している。しかしながら、上記２つの明
細書は共にリン化水素が発火しない程度に低濃度のリン
化水素を発生するよう制御されたリン化水素の発生装置
を提案しており、鮮度の要求される短時間の燻蒸には使
用できない。Japanese Patent Publication No. 6-500761 proposes a method and apparatus for producing hydrogen phosphide, and European Patent Publication No. 0318040 also proposes an apparatus for producing hydrogen phosphide. However, both of the above two specifications propose a hydrogen phosphide generator controlled to generate a low concentration of hydrogen phosphide to the extent that hydrogen phosphide does not ignite. Cannot be used for fumigation.
【０００４】一方、リン化水素をボンベに充填して燻蒸
に使用する方法も知られている。しかしながら、上記の
ようにリン化水素は極めて発火し易く危険であるため、
高濃度のリン化水素を不活性ガスで約１.５容量％程度
に希釈し、これをボンベに充填して燻蒸に使用してい
る。従ってかかる方法では、低濃度のリン化水素含有ガ
スを使用するため長期間の燻蒸時間が必要であり、やは
り鮮度の要求されるものには使用できない欠点がある。On the other hand, a method of filling a cylinder with hydrogen phosphide and using it for fumigation is also known. However, since hydrogen phosphide is extremely ignitable and dangerous as described above,
A high concentration of hydrogen phosphide is diluted with an inert gas to about 1.5% by volume, and this is filled in a cylinder and used for fumigation. Therefore, in such a method, since a low concentration hydrogen phosphide-containing gas is used, a long fumigation time is required, and there is a drawback that it cannot be used for a freshness-required one.
【０００５】さらにこの欠点を改良する方法として、特
開平５−１６１４４４号公報には、高濃度のリン化水素
と臭化メチルとを混合使用することにより発火を防止
し、しかも短時間で燻蒸できる燻蒸用装置を提案してい
る。この提案された装置において高濃度のリン化水素
は、ボンベに充填されたリン化水素を使用している。し
かしながら、リン化水素ボンベは特殊高圧ガスに属し、
その保存、運搬および使用は厳重な取扱いが必要であ
る。ボンベを使用せず、燻蒸場所で、容易かつ安全に高
濃度のリン化水素ガスを提供でき、短期間で生植物、穀
物、木材または飼料を燻蒸しうる方法および燻蒸システ
ムの開発が求められている。As a method for improving this drawback, JP-A-5-161444 discloses that a mixture of a high concentration of hydrogen phosphide and methyl bromide is used to prevent ignition and to allow fumigation in a short time. A fumigation device is proposed. The high concentration of hydrogen phosphide in the proposed device uses hydrogen phosphide filled in cylinders. However, hydrogen phosphide cylinders belong to special high pressure gas,
Its storage, transportation and use require strict handling. There is a need for a method and a fumigation system that can easily and safely provide high-concentration hydrogen phosphide gas in a fumigation place without using a cylinder, and can fumigate a raw plant, grain, wood or feed in a short period of time. There is.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、燻蒸
場所で高濃度のリン化水素ガスが得られ、発火の心配な
く安全に、生植物、穀物、木材または飼料の害虫を短期
間に死滅させることができ、穀物、木材、飼料または鮮
度の要求される生植物に対し好適に使用される燻蒸方法
および燻蒸システムを提供することにある。本発明者は
この目的を達成せんとして鋭意研究を重ねた結果、特定
のリン化金属化合物と水または硫酸水溶液とを反応さ
せ、得られたリン化水素を臭化メチルと混合してリン化
水素含有ガスとし、このガスにより生植物、穀物、木材
または飼料を燻蒸する方法および特定の手段よりなる燻
蒸システムを見出し、本発明に到達した。An object of the present invention is to obtain a high concentration of hydrogen phosphide gas in a fumigation place, safely and safely without any fear of ignition, in a short period of time with no harmful insects of raw plants, grains, woods or feeds. It is an object of the present invention to provide a fumigation method and a fumigation system which can be killed and are suitably used for grain, wood, feed or fresh plants requiring freshness. The present inventor has conducted extensive studies to achieve this object, and as a result, reacts a specific metal phosphide compound with water or an aqueous solution of sulfuric acid, and mixes the obtained hydrogen phosphide with methyl bromide to produce hydrogen phosphide. The present invention has been accomplished by discovering a fumigation system comprising a method of containing a gas and fumigating a living plant, a grain, a wood or a feed with this gas and a specific means.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明によれ
ば（１）リン化アルミニウム、リン化マグネシウム、リ
ン化亜鉛およびリン化カルシウムよりなる群から選ばれ
た少なくとも１種のリン化金属化合物と水とを接触反応
させ、（２）得られたリン化水素を臭化メチルと混合し
てリン化水素含有ガスとして導管を通じて燻蒸室へ流通
させ、次いで該燻蒸室内において該リン化水素含有ガス
を噴出させ、そして（３）該燻蒸室中において、燻蒸さ
れるべき生植物、穀物、木材または飼料を処理すること
を特徴とする燻蒸方法が提供される。That is, according to the present invention, (1) at least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide (2) The obtained hydrogen phosphide is mixed with methyl bromide and allowed to flow as a hydrogen phosphide-containing gas into a fumigation chamber through a conduit, and then the hydrogen phosphide-containing gas is reacted in the fumigation chamber. And (3) providing a fumigation method characterized by treating raw plants, grains, wood or feed to be fumigated in the fumigation chamber.
【０００８】本発明に使用されるリン化水素は、リン化
アルミニウム、リン化マグネシウム、リン化亜鉛および
リン化カルシウムよりなる群から選ばれた少くとも１種
のリン化金属化合物と水とを接触反応させて得られる。The hydrogen phosphide used in the present invention comprises contacting water with at least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide. Obtained by reacting.
【０００９】リン化金属化合物と水との接触反応におい
て、リン化金属化合物１重量部当り水１〜１０重量部を
使用することが好ましい。１重量部未満では、反応速度
が遅くなり本発明の目的を達成し難く、１０重量部を超
えると副生する金属の水酸化物のため、リン化水素が発
泡し易くなる傾向にある。In the catalytic reaction between the metal phosphide compound and water, it is preferable to use 1 to 10 parts by weight of water per 1 part by weight of the metal phosphide compound. If it is less than 1 part by weight, the reaction rate becomes slow and it is difficult to achieve the object of the present invention. If it exceeds 10 parts by weight, hydrogen phosphide tends to be easily foamed due to the metal hydroxide produced as a by-product.
【００１０】接触反応における反応温度は３０〜９８℃
が好ましく、４５〜９５℃の範囲がより好ましい。反応
温度が３０℃より低くなると反応の進行が不充分にな
り、９８℃より高くなると反応が激しく、制御できなく
なり好ましくない。また、この接触反応において、コン
デンサーが高温での反応を維持したまま水量を一定に保
つことができ、有利に使用される。この接触反応は、回
分式で行うことが好ましい。その理由は、燻蒸室の規
模、燻蒸すべき対象物の量と種類に対応して燻蒸場所で
高濃度のリン化水素の特定量を得る方法として適してい
る。また、この接触反応は、リン化金属化合物に水を添
加しながら実施する方法が推奨される。この接触方法は
本発明の目的である高濃度のリン化水素を安全に得る方
法として好適である。この方法は所定量のリン化金属化
合物を容器に仕込んでおき、水を連続的または間歇的に
導入することにより実施される。The reaction temperature in the catalytic reaction is 30 to 98 ° C.
Is preferable and the range of 45-95 degreeC is more preferable. If the reaction temperature is lower than 30 ° C., the progress of the reaction becomes insufficient, and if it is higher than 98 ° C., the reaction is violent and uncontrollable, which is not preferable. Further, in this catalytic reaction, the condenser can keep the amount of water constant while maintaining the reaction at high temperature, which is advantageously used. This contact reaction is preferably performed in a batch system. The reason is that it is suitable as a method for obtaining a specific amount of high-concentration hydrogen phosphide at a fumigation site according to the scale of the fumigation chamber, the amount and type of the object to be fumigated. Further, it is recommended that this catalytic reaction be carried out while adding water to the metal phosphide compound. This contact method is suitable as a method for safely obtaining a high concentration of hydrogen phosphide, which is the object of the present invention. This method is carried out by charging a container with a predetermined amount of a metal phosphide compound and introducing water continuously or intermittently.
【００１１】本発明の燻蒸を行うに当り、導管並びに容
器中の空気を予め、炭酸ガス、窒素ガス等の不活性ガス
で置換しておくことは安全操作のために好ましいことで
ある。In carrying out the fumigation of the present invention, it is preferable for safe operation to replace the air in the conduit and the container with an inert gas such as carbon dioxide gas or nitrogen gas in advance.
【００１２】得られたリン化水素は臭化メチルと混合し
てリン化水素含有ガスとし、このガスは導管を通じて燻
蒸室へ流通させ、次いで該燻蒸室内においてリン化水素
含有ガスを噴出させる。リン化水素含有ガスの燻蒸室へ
の導管における流速は、少なくとも０.０３ｍ／秒の流
速に保持されることが好ましく、０.１ｍ／秒以上の流
速に保持されることがより好ましい。流速が０.０３ｍ
／秒より遅くなると、リン化水素が発火し易くなり好ま
しくない。またリン化水素含有ガスの燻蒸室への噴出
は、少なくとも０.３ｍ／秒の流速で行うことが好まし
く、０.５ｍ／秒以上の流速で行うことがより好まし
く、１.０ｍ／秒以上の流速で行うことがさらに好まし
い。流速が０.３ｍ／秒より遅くなると、リン化水素が
発火し易くなり好ましくない。The obtained hydrogen phosphide is mixed with methyl bromide to give a hydrogen phosphide-containing gas, which gas is passed through a conduit into the fumigation chamber, and then the hydrogen phosphide-containing gas is jetted in the fumigation chamber. The flow rate of the hydrogen phosphide-containing gas in the conduit to the fumigation chamber is preferably maintained at a flow rate of at least 0.03 m / sec, more preferably at least 0.1 m / sec. Flow velocity is 0.03m
If it is slower than / sec, hydrogen phosphide is likely to ignite, which is not preferable. In addition, the ejection of the hydrogen phosphide-containing gas into the fumigation chamber is preferably performed at a flow rate of at least 0.3 m / sec, more preferably 0.5 m / sec or more, and 1.0 m / sec or more. More preferably, it is carried out at a flow rate. When the flow velocity is slower than 0.3 m / sec, hydrogen phosphide is easily ignited, which is not preferable.
【００１３】燻蒸室内へ噴出されるリン化水素含有ガス
中のリン化水素の含有割合は４容量％以上が好ましく、
３０容量％以上が特に好ましい。４容量％より少なくな
ると、高濃度のリン化水素を提供し、短期間で燻蒸する
という本発明の目的に適さなくなる。The content ratio of hydrogen phosphide in the hydrogen phosphide-containing gas ejected into the fumigation chamber is preferably 4% by volume or more,
30% by volume or more is particularly preferable. When it is less than 4% by volume, it provides a high concentration of hydrogen phosphide and is not suitable for the purpose of the present invention of fumigating in a short period of time.
【００１４】本発明において得られるリン化水素含有ガ
スは臭化メチルを少なくとも２５容量％含有しているの
が望ましく、リン化水素と臭化メチルの割合が容量比で
７５：２５〜４：９６の範囲であることが特に好まし
い。臭化メチルは、リン化水素の発火を抑制しまたそれ
自体燻蒸作用を有しているため好ましく用いられる。ま
た、臭化メチルがリン化水素含有ガス中に占める割合
が、容量で２５％以上になると流速に関係なく発火が抑
制され、この点においても好ましく用いられる。臭化メ
チルが９６容量％より多くなると、高濃度のリン化水素
を提供し、短期間で燻蒸するという本発明の目的に適さ
なくなる。The hydrogen phosphide-containing gas obtained in the present invention preferably contains at least 25% by volume of methyl bromide, and the volume ratio of hydrogen phosphide to methyl bromide is 75:25 to 4:96. It is particularly preferable that the range is. Methyl bromide is preferably used because it suppresses ignition of hydrogen phosphide and has a fumigating action itself. Further, when the proportion of methyl bromide in the hydrogen phosphide-containing gas is 25% or more in volume, ignition is suppressed regardless of the flow rate, and this point is also preferably used. Methyl bromide greater than 96% by volume provides a high concentration of hydrogen phosphide and is unsuitable for the purpose of the invention of fumigating in a short period of time.
