WO2020137905A1 - 燻蒸用ホスフィン及びその製造方法、並びに燻蒸方法 - Google Patents
燻蒸用ホスフィン及びその製造方法、並びに燻蒸方法 Download PDFInfo
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- WO2020137905A1 WO2020137905A1 PCT/JP2019/050165 JP2019050165W WO2020137905A1 WO 2020137905 A1 WO2020137905 A1 WO 2020137905A1 JP 2019050165 W JP2019050165 W JP 2019050165W WO 2020137905 A1 WO2020137905 A1 WO 2020137905A1
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- Prior art keywords
- phosphine
- fumigation
- mass ppm
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- less
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 285
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000003958 fumigation Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 239000002316 fumigant Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 17
- 238000002485 combustion reaction Methods 0.000 abstract description 9
- 150000003003 phosphines Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- 239000007787 solid Substances 0.000 description 14
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- -1 phosphorus compound Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000006011 Zinc phosphide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 229940048462 zinc phosphide Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052676 chabazite Inorganic materials 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052675 erionite Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- JEWHCPOELGJVCB-UHFFFAOYSA-N aluminum;calcium;oxido-[oxido(oxo)silyl]oxy-oxosilane;potassium;sodium;tridecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.[Na].[Al].[K].[Ca].[O-][Si](=O)O[Si]([O-])=O JEWHCPOELGJVCB-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 229910052908 analcime Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910001743 phillipsite Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P15/00—Biocides for specific purposes not provided for in groups A01P1/00 - A01P13/00
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/26—Phosphorus; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/06—Hydrogen phosphides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
Definitions
- the present invention relates to a fumigation phosphine and a fumigation method using the same.
- Phosphine is a compound represented by PH 3 . Phosphine has an excellent insecticidal action and is used as a fumigant.
- Phosphine is generally obtained by reacting yellow phosphorus (main component: P 4 ) with an alkali, hydrolyzing yellow phosphorus at a high temperature, reacting a metal phosphorus compound such as aluminum phosphide or zinc phosphide with water or an acid.
- the phosphine before purification hereinafter also referred to as “crude phosphine” obtained by any method has impurities.
- Patent Document 1 when a lower phosphorus hydride compound is contained in a crude phosphine, a yellow tar-like or powder-like substance is deposited on the inner wall of a valve or the like and clogs it, resulting in operational danger. However, it can be dangerous and the use of activated carbon for the removal of lower phosphorus hydride compounds is described. Further, Patent Document 2 describes that moisture of phosphine is removed by zeolite in order to obtain high-purity phosphine for semiconductor production.
- phosphine itself has spontaneous pyrophoricity and also has spontaneous pyrophoricity due to impurities. Therefore, for the safety of fumigation, there is a demand for phosphine having a low self-ignitability.
- An object of the present invention is to provide a phosphine for fumigation, which effectively suppresses clogging and scaling of pipes and valves due to impurities and has low self-ignitability.
- the present invention provides a fumigant phosphine having a P 4 content of 10 mass ppm or less and a water content of 10 mass ppm or less.
- the present invention also provides a fumigation method for fumigating a substance to be fumigated using phosphine having a P 4 content of 10 mass ppm or less and a water content of 10 mass ppm or less.
- the phosphine used in the present invention is a compound represented by PH 3 .
- the property of phosphine may be any of solid, liquid and gas. Phosphine is circulated and/or stored, for example, in a liquid state housed in a pressure resistant container, and used for fumigation in a gas state.
- the present inventor diligently studied the cause of the conventional fumigation phosphine blocking the pipe of the fumigation gas supply device. As a result, it was found that the presence or absence of blockage of the pipe was related to the amount of P 4 in phosphine. The reason is not clear, precipitates in the piping is phosphine component of the solid P 4 and behavior contained in a phosphine as P 4 or impurities are similar and also decompose phosphine solid P I suspect that it will be 4 . The present inventor believes that the pipe can be prevented from being blocked by reducing the amount of P 4 as an index of impurities in phosphine. Furthermore, the present inventor has found that the spontaneous combustion can be lowered by reducing the amount of water together with the amount of P 4 as described later.
