Aluminium phosphide 磷化铝

磷化铝

磷化铝是用赤磷和铝粉烧制而成。因杀虫效率高、经济方便而应用广泛。用作粮仓熏蒸的磷化铝含量为56.0%～58.5%，3.20g/片的规格较多。薰蒸每吨粮食只需3～7片，每立方米仅用1～2片。磷化铝毒性主要为遇水、酸时则迅速分解，放出吸收很快、毒性剧烈的磷化氢气体。与氨基甲酸铵的混合物可作为一种农药，也用于焊接。

中文名称：磷化铝
英文名称：aluminium phosphide；aluminum monophosphide;Detia;phostoxin
国标编号：43036
CAS号：20859-73-8
分子式：AlP
外观性状：浅黄色或灰绿色粉末，无味，易潮解
分子量：57.95
沸 点：升华
熔 点：>1000℃
溶解性：不溶于冷水，溶于乙醇、乙醚
密 度：相对密度(水=1)2.85(15℃)
稳定性：稳定
危险标记：10(遇湿易燃物品)，40(有毒品)
主要用途：用作粮仓熏蒸杀虫剂，与氨基甲酸铵的混合物可作为一种农药，也用于焊接

农药制剂及登记证号：
90%磷化铝原药
85%磷化铝大粒剂
56%磷化铝片剂
56%磷化铝粉剂
56%磷化铝丸剂

对环境的影响
一、健康危害
侵入途径：吸入、食入。
健康危害：本品遇水或酸产生磷化氢而中毒。吸入磷化氢气体引起头晕、头痛、乏力、食欲减退、胸闷及上腹部疼痛等。严重者有中毒性精神症状，脑水肿，肺水肿，肝肾及心肌损害，心律紊乱等。口服产生磷化氢中毒，有胃肠道症状，以及发热、畏寒、头晕、兴奋及心律紊乱，严重者有气急、少尿、抽搐、休克及昏迷等。

二、毒理学资料及环境行为
毒性：对人畜高毒。
急性毒性：LD5020mg/kg(人经口)
危险特性：现酸或水和潮气时，能发生剧烈反应，放出剧毒的自燃的磷化氢气体，当温度超过60℃时会立即在空气中自燃。与氧化剂能发生强烈反应，引起燃烧或爆炸。
燃烧(分解)产物：磷烷。[1]

实验室监测方法
原子吸收法(NIOSH方法7013)
等离子化光谱法(NIOSH方法7300)

应急处理处置方法
一、泄漏应急处理
隔离泄漏污染区，限制出入。切断火源。建议应急处理人员戴自吸过滤式防尘口罩，穿一般作业工作服。小量泄漏：避免扬尘，用洁净的铲子收集于干燥、洁净、有盖的容器中。大量泄漏：用塑料布、帆布覆盖，减少飞散。然后收集回收或运至废物处理场所置。

二、防护措施
呼吸系统防护：作业时，应该佩戴自吸过滤式防尘口罩。空气中浓度较高时，建议佩戴自给式呼吸器。
眼睛防护：戴化学安全防护眼镜。
身体防护：穿化学防护服。
手防护：戴橡胶手套。
其它：工作毕，淋浴更衣。注意个人清洁卫生。

三、急救措施
皮肤接触：立即脱去被污染的衣着，用肥皂水和清水彻底冲洗皮肤。
眼睛接触：提起眼睑，用流动清水或生理盐水冲洗。就医。
吸入：迅速脱离现场至空气新鲜处。保持呼吸道通畅。如呼吸困难，给输氧。如呼吸停止，立即进行人工呼吸。就医。
食入：饮足量温水，催吐，洗胃。就医。
灭火方法：消防人员必须穿戴全身防火防毒服。灭火剂：干粉、干燥砂土、二氧化碳灭火剂。禁止用水、泡沫和酸式灭火剂灭火。[1]