【００１５】臭化メチルの供給速度および量は、リン化
水素含有ガス中の臭化メチルの占める割合が少なくとも
２５容量％を保つように臭化メチルの供給速度および量
を一定に保持するかあるいは反応により発生したリン化
水素の濃度変化に従い経時的に変化させることが好まし
く、また反応により発生したリン化水素の濃度が次第に
低下し、その量が少なくなるに従って臭化メチルの供給
速度を増大させ、燻蒸室内へ噴出されるリン化水素含有
ガスの流速が一定速度以上を維持するよう経時的に変化
させることも好ましい。なかでも、操作性から臭化メチ
ルの供給速度および量を一定量保持する方法が好まし
い。The feed rate and amount of methyl bromide are kept constant so that the proportion of methyl bromide in the hydrogen phosphide-containing gas remains at least 25% by volume, or It is preferable to change over time according to the change in the concentration of hydrogen phosphide generated by the reaction, and the concentration of hydrogen phosphide generated by the reaction gradually decreases, and the feed rate of methyl bromide increases as the amount decreases. It is also preferable to change the flow rate of the hydrogen phosphide-containing gas ejected into the fumigation chamber with time so that the flow rate is maintained at a constant rate or higher. Above all, a method of maintaining a constant supply rate and amount of methyl bromide is preferable from the viewpoint of operability.
【００１６】リン化水素含有ガスはさらに加湿するのが
有利である。ここでいう加湿は、リン化水素含有ガスに
水蒸気を加えるか或いはリン化水素含有ガスを水と接触
させる手段により行われる。加湿により、リン化水素の
発火が抑制され、リン化金属化合物と水との反応で副生
する微量のリン化水素よりも発火し易いジホスフィンが
除去され、それにより一層発火を抑制できる。また、殊
にリン化金属化合物として、例えば帝人化成（株）より
市販されているリン化アルミニウム粒剤（商標名エピヒ
ューム）を使用する場合は、反応抑制剤としてカルバミ
ン酸アンモニウムが含有されており、水との反応により
炭酸ガスの発生と共にアンモニアガスが副生するため、
このアンモニアガスの除去に有利である後者の水と接触
させる手段が好ましく採用される。さらに、副生するア
ンモニアガスは、水に吸収させても飛散し易いので、１
〜１０重量％濃度の硫酸水溶液と接触させることにより
加湿とアンモニア除去を効率良く行うことができるため
より好ましく採用される。The hydrogen phosphide-containing gas is advantageously further humidified. The humidification here is performed by adding water vapor to the hydrogen phosphide-containing gas or by bringing the hydrogen phosphide-containing gas into contact with water. By humidification, ignition of hydrogen phosphide is suppressed, and diphosphine, which is more easily ignited than a trace amount of hydrogen phosphide produced as a by-product of the reaction between the metal phosphide compound and water, is removed, whereby ignition can be further suppressed. Further, especially when using aluminum phosphide granules (trade name Epifume) commercially available from Teijin Kasei Co., Ltd. as a metal phosphide compound, ammonium carbamate is contained as a reaction inhibitor, Since ammonia gas is by-produced with the generation of carbon dioxide gas due to the reaction with water,
The latter means for contacting with water, which is advantageous for removing this ammonia gas, is preferably adopted. Furthermore, the by-produced ammonia gas easily scatters even when absorbed in water, so 1
It is more preferably adopted because it is possible to efficiently perform humidification and ammonia removal by contacting with a sulfuric acid aqueous solution having a concentration of 10 wt%.
【００１７】そして、燻蒸室内に噴出させたリン化水素
含有ガスにより、生植物、穀物、木材または飼料は燻蒸
処理される。本発明で燻蒸処理されるものは、通常燻蒸
処理されるべきものであればよく、その例として、バナ
ナ、パイナップル、レモン、グレープフルーツ、オレン
ジ、キウイフルーツ、アボガド等の青果物類、レタス、
オクラ、アスパラガス、エンドウ等の野菜類、キク、カ
ーネーション、ラン、シダ等の切花類、チューリップ、
グラジオラス等の球根類、ラン等の苗、その他苗木、穂
木、種子等を含む生植物、米、小麦、大豆等の穀物、油
粕、アルファルファペレット等の飼料および米材、南洋
材等の木材等が挙げられる。Then, the hydrogen phosphide-containing gas ejected into the fumigation chamber fumigates the raw plant, grain, wood or feed. What is fumigated in the present invention may be what is usually fumigated, as examples, banana, pineapple, lemon, grapefruit, orange, kiwifruit, fruits and vegetables such as avocado, lettuce,
Vegetables such as okra, asparagus, peas, cut flowers such as chrysanthemums, carnations, orchids, ferns, tulips,
Bulbs such as gladiolus, seedlings such as orchids, other vegetation including seedlings, spikes, seeds, grains such as rice, wheat, soybeans, feed such as oil cake, alfalfa pellets, and wood such as South Sea timber, etc. Is mentioned.
【００１８】また、本発明によれば（１）リン化アルミ
ニウム、リン化マグネシウム、リン化亜鉛およびリン化
カルシウムよりなる群から選ばれた少なくとも１種のリ
ン化金属化合物と１〜９８重量％濃度の硫酸水溶液とを
接触反応させ、（２）得られたリン化水素を臭化メチル
と混合してリン化水素含有ガスとして導管を通じて燻蒸
室へ流通させ、次いで該燻蒸室内において該リン化水素
含有ガスを噴出させ、そして（３）該燻蒸室中におい
て、燻蒸されるべき生植物、穀物、木材または飼料を処
理することを特徴とする燻蒸方法が提供される。According to the present invention, (1) at least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide and a concentration of 1 to 98% by weight. (2) mixing the obtained hydrogen phosphide with methyl bromide and passing it as a hydrogen phosphide-containing gas through a conduit to the fumigation chamber, and then containing the hydrogen phosphide-containing solution in the fumigation chamber. A fumigation method is provided, characterized in that gas is blown out and (3) a raw plant, grain, wood or feed to be fumigated is treated in the fumigation chamber.
【００１９】本発明に使用されるリン化水素は、リン化
アルミニウム、リン化マグネシウム、リン化亜鉛および
リン化カルシウムよりなる群から選ばれた少くとも１種
のリン化金属化合物と１〜９８重量％濃度の硫酸水溶液
とを接触反応させて得られる。硫酸水溶液の代わりに他
の酸性水溶液たとえば塩酸または硝酸を使用した場合
は、発生したリン化水素と反応するため、リン化水素の
純度および収率が低くなるという欠点がある。The hydrogen phosphide used in the present invention is at least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide and 1 to 98 weight parts. It is obtained by contacting with a sulfuric acid aqueous solution having a concentration of%. If another acidic aqueous solution such as hydrochloric acid or nitric acid is used in place of the sulfuric acid aqueous solution, it reacts with the generated hydrogen phosphide, resulting in a drawback that the hydrogen phosphide purity and yield are lowered.
【００２０】水を使用する場合と硫酸水溶液を使用する
場合とを比較すると、硫酸水溶液を使用した場合は特に
反応温度が３０℃以下でも反応速度が速く、高濃度のリ
ン化水素が得られ、本発明の目的を低温において達成で
き、また、副生する硫酸金属塩は硫酸水溶液に溶け、反
応を阻害されることがないという利点がある。一方、水
を使用した場合は、リン化金属化合物として、例えば前
記リン化アルミニウム粒剤を使用すると、反応終了後の
残査は、硫酸水溶液を使用した場合と比較して粘着性が
なく、リン化水素発生槽の壁に付着し難く、導管等の閉
塞がなく安全で、また洗浄も容易であるという利点があ
る。この理由は、副生した水に不溶な金属の水酸化物が
残査中のパラフィン等の粒剤成分を内包するためと考え
られる。Comparing the case of using water and the case of using an aqueous solution of sulfuric acid, the reaction rate is fast and a high concentration of hydrogen phosphide can be obtained especially when the aqueous solution of sulfuric acid is used, even if the reaction temperature is 30 ° C. or lower. The object of the present invention can be achieved at a low temperature, and the metal sulfate produced as a by-product can be dissolved in an aqueous solution of sulfuric acid so that the reaction is not hindered. On the other hand, when water is used, for example, when the aluminum phosphide granules are used as the metal phosphide compound, the residue after the reaction is not sticky as compared with the case of using the aqueous sulfuric acid solution, It has the advantages that it is unlikely to adhere to the wall of the hydrogen fluoride generation tank, it is safe without clogging of conduits, etc., and is easy to clean. The reason for this is considered to be that the by-produced water-insoluble metal hydroxide encapsulates the remaining granule components such as paraffin.
【００２１】硫酸水溶液の濃度は１〜９８重量％であ
り、２〜８０重量％が好ましく、５〜６０重量％がより
好ましい。この濃度を外れると、副生する硫酸金属塩が
硫酸水溶液に溶けないためリン化水素が破泡し難くなり
反応が阻害され好ましくない。接触反応における反応温
度は１０〜９８℃が好ましく、４５〜９５℃の範囲がよ
り好ましい。反応温度が１０℃より低くなると反応の進
行が不充分になり、９８℃より高くなると反応が激し
く、制御できなくなり好ましくない。また、この接触反
応において、コンデンサーが高温での反応を維持したま
ま水量を一定に保つことができ、有利に使用される。こ
の接触反応は、回分式で行うことが好ましい。その理由
は、燻蒸室の規模、燻蒸すべき対象物の量と種類に対応
して燻蒸場所で高濃度のリン化水素の特定量を得る方法
として適している。また、この接触反応は、リン化金属
化合物に硫酸水溶液を添加しながら実施する方法が推奨
される。この接触方法は本発明の目的である高濃度のリ
ン化水素を安全に得る方法として好適である。この方法
は所定量のリン化金属化合物を容器に仕込んでおき、硫
酸水溶液を連続的または間歇的に導入することにより実
施される。The concentration of the sulfuric acid aqueous solution is 1 to 98% by weight, preferably 2 to 80% by weight, more preferably 5 to 60% by weight. If the concentration is out of this range, the by-produced metal sulfate is not dissolved in the aqueous sulfuric acid solution, and thus hydrogen phosphide is less likely to be foamed and the reaction is inhibited, which is not preferable. The reaction temperature in the catalytic reaction is preferably 10 to 98 ° C, more preferably 45 to 95 ° C. If the reaction temperature is lower than 10 ° C, the progress of the reaction becomes insufficient, and if it is higher than 98 ° C, the reaction is violent and uncontrollable, which is not preferable. Further, in this catalytic reaction, the condenser can keep the amount of water constant while maintaining the reaction at high temperature, which is advantageously used. This contact reaction is preferably performed in a batch system. The reason is that it is suitable as a method for obtaining a specific amount of high-concentration hydrogen phosphide at a fumigation site according to the scale of the fumigation chamber, the amount and type of the object to be fumigated. Further, it is recommended that this contact reaction be carried out while adding an aqueous sulfuric acid solution to the metal phosphide compound. This contact method is suitable as a method for safely obtaining a high concentration of hydrogen phosphide, which is the object of the present invention. This method is carried out by charging a predetermined amount of a metal phosphide compound into a container and introducing a sulfuric acid aqueous solution continuously or intermittently.