- P 4 exists as a solid in liquid phosphine and as a vapor or mist in gaseous phosphine. It is presumed that P 4 is mixed in the phosphine due to the raw material for phosphine production. Further, as described above, the present inventor believes that the further decomposition of the solid hydrogen phosphide may generate P 4 .
- the content of P 4 in phosphine is 10 mass ppm or less, and more preferably 5 mass ppm or less.
- P 4 in the phosphine is not substantially contained, it is preferably 0.1 mass ppm or more from the viewpoint of the manufacturing cost of the phosphine for fumigation.
- the amount of P 4 is a ratio with respect to phosphine (PH 3 ).
- reducing the amount of water in the phosphine is also important for suppressing clogging of the phosphine piping and suppressing spontaneous combustion. Found out. The reason is not clear, phosphine reacts in contact with water, may change the phosphine solid with a behavior similar to P 4 or P 4. Therefore, such a reaction can be prevented by setting the water content in the phosphine to a certain level or less. The present inventor believes that, due to this, the clogging of the pipe due to the precipitation of solids can be effectively suppressed, and the spontaneous combustion can be reduced.
- the amount of water in phosphine is 10 mass ppm or less, and more preferably 5 mass ppm or less.
- the water content is a ratio with respect to phosphine (PH 3 ).
- the crude phosphine may be subjected to a specific purification method described below.
- a method of reacting yellow phosphorus with an alkali a method of reacting yellow phosphorus with an alkali, a method of hydrolyzing yellow phosphorus at high temperature, a metal phosphorus compound such as aluminum phosphide, zinc phosphide, etc.
- yellow phosphorus and alkali are allowed to act to produce phosphine.
- Any of the following (1) and (2) may be used as the method for causing the yellow phosphorus and the alkali to act.
- the conventional fumigation phosphine was produced by bringing aluminum phosphide or zinc phosphide into contact with water and used as it is for fumigation.
- the crude phosphine produced by each of the above-mentioned methods has been simply purified with activated carbon, zeolite or the like before use.
- the water content and the P 4 content of such a conventional fumigation phosphine were larger than the above upper limits.
- P or P It is possible to use a method in which a method of adsorbing and removing 4 ; a method of dehydrating phosphine by cooling below freezing point; and a method of dehydrating phosphine using silica gel or zeolite are combined. Further, the above method may be combined with a method of washing the crude phosphine obtained by each of the above methods with water. It is necessary to carry out drying after the method of washing with water, but other than that, there is no particular limitation on the order of these methods.
- phosphine may react with water to react, and may be converted into solid hydrogen phosphide having a behavior similar to that of P 4 or P 4 , so that water in the phosphine can be removed first, It is possible to suppress the by-product of P 4 or solid hydrogen phosphide.
- the above-mentioned zeolite and silica gel used for dehydrating phosphine have pores that function to remove water, and the presence of P 4 or solid hydrogen phosphide in the phosphine blocks these pores. This may make it difficult to obtain a sufficient dehydration effect.
- the accumulation of P 4 and solid hydrogen phosphide may cause ignition.
- the zeolite is not particularly limited, and may be either natural or synthetic.
- the specific surface area is preferably 150 m 2 /g or more, and the average particle size is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m.
- the activated carbon is not particularly limited, coal, petroleum pitch, activated carbon derived from minerals such as tar, coconut shell, wood, activated carbon derived from plants such as bamboo, phenolic resins, melamine resins, polyimide resins, resins such as polyester resins.
- Examples of the activated carbon include a raw material of activated carbon and an activated carbon composed of molecular sieving carbon.
- Examples of the shape of the activated carbon include powdered activated carbon, granular activated carbon, crushed activated carbon, fibrous activated carbon and the like.
- the specific surface area of the activated carbon is preferably 150 m 2 /g or more, more preferably 300 m 2 /g or more.
- the silica gel may be amorphous silica excluding silica sol.
- silica gel conforming to the JIS Z0701 standard fine powder silicic acid obtained by a wet method such as white carbon, or a dry method such as aerosil is obtained.
- the fine powder silicic acid thus obtained, dust as a by-product from the production process of silicon or ferrosilicon, or naturally produced soft silica stone, etc. may be mentioned.
