WO2017012457A1 - 一种粮食储存方法 - Google Patents

一种粮食储存方法 Download PDF

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Publication number
WO2017012457A1
WO2017012457A1 PCT/CN2016/087974 CN2016087974W WO2017012457A1 WO 2017012457 A1 WO2017012457 A1 WO 2017012457A1 CN 2016087974 W CN2016087974 W CN 2016087974W WO 2017012457 A1 WO2017012457 A1 WO 2017012457A1
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Prior art keywords
fumigant
fumigation
rice
grain
mold
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PCT/CN2016/087974
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English (en)
French (fr)
Inventor
姜标
张琛
陶黎明
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中国科学院上海有机化学研究所
华东理工大学
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Publication of WO2017012457A1 publication Critical patent/WO2017012457A1/zh

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    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B9/00—Preservation of edible seeds, e.g. cereals
    • A23B9/16—Preserving with chemicals
    • A23B9/18—Preserving with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B9/22—Preserving with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O

Definitions

  • the invention relates to a food storage method and belongs to the technical field of food preservation.
  • the total loss of waste in the storage, transportation, processing and other circulation links in China is about 70 billion jin, of which only about 40 billion jin is lost in the circulation.
  • the annual food loss of postpartum mold in China cannot be underestimated, and fungal and toxin pollution poses a serious threat to China's food security.
  • Liu Yang a researcher at the Agricultural Products Processing Research Institute of the Chinese Academy of Agricultural Sciences, "China has invested hundreds of billions of dollars every year to strive for 1% increase in grain production, but the annual post-harvest loss caused by mildew is as high as 21 million tons, accounting for the country's total grain output. 4.2%, the direct economic loss is about 18 billion to 24 billion yuan.”
  • mycotoxins are the most dangerous food contaminants naturally occurring, and the toxicity of aflatoxins is 10 times that of potassium cyanide and 68 times that of arsenic, which is one of the most important causes of liver cancer.
  • Mycotoxins are mainly produced during post-harvest food storage.
  • molds are mainly Aspergillus flavus, Fusarium oxysporum, and Fusarium graminearum.
  • Aspergillus flavus and Fusarium graminearum In Europe and the United States, except for mold, Aspergillus flavus and Fusarium graminearum
  • there are parasitic Aspergillus and yellow Fusarium are mainly characterized by high bacteria, long storage period, wide source, variety and quantity.
  • the fumigants used are mainly phosphine, ethylene oxide, methyl bromide and sulfuryl fluoride, which are environmentally friendly and safe.
  • a food storage method comprising the steps of: placing a fumigant under or/and around a grain pile at room temperature to 40 ° C; the fumigant is a thiosulfinate compound and a thiosulfonate A compound of an acid ester compound.
  • the fumigant is placed below or/and around the grain pile in a closed environment at room temperature.
  • the fumigant is supported on a carrier material having an adsorption function, which may be filter paper, silica gel, dextrin, filter membrane, cotton, sponge or cloth, and the like.
  • a carrier material having an adsorption function which may be filter paper, silica gel, dextrin, filter membrane, cotton, sponge or cloth, and the like.
  • the carrier material loaded with the fumigant is placed in a hollow device having an outwardly diffusing port or mesh surface
  • the hollow device may be a box structure, a box structure, a cage structure, a bag, or the like.
  • the hollow device has a fan and a speed control function.
  • the hollow device has a self-heating and temperature regulating function.
  • the fumigant is a compound having a volume ratio of 1:1 to 1:5 by a thiosulfinate compound and a thiosulfonate compound.
  • the thiosulfinate compound has the following structural formula: a compound wherein: R 1 and R 2 are the same or different and are each selected from a C 1 -C 4 alkane group (for example, methyl, ethyl, propyl, butyl) or a C 2 -C 4 alkene group. (Example: allyl).
  • R 1 is the same as R 2 .
  • the thiosulfonate compound has the following structural formula: a compound wherein: R 3 and R 4 are the same or different and are each selected from a C 1 -C 4 alkane group (for example, methyl, ethyl, propyl, butyl) or a C 2 -C 4 alkene group. (Example: allyl).
  • R 3 is the same as R 4 .
  • the present invention has the following beneficial effects:
  • the invention adopts a compound of a thiosulfinate compound and a thiosulfonate compound as a fumigant, which not only realizes safe and effective sterilization and disinfection of food, but also has the lowest environmental pollution and no fumigant residue.
  • the problem does not affect the food itself and human health, and has the advantages of green environmental protection; in particular, the present invention can realize one-time treatment of various foods and various bacterial molds in the same fumigation environment, and after the fumigation treatment of the present invention