【００２２】本発明の燻蒸を行うに当り、導管並びに容
器中の空気を予め、炭酸ガス、窒素ガス等の不活性ガス
で置換しておくことは安全操作のために好ましいことで
ある。In carrying out the fumigation of the present invention, it is preferable for the safe operation to replace the air in the conduit and the container with an inert gas such as carbon dioxide gas or nitrogen gas in advance.
【００２３】得られたリン化水素は臭化メチルと混合し
てリン化水素含有ガスとし、このガスは導管を通じて燻
蒸室へ流通させ、次いで該燻蒸室内においてリン化水素
含有ガスを噴出させる。リン化水素含有ガスの燻蒸室へ
の導管における流速は、少なくとも０.０３ｍ／秒の流
速に保持されることが好ましく、０.１ｍ／秒以上の流
速に保持されることがより好ましい。流速が０.０３ｍ
／秒より遅くなると、リン化水素が発火し易くなり好ま
しくない。またリン化水素含有ガスの燻蒸室への噴出
は、少なくとも０.３ｍ／秒の流速で行うことが好まし
く、０.５ｍ／秒以上の流速で行うことがより好まし
く、１.０ｍ／秒以上の流速で行うことがさらに好まし
い。流速が０.３ｍ／秒より遅くなると、リン化水素が
発火し易くなり好ましくない。The resulting hydrogen phosphide is mixed with methyl bromide to give a hydrogen phosphide-containing gas, which gas is passed through a conduit into the fumigation chamber, and then the hydrogen phosphide-containing gas is jetted in the fumigation chamber. The flow rate of the hydrogen phosphide-containing gas in the conduit to the fumigation chamber is preferably maintained at a flow rate of at least 0.03 m / sec, more preferably at least 0.1 m / sec. Flow velocity is 0.03m
If it is slower than / sec, hydrogen phosphide is likely to ignite, which is not preferable. In addition, the ejection of the hydrogen phosphide-containing gas into the fumigation chamber is preferably performed at a flow rate of at least 0.3 m / sec, more preferably 0.5 m / sec or more, and 1.0 m / sec or more. More preferably, it is carried out at a flow rate. When the flow velocity is slower than 0.3 m / sec, hydrogen phosphide is easily ignited, which is not preferable.
【００２４】燻蒸室内へ噴出されるリン化水素含有ガス
中のリン化水素の含有割合は４容量％以上が好ましく、
３０容量％以上が特に好ましい。４容量％より少なくな
ると、高濃度のリン化水素を提供し、短期間で燻蒸する
という本発明の目的に適さなくなる。The content ratio of hydrogen phosphide in the hydrogen phosphide-containing gas ejected into the fumigation chamber is preferably 4% by volume or more,
30% by volume or more is particularly preferable. When it is less than 4% by volume, it provides a high concentration of hydrogen phosphide and is not suitable for the purpose of the present invention of fumigating in a short period of time.
【００２５】本発明において得られるリン化水素含有ガ
スは臭化メチルを少なくとも２５容量％含有しているの
が望ましく、リン化水素と臭化メチルの割合が容量比で
７５：２５〜４：９６の範囲であることが特に好まし
い。臭化メチルは、リン化水素の発火を抑制しまたそれ
自体燻蒸作用を有しているため好ましく用いられる。ま
た、臭化メチルがリン化水素含有ガス中に占める割合
が、容量で２５％以上になると流速に関係なく発火が抑
制され、この点においても好ましく用いられる。臭化メ
チルが９６容量％より多くなると、高濃度のリン化水素
を提供し、短期間で燻蒸するという本発明の目的に適さ
なくなる。The hydrogen phosphide-containing gas obtained in the present invention preferably contains at least 25% by volume of methyl bromide, and the volume ratio of hydrogen phosphide to methyl bromide is 75:25 to 4:96. It is particularly preferable that the range is. Methyl bromide is preferably used because it suppresses ignition of hydrogen phosphide and has a fumigating action itself. Further, when the proportion of methyl bromide in the hydrogen phosphide-containing gas is 25% or more in volume, ignition is suppressed regardless of the flow rate, and this point is also preferably used. Methyl bromide greater than 96% by volume provides a high concentration of hydrogen phosphide and is unsuitable for the purpose of the invention of fumigating in a short period of time.
【００２６】臭化メチルの供給速度および量は、リン化
水素含有ガス中の臭化メチルの占める割合が少なくとも
２５容量％を保つように臭化メチルの供給速度および量
を一定に保持するかるいは反応により発生したリン化水
素の濃度変化に従い経時的に変化させることが好まし
く、また反応により発生したリン化水素の濃度が次第に
低下し、その量が少なくなるに従って臭化メチルの供給
速度を増大させ、燻蒸室内へ噴出されるリン化水素含有
ガスの流速が一定速度以上を維持するよう経時的に変化
させることも好ましい。なかでも、操作性から臭化メチ
ルの供給速度および量を一定量保持する方法が好まし
い。The feed rate and amount of methyl bromide should be kept constant so that the proportion of methyl bromide in the hydrogen phosphide-containing gas should be kept at least 25% by volume. It is preferable to change over time according to the change in the concentration of hydrogen phosphide generated by the reaction, and the concentration of hydrogen phosphide generated by the reaction gradually decreases, and the feed rate of methyl bromide increases as the amount decreases. It is also preferable to change the flow rate of the hydrogen phosphide-containing gas ejected into the fumigation chamber with time so that the flow rate is maintained at a constant rate or higher. Above all, a method of maintaining a constant supply rate and amount of methyl bromide is preferable from the viewpoint of operability.
【００２７】リン化水素含有ガスはさらに加湿するのが
有利である。ここでいう加湿は、リン化水素含有ガスに
水蒸気を加えるか或いはリン化水素含有ガスを水と接触
させる手段により行なわれる。加湿によりリン化水素の
発火が抑制され、また水と接触する方法によればリン化
金属化合物と硫酸水溶液との反応で副生する微量のリン
化水素よりも発火し易いジホスフィンが除去され、それ
により一層発火を抑制できる。The hydrogen phosphide-containing gas is advantageously further humidified. The humidification here is performed by adding water vapor to the hydrogen phosphide-containing gas or by bringing the hydrogen phosphide-containing gas into contact with water. Ignition of hydrogen phosphide is suppressed by humidification, and the method of contacting with water removes diphosphine, which is easier to ignite than the trace amount of hydrogen phosphide produced as a by-product of the reaction between the metal phosphide compound and the aqueous sulfuric acid solution. With this, ignition can be further suppressed.
【００２８】そして、燻蒸室内に噴出させたリン化水素
含有ガスにより、生植物、穀物、木材または飼料は燻蒸
処理される。本発明で燻蒸処理されるものは、通常燻蒸
処理されるべきものであればよく、その例として、バナ
ナ、パイナップル、レモン、グレープフルーツ、オレン
ジ、キウイフルーツ、アボガド等の青果物類、レタス、
オクラ、アスパラガス、エンドウ等の野菜類、キク、カ
ーネーション、ラン、シダ等の切花類、チューリップ、
グラジオラス等の球根類、ラン等の苗、その他苗木、穂
木、種子等を含む生植物、米、小麦、大豆等の穀物、油
粕、アルファルファペレット等の飼料および米材、南洋
材等の木材等が挙げられる。Then, the hydrogen phosphide-containing gas ejected into the fumigation chamber fumigates the raw plant, grain, wood or feed. What is fumigated in the present invention may be what is usually fumigated, as examples, banana, pineapple, lemon, grapefruit, orange, kiwifruit, fruits and vegetables such as avocado, lettuce,
Vegetables such as okra, asparagus, peas, cut flowers such as chrysanthemums, carnations, orchids, ferns, tulips,
Bulbs such as gladiolus, seedlings such as orchids, other vegetation including seedlings, spikes, seeds, grains such as rice, wheat, soybeans, feed such as oil cake, alfalfa pellets, and wood such as South Sea timber, etc. Is mentioned.
【００２９】さらに、本発明によれば、 （ａ）リン化水素発生手段 （ｂ）臭化メチル供給手段 （ｃ）リン化水素精製手段 （ｄ）リン化水素含有ガスの噴出手段 （ｅ）燻蒸室 および （ｆ）（ｆ−１）該リン化水素発生手段から発生し、続
いて該リン化水素精製手段を介したリン化水素が該臭化
メチル供給手段から供給された臭化メチルと混合され、
次いで該燻蒸室へ導入され噴出されるように前記（ａ）
〜（ｅ）が導管により接続されている流通手段 または
（ｆ−２）該臭化メチル供給手段から供給された臭化メ
チルが該リン化水素発生手段から発生したリン化水素と
混合され、次いで該リン化水素精製手段を介して該燻蒸
室へ導入され噴出されるように前記（ａ）〜（ｅ）が導
管により接続されている流通手段、よりなる燻蒸システ
ムが提供される。Further, according to the present invention, (a) hydrogen phosphide generation means (b) methyl bromide supply means (c) hydrogen phosphide purification means (d) hydrogen phosphide-containing gas ejection means (e) fumigation Chamber and (f) (f-1) hydrogen phosphide generated from the hydrogen phosphide generation means, and subsequently passed through the hydrogen phosphide purification means is mixed with methyl bromide supplied from the methyl bromide supply means. Is
Then, in order to be introduced into the fumigation chamber and ejected, the above (a)
~ (E) a flow means connected by a conduit or (f-2) methyl bromide supplied from the methyl bromide supply means is mixed with hydrogen phosphide generated from the hydrogen phosphide generation means, and then There is provided a fumigation system comprising a distribution means (a) to (e) connected by a conduit so as to be introduced into the fumigation chamber through the hydrogen phosphide purification means and ejected.
【００３０】この燻蒸システムにおいて、リン化水素発
生手段は、リン化アルミニウム、リン化マグネシウム、
リン化亜鉛およびリン化カルシウムよりなる群から選ば
れた少なくとも１種のリン化金属化合物に水または硫酸
水溶液を添加反応させる手段が好ましく採用される。反
応条件としては、リン化金属化合物に水を添加反応させ
る方法においては、リン化金属化合物１重量部当り、水
１〜１０重量部を用い、反応温度３０〜９８℃で行うこ
とが好ましく、一方、リン化金属化合物に硫酸水溶液を
添加反応させる方法においては、１〜９８重量％濃度の
硫酸水溶液を用い、反応温度１０〜９８℃で行うことが
好ましい。In this fumigation system, the means for generating hydrogen phosphide is aluminum phosphide, magnesium phosphide,
Means for reacting at least one metal phosphide compound selected from the group consisting of zinc phosphide and calcium phosphide with water or an aqueous sulfuric acid solution is preferably employed. As the reaction conditions, in the method of adding water to the metal phosphide compound and reacting, it is preferable to use 1 to 10 parts by weight of water per 1 part by weight of the metal phosphide compound and to carry out at a reaction temperature of 30 to 98 ° C. In the method of adding and reacting the sulfuric acid aqueous solution to the metal phosphide compound, it is preferable to use a sulfuric acid aqueous solution having a concentration of 1 to 98% by weight at a reaction temperature of 10 to 98 ° C.
【００３１】本発明の燻蒸システムにおける臭化メチル
供給手段は、該リン化水素発生手段から燻蒸室へ導入さ
れるリン化水素含有ガスの導管中の流速が、少なくとも
０.０３ｍ／秒、より好ましくは０.１ｍ／秒以上に維持
されており、また該燻蒸室へ導入されるリン化水素含有
ガスの流速が、少なくとも０.３ｍ／秒、好ましくは０.