- the specific surface area is preferably 150 m 2 /g or more, and the average particle size is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m.
- the amount of diphosphine which is one of the impurities, is not more than a certain amount.
- Diphosphine is a compound represented by H 4 P 2 . Diphosphines can decompose to form solid phosphorus hydrides that behave similarly to P 4 .
- the phosphine used in the present invention preferably has an amount of diphosphine of 100 mass ppm or less, preferably 70 mass ppm or less, more preferably 50 mass ppm or less, still more preferably 30 mass ppm or less.
- the amount of diphosphine is preferably 1 mass ppm or more from the viewpoint of easy production of phosphine.
- the amount of diphosphine is the ratio with respect to phosphine (PH 3 ).
- the amount of water in the phosphine, the amount of P 4 and the amount of diphosphine are all measured with the phosphine in the gas state.
- the water content in phosphine is measured by the Karl Fischer method.
- the amount of P 4 is measured by the phosphovanadomolybdic acid colorimetric method.
- the amount of diphosphine is measured by the nuclear magnetic resonance method.
- the amount of impurities other than the above-mentioned water, P 4 and diphosphine is as small as possible.
- the amount of H 2 in the phosphine is preferably 100 mass ppm or more and 10000 mass ppm or less, and more preferably 200 mass ppm or more and 9000 mass ppm or less.
- the amount of N 2 is preferably 1 mass ppm or more and 500 mass ppm or less, and more preferably 10 mass ppm or more and 300 mass ppm or less.
- the amount of O 2 is preferably 0.1 mass ppm or more and 50 mass ppm or less, and more preferably 0.5 mass ppm or more and 30 mass ppm or less.
- the amount of AsH 3 is preferably 1 mass ppm or more and 500 mass ppm or less, and more preferably 10 mass ppm or more and 300 mass ppm or less.
- the amount of CO 2 is preferably 0.01 mass ppm or more and 1 mass ppm or less, and more preferably 0.05 mass ppm or more and 0.5 mass ppm or less.
- a fumigant phosphine having impurities in the above range is preferable because it can achieve both production cost and ease of production and safety.
- the amount of these impurities is the amount with respect to phosphine, and can be measured by, for example, gas chromatography or atomic absorption spectrometry.
- the purity of the phosphine used in the present invention is preferably 98% by mass or more, and more preferably 99% by mass or more.
- the purity of phosphine is preferably 99.9% by mass or less from the viewpoint of easy production of phosphine.
- the phosphine used in the present invention has the above-mentioned low water content and low P 4 content, it has a low spontaneous ignition property and is easy to handle as compared with conventional ones.
- the phosphine used in the present invention preferably does not spontaneously ignite when it has a concentration of more than 1% by volume, preferably 1.3% by volume or more in air at 54°C or lower.
- “not spontaneously igniting when it has a concentration of more than 1% by volume and 1.3% by volume or more” means that it does not spontaneously ignite at any concentration of more than 1% by volume and 1.3% by volume or more, respectively. It does not mean that spontaneous combustion does not occur at all concentrations above 1% by volume and above 1.3% by volume.
- the spontaneous firing temperature of phosphine is measured under the atmospheric pressure based on the regulation of IEC60079-20-1 2010, the spontaneous firing temperature is preferably more than 54°C.
- the method described below can be used as a specific method for measuring the spontaneous ignition temperature.
- phosphine is used for fumigation after being stored and distributed as a liquid in a pressure vessel such as a cylinder or a storage tank, then vaporized at room temperature and atmospheric pressure, as it is or mixed with an inert gas.
- a pressure vessel such as a cylinder or a storage tank
- the inert gas include carbon dioxide and nitrogen.
- fumigation refers to a gas having a controlling effect against various pests such as mold, bacteria and insects, which is brought into contact with an object (hereinafter, also referred to as “fumigation object”).
- object hereinafter, also referred to as “fumigation object”.
- fumigants include cultivated plants, foods other than cultivated plants, soils, buildings, cultural properties, and the like. The cultivated plant may be before harvest or after harvest.