  • the grain can be placed in the granary environment or transportation conditions for at least half a year to no longer regenerate the bacterial mold; in addition, the method of the invention has the advantages of simple operation, low cost, wide range of applicable grain varieties and bacterial molds, and safety for storing grain. Long-term preservation is of great value and far-reaching significance.
  • Methyl methylthiosulfinate and ethyl thiosulfonate were stirred and mixed at a volume ratio of 1:3 at room temperature; abbreviated as fumigant A; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Ethyl ethyl thiosulfinate and methyl methyl sulfonate were stirred and mixed at a volume ratio of 1:2 at room temperature; abbreviated as fumigant B; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Ethyl ethyl thiosulfinate and ethyl thiosulfonate were stirred and mixed at room temperature 1:1 at room temperature; abbreviated as fumigant C; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Methyl methylthiosulfinate and methyl methylsulfonate were stirred and mixed at a volume ratio of 1:1.5 at room temperature; abbreviated as fumigant D; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • the propyl thiosulfinate sulfonate and ethyl thiosulfonate were stirred and mixed at a volume ratio of 1:2.5 at room temperature; abbreviated as fumigant E; the oral LD 50 >500 mg/Kg was determined. It belongs to low toxicity.
  • the propyl thiosulfinate propyl ester and allyl thiosulfonic acid allyl ester were stirred and mixed at a volume ratio of 1:4 at room temperature; abbreviated as fumigant F; determination of oral LD 50 >500 mg in mice /Kg, which is low in toxicity.
  • Ethyl ethyl thiosulfinate and butyl butyl sulfonate were stirred and mixed at a volume ratio of 1:5 at room temperature; abbreviated as fumigant G; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Ethyl methylthiosulfinate and methyl thiosulfonate were stirred and mixed at a volume ratio of 1:3 at room temperature; abbreviated as fumigant H; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Allyl allysulfinyl sulfinate and allyl methylthiosulfonate were stirred and mixed at a volume ratio of 1:2.5 at room temperature; abbreviated as fumigant I; determination of oral LD 50 in mice > 500mg/Kg, which is low in toxicity.
  • the fumigant C is first loaded on the filter paper, and then the corn sample is placed on top of the filter paper (which can be achieved by setting a fixed frame) and fumigation at room temperature.
  • the corn sample subjected to the fumigation treatment of the present embodiment is placed in a room temperature environment, and the mold tracking test is performed regularly.
  • the test results are shown in the table below:
  • Grain variety rice
  • the fumigant C is loaded on the filter paper, and then the filter paper is placed at the bottom of the glass cylinder, and then the rice sample is placed on top of the filter paper (can be realized by providing a fixed frame in the glass cylinder), the closed glass cylinder is at room temperature. Fumigation under.
  • the rice samples subjected to the fumigation treatment of the present example were placed in a room temperature environment, and the mold tracking test was performed regularly, and the test results are shown in the following table:
  • Grain variety rice
  • the fumigant C is first loaded on the filter paper, and then the filter paper is placed in a hollow box having a mesh surface, a fan and a speed control function, and the box is placed at the bottom of the glass cylinder to prepare the rice sample. It is placed above the box (can be realized by providing a fixing frame in the glass cylinder), the glass jar is sealed, and the fan is turned on at room temperature (the wind speed is set to medium speed) for fumigation.
  • the rice sample subjected to the fumigation treatment of the present embodiment is placed in a room temperature environment, and the mold tracking test is performed regularly.
  • the test results are shown in the table below:
  • Grain variety rice
  • the fumigant C is first loaded on the filter paper, and then the filter paper is placed in a hollow box having a mesh surface, self-heating and temperature-regulating function, and the box is placed at the bottom of the glass jar to prepare the rice sample. It is placed above the box (can be realized by providing a fixing frame in the glass cylinder), and the glass jar is sealed, and the temperature of the adjusting box is fumigation at 30 °C.
  • the rice samples subjected to the fumigation treatment of the present example were placed in a room temperature environment, and the mold tracking test was performed regularly, and the test results are shown in the following table:
  • Grain variety rice
  • the fumigant C is first loaded on the filter paper, and then the filter paper is placed in a hollow box having a mesh surface and self-heating function, and the box is placed at the bottom of the glass jar to place the rice sample.
  • the casing which can be realized by providing a fixing frame in the glass cylinder
  • the glass cylinder is sealed, and the temperature of the casing is adjusted to be 40 ° C for fumigation.
  • the rice sample subjected to the fumigation treatment of the present embodiment is placed in a room temperature environment, and the mold tracking test is performed regularly.
  • the test results are shown in the table below:
  • Grain variety rice
  • the fumigant C is first loaded on the filter paper, and then the filter paper is placed in a hollow box having a mesh surface, a fan and a temperature regulating function, and the box is placed at the bottom of the glass jar to prepare the rice sample. It is placed above the box (can be realized by providing a fixing frame in the glass cylinder), the glass jar is sealed, the temperature of the box is adjusted to 30 ° C, and the fan is turned on (the wind speed is set to low speed) for fumigation.