５ｍ／秒、より好ましくは１.０ｍ／秒以上に維持され
るように臭化メチルの供給が制御されている手段である
かまたは臭化メチルのリン化水素含有ガスに占める割合
が、少なくとも２５容量％、より好ましくはリン化水素
と臭化メチルの割合が容量比で７５：２５〜４：９６の
範囲に保持されるように臭化メチルの供給が抑制されて
いる手段である。導管中の流速が０.０３ｍ／秒より遅
く、また燻蒸室へ噴出する流速が０.３ｍ／秒より遅
く、さらに臭化メチルのリン化水素含有ガスに占める割
合が２５容量％より少なくなると、リン化水素が発火し
易くなり好ましくない。臭化メチルはそれ自体燻蒸作用
を有しており、好ましく用いられる。In the methyl bromide supplying means in the fumigation system of the present invention, the flow rate of the hydrogen phosphide-containing gas introduced into the fumigation chamber from the hydrogen phosphide generating means in the conduit is at least 0.03 m / sec, more preferably. Is maintained at 0.1 m / sec or more, and the flow rate of the hydrogen phosphide-containing gas introduced into the fumigation chamber is at least 0.3 m / sec, preferably 0.1 m / sec.
It is a means in which the supply of methyl bromide is controlled so as to be maintained at 5 m / sec, more preferably 1.0 m / sec or more, or the proportion of methyl bromide in the hydrogen phosphide-containing gas is at least 25. This is a means for suppressing the supply of methyl bromide so that the volume ratio, more preferably the ratio of hydrogen phosphide to methyl bromide, is maintained in the range of 75:25 to 4:96 by volume. If the flow velocity in the conduit is slower than 0.03 m / sec, the flow velocity ejected to the fumigation chamber is slower than 0.3 m / sec, and the proportion of methyl bromide in the hydrogen phosphide-containing gas is less than 25% by volume, Hydrogen phosphide is apt to ignite, which is not preferable. Methyl bromide itself has a fumigating action and is preferably used.
【００３２】本発明の燻蒸システムにおけるリン化水素
精製手段は、リン化水素発生手段より導入されたリン化
水素ガスと水とを接触させる手段またはリン化水素ガス
中のアンモニアを除去する手段、好ましくはリン化水素
ガスと１〜１０重量％の硫酸水溶液とを接触させる手段
が採用される。水との接触により、該リン化水素発生手
段で副生する微量のリン化水素よりも発火し易いジホス
フィンがリン化水素ガスから除去され、発火を一層抑制
することができ、また硫酸水溶液との接触等によりアン
モニアを除去することで、アンモニアによる被燻蒸物の
薬害を防止できる。The hydrogen phosphide purification means in the fumigation system of the present invention is a means for bringing the hydrogen phosphide gas introduced from the hydrogen phosphide generation means into contact with water or a means for removing ammonia in the hydrogen phosphide gas, preferably Is a means for bringing hydrogen phosphide gas into contact with a 1 to 10 wt% sulfuric acid aqueous solution. Upon contact with water, diphosphine, which is more easily ignited than a small amount of hydrogen phosphide by-produced in the hydrogen phosphide generation means, is removed from the hydrogen phosphide gas, and ignition can be further suppressed, and with the aqueous solution of sulfuric acid. By removing the ammonia by contact or the like, it is possible to prevent the chemical damage of the fumigants due to the ammonia.
【００３３】本発明の燻蒸システムにおいて、燻蒸室へ
導入されるリン化水素含有ガス中のリン化水素濃度は４
容量％以上が好ましく、３０容量％以上が特に好まし
い。４容量％より少なくなると、高濃度のリン化水素を
提供し、短期間で燻蒸するという本発明の目的に適さな
くなる。また燻蒸室へ噴出するリン化水素含有ガスの流
速は、少なくとも０.３ｍ／秒に制御されることが好ま
しく、０.５ｍ／秒以上に制御されることがより好まし
く、１.０ｍ／秒以上に制御されることがさらに好まし
い。流速が０.３ｍ／秒より遅くなると、リン化水素が
発火し易くなり好ましくない。In the fumigation system of the present invention, the concentration of hydrogen phosphide in the hydrogen phosphide-containing gas introduced into the fumigation chamber is 4
Volume% or more is preferable, and 30 volume% or more is particularly preferable. When it is less than 4% by volume, it provides a high concentration of hydrogen phosphide and is not suitable for the purpose of the present invention of fumigating in a short period of time. The flow rate of the hydrogen phosphide-containing gas ejected to the fumigation chamber is preferably controlled to at least 0.3 m / sec, more preferably 0.5 m / sec or more, and 1.0 m / sec or more. More preferably, When the flow velocity is slower than 0.3 m / sec, hydrogen phosphide is easily ignited, which is not preferable.
【００３４】本発明の燻蒸システムにおいて、前記
（ａ）〜（ｅ）が導管により接続されている流通手段と
しては、（ｆ−１）該リン化水素発生手段から発生し、
続いて該リン化水素精製手段を介したリン化水素が該臭
化メチル供給手段から供給された臭化メチルと混合さ
れ、次いで該燻蒸室へ導入され噴出されるように前記
（ａ）〜（ｅ）が導管により接続されている流通手段
または（ｆ−２）該臭化メチル供給手段から供給された
臭化メチルが該リン化水素発生手段から発生したリン化
水素と混合され、次いで該リン化水素精製手段を介して
該燻蒸室へ導入され噴出されるように前記（ａ）〜
（ｅ）が導管により接続されている流通手段がある。In the fumigation system of the present invention, (a) to (e) are connected as a flow means by means of (f-1) the hydrogen phosphide generating means,
Subsequently, the hydrogen phosphide obtained through the hydrogen phosphide purification means is mixed with the methyl bromide supplied from the methyl bromide supply means, and then introduced into the fumigation chamber so as to be jetted (a) to (). distribution means in which e) is connected by a conduit
Or (f-2) methyl bromide supplied from the methyl bromide supply means is mixed with hydrogen phosphide generated from the hydrogen phosphide generation means, and then to the fumigation chamber via the hydrogen phosphide purification means. In order to be introduced and ejected, the above (a)-
There is a distribution means in which (e) is connected by a conduit.
【００３５】（ｆ−１）の流通手段は（ｆ−２）の流通
手段と比較して、臭化メチルがリン化水素発生手段また
はリン化水素精製手段で使用される水あるいは硫酸水溶
液等に接触しないため、臭化メチルが水あるいは硫酸水
溶液に溶解したり、結晶水和物を生成したり、加水分解
を起こす等の影響がなく、好ましく採用される。The distribution means (f-1) is different from the distribution means (f-2) in that the methyl bromide is added to water or an aqueous sulfuric acid solution used in the hydrogen phosphide generation means or the hydrogen phosphide purification means. Since it does not come into contact with methyl bromide, there is no influence such as dissolution of methyl bromide in water or an aqueous solution of sulfuric acid, formation of a crystalline hydrate, or occurrence of hydrolysis.
【００３６】また、（ｆ−２）の流通手段において、該
臭化メチルと該リン化水素を混合する方法としては、該
臭化メチルが該リン化水素発生手段を通じてリン化水素
と混合されるように導管を接続してもよく、また該臭化
メチルが該リン化水素発生手段の後、該リン化水素精製
手段の前に、発生したリン化水素と混合されるように導
管を接続してもよい。As the method of mixing the methyl bromide and the hydrogen phosphide in the distribution means (f-2), the methyl bromide is mixed with the hydrogen phosphide through the hydrogen phosphide generating means. The conduit may be connected so that the methyl bromide is mixed with the generated hydrogen phosphide after the hydrogen phosphide generating means and before the hydrogen phosphide purification means. May be.
【００３７】本発明の燻蒸システムには、臭化メチルと
リン化水素の混合器を取り付けることが望ましい。この
混合器は（ｆ−１）の流通手段を用いる場合、リン化水
素精製手段の後、リン化水素含有ガスの噴出手段の前の
位置に、（ｆ−２）の流通手段を用いる場合、リン化水
素発生手段の後、リン化水素精製手段の前の位置に取り
付けることが好ましい。The fumigation system of the present invention is preferably equipped with a mixer of methyl bromide and hydrogen phosphide. In the case where the mixing means (f-1) is used, when the mixing means (f-2) is used at a position after the hydrogen phosphide refining means and before the jetting means of the hydrogen phosphide-containing gas, After the hydrogen phosphide generating means, it is preferably attached at a position before the hydrogen phosphide purification means.
【００３８】本発明の燻蒸システムにおいて、得られた
リン化水素含有ガスを燻蒸室から循環されたガス中へ噴
出させ、該燻蒸室に導入させる循環システムを用いるこ
とが有利である。この循環システムにより、噴出ノズル
径が大きく、リン化水素含有ガスの流速が維持できず発
火の危険性がある場合、リン化水素含有ガスを燻蒸室か
ら循環されたガス中へ噴出、混合して、リン化水素含有
ガス中のリン化水素濃度を発火しない濃度まで急速に希
釈することが可能となる。In the fumigation system of the present invention, it is advantageous to use a circulation system in which the obtained hydrogen phosphide-containing gas is ejected from the fumigation chamber into the gas circulated and introduced into the fumigation chamber. With this circulation system, when the jet nozzle diameter is large and the flow rate of the hydrogen phosphide-containing gas cannot be maintained and there is a risk of ignition, the hydrogen phosphide-containing gas is jetted from the fumigation chamber into the circulated gas and mixed. It is possible to rapidly dilute the hydrogen phosphide concentration in the hydrogen phosphide-containing gas to a concentration at which ignition does not occur.
【００３９】本発明の燻蒸システムにはリン化水素の除
毒装置を取り付けることができる。除毒は吸着方式、分
解方式、燃焼方式等任意の方法が採用される。特に次亜
塩素酸ソーダで処理する方法が好ましい。The fumigation system of the present invention may be equipped with a detoxification device for hydrogen phosphide. For detoxification, an arbitrary method such as an adsorption method, a decomposition method, or a combustion method is adopted. The method of treating with sodium hypochlorite is particularly preferable.
【００４０】ここで本発明の燻蒸システムの一例を図
１、図２および図３に示す。図中、１は臭化メチル供給
手段、２はリン化水素発生手段、３はリン化水素精製手
段、４はリン化水素含有ガスの噴出手段、５は燻蒸室、
６はバルブ、７、８は流量計、９、１０は流量制御シス
テム、１１は三方コック、１２はブロワー、１３は循環
配管、１４、１５、１６は導管である。Here, an example of the fumigation system of the present invention is shown in FIGS. 1, 2 and 3. In the figure, 1 is methyl bromide supply means, 2 is hydrogen phosphide generation means, 3 is hydrogen phosphide purification means, 4 is hydrogen phosphide-containing gas ejection means, 5 is a fumigation chamber,
6 is a valve, 7 and 8 are flowmeters, 9 and 10 are flow control systems, 11 is a three-way cock, 12 is a blower, 13 is a circulation pipe, and 14, 15 and 16 are conduits.
【００４１】さらに本発明の燻蒸システムの一例を詳細
に図４および図５に示す。図中、１は臭化メチル供給手
段であり、臭化メチル貯槽１７、臭化メチル気化器５
８、バルブ６および臭化メチル積算流量調節計１８（流
量計７または６０で測定されるリン化水素流量により制
御される）よりなる。窒素ガス貯槽１９および真空ポン
プ２２は、リン化金属化合物を反応させる前に導管およ
び容器中の空気を除去し、リン化水素の発火を抑制する
目的で用いられる。Further, an example of the fumigation system of the present invention is shown in detail in FIGS. In the figure, 1 is a methyl bromide supply means, a methyl bromide storage tank 17, a methyl bromide vaporizer 5
8, a valve 6 and a methyl bromide integrated flow controller 18 (controlled by the flow rate of hydrogen phosphide measured by the flow meter 7 or 60). The nitrogen gas storage tank 19 and the vacuum pump 22 are used for the purpose of removing air in the conduit and the container before reacting the metal phosphide compound and suppressing ignition of hydrogen phosphide.