- the resulting crude phosphine was passed through a column having an inner diameter of 40 mm and a length of 400 mm filled with 300 ml of activated carbon (Granular Shirasagi G2c manufactured by Osaka Gas Chemical Co., Ltd.) at a flow rate of 1 L/min, and then passed through a cooling tower to 10°C. After cooling, it was passed through a column having an inner diameter of 40 mm and a length of 400 mm filled with 300 ml of type A silica gel (JIS Z0701) at a flow rate of 1 L/min to obtain purified phosphine.
- Table 1 shows the amount of water, the amount of P 4 and the amount of diphosphine of the obtained purified phosphine.
- the water content of the obtained purified phosphine, impurities other than P 4 and diphosphine are H 2 3000 mass ppm, N 2 41.2 mass ppm, O 2 0.94 mass ppm, AsH 3 100 mass ppm. , CO 2 was 0.1 mass ppm.
- Example 2 A purified phosphine was obtained in the same manner as in Example 1 except that the A type silica gel was passed through A type zeolite (Wako Pure Chemical Industries, Ltd., Molecular Sieve 3A) in Example 1.
- Table 1 shows the amount of water, the amount of P 4 and the amount of diphosphine of the obtained purified phosphine.
- Example 3 Purified phosphine was obtained in the same manner as in Example 1 except that the crude phosphine obtained in the same manner as in Example 1 was passed through activated carbon and A-type silica gel at a flow rate of 3 L/min.
- Table 1 shows the amount of water, the amount of P 4 and the amount of diphosphine of the obtained purified phosphine. Further, the water content of the obtained purified phosphine, impurities other than P 4 and diphosphine, H 2 is 3100 mass ppm, N 2 is 42.2 mass ppm, O 2 is 0.1 mass ppm, AsH 3 is 105 mass ppm. , CO 2 was 0.1 mass ppm.
- Example 1 The crude phosphine obtained in Example 1 was designated as Comparative Example 1.
- Table 1 shows the amount of water, the amount of P 4 , and the amount of diphosphine in the obtained crude phosphine.
- Example 2 Purified phosphine was obtained in the same manner as in Example 1 except that the crude phosphine obtained in the same manner as in Example 1 was passed through activated carbon and A-type silica gel at a flow rate of 10 L/min.
- Table 1 shows the amount of water, the amount of P 4 and the amount of diphosphine of the obtained purified phosphine.
- the water content of the obtained purified phosphine, impurities other than P 4 and diphosphine H 2 is 3200 mass ppm
- N 2 is 62.2 mass ppm
- O 2 is 2 mass ppm
- AsH 3 is 200 mass ppm
- CO. 2 was 0.2 mass ppm.
- Example 4 To 300 g of aluminum phosphide, 1 liter of water heated to 40° C. was gradually added and reacted in a usual manner to generate 30 L of gas. This generated gas was immersed in liquid nitrogen at ⁇ 200° C. and introduced into a cooled pressure vessel to condense phosphine to remove a part of water. Then, the pressure vessel was taken out from the liquid nitrogen and the temperature was gradually raised to room temperature to obtain a crude phosphine. The obtained crude phosphine was purified by the same method as in Example 1 to obtain purified phosphine. Table 1 shows the amount of water, the amount of P 4 , and the amount of diphosphine of the obtained purified phosphine.
- Example 3 The crude phosphine obtained in Example 4 was designated as Comparative Example 3.
- Table 1 shows the amount of water, the amount of P 4 , and the amount of diphosphine in the obtained crude phosphine.
- Purity of phosphine and H 2 , N 2 , O 2 and CO 2 measuring method It was measured by gas chromatography (Shimadzu Corporation, GC-7A) analysis under the following conditions.
- the purity of phosphine was a value obtained by subtracting the amount of water in phosphine, the amounts of P 4 , diphosphine and AsH 3 and the analytical values of gas components other than phosphine detected by gas chromatography analysis.
- H 2 , N 2 , O 2 and CO 2 were detected as gases other than phosphine.