制剂产品使用技术
一、作用方式
磷化铝通常是作为一种广谱性熏蒸杀虫剂，主要用于熏杀货物的仓储害虫、空间的多种害虫、粮食的储粮害虫、种子的储粮害虫、洞穴的室外啮齿动物等。磷化铝吸水后会立即产生高毒的磷化氢气体，通过昆虫（或者老鼠等动物）的呼吸系统进入体内，作用于细胞线粒体的呼吸链和细胞色素氧化酶，抑制其的正常呼吸而致死。在无氧情况下磷化氢不易被昆虫吸入，不表现毒性，有氧情况下磷化氢可被吸入而使昆虫致死。昆虫在高浓度的磷化氢中会产生麻痹或保护性昏迷，呼吸降低。制剂产品可熏蒸原粮、成品粮、油料和薯干等。若熏蒸种子时，其水分因不同作物而要求不同。

二、应用范围
在密封的仓库或者容器里，可直接灭除各类贮粮害虫，并能杀灭仓库内老鼠，粮仓已出现害虫，也能很好地杀灭。对家庭、商店物品的螨类、虱，皮衣、羽绒类虫蛀，或避免害虫为害时，也可用磷化氢。在密封的温室、玻璃房、塑料大棚中使用，可直接杀死所有的地下、地上害虫和老鼠，并可穿透到植物体内杀死钻蛀性害虫、根基线虫。用质地较厚的密封塑料袋和大棚，可处理露地花卉基地和出口盆栽花卉，杀死地下和植株内的线虫和植株上的各类害虫。[2]

三、使用方法
以56%含量的制剂为例：
1.每吨储粮或货品3~8片；每立方米囤垛或货品2~5片；每立方米熏蒸空间1－4片。
2.蒸完毕后，掀开账幕或塑料薄膜，开启门窗或通风闸口，采用自然或机械通风，充分散气，排净毒气。
3.入库时，用5%~10%硝酸银溶液浸制的试纸检验毒气，确无磷化氢气体时方可入内。
4.熏蒸时间视温度和湿度而定，5℃以下，不宜熏蒸；5℃~9℃不少于14天；10℃~16℃不少于7天；16℃~25℃不少于4天；25℃以上不少于3天。熏杀田鼠，每鼠洞1~2片。

四、注意事项：
1.严禁和药剂直接接触。
2.用本剂应严格遵守磷化铝熏蒸的有关法规和安全措施，本剂熏蒸时，须有熟练的技术人员或有经验的工作人员指导，严禁单人作业，在晴朗的天气下进行不要在夜间进行。
3.药桶应在室外开封，熏蒸场所四周，应设危险警戒线，眼、脸勿正对桶口，投药24小时，要有专人检查有无漏气、起火现象。
4.磷化氢对铜有强腐蚀性，对电灯开关、灯头等铜质部件涂以机油或用塑料薄膜密封保护。熏蒸场所的金属器件可暂时移出。
5.散气后，如数收集药袋残渣。可在远离生活区的空旷处，将残渣连袋投入盛水钢桶中，充分浸泡，令残余磷化铝完全分解（液面无气泡发生为止），无害化渣浆可弃置于环保管理部门允许的废渣排放场。
6.磷化氢吸收剂袋的处理：软包装袋拆封后，袋内附带的吸收剂小袋应收集一处，并在野外深埋土中。
7.用过的空容器，勿做他用，应及时销毁。
8.本品对蜜蜂、鱼类、家蚕有毒、施药期间避免对周围的影响，蚕室禁用。
9.施药时，应佩戴合适的防毒面具，穿工作服，戴专用手套。禁止吸烟或进食，施药后洗净手脸或洗澡。