【００４２】２はリン化水素発生手段であり、計量槽２
７中の水または硫酸水溶液２８を、リン化水素発生槽３
０に添加し、リン化金属化合物３２と反応させる。３は
リン化水素精製手段であり、リン化水素含有ガスが導管
１５を通じて精製槽３６内の水または硫酸水溶液３８に
より精製される。３７はバブリングノズルであり、リン
化水素含有ガス中のジホスフィンおよびアンモニアガス
を除去し易くするために使用される。Reference numeral 2 is a hydrogen phosphide generating means, which is a measuring tank 2
The water or sulfuric acid solution 28 in 7 is added to the hydrogen phosphide generation tank 3
0 and reacted with the metal phosphide compound 32. Reference numeral 3 is a hydrogen phosphide purification means, and the hydrogen phosphide-containing gas is purified by the water or sulfuric acid aqueous solution 38 in the purification tank 36 through the conduit 15. A bubbling nozzle 37 is used to facilitate removal of diphosphine and ammonia gas in the hydrogen phosphide-containing gas.
【００４３】４はリン化水素含有ガスの噴出手段であ
り、リン化水素含有ガスが導管１６を通じて噴出ノズル
４１より循環配管１３へ噴出され、リン化水素ガス濃度
を発火しない濃度まで急速に希釈させる。このリン化水
素含有ガスは燻蒸室５へ供給される。燻蒸後は４５のリ
ン化水素除毒装置により、リン化水素は処理される。Reference numeral 4 is a means for ejecting the hydrogen phosphide-containing gas, and the hydrogen phosphide-containing gas is ejected from the ejection nozzle 41 to the circulation pipe 13 through the conduit 16 to rapidly dilute the hydrogen phosphide gas concentration to a concentration that does not ignite. . This hydrogen phosphide-containing gas is supplied to the fumigation chamber 5. After the fumigation, 45 hydrogen phosphide detoxification equipment treats the hydrogen phosphide.
【００４４】[0044]
【実施例】以下に実施例を挙げて本発明をさらに説明す
る。なお、評価は下記の方法によった。 （１）リン化水素ガスおよび炭酸ガス濃度 ガスクロマトグラフィー（大倉理研（株）製）を使用し
カラム充填剤としてPorapak Q 80/100 mesh（ジーエル
サイエンス（株）製）を用いて測定した。 （２）臭化メチルガス濃度 ガスクロマトグラフィー（（株）島津製作所製）を使用
しカラム充填剤としてＳＰ１２００＋ベントン３４（ジ
ーエルサイエンス（株）製）を用いて測定した。 （３）ジホスフィンガス濃度 アセトン・ドライアイス溶液に吸収させ、ＮＭＲ（バリ
アン（株）製）を用いて測定した。 （４）アンモニアガス濃度 水に吸収させ、フェノールフタレインを指示薬として、
０.１Ｎ塩酸で滴定した。The present invention will be further described with reference to the following examples. The evaluation was based on the following method. (1) Hydrogen phosphide gas and carbon dioxide gas concentrations Gas chromatography (manufactured by Okura Riken Co., Ltd.) was used and measurement was performed using Porapak Q 80/100 mesh (manufactured by GL Sciences Inc.) as a column packing material. (2) Methyl bromide gas concentration It was measured using gas chromatography (manufactured by Shimadzu Corporation) and SP1200 + Benton 34 (manufactured by GL Sciences Inc.) as a column packing material. (3) Diphosphine gas concentration It was absorbed in an acetone / dry ice solution and measured using NMR (manufactured by Varian Co., Ltd.). (4) Ammonia gas concentration Absorbed in water, phenolphthalein as an indicator,
Titrated with 0.1N hydrochloric acid.
【００４５】実施例１ 図６に示した装置を用い、以下の方法でリン化水素含有
ガスを得た。３００ｍｌのリン化水素発生槽３０にリン
化アルミニウム剤（リン化アルミニウム純度５６％、帝
人化成（株）市販のエピヒューム）９ｇを投入口５３よ
り入れた。次にリン化水素発生槽３０、流量計７、６
０、混合器５７、リン化水素ガスの精製槽３６（５重量
％硫酸水溶液が入っている）および導管内の空気を除去
した。その手順は二方コック２９、３４、５５を閉、二
方コック２５を開とし、真空ライン４８の真空用調節バ
ルブ２３を開、三方コック２１をリン化水素発生槽３０
の方向に開き、また三方コック５９を臭化メチル槽１７
のライン６１および混合器５７のライン１４の方向に開
き、真空ポンプ２２によりリン化水素発生槽３０、導管
内の空気を除去後、窒素ライン４７の窒素パージ用調節
バルブ２０を開、三方コック２１を窒素ライン４７とリ
ン化水素発生槽３０の方向に切換え、窒素ガス貯槽１９
から窒素ガスを流し、二方コック３４、５５、ニードル
バルブ４０、４４を開として、流量計７、６０、混合器
５７、精製槽３６および導管内の空気をほぼ完全に除去
した。除去後、窒素パージ用調節バルブ２０、ニードル
バルブ４０、４４、二方コック２５、３４、５５を閉と
した。Example 1 Using the apparatus shown in FIG. 6, a hydrogen phosphide-containing gas was obtained by the following method. 9 g of an aluminum phosphide agent (aluminum phosphide purity 56%, Epifume commercially available from Teijin Kasei Co., Ltd.) was put into a 300 ml hydrogen phosphide generation tank 30 through an inlet port 53. Next, the hydrogen phosphide generation tank 30 and the flow meters 7 and 6
0, the mixer 57, the hydrogen phosphide gas purification tank 36 (containing a 5 wt% sulfuric acid aqueous solution) and the air in the conduit were removed. The procedure is to close the two-way cocks 29, 34, 55, open the two-way cock 25, open the vacuum control valve 23 of the vacuum line 48, and open the three-way cock 21 in the hydrogen phosphide generation tank 30.
The three-way cock 59 and the methyl bromide tank 17
Line 61 of the mixer 57 and the line 14 of the mixer 57, and after removing the air in the hydrogen phosphide generation tank 30 and the conduit by the vacuum pump 22, the nitrogen purge control valve 20 of the nitrogen line 47 is opened, and the three-way cock 21 is opened. Is switched to the direction of the nitrogen line 47 and the hydrogen phosphide generation tank 30, and the nitrogen gas storage tank 19
The nitrogen gas was flown from the two-way cocks 34 and 55, the needle valves 40 and 44 were opened, and the air in the flowmeters 7 and 60, the mixer 57, the purification tank 36, and the conduit was almost completely removed. After the removal, the nitrogen purge control valve 20, the needle valves 40 and 44, and the two-way cocks 25, 34 and 55 were closed.
【００４６】次に、計量槽２７に水７０ｍｌを入れ、二
方コック２９を開いて、リン化水素発生槽３０に水６０
ｍｌを添加した。このとき、リン化水素発生槽３０は水
が添加し易くなるように減圧にしておいた。また計量槽
２７の空気がリン化水素発生槽３０に入らないように水
を１０ｍｌ程度残して二方コック２９を閉じた。水を添
加後直ちにリン化水素発生槽３０をヒーター３１で約８
３℃まで加熱した。リン化アルミニウム剤が反応して、
リン化水素発生槽内の圧力を示す圧力指示計２４が０.
１ｋｇ／ｃｍ2程度になったところで二方コック３４、
ニードルバルブ４０を開とし発生したリン化水素ガスを
１ｍ3燻蒸室５に噴出ノズル４１より噴出した。Next, 70 ml of water is put in the measuring tank 27, the two-way cock 29 is opened, and water 60 is put in the hydrogen phosphide generation tank 30.
ml was added. At this time, the hydrogen phosphide generation tank 30 was depressurized so that water could be easily added. The two-way cock 29 was closed while leaving about 10 ml of water so that the air in the measuring tank 27 did not enter the hydrogen phosphide generation tank 30. Immediately after adding water, the hydrogen phosphide generation tank 30 is heated to about 8 by the heater 31.
Heated to 3 ° C. Aluminum phosphide agent reacts,
The pressure indicator 24 showing the pressure in the hydrogen phosphide generation tank is 0.
Two-way cock 34 when it reaches about 1 kg / cm 2 .
When the needle valve 40 was opened, the generated hydrogen phosphide gas was ejected from the ejection nozzle 41 into the 1 m 3 fumigation chamber 5.
【００４７】流量計７で内径２ｍｍの導管の流速を計測
しリン化水素ガスの発生が少なくなり導管の流速が低下
し、内径２ｍｍの噴出ノズル４１の流速が０.５ｍ／ｓ
に近づいてきたところで、気化器５８で約２５℃に加温
した臭化メチル槽１７の元バルブ、臭化メチル調節バル
ブ６、二方コック５５を開とし、三方コック５９を臭化
メチル槽１７のライン６１と混合器５７のライン１４の
方向に切り換え、臭化メチルガス積算流量調節計１８を
用いて、噴出ノズルの流速が０.５ｍ／ｓ以上に保持さ
れるように臭化メチルを、リン化アルミニウム剤の反応
が終了しリン化水素が発生しなくなるまで流し続けた。
流量計７でリン化水素ガスの発生が終了したのを確認
後、二方コック５５を閉とし、次いで窒素ガス貯槽１９
から窒素パージ用バルブ２０、二方コック２５を開と
し、リン化水素発生槽内と導管に残存しているリン化水
素を窒素ガスで１ｍ 3燻蒸室５へ流した。この方法によ
るリン化水素ガス、臭化メチルガス、炭酸ガス、ジホス
フィンガスおよびアンモニアガスのそれぞれの濃度、導
管中の流速、噴出ノズルの流速、臭化メチルガスの流量
および発火の有無の結果を表１に示した。The flow velocity of the conduit having an inner diameter of 2 mm is measured by the flow meter 7.
The generation of hydrogen phosphide gas decreases and the flow velocity of the conduit decreases.
However, the flow velocity of the jet nozzle 41 having an inner diameter of 2 mm is 0.5 m / s.
Heated to about 25 ℃ with a vaporizer 58 when approaching
The original valve of the methyl bromide tank 17 and the methyl bromide control valve
Open the 6-way cock 55 and bromide the 3-way cock 59.
Of the line 61 of the methyl tank 17 and the line 14 of the mixer 57
Direction and switch the methyl bromide gas integrated flow controller 18
Use the jet nozzle to keep the flow velocity at 0.5m / s or more.
Reaction of methyl bromide with aluminum phosphide
Was continued until hydrogen phosphide was no longer generated.
Confirm that the generation of hydrogen phosphide gas has ended with the flow meter 7.
After that, the two-way cock 55 was closed, and then the nitrogen gas storage tank 19
Open the nitrogen purge valve 20 and the two-way cock 25 from
However, the phosphating water remaining in the hydrogen phosphide generation tank and in the conduit
Element is 1m with nitrogen gas ThreeIt was poured into the fumigation chamber 5. By this method
Hydrogen phosphide gas, methyl bromide gas, carbon dioxide gas, diphos
Fin gas and ammonia gas concentrations,
Flow velocity in pipe, flow velocity of jet nozzle, flow rate of methyl bromide gas
Table 1 shows the results with and without ignition.
【００４８】なお、導管中のガス濃度はサンプリング口
（Ａ）５０とサンプリング口（Ｂ）５２より経時的にサ
ンプリングして、それぞれの濃度は所定の方法で測定し
た。また導管中の流速は流量計７および流量計６０で計
測し、噴出ノズルの流速は導管中の流速より算出し、臭
化メチルの流量は積算流量調節計１８で計測した。また
噴出ノズルから流出するリン化水素含有ガスの発火の有
無は目視で確認した。The gas concentration in the conduit was sampled with time from the sampling port (A) 50 and the sampling port (B) 52, and the respective concentrations were measured by a predetermined method. The flow velocity in the conduit was measured by the flow meter 7 and the flow meter 60, the flow velocity of the jet nozzle was calculated from the flow velocity in the conduit, and the flow rate of methyl bromide was measured by the integrated flow controller 18. Further, the presence or absence of ignition of the hydrogen phosphide-containing gas flowing out from the jet nozzle was visually confirmed.