- Gas chromatography measurement conditions The measurement sample is subdivided in a container with a septum cap under an inert gas atmosphere, and 0.2 ⁇ L of the measurement sample is injected into a gas chromatograph (“GC-7A” manufactured by Shimadzu Corporation) with a syringe and measured under the following conditions. did. ⁇ Column: Porapak T 50-80 mesh (manufactured by GL Sciences Inc.) ⁇ Column temperature: 60°C ⁇ Detector: TCD, carrier gas: He (100 kPa pressure) The amount of the impurity gas component was determined by the area percentage method in which the detected peak total area was 100% and the ratio of the peak to that was calculated.
- GC-7A gas chromatograph
- the self-ignition temperature was measured according to the regulations of IEC60079-20-1:2010. According to the regulation, the spontaneous ignition temperature is measured by injecting a gas sample into a 200 ml Erlenmeyer flask which is heated to a predetermined temperature and is in an open state and filled with air to confirm whether spontaneous ignition occurs. I went by. A 20 ml gas sample (phosphine) was injected into the Erlenmeyer flask by a 200 ml airtight syringe at a speed of 25 ml per second. After the injection was completed, it was observed that there was spontaneous ignition if the ignition occurred within 5 minutes. The spontaneous ignition temperature was measured every 20°C to 1°C.
- the fumigation phosphine of the present invention effectively suppresses the clogging of the piping and valves of the fumigation gas supply device due to impurities, and has a low spontaneous ignition property. Further, the fumigation method of the present invention is safe because the piping of the fumigant gas supply device is prevented from being blocked and the possibility of spontaneous combustion is reduced.
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Abstract
Description
好ましくは、黄リンとアルカリを作用させてホスフィンを製造する。
黄リンとアルカリを作用させる方法としては、次の(1)及び(2)のいずれであってもよい。
(1)P4+3NaOH+3H2O→3PH3+3NaH2PO2
(2)P4+4H2O+2NaOH→2PH3+2NaH2PO3
N2の量は1質量ppm以上500質量ppm以下であることが好ましく、10質量ppm以上300質量ppm以下であることがより好ましい。
O2の量は0.1質量ppm以上50質量ppm以下であることが好ましく、0.5質量ppm以上30質量ppm以下であることがより好ましい。
AsH3の量は1質量ppm以上500質量ppm以下であることが好ましく、10質量ppm以上300質量ppm以下であることがより好ましい。
CO2の量は0.01質量ppm以上1質量ppm以下であることが好ましく、0.05質量ppm以上0.5質量ppm以下であることがより好ましい。