五、储存和运输
制剂产品在装卸、运输过程中，要轻拿轻放，严防潮湿、高温或日晒。本品应储藏在凉冷、干燥、通风良好处，必须密闭贮藏。远离家畜、家禽，并要有专人保管。仓库处严禁烟火。贮藏过程中，遇有药品着火，千万不能用水或酸性物质灭火，可用二氧化碳或干沙灭火。远离儿童，不能于食品、饮料、粮食、饲料等物品同贮同运。

aluminium phosphide
Insecticide, rodenticide
IRAC 8B; fumigant

NOMENCLATURE
aluminium phosphide
Common name aluminium phosphide (E-ISO, accepted in lieu of a common name); aluminum phosphide (JMAF, accepted in lieu of a common name)
IUPAC name aluminium phosphide
Chemical Abstracts name aluminum phosphide
CAS RN [20859-73-8] EEC no. 244-088-0

magnesium phosphide
IUPAC name magnesium phosphide
Chemical Abstracts name magnesium phosphide
CAS RN [12057-74-8] EEC no. 235-023-7

zinc phosphide
Common name zinc phosphide (E-ISO, JMAF, accepted in lieu of a common name); phosphure de zinc (F-ISO, accepted in lieu of a common name)
IUPAC name trizinc diphosphide
Chemical Abstracts name zinc phosphide
CAS RN [1314-84-7] EEC no. 215-244-5

PHYSICAL CHEMISTRY
phosphine
Mol. wt. 34.0 M.f. H3P Form Colourless, odourless, flammable gas; (tech., garlic or rotting fish odour). M.p. -132.5 ºC B.p. -87.4 ºC V.p. High Henry 33 269 Pa m3 mol-1 Solubility In water 26 cm3/100 ml (17 ºC). In ethanol 0.5, ether 2, oil of turpentine 3.25 (all in vol. phosphine per vol. solvent, 18 ºC). In cyclohexanol 285.6 cm3/100 ml (26 ºC). Stability Oxidised to phosphoric acid by oxidising agents and atmospheric oxygen. F.p. It is spontaneously flammable in air (due to the presence of traces of other hydrides of phosphorus) with an explosion limit of 26.1-27.1 mg/l

aluminium phosphide
Mol. wt. 58.0 M.f. AlP Form Dark grey or yellowish crystals. M.p. >1000 ºC V.p. Very low, even at 1000 ºC S.g./density 2.85 (25 °C) Stability Though stable when dry, it reacts with moist air, violently with acids, producing phosphine.

magnesium phosphide
Mol. wt. 134.9 M.f. Mg3P2 Form Yellow-green crystals. M.p. >750 °C S.g./density 2.055 Stability Stable when dry, but reacts with atmospheric moisture, and violently with acids, producing phosphine; used to generate this fumigant, reacting more rapidly than aluminium phosphide.

zinc phosphide
Composition Tech. grade is 80-95% pure. Mol. wt. 258.1 M.f. P2Zn3 Form Amorphous grey-black powder, with a garlic-like odour. M.p. 420 ºC (when heated in the absence of oxygen) V.p. Negligible in the dry state S.g./density 4.55 Solubility Practically insoluble in water (decomposes slowly). Slightly soluble in carbon disulfide and benzene. Practically insoluble in alcohols. Stability Stable when dry, but decomposes slowly in moist air; it is decomposed violently by acids to produce phosphine, which is a potent mammalian poison, and impurities which render the gas spontaneously flammable.

COMMERCIALISATION
phosphine
Manufacturers United Phosphorus

aluminium phosphide
History Introduced as a source of fumigant insecticide by Dr. Werner Freyberg Chemische Fabrik (now Detia Freyberg). Patents GB 461997; US 2117158 Manufacturers Ag Pesticides; Aimco; Detia Freyberg; Excel; Sharda; United Phosphorus; Youngil

magnesium phosphide
History Introduced by Degesch AG to generate phosphine and so fumigate stored foodstuffs. Patents DE 923999 to Edmund Manufacturers Detia Freyberg; United Phosphorus

zinc phosphide
History It has long been used as a poison against rodents. Manufacturers Ag Pesticides; Aimco; Bell; Excel; HACCO; Liphatech Inc.; Sharda; UAP; United Phosphorus