【００４９】[0049]
【表１】 [Table 1]
【００５０】実施例２ 図６に示した装置を用い、以下の方法でリン化水素含有
ガスを得た。３００ｍｌのリン化水素発生槽３０にリン
化アルミニウム剤（リン化アルミニウム純度５６％、帝
人化成（株）市販のエピヒューム）９ｇを投入口５３よ
り入れた。次にリン化水素発生槽３０、流量計７、６
０、混合器５７、リン化水素ガスの精製槽３６（水が入
っている）および導管内の空気を除去した。その手順は
二方コック２９、３４、５５を閉、二方コック２５を開
とし、真空ライン４８の真空用調節バルブ２３を開、三
方コック２１をリン化水素発生槽３０の方向に開き、ま
た三方コック５９を臭化メチル槽１７のライン６１およ
び混合器５７のライン１４の方向に開き、真空ポンプ２
２によりリン化水素発生槽３０、導管内の空気を除去
後、窒素ライン４７の窒素パージ用調節バルブ２０を
開、三方コック２１を窒素ライン４７とリン化水素発生
槽３０の方向に切換え、窒素ガス貯槽１９から窒素ガス
を流し、二方コック３４、５５、ニードルバルブ４０、
４４を開として、流量計７、６０、混合器５７、精製槽
３６および導管内の空気をほぼ完全に除去した。除去
後、窒素パージ用調節バルブ２０、ニードルバルブ４
０、４４、二方コック２５、３４、５５を閉とした。Example 2 Using the apparatus shown in FIG. 6, a hydrogen phosphide-containing gas was obtained by the following method. 9 g of an aluminum phosphide agent (aluminum phosphide purity 56%, Epifume commercially available from Teijin Kasei Co., Ltd.) was put into a 300 ml hydrogen phosphide generation tank 30 through an inlet port 53. Next, the hydrogen phosphide generation tank 30 and the flow meters 7 and 6
0, the mixer 57, the hydrogen phosphide gas purification tank 36 (containing water) and the air in the conduit were removed. The procedure is to close the two-way cocks 29, 34, 55, open the two-way cock 25, open the vacuum control valve 23 of the vacuum line 48, open the three-way cock 21 toward the hydrogen phosphide generation tank 30, and The three-way cock 59 is opened toward the line 61 of the methyl bromide tank 17 and the line 14 of the mixer 57, and the vacuum pump 2
After removing the air in the hydrogen phosphide generation tank 30 and the conduit by 2, the nitrogen purge control valve 20 of the nitrogen line 47 is opened, and the three-way cock 21 is switched to the direction of the nitrogen line 47 and the hydrogen phosphide generation tank 30. Nitrogen gas is made to flow from the gas storage tank 19, the two-way cocks 34, 55, the needle valve 40,
The air in the flowmeters 7, 60, the mixer 57, the purification tank 36 and the conduit was almost completely removed by opening 44. After removal, nitrogen purge control valve 20, needle valve 4
0, 44 and two-way cocks 25, 34, 55 were closed.
【００５１】次に、計量槽２７に１０重量％硫酸水溶液
１７０ｍｌを入れ、二方コック２９を開いて、リン化水
素発生槽３０に硫酸水溶液１６０ｍｌを添加した。この
とき、リン化水素発生槽３０は硫酸水溶液が添加し易く
なるように減圧にしておいた。また計量槽２７の空気が
リン化水素発生槽３０に入らないように硫酸水溶液を１
０ｍｌ程度残して二方コック２９を閉じた。硫酸水溶液
を添加後直ちにリン化水素発生槽３０をヒーター３１で
約７０℃まで加熱した。リン化アルミニウム剤が反応し
て、リン化水素発生槽内の圧力を示す圧力指示計２４が
０.１ｋｇ／ｃｍ2程度になったところで二方コック３
４、ニードルバルブ４０を開とし発生したリン化水素ガ
スを１ｍ3燻蒸室５に噴出ノズル４１より噴出した。Next, 170 ml of 10 wt% sulfuric acid aqueous solution was put into the measuring tank 27, the two-way cock 29 was opened, and 160 ml of sulfuric acid aqueous solution was added to the hydrogen phosphide generation tank 30. At this time, the hydrogen phosphide generation tank 30 was depressurized so that the sulfuric acid aqueous solution was easily added. Also, to prevent the air in the measuring tank 27 from entering the hydrogen phosphide generation tank 30, add 1% sulfuric acid solution.
The two-way cock 29 was closed, leaving about 0 ml. Immediately after adding the aqueous sulfuric acid solution, the hydrogen phosphide generation tank 30 was heated to about 70 ° C. by the heater 31. When the aluminum phosphide agent reacted and the pressure indicator 24 showing the pressure in the hydrogen phosphide generation tank reached about 0.1 kg / cm 2 , the two-way cock 3
4. With the needle valve 40 opened, the generated hydrogen phosphide gas was ejected from the ejection nozzle 41 into the 1 m 3 fumigation chamber 5.
【００５２】流量計７で内径２ｍｍの導管の流速を計測
しリン化水素ガスの発生が少なくなり導管の流速が低下
し、内径２ｍｍの噴出ノズル４１の流速が０.５ｍ／ｓ
に近づいてきたところで、気化器５８で約２５℃に加温
した臭化メチル槽１７の元バルブ、臭化メチル調節バル
ブ６、二方コック５５を開とし、三方コック５９を臭化
メチル槽１７のライン６１と混合器５７のライン１４の
方向に切り換え、臭化メチルガス積算流量調節計１８を
用いて、噴出ノズルの流速が０.５ｍ／ｓ以上に保持さ
れるように臭化メチルを、リン化アルミニウム剤の反応
が終了しリン化水素が発生しなくなるまで流し続けた。
流量計７でリン化水素ガスの発生が終了したのを確認
後、二方コック５５を閉とし、次いで窒素ガス貯槽１９
から窒素パージ用バルブ２０、二方コック２５を開と
し、リン化水素発生槽内と導管に残存しているリン化水
素を窒素ガスで１ｍ 3燻蒸室５へ流した。この方法によ
るリン化水素ガス、臭化メチルガス、炭酸ガス、ジホス
フィンガスおよびアンモニアガスのそれぞれの濃度、導
管中の流速、噴出ノズルの流速、臭化メチルガスの流量
および発火の有無の結果を表２に示した。The flow velocity of the conduit having an inner diameter of 2 mm is measured by the flow meter 7.
The generation of hydrogen phosphide gas decreases and the flow velocity of the conduit decreases.
However, the flow velocity of the jet nozzle 41 having an inner diameter of 2 mm is 0.5 m / s.
Heated to about 25 ℃ with a vaporizer 58 when approaching
The original valve of the methyl bromide tank 17 and the methyl bromide control valve
Open the 6-way cock 55 and bromide the 3-way cock 59.
Of the line 61 of the methyl tank 17 and the line 14 of the mixer 57
Direction and switch the methyl bromide gas integrated flow controller 18
Use the jet nozzle to keep the flow velocity at 0.5m / s or more.
Reaction of methyl bromide with aluminum phosphide
Was continued until hydrogen phosphide was no longer generated.
Confirm that the generation of hydrogen phosphide gas has ended with the flow meter 7.
After that, the two-way cock 55 was closed, and then the nitrogen gas storage tank 19
Open the nitrogen purge valve 20 and the two-way cock 25 from
However, the phosphating water remaining in the hydrogen phosphide generation tank and in the conduit
Element is 1m with nitrogen gas ThreeIt was poured into the fumigation chamber 5. By this method
Hydrogen phosphide gas, methyl bromide gas, carbon dioxide gas, diphos
Fin gas and ammonia gas concentrations,
Flow velocity in pipe, flow velocity of jet nozzle, flow rate of methyl bromide gas
Table 2 shows the results with and without ignition.
【００５３】なお、導管中のガス濃度はサンプリング口
（Ａ）５０とサンプリング口（Ｂ）５２より経時的にサ
ンプリングして、それぞれの濃度は所定の方法で測定し
た。また導管中の流速は流量計７および流量計６０で計
測し、噴出ノズルの流速は導管中の流速より算出し、臭
化メチルの流量は積算流量調節計１８で計測した。また
噴出ノズルから流出するリン化水素含有ガスの発火の有
無は目視で確認した。The gas concentration in the conduit was sampled with time from the sampling port (A) 50 and the sampling port (B) 52, and the respective concentrations were measured by a predetermined method. The flow velocity in the conduit was measured by the flow meter 7 and the flow meter 60, the flow velocity of the jet nozzle was calculated from the flow velocity in the conduit, and the flow rate of methyl bromide was measured by the integrated flow controller 18. Further, the presence or absence of ignition of the hydrogen phosphide-containing gas flowing out from the jet nozzle was visually confirmed.
【００５４】[0054]
【表２】 [Table 2]
【００５５】実施例３ 図６に示した装置を用い、以下の方法でリン化水素含有
ガスを得た。３００ｍｌのリン化水素発生槽３０にリン
化アルミニウム剤（リン化アルミニウム純度５６％、帝
人化成（株）市販のエピヒューム）９ｇを投入口５３よ
り入れた。次にリン化水素発生槽３０、流量計７、６
０、混合器５７、リン化水素ガスの精製槽３６（５重量
％硫酸水溶液が入っている）および導管内の空気を除去
した。その手順は二方コック２９、３４、５５を閉、二
方コック２５を開とし、真空ライン４８の真空用調節バ
ルブ２３を開、三方コック２１をリン化水素発生槽３０
の方向に開き、三方コック５９を臭化メチル槽１７のラ
イン６１および混合器５７のライン１４の方向に開き、
真空ポンプ２２によりリン化水素発生槽３０、導管内の
空気を除去後、窒素ライン４７の窒素パージ用調節バル
ブ２０を開、三方コック２１を窒素ライン４７とリン化
水素発生槽３０の方向に切換え、窒素ガス貯槽１９から
窒素ガスを流し、二方コック３４、５５、ニードルバル
ブ４０、４４を開として、流量計７、６０、混合器５
７、精製槽３６および導管内の空気をほぼ完全に除去し
た。除去後、窒素パージ用調節バルブ２０、ニードルバ
ルブ４０、４４、二方コック２５、３４、５５を閉とし
た。さらに、臭化メチル貯槽１７の元バルブ、臭化メチ
ル調節バルブ６、二方コック５５、ニードルバルブ４０
を開とし、臭化メチル積算流量調節計１８により０.１
リットル／分の流量で連続的に混合器５７に臭化メチル
を流した。Example 3 Using the apparatus shown in FIG. 6, a hydrogen phosphide-containing gas was obtained by the following method. 9 g of an aluminum phosphide agent (aluminum phosphide purity 56%, Epifume commercially available from Teijin Kasei Co., Ltd.) was put into a 300 ml hydrogen phosphide generation tank 30 through an inlet port 53. Next, the hydrogen phosphide generation tank 30 and the flow meters 7 and 6
0, the mixer 57, the hydrogen phosphide gas purification tank 36 (containing a 5 wt% sulfuric acid aqueous solution) and the air in the conduit were removed. The procedure is to close the two-way cocks 29, 34, 55, open the two-way cock 25, open the vacuum control valve 23 of the vacuum line 48, and open the three-way cock 21 in the hydrogen phosphide generation tank 30.
, And open the three-way cock 59 in the direction of the line 61 of the methyl bromide tank 17 and the line 14 of the mixer 57,
After removing the air in the hydrogen phosphide generation tank 30 and the conduit by the vacuum pump 22, the nitrogen purge control valve 20 of the nitrogen line 47 is opened, and the three-way cock 21 is switched to the direction of the nitrogen line 47 and the hydrogen phosphide generation tank 30. , Nitrogen gas is made to flow from the nitrogen gas storage tank 19, the two-way cocks 34, 55, the needle valves 40, 44 are opened, and the flow meters 7, 60, the mixer 5
7. The air in the purification tank 36 and the conduit was almost completely removed. After the removal, the nitrogen purge control valve 20, the needle valves 40 and 44, and the two-way cocks 25, 34 and 55 were closed. Further, the main valve of the methyl bromide storage tank 17, the methyl bromide control valve 6, the two-way cock 55, the needle valve 40.