  • the rice samples subjected to the fumigation treatment of the present example were placed in a room temperature environment, and the mold tracking test was performed regularly, and the test results are shown in the following table:
  • the fumigant C is loaded on the silica gel particles, and then the silica gel particles are placed in a bag having a mesh on the surface, and then the bag is placed at the bottom of the glass jar, and the bean sample is placed above the bag (through A fixed frame is provided in the glass cylinder), a closed glass cylinder, and fumigation at room temperature.
  • soybean samples such as soybeans subjected to the fumigation treatment of the present embodiment are placed in a room temperature environment, and the mold tracking test is performed regularly, and the test results are shown in the following table:
  • the color of the bean sample such as soybean after the above-described fumigation treatment was not observed to be significantly changed by a color difference meter.
  • Grain varieties potato, sweet potato and other potatoes
  • the fumigant C is loaded on the cyclodextrin, and then the cyclodextrin device is placed in a bag having a mesh on the surface, and the bag is placed at the bottom of the glass jar, and a potato sample such as potato or sweet potato is placed in the bag.
  • a potato sample such as potato or sweet potato is placed in the bag.
  • Above can be achieved by placing a fixed frame in the glass jar), sealed glass jar, fumigation at room temperature.
  • the potato and sweet potato samples which have been subjected to the fumigation treatment of this embodiment are placed in a room temperature environment, and the mold tracking test is performed regularly, and the test results are shown in the following table:
  • the color of the potato sample such as potato and sweet potato after the above-mentioned fumigation treatment was not observed to be significantly changed by a color difference meter.
  • Grain varieties wheat, barley and other wheat
  • the fumigant C is loaded on the filter paper, and then the filter paper is placed at the bottom of the glass jar, and wheat samples such as wheat and barley are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass Cylinder, fumigation at room temperature.
  • the wheat samples subjected to the fumigation treatment of the present embodiment are placed in a room temperature environment, and the mold tracking test is performed regularly, and the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant C is first loaded on the filter paper, and then the filter paper is placed at the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant A is loaded on the filter paper, and then the filter paper is placed on the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant B is loaded on the filter paper, and then the filter paper is placed at the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant D is first loaded on the filter paper, and then the filter paper is placed on the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant E is loaded on the filter paper, and then the filter paper is placed on the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant F is first loaded on the filter paper, and then the filter paper is placed at the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant G is loaded on the filter paper, and then the filter paper is placed at the bottom of the glass jar, and the wheat, rice, and jade are placed.
  • the meter sample is placed above the filter paper (can be achieved by placing a fixed frame in the glass jar), sealed glass jar, and fumigated at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant H is first loaded on the filter paper, and then the filter paper is placed at the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties wheat, rice, corn
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant I is loaded on the filter paper, and then the filter paper is placed on the bottom of the glass jar, and the wheat, rice, and corn samples are placed on top of the filter paper (can be realized by providing a fixing frame in the glass cylinder), the closed glass cylinder , fumigation at room temperature.
  • the wheat, rice, and corn samples subjected to fumigation treatment in this example were placed in a room temperature environment, and the bacteria tracking test was performed periodically.
  • the test results are shown in the following table:
  • Grain varieties corn, rice, wheat, soybeans, soybeans, broad beans, potatoes, sweet potatoes, etc.
  • the fumigant C is loaded on the filter paper, and then the filter paper is placed at the bottom of the glass cylinder, and the mixed food sample is placed above the filter paper (can be realized by providing a fixing frame in the glass cylinder), and the closed glass cylinder is Fumigation was carried out at room temperature.
  • the color of the mixed grain samples after the above-mentioned fumigation treatment such as corn, rice, wheat, soybean, soybean, broad bean, potato, sweet potato, and the like, were not changed significantly by the color difference meter. It is indicated that the method of the invention can realize one-time treatment of multi-species grain and various bacterial molds in the same fumigation environment.