APPLICATIONS
phosphine
Uses As a fumigant, to control a broad spectrum of insects for non-food commodities in sealed containers or structures.

aluminium phosphide
Mode of action Insecticide and rodenticide which is a respiratory, metabolic, and nerve poison. Evolves a non-flammable mixture of phosphine (the toxicant), ammonia and carbon dioxide. Uses Fumigation control of insect and rodent pests in stored grains (wheat, rye, barley, rice, sorghum, maize, etc.), seed grains, grain products (flour, noodles, semolina, etc.), pulses (peas, beans, lentils, etc.), tobacco, tapioca (roots and flour), oil seeds, expeller cake, nuts, nut kernels, dried fruit, coffee beans, cocoa beans, tea, etc.; and in empty warehouses, silos, packing materials, transport containers, etc. Phytotoxicity Living plants, fresh vegetables and fruits, with few exceptions, should not be fumigated. Formulation types GE; Fumigant. Selected products: 'Agtoxin' (Ag Pesticides); 'Al-Phos' (Aimco); 'Celphide' (Excel); 'Celphos' (Excel); 'Phostoxin' (Detia Degesch); 'Quickphos' (United Phosphorus); 'Shaphos' (Sanonda); 'Timifos' (Tide)

magnesium phosphide
Mode of action Insecticide and rodenticide which is a respiratory, metabolic, and nerve poison. Liberates phosphine, which is the toxicant. Uses As for aluminium phosphide. Also used for control of moles, voles, rats, hamsters, and rabbits by fumigation of burrows. Phytotoxicity Living plants, fresh vegetables and fruits, with few exceptions, should not be fumigated. Formulation types GE; Fumigant. Selected products: 'Magnaphos' (United Phosphorus); 'Magtoxin' (Detia Degesch)

zinc phosphide
Mode of action Rodenticide (for single ingestion). Reacts with stomach acids to liberate poisonous phosphine, which enters the bloodstream, and results in damage to the liver, kidneys and heart. Uses Bait rodenticide for control of rats, mice, voles, ground squirrels, and gophers. Also used in tracking powder form for house mouse control. Formulation types AB; CP; PA; RB; SB. Selected products: 'Agzinphos' (Ag Pesticides); 'Commando' (Excel); 'Fokeba' (Vipesco); 'Ratol' (United Phosphorus); 'Rattekal-Plus' (Frunol); 'Zawa' (Sanonda); 'Zinc-Tox' (Aimco)

OTHER PRODUCTS
phosphine
'Eco2Fume' (Cytec)

aluminium phosphide
'Celphine' (Excel); 'Detia-Gas-Ex-B' (and Ex-T, Ex-P) (Detia Degesch); 'Fumitoxin' (Pestcon); 'Gastoxin' (Bernardo); 'Gran Quick Phos' (Agricultura Nacional); 'L-Fume' (Excel); 'Talunex' (Luxan) Discontinued products: 'DeliciaGastoxin' * (Delicia); 'Phostek' * (Killgerm)

magnesium phosphide
'Degesch Plates' (Detia Degesch); 'Fumi-Cel' (Degesch America); 'Fumi-Strip' (Degesch America) Discontinued products: 'Detiaphos' * (Detia Degesch)

zinc phosphide
'Arrex' (BASF); 'Ridall-Zinc' (LiphaTech Inc.); 'ZP' (Antec) Discontinued products: 'Denkarin Grains' * (Denka)

ANALYSIS
phosphine
Phosphine present during fumigation can be determined using commercially available detector tubes, by glc (B. Chakrabarti & H. E. Wainman, Chem. Ind. (London), 1972, p. 300) or by aspiration through aqueous mercuric chloride and measuring the change in electrical conductivity (A. H. Harris, Proc. GASGA Tech. Seminar, TDRI, Slough, 1986). Methods for residues in foods reviewed, with details by J. L. Daft in Comp. Anal. Profiles, p. 274.