Open and open the methyl bromide integrated flow controller 18 to 0.1.
Mixer 57 was continuously flushed with methyl bromide at a flow rate of 1 liter / min.
【００５６】次に、計量槽２７に水７０ｍｌを入れ、二
方コック２９を開いて、リン化水素発生槽３０に水６０
ｍｌを添加した。このとき、リン化水素発生槽３０は水
が添加し易くなるように減圧にしておいた。また計量槽
２７の空気がリン化水素発生槽３０に入らないように水
を１０ｍｌ程度残して二方コック２９を閉じた。水を添
加後直ちにリン化水素発生槽３０をヒーター３１で約８
３℃まで加熱した。リン化アルミニウム剤が反応して、
リン化水素発生槽内の圧力を示す圧力指示計２４が０.
１ｋｇ／ｃｍ2程度になったところで二方コック３４を
開とし発生したリン化水素ガスを混合器５７で臭化メチ
ルと混合した後、１ｍ3燻蒸室５に噴出ノズル４１より
噴出した。Next, 70 ml of water is put in the measuring tank 27, the two-way cock 29 is opened, and water 60 is put in the hydrogen phosphide generation tank 30.
ml was added. At this time, the hydrogen phosphide generation tank 30 was depressurized so that water could be easily added. The two-way cock 29 was closed while leaving about 10 ml of water so that the air in the measuring tank 27 did not enter the hydrogen phosphide generation tank 30. Immediately after adding water, the hydrogen phosphide generation tank 30 is heated to about 8 by the heater 31.
Heated to 3 ° C. Aluminum phosphide agent reacts,
The pressure indicator 24 showing the pressure in the hydrogen phosphide generation tank is 0.
At about 1 kg / cm 2 , the two-way cock 34 was opened and the generated hydrogen phosphide gas was mixed with methyl bromide in the mixer 57, and then sprayed from the spray nozzle 41 to the 1 m 3 fumigation chamber 5.
【００５７】反応終了後、すなわち流量計７でリン化水
素ガスの発生が終了したのを確認後、二方コック５５を
閉とし、次いで窒素パージ用調節バルブ２０、二方コッ
ク２５を開とし、リン化水素発生槽内と導管に残存して
いるリン化水素含有ガスを窒素ガスで１ｍ3燻蒸室５へ
流した。臭化メチルは臭化メチルの投薬量が燻蒸室５の
容積当り１３ｇ（臭化メチルガス量：３０.６リット
ル、０℃、１ａｔｍ）になるまで流し続けた。この方法
によるリン化水素ガス、臭化メチルガス、炭酸ガス、ジ
ホスフィンガスおよびアンモニアガスのそれぞれの濃
度、導管中の流速、噴出ノズルの流速、臭化メチルの流
量および発火の有無の結果を表３に示した。After completion of the reaction, that is, after confirming that the flow meter 7 has finished generating hydrogen phosphide gas, the two-way cock 55 is closed, and then the nitrogen purge control valve 20 and the two-way cock 25 are opened. The hydrogen phosphide-containing gas remaining in the hydrogen phosphide generation tank and in the conduit was flushed with nitrogen gas into the fumigation chamber 5 of 1 m 3 . Methyl bromide was kept flowing until the dosage of methyl bromide reached 13 g per volume of fumigation chamber 5 (methyl bromide gas amount: 30.6 liters, 0 ° C., 1 atm). Table 3 shows the results of hydrogen phosphide gas, methyl bromide gas, carbon dioxide gas, diphosphine gas, and ammonia gas concentrations, the flow velocity in the conduit, the flow velocity of the jet nozzle, the flow rate of methyl bromide, and the presence or absence of ignition by this method. Indicated.
【００５８】なお、導管中のガス濃度はサンプリング口
（Ａ）５０とサンプリング口（Ｂ）５２より経時的にサ
ンプリングして、それぞれの濃度は所定の方法で測定し
た。また導管中の流速は流量計７および流量計６０で計
測し、噴出ノズルの流速は導管中の流速より算出し、臭
化メチルの流量は積算流量調節計１８で計測した。また
噴出ノズルから流出するリン化水素含有ガスの発火の有
無は目視で確認した。The gas concentration in the conduit was sampled with time from the sampling port (A) 50 and the sampling port (B) 52, and the respective concentrations were measured by a predetermined method. The flow velocity in the conduit was measured by the flow meter 7 and the flow meter 60, the flow velocity of the jet nozzle was calculated from the flow velocity in the conduit, and the flow rate of methyl bromide was measured by the integrated flow controller 18. Further, the presence or absence of ignition of the hydrogen phosphide-containing gas flowing out from the jet nozzle was visually confirmed.
【００５９】[0059]
【表３】 [Table 3]
【００６０】実施例４ 実施例３の方法により得られたリン化水素含有ガスを噴
出させた１ｍ3の燻蒸室中に、被燻蒸物として青バナ
ナ、オクラ、グレープフルーツ、切花のデンファレ種ラ
ン、パキラ苗木およびチューリップの球根をそれぞれ１
ケース入れ、また害虫は飼育したコナカイガラムシ、マ
ルカイガラムシ、ハダニ、ゾウムシ、キクイムシ、コク
ゾウムシの付いたそれぞれのホストと一緒に入れ、１５
℃で４時間燻蒸した。この方法による１ｍ3燻蒸室中の
ガス濃度の経時変化を表４に、害虫の殺虫効果を表５
に、被燻蒸物の薬害の評価を表６に示した。Example 4 In a fumigation chamber of 1 m 3 in which the hydrogen phosphide-containing gas obtained by the method of Example 3 was ejected, blue banana, okra, grapefruit, cut flowers of denfare orchid, and pachira were used as fumigants. 1 sapling and 1 tulip bulb each
Put in a case, and put the pests together with each host that has a reared scale bug, scale bug, spider mite, weevil, bark beetle, weevil, 15
It was fumigated at ℃ for 4 hours. Table 4 shows the time-dependent changes in the gas concentration in the 1 m 3 fumigation chamber by this method, and Table 5 shows the insecticidal effect of harmful insects.
Table 6 shows the evaluation of phytotoxicity of fumigants.
【００６１】なお、燻蒸室中のガス濃度は所定の方法で
測定を行った。害虫の殺虫効果は２５〜２７℃、湿度７
０％の調湿付恒温器に燻蒸処理した害虫付ホストを入
れ、コナカイガラムシ、マルカイガラムシの成虫は７日
後に、ハダニ、ゾウムシ、キクイムシ、コクゾウムシの
成虫は３日後に、コナカイガラムシ、マルカイガラム
シ、ゾウムシ、キクイムシ、コクゾウムシの卵は３０日
から３５日後に、ハダニは１５日後にふ化虫の有無で調
べた。燻蒸処理した被燻蒸物の薬害については、１ケー
スの全てについて青バナナ、オクラ、グレープフルー
ツ、デンファレ種ランは１５℃の恒温室に未燻蒸品と一
緒に２０日間収納し、未燻蒸品と比較対照して外観変化
を調べた。パキラ苗木、チューリップの球根は苗床用土
壌に植付け、未燻蒸品と比較対照して発芽状況、生育状
況、チューリップ球根については開花状況についても調
べた。The gas concentration in the fumigation chamber was measured by a predetermined method. The insecticidal effect of pests is 25-27 ° C, humidity 7
A fumigated host with insects was placed in a 0% humidity-controlled incubator, and adult insects of scale insects, scale insects, 7 days later, adult insects of mite, weevil, beetle, weevil, 3 days later, insects of scale insects, scale insects, Weevil, beetle and weevil eggs were examined 30 to 35 days later and spider mites were examined 15 days later for the presence of hatchers. Regarding the phytotoxicity of fumigation-treated fumigants, in all one case, green banana, okra, grapefruit and orchid varieties orchid were stored together with the non-fumigated products in a temperature-controlled room at 15 ℃ for 20 days. And examined the change in appearance. Bulbs of Pachira seedlings and tulips were planted in the nursery soil, and the germination status, growth status, and flowering status of tulip bulbs were also examined in comparison with the non-fumigated products.
【００６２】[0062]
【表４】 [Table 4]
【００６３】[0063]
【表５】 [Table 5]
【００６４】[0064]
【表６】 [Table 6]
【００６５】[0065]
【発明の効果】本発明の燻蒸方法および燻蒸システム
は、燻蒸場所で高濃度のリン化水素が得られ、発火の心
配がなく安全に使用でき、燻蒸時間を大幅に短縮できる
という優れた効果を有する。EFFECTS OF THE INVENTION The fumigation method and fumigation system of the present invention have the excellent effects that a high concentration of hydrogen phosphide can be obtained at a fumigation site, can be used safely without fear of ignition, and that the fumigation time can be greatly shortened. Have.
【図１】本発明の燻蒸システムの一例を示す図である。FIG. 1 is a diagram showing an example of a fumigation system of the present invention.
【図２】本発明の燻蒸システムの一例を示す図である。FIG. 2 is a diagram showing an example of a fumigation system of the present invention.
【図３】本発明の燻蒸システムの一例を示す図である。FIG. 3 is a diagram showing an example of a fumigation system of the present invention.
【図４】本発明の燻蒸システムの一例を詳細に示す図で
ある。FIG. 4 is a diagram showing an example of the fumigation system of the present invention in detail.
【図５】本発明の燻蒸システムの一例を詳細に示す図で
ある。FIG. 5 is a diagram showing an example of the fumigation system of the present invention in detail.
【図６】本発明の一態様の系統図を示す図である。FIG. 6 is a diagram showing a system diagram of one embodiment of the present invention.
１ 臭化メチル供給手段 ２ リン化水素発生手段 ３ リン化水素精製手段 ４ リン化水素含有ガスの噴出手段 ５ 燻蒸室 ６ バルブ ７ 流量計 ８ 流量計 ９ 流量制御システム １０ 流量制御システム １１ 三方コック １２ ブロワー １３ 循環配管 １４ 導管 １５ 導管 １６ 導管 １７ 臭化メチル貯槽 １８ 臭化メチル積算流量調節計 １９ 窒素ガス貯槽 ２０ バルブ ２１ 三方コック ２２ 真空ポンプ ２３ バルブ ２４ 圧力指示計 ２５ 二方コック ２６ 二方コック ２７ 計量槽 ２８ 水または硫酸水溶液 ２９ 二方コック ３０ リン化水素発生槽 ３１ 加熱ヒーター ３２ リン化金属化合物 ３３ 温度計 ３４ 二方コック ３５ 逆止弁 ３６ リン化水素ガスの精製槽 ３７ バブリングノズル ３８ 水または硫酸水溶液 ３９ 逆止弁 ４０ バルブ ４１ 噴出ノズル ４２ バルブ ４３ バルブ ４４ バルブ ４５ リン化水素除毒装置 ４６ ブロワー ４７ 窒素ライン ４８ 真空ライン ４９ 二方コック ５０ サンプリング口（Ａ） ５１ 二方コック ５２ サンプリング口（Ｂ） ５３ リン化金属化合物投入口 ５４ バルブ ５５ 二方コック ５６ 導管 ５７ 混合器 ５８ 気化器 ５９ 三方コック ６０ 流量計 ６１ 導管 1 Methyl bromide supply means 2 Hydrogen phosphide generation means 3 Hydrogen phosphide purification means 4 Hydrogen phosphide-containing gas ejection means 5 Fumigation chamber 6 Valves 7 Flowmeter 8 Flowmeter 9 Flow control system 10 Flow control system 11 Three-way cock 12 Blower 13 Circulation piping 14 Conduit 15 Conduit 16 16 Conduit 17 Methyl bromide storage tank 18 Methyl bromide integrated flow controller 19 Nitrogen gas storage tank 20 Valve 21 Three-way cock 22 Vacuum pump 23 Valve 24 Pressure indicator 25 Two-way cock 26 Two-way cock 27 Measuring tank 28 Water or aqueous sulfuric acid solution 29 Two-way cock 30 Hydrogen phosphide generation tank 31 Heating heater 32 Metal phosphide compound 33 Thermometer 34 Two-way cock 35 Check valve 36 Hydrogen phosphide gas purification tank 37 Bubbling nozzle 38 Water or Aqueous sulfuric acid solution 39 Check valve 40 Valve 41 Jet nozzle 42 valve 43 valve 44 valve 45 hydrogen phosphide detoxification device 46 blower 47 nitrogen line 48 vacuum line 49 two-way cock 50 sampling port (A) 51 two-way cock 52 sampling port (B) 53 phosphide metal compound input port 54 valve 55 Two-way cock 56 Conduit 57 Mixer 58 Vaporizer 59 Three-way cock 60 Flowmeter 61 Conduit
Claims (29)
ネシウム、リン化亜鉛およびリン化カルシウムよりなる
群から選ばれた少なくとも１種のリン化金属化合物と水
とを接触反応させ、（２）得られたリン化水素を臭化メ
チルと混合してリン化水素含有ガスとして導管を通じて
燻蒸室へ流通させ、次いで該燻蒸室内において該リン化
水素含有ガスを噴出させ、そして（３）該燻蒸室中にお
いて燻蒸されるべき生植物、穀物、木材または飼料を処
理する、ことを特徴とする燻蒸方法。1. A method of contacting at least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide with water to obtain (2). The obtained hydrogen phosphide is mixed with methyl bromide and passed as a hydrogen phosphide-containing gas through a conduit to the fumigation chamber, and then the hydrogen phosphide-containing gas is ejected in the fumigation chamber, and (3) in the fumigation chamber. A method of fumigation, characterized in that a raw plant, grain, wood or feed to be fumigated in is treated.