不純物が前記の範囲内である燻蒸用ホスフィンは、製造コストや製造容易性と安全性の両立を図ることができるため好ましい。これらの不純物の量は、ホスフィンに対する量であり、例えばガスクロマトグラフィーや原子吸光分析法により測定することができる。
黄リン30gに25質量%の水酸化ナトリウム水溶液102.4gを加え、常法によって反応させて体積比でホスフィン:水素=1:1である混合ガス10.5Lを発生させた。この発生ガスを-200℃の液体窒素に浸漬して冷却した加圧容器に導入してホスフィンを凝縮させ、水分の一部を除去した。その後、液体窒素から加圧容器を取り出して徐々に室温まで昇温することにより未凝縮の水素を放出して粗製ホスフィンを得た。
実施例1において、A型シリカゲルに変えてA型ゼオライト(和光純薬社製、モレキュラーシーブ3A)に通すこと以外は実施例1と同じ方法で精製ホスフィンを得た。得られた精製ホスフィンの水分量、P4の量及びジホスフィン量を表1に示す。また、得られた精製ホスフィンの水分、P4及びジホスフィン以外の不純物は、H2が2950質量ppm、N2が41.8質量ppm、O2が0.95質量ppm、AsH3が99質量ppm、CO2が0.1質量ppmであった。
実施例1と同様の方法で得られた粗製ホスフィンを、3L/minの流量で活性炭及びA型シリカゲルに通すこと以外は実施例1と同じ方法で精製ホスフィンを得た。得られた精製ホスフィンの水分量、P4の量及びジホスフィン量を表1に示す。また、得られた精製ホスフィンの水分、P4及びジホスフィン以外の不純物は、H2が3100質量ppm、N2が42.2質量ppm、O2が0.1質量ppm、AsH3が105質量ppm、CO2が0.1質量ppmであった。
実施例1において得られた粗製ホスフィンを比較例1とした。得られた粗製ホスフィンの水分量、P4の量及びジホスフィン量を表1に示す。
実施例1と同様の方法で得られた粗製ホスフィンを、10L/minの流量で活性炭及びA型シリカゲルに通すこと以外は実施例1と同じ方法で行い精製ホスフィンを得た。得られた精製ホスフィンの水分量、P4の量及びジホスフィン量を表1に示す。また、得られた精製ホスフィンの水分、P4及びジホスフィン以外の不純物は、H2が3200質量ppm、N2が62.2質量ppm、O2が2質量ppm、AsH3が200質量ppm、CO2が0.2質量ppmであった。
リン化アルミニウム300gに、40℃に加温した水1リットルを徐々に加え、常法によって反応させてガス30Lを発生させた。この発生ガスを-200℃の液体窒素に浸漬して冷却した加圧容器に導入してホスフィンを凝縮させ、水分の一部を除去した。その後、液体窒素から加圧容器を取り出して徐々に室温まで昇温することにより粗製ホスフィンを得た。
得られた粗製ホスフィンを、実施例1と同じ方法で精製し、精製ホスフィンを得た。得られた精製ホスフィンの水分量、P4の量及びジホスフィン量を表1に示す。また、得られた精製ホスフィンの水分、P4及びジホスフィン以外の不純物は、H2が3100質量ppm、N2が42.2質量ppm、O2が1質量ppm、AsH3が100質量ppm、CO2が0.1質量ppmであった。
実施例4において得られた粗製ホスフィンを比較例3とした。得られた粗製ホスフィンの水分量、P4の量及びジホスフィン量を表1に示す。
875KFガス用水分計(メトローム社製)を用いてカールフィッシャー法により測定した。測定温度は25℃とした。
ホスフィンガスを冷却ベンゼン中に通気してP4を吸収させ、脱気によりホスフィンを除去して得られた溶液を、リンバナドモリブデン酸比色法により測定した。測定温度は25℃とした。
ホスフィンガスをアセトン・ドライアイス溶液に吸収させた溶液を、核磁気共鳴(NMR)装置(日本電子株式会社製、JNM-ECA500)を用いて測定した。
原子吸光分析装置として、VARIAN―AA240(アジレント・テクノロジー社製)を使用した。検量線に使用する標準液はヒ素標準液原子吸光用標準液(和光純薬工業(株)社製、1000ppm)を使用した。サンプルは100mlのホスフィンガスを、1規定の過マンガン酸カリウム水溶液50mlに完全に吸収させこの吸収液をヒ素量について原子吸光法絶対検量線法で分析した。測定したヒ素量からAsH3としてのモル数を算出して、ホスフィン中のアルシン換算の質量基準濃度を算出した。
下記の条件のガスクロマトグラフィー(株式会社島津製作所製、GC-7A)分析により測定した。ホスフィンの純度は、ホスフィン中の水分量、P4、ジホスフィン及びAsH3の各量並びにガスクロマトグラフィー分析により検出されたホスフィン以外のガス成分の分析値を差し引いた数値とした。なお実施例及び比較例ではホスフィン以外のガスとして、H2、N2、O2及びCO2が検出された。
測定試料を不活性ガス雰囲気下でセプタムキャップ付きの容器に小分けし、シリンジで測定試料0.2μLをガスクロマトグラフィー(株式会社島津製作所製、「GC-7A」)に打ち込み、下記条件にて測定した。
・カラム:Porapak T 50~80メッシュ(ジーエルサイエンス(株)製)
・カラム温度:60℃
・検出器:TCD、キャリアガス:He(100kPa圧)
不純物ガス成分の量は、検出したピーク総面積を100%として、それに対するピークの比率を計算する面積百分率法により求めた。