aluminium phosphide
Product and residue analysis depend upon determining the phosphine liberated by acid treatment. Measurement is by glc (B. Berck et al., J. Agric. Food Chem., 1970, 18, 143; T. Dumas, J. Assoc. Off. Anal. Chem., 1978, 61, 51; Anal. Methods Residues Pestic., 1988, Part II, M8; K. A. Scudamore, Anal. Methods Pestic. Plant Growth Regul., 1988, 16, 251; K. A. Scudamore & G. Goodship, Pestic. Sci., 1986, 37, 385).

magnesium phosphide
Product analysis by determining the phosphine liberated on treatment with acid, by glc (T. Dumas, J. Assoc. Off. Anal. Chem., 1978, 61, 51) or phosphate produced after reaction with bromine water (R. B. Bruce et al., J. Agric. Food Chem., 1962, 10, 18).

zinc phosphide
Product analysis by reaction with acid, the phosphine produced is estimated by titration (CIPAC Handbook, 1970, 1, 703), or oxidised to phosphoric acid which is estimated by standard methods (J. W. Elmore & F. R. Roth, J. Assoc. Off. Agric. Chem., 1943, 26, 559; 1947, 30, 213; B. L. Griswold et al., Anal. Chem., 1951, 23, 192).

MAMMALIAN TOXICOLOGY
phosphine
Reviews FAO/WHO 6, 7 (see part 2 of the Bibliography). Skin and eye No absorption through the skin. Inhalation Powerful respiratory poison. LC50 (4 h) for rats 11 ppm (0.015 mg/l) (R. S. Waritz & R. M. Brown, Am. Ind. Assoc. J., 36, 452-458 (1975)). Inhalation at 10 mg/m3 can cause death within 6 h, and at 300 ml gas/m3 for one hour, there is danger to life. No symptoms of chronic poisoning are observed. ADI (JMPR) Not necessary on basis of no residue in food [1966]. Other Phosphine is a potent, acute mammalian poison, but feeding trials with fumigated foodstuffs have shown no chronic effects on rats (U. Hackenberg, Toxicol. Appl. Pharmacol., 1972, 23,147). Toxicity class WHO (a.i.) FM; EPA (formulation) I

aluminium phosphide
Oral Acute oral LD50 for rats 8.7 mg/kg. Toxicity class WHO (a.i.) FM EC classification F; R15/29| T+; R28| R32| N; R50

magnesium phosphide
Oral Acute oral LD50 for rats 11.2 mg/kg. Toxicity class WHO (a.i.) FM EC classification F; R15/29| T+; R28| N; R50

zinc phosphide
Oral Acute oral LD50 for rats 45.7, sheep 60-70 mg/kg (M. A. Nekrasova, Sb. Rab., Leningr. Vet. Inst., 1964, No. 25, 372). Skin and eye Acute percutaneous LD50 for rabbits 2000-5000 mg/kg. Non-irritating to skin and eyes. Toxicity class WHO (a.i.) Ib; EPA (formulation) I EC classification F; R15/29| T+; R28| R32| N; R50, R53

ECOTOXICOLOGY
phosphine
Fish LC50 (96 h) for rainbow trout 9.7 ´ 10-3 ppm. Daphnia EC50 (24 h) 0.2 mg/l.

zinc phosphide
Birds Acute oral LD50 for mallard ducks 37.5, bobwhite quail 13.5, pheasants 9 mg/kg (D. W. Hayne, Mich. Agric. Exp. Stn., Q. Bull., 1951, No. 33, 412); for fowls, the lethal dose is 7-17 mg/kg (G. D. Shearer, J. Comp. Pathol. Therap., 1945, 55, 301). Fish Acute LC50 for bluegill sunfish 0.8, rainbow trout 0.5 mg/l.

ENVIRONMENTAL FATE
EHC 73 (WHO, 1988; a review of phosphine and metal phosphides). Animals In mammals, phosphine is probably metabolised to non-toxic phosphates. Plants In stored products, phosphine undergoes oxidation to phosphoric acid.