で行う請求項１記載の燻蒸方法。2. The fumigation method according to claim 1, wherein the catalytic reaction is carried out at a temperature in the range of 30 to 98 ° C.
出は、少なくとも０.３ｍ／秒の流速で行う請求項１記
載の燻蒸方法。3. The fumigation method according to claim 1, wherein the hydrogen phosphide-containing gas is jetted into the fumigation chamber at a flow rate of at least 0.3 m / sec.
における流通は、少なくとも０.０３ｍ／秒の流速に保
持しながら行なわれる請求項１記載の燻蒸方法。4. The fumigation method according to claim 1, wherein the flow of the hydrogen phosphide-containing gas through the conduit to the fumigation chamber is carried out while maintaining a flow rate of at least 0.03 m / sec.
ガス中のリン化水素の含有割合は４容量％以上である請
求項１記載の燻蒸方法。5. The fumigation method according to claim 1, wherein the content ratio of hydrogen phosphide in the hydrogen phosphide-containing gas ejected into the fumigation chamber is 4% by volume or more.
少なくとも２５容量％含有している請求項１記載の燻蒸
方法。6. The fumigation method according to claim 1, wherein the hydrogen phosphide-containing gas contains at least 25% by volume of methyl bromide.
臭化メチルの割合が容量比で７５：２５〜４：９６であ
る請求項１記載の燻蒸方法。7. The fumigation method according to claim 1, wherein the hydrogen phosphide-containing gas has a volume ratio of hydrogen phosphide to methyl bromide of 75:25 to 4:96.
る請求項１記載の燻蒸方法。8. The fumigation method according to claim 1, wherein the hydrogen phosphide-containing gas is humidified.
記載の燻蒸方法。9. The catalytic reaction is a batch reaction.
The fumigation method described.
水を添加しながら実施する請求項１記載の燻蒸方法。10. The fumigation method according to claim 1, wherein the catalytic reaction is carried out while adding water to the metal phosphide compound.
グネシウム、リン化亜鉛およびリン化カルシウムよりな
る群から選ばれた少なくとも１種のリン化金属化合物と
１〜９８重量％濃度の硫酸水溶液とを接触反応させ、
（２）得られたリン化水素を臭化メチルと混合してリン
化水素含有ガスとして導管を通じて燻蒸室へ流通させ、
次いで該燻蒸室内において該リン化水素含有ガスを噴出
させ、そして（３）該燻蒸室中において燻蒸されるべき
生植物、穀物、木材または飼料を処理する、ことを特徴
とする燻蒸方法。11. (1) At least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide and an aqueous sulfuric acid solution having a concentration of 1 to 98% by weight. Contact reaction,
(2) The obtained hydrogen phosphide is mixed with methyl bromide and passed as a hydrogen phosphide-containing gas through a conduit to a fumigation chamber,
Then, the hydrogen phosphide-containing gas is ejected in the fumigation chamber, and (3) a raw plant, grain, wood or feed to be fumigated is treated in the fumigation chamber.
度で行う請求項１１記載の燻蒸方法。12. The fumigation method according to claim 11, wherein the catalytic reaction is carried out at a temperature in the range of 10 to 98 ° C.
噴出は、少なくとも０.３ｍ／秒の流速で行う請求項１
１記載の燻蒸方法。13. The jet of the hydrogen phosphide-containing gas into the fumigation chamber is performed at a flow rate of at least 0.3 m / sec.
The fumigation method described in 1.
管における流通は、少なくとも０.０３ｍ／秒の流速に
保持しながら行われる請求項１１記載の燻蒸方法。14. The fumigation method according to claim 11, wherein the flow of the hydrogen phosphide-containing gas in the conduit to the fumigation chamber is carried out while maintaining a flow rate of at least 0.03 m / sec.
有ガス中のリン化水素の含有割合は４容量％以上である
請求項１１記載の燻蒸方法。15. The fumigation method according to claim 11, wherein the hydrogen phosphide-containing gas ejected into the fumigation chamber has a hydrogen phosphide content of 4% by volume or more.
を少なくとも２５容量％含有している請求項１１記載の
燻蒸方法。16. The fumigation method according to claim 11, wherein the hydrogen phosphide-containing gas contains at least 25% by volume of methyl bromide.
と臭化メチルの割合が容量比で７５：２５〜４：９６で
ある請求項１１記載の燻蒸方法。17. The fumigation method according to claim 11, wherein the hydrogen phosphide-containing gas has a volume ratio of hydrogen phosphide to methyl bromide of 75:25 to 4:96.
いる請求項１１記載の燻蒸方法。18. The fumigation method according to claim 11, wherein the hydrogen phosphide-containing gas is humidified.
１１記載の燻蒸方法。19. The fumigation method according to claim 11, wherein the catalytic reaction is a batch reaction.
硫酸水溶液を添加しながら実施する請求項１１記載の燻
蒸方法。20. The fumigation method according to claim 11, wherein the catalytic reaction is carried out while adding an aqueous sulfuric acid solution to the metal phosphide compound.
いて該リン化水素精製手段を介したリン化水素が該臭化
メチル供給手段から供給された臭化メチルと混合され、
次いで該燻蒸室へ導入され噴出されるように前記（ａ）
〜（ｅ）が導管により接続されている流通手段 または
（ｆ−２）該臭化メチル供給手段から供給された臭化メ
チルが該リン化水素発生手段から発生したリン化水素と
混合され、次いで該リン化水素精製手段を介して該燻蒸
室へ導入され噴出されるように前記（ａ）〜（ｅ）が導
管により接続されている流通手段、よりなる燻蒸システ
ム。21. (a) Hydrogen phosphide generation means (b) Methyl bromide supply means (c) Hydrogen phosphide purification means (d) Hydrogen phosphide-containing gas ejection means (e) Fumigation chamber and (f) ( f-1) the hydrogen phosphide generated from the hydrogen phosphide generation means, and subsequently the hydrogen phosphide via the hydrogen phosphide purification means is mixed with the methyl bromide supplied from the methyl bromide supply means,
Then, in order to be introduced into the fumigation chamber and ejected, the above (a)
~ (E) a flow means connected by a conduit or (f-2) methyl bromide supplied from the methyl bromide supply means is mixed with hydrogen phosphide generated from the hydrogen phosphide generation means, and then A fumigation system comprising a flow means in which (a) to (e) are connected by a conduit so as to be introduced into the fumigation chamber through the hydrogen phosphide refining means and ejected.
ミニウム、リン化マグネシウム、リン化亜鉛およびリン
化カルシウムよりなる群から選ばれた少なくとも１種の
リン化金属化合物に水または硫酸水溶液を添加反応させ
る手段である請求項２１記載のシステム。22. The hydrogen phosphide generating means adds water or an aqueous sulfuric acid solution to at least one metal phosphide compound selected from the group consisting of aluminum phosphide, magnesium phosphide, zinc phosphide and calcium phosphide. The system according to claim 21, which is a means for reacting.
生手段より導入されたリン化水素ガスと水とを接触させ
る手段または該リン化水素ガス中のアンモニアを除去す
る手段である請求項２１記載のシステム。23. The hydrogen phosphide purification means is a means for bringing the hydrogen phosphide gas introduced from the hydrogen phosphide generation means into contact with water, or a means for removing ammonia in the hydrogen phosphide gas. The system described.
素発生手段から燻蒸室へ導入されるリン化水素含有ガス
の導管中の流速が少なくとも０.０３ｍ／秒に保持され
るように臭化メチルの供給が制御されている請求項２１
記載のシステム。24. The methyl bromide supply means has an odor so that the flow rate of the hydrogen phosphide-containing gas introduced into the fumigation chamber from the hydrogen phosphide generation means in the conduit is maintained at least 0.03 m / sec. 22. The supply of methyl iodide is controlled.
The system described.
ガス中のリン化水素濃度は４容量％以上に制御されてい
る請求項２１記載のシステム。25. The system according to claim 21, wherein the hydrogen phosphide concentration in the hydrogen phosphide-containing gas introduced into the fumigation chamber is controlled to 4% by volume or more.
を少なくとも２５容量％含有している請求項２１記載の
燻蒸方法。26. The fumigation method according to claim 21, wherein the hydrogen phosphide-containing gas contains at least 25% by volume of methyl bromide.
と臭化メチルの割合が容量比で７５：２５〜４：９６で
ある請求項２１記載の燻蒸方法。27. The fumigation method according to claim 21, wherein the hydrogen phosphide-containing gas has a volume ratio of hydrogen phosphide to methyl bromide of 75:25 to 4:96.
スの流速は少なくとも０.３ｍ／秒に制御されている請
求項２１記載のシステム。28. The system according to claim 21, wherein the flow rate of the hydrogen phosphide-containing gas ejected to the fumigation chamber is controlled to be at least 0.3 m / sec.
循環されたガス中へ噴出させ該燻蒸室に導入させる請求
項２１記載のシステム。29. The system according to claim 21, wherein the hydrogen phosphide-containing gas is jetted into the gas circulated from the fumigation chamber and introduced into the fumigation chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10701796A JP3795572B2 (en) | 1996-04-26 | 1996-04-26 | Fumigation method and fumigation system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10701796A JP3795572B2 (en) | 1996-04-26 | 1996-04-26 | Fumigation method and fumigation system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09291007A true JPH09291007A (en) | 1997-11-11 |
| JP3795572B2 JP3795572B2 (en) | 2006-07-12 |
Family
ID=14448407
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| JP2014117275A (en) * | 2012-12-19 | 2014-06-30 | Nippon Ekitan Corp | Insecticidal facilities and method by carbon dioxide gas for plant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010252749A (en) * | 2009-04-28 | 2010-11-11 | Ikeda Kogyo Co Ltd | Fumigation apparatus and fumigation method |
| JP2014117275A (en) * | 2012-12-19 | 2014-06-30 | Nippon Ekitan Corp | Insecticidal facilities and method by carbon dioxide gas for plant |
| CN109819966A (en) * | 2019-03-19 | 2019-05-31 | 穗港(广州)生物科技有限公司 | A kind of fumigation system of achievable fumigant cycling and reutilization |
| CN113970467A (en) * | 2021-10-18 | 2022-01-25 | 苏州南大光电材料有限公司 | Sampling system and sampling method for metal ions in highly toxic gas of phosphane and arsane |
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