(1)異物析出性
実施例及び比較例で得られたホスフィンガスを、それぞれ加圧して液化ホスフィンとし、47L高圧ガスボンベに充填した。このボンベから内径3.18mm、長さ2mのステンレスBA管(SUS304 TP-SC-BA JIS G3459)に20L/分の速度で通気した。9時間経過後、目視にて配管内部の粉末析出の有無を確認し、以下の評価基準で評価した。結果を表2に示す。
-:配管内部に全く粉末が検出されなかった。
+:配管内部に粉末が析出し、配管内壁にスケーリングが検出された。
IEC60079-20-1:2010の規定の通りに、自然発火温度を測定した。当該規定では、自然発火温度の測定は、所定温度に加熱された開放状態にあり内部が空気で満たされた200mlの三角フラスコにガスサンプルを注入し、自然発火が起こるか否かを確認することにより行った。20mlのガスサンプル(ホスフィン)は200mlの気密なシリンジにより、毎秒25mlのスピードで、三角フラスコ内に注入された。注入完了後、5分間以内に発火が起きる場合を自然発火性があると観察した。自然発火温度は、20℃から1℃ごとに測定した。
試験に使用するフラスコ及びフラスコを加熱する窯としては、「IEC60079-20-1:2000」におけるFigure A.1に記載のものを用いた。フラスコの材質としてはホウケイ酸ガラスを用いた。
ガスサンプルを注入する装置としては、「IEC60079-20-1:2000」におけるFigure A.9に記載のものを用いた。
結果を表3に示す。
Claims (8)
- P4の含有量が10質量ppm以下であり、水分の含有量が10質量ppm以下である燻蒸用ホスフィン。
- ジホスフィンの含有量が100質量ppm以下である請求項1に記載の燻蒸用ホスフィン。
- 54℃以下の空気中で1容量%超の濃度を有したときに自然発火しない請求項1又は2に記載の燻蒸用ホスフィン。
- ホスフィン中のP4を除去した後、水分を除去する精製工程を有する燻蒸用ホスフィンの製造方法。
- 前記P4の除去を活性炭で行う請求項4に記載の燻蒸用ホスフィンの製造方法。
- 前記水分の除去をシリカゲル又はゼオライトで行う請求項4に記載の燻蒸用ホスフィンの製造方法。
- P4の含有量が10質量ppm以下であり、水分の含有量が10質量ppm以下であるホスフィンを用いて被燻蒸物を燻蒸する燻蒸方法。
- 前記被燻蒸物が、栽培植物、栽培植物以外の食品、土壌、建造物、文化財から選ばれる少なくとも一種である、請求項7に記載の燻蒸方法。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1570868A (en) * | 1977-05-12 | 1980-07-09 | Hoechst Ag | Production of phosphine |
JPS62138313A (ja) * | 1985-12-13 | 1987-06-22 | Nippon Chem Ind Co Ltd:The | 高純度ホスフインの製造方法 |
JPH01164711A (ja) * | 1987-12-21 | 1989-06-28 | Seitetsu Kagaku Co Ltd | 純粋ホスフィンの製造法 |
JPH09165209A (ja) * | 1995-06-07 | 1997-06-24 | Degesch De Chile Ltda | ホスフィン含有ガス製造用の組成物、方法及び装置 |
JP2015136368A (ja) * | 2014-01-24 | 2015-07-30 | グン キム、フェ | 燻蒸気化装置 |
JP2017536115A (ja) * | 2014-11-10 | 2017-12-07 | アルケマ フランス | 土壌燻蒸のための自己接着性フィルム |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1570868A (en) * | 1977-05-12 | 1980-07-09 | Hoechst Ag | Production of phosphine |
JPS62138313A (ja) * | 1985-12-13 | 1987-06-22 | Nippon Chem Ind Co Ltd:The | 高純度ホスフインの製造方法 |
JPH01164711A (ja) * | 1987-12-21 | 1989-06-28 | Seitetsu Kagaku Co Ltd | 純粋ホスフィンの製造法 |
JPH09165209A (ja) * | 1995-06-07 | 1997-06-24 | Degesch De Chile Ltda | ホスフィン含有ガス製造用の組成物、方法及び装置 |
JP2015136368A (ja) * | 2014-01-24 | 2015-07-30 | グン キム、フェ | 燻蒸気化装置 |
JP2017536115A (ja) * | 2014-11-10 | 2017-12-07 | アルケマ フランス | 土壌燻蒸のための自己接着性フィルム |
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