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Abstract

一种粮食储存方法，其包括如下操作：在室温至40℃环境下，将熏蒸剂放置在粮堆的下方或/和四周；所述的熏蒸剂为硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物。本方法不仅实现了对粮食的安全有效杀菌消毒，而且具有绿色环保的优点；尤其是，可实现在同一熏蒸环境下对多种粮食和各种细菌霉菌进行一次性处理，并且经过熏蒸处理后的粮食，能在粮仓环境或运输条件下放置至少半年以上不再复生细菌霉菌；另外，本方法还具有操作简单，成本低，适用的粮食品种和细菌霉菌范围广等优点，对储粮的安全长久保存具有重要价值和深远意义。

Description

一种粮食储存方法 技术领域
本发明是涉及一种粮食储存方法，属于粮食保存技术领域。
背景技术
2014年据国家统计局报道全国粮食总产量60709.9万吨(12142亿斤)，比2013年增加516万吨(103.2亿斤)，增长0.9％。全国政协委员、国家粮食局局长任正晓今年5月在参加全国政协小组讨论会期间接受记者采访时表示：目前，我国每年粮食损失浪费量在1000亿斤左右，大约相当于我国第一产粮大省——黑龙江省一年的粮食产量。粮食从地里生产出来到摆上餐桌，每一环节都存在损失浪费现象。据测算，我国粮食产后仅储藏、运输、加工等流通环节损失浪费总量达700亿斤左右，其中流通环节中仅储粮环节损失约400亿斤。我国每年产后霉掉的粮食损失不容小觑，真菌及毒素污染对我国粮食安全造成的严重威胁。据中国农业科学院农产品加工研究所研究员刘阳介绍：“我国每年投入上千亿元全力争取1％的粮食增产，但每年因霉变造成的粮食产后损失高达2100万吨，占全国粮食总产量的4.2％，造成的直接经济损失约为180亿到240亿元。”
另外，真菌毒素污染也严重制约我国对外贸易。近年来，真菌毒素污染食品造成的安全事件频发，不仅严重威胁我国人畜健康，同时也制约我国农产品对外贸易。从2002～2011年近10年中我国出口欧盟食用农产品违例事件统计分析后发现：在重金属、农兽药残留等众多制约我国对外贸易的因素中，真菌毒素超标是最主要的原因，因真菌毒素引发的违例事件达28.6％。据了解，真菌毒素是自然发生的最危险的食品污染物，而黄曲霉毒素的毒性是氰化钾的10倍，砒霜的68倍，是引发肝癌的最主要诱因之一。真菌毒素主要是在产后粮食储藏过程中产生的，在我国粮食储藏过程中，霉菌以黄曲霉、亚洲镰刀菌、禾谷镰刀菌为主；在欧美国家，除霉菌除黄曲霉、禾谷镰刀菌外，还有寄生曲霉、黄色镰刀菌。同时，与欧美国家储粮储藏期短，来源单一，数量小等特点相比，我国储粮特点主要表现为带菌量高、储藏期长、来源广泛、品种多杂、数量大。
目前，大多数粮库采用粮面施药、布袋埋藏和探管法熏蒸杀虫等方式，所用熏蒸剂主要为磷化氢、环氧乙烷、溴甲烷和硫酰氟，随着人们环保和安全意识的提高，以上熏蒸剂的局限性逐步体现出来，如：磷化氢强致毒性，损害肺、心、肝、肾、中枢神经系统和骨骼，过度暴露造成哮喘、肺炎或肺纤维化疾病，以及易自燃烧等不安全因素；环氧乙烷的 致变性和爆炸性；溴甲烷对大气平流层的臭氧的破坏性以及直接对人类产生毒害已引起人们的高度关注。自1997年第九次“蒙特利尔议定书缔约国会议”后开始，发达国家已经约定从2005年起逐步停止使用溴甲烷消毒剂，我国也在2003年4月正式签署了《蒙特利尔议定书》哥本哈根修正案，承诺将于2015年1月1日前全面停止甲基溴在农业、仓储、烟草等行业上的使用。当然，在粮食消毒上也将执行这一承诺；硫酰氟在常温常压下是一种无色、有毒，具强刺激性气体，急性毒性主要损害中枢神经系统，引起惊厥；另外，还会在人体骨骼中沉积，具有累积中毒危险性。最新研究发现化学熏蒸剂硫酰氟，散发到空气后会成为一种强效温室气体，一公斤硫酰氟排放到大气中对全球变暖的效果是一公斤二氧化碳的4800倍；现在虽然空气中只存在极少量的硫酰氟，约1.5兆分之一，即每一兆个空气分子中，只有1.5个是硫酰氟，但它却以每年5％的速度在增加，未来作为溴甲烷的替代物，硫酰氟的应用而造成的大气温室效应应该引起足够重视！
综上所述，解决粮食霉变问题已成为保障国家粮食安全的重大需求，探索适合我国粮食贮藏中真菌毒素的有效防控方法已成为当前急需解决的研究课题。
发明内容
针对现有技术存在的上述问题和需求，本发明的目的是提供一种绿色环保、安全有效的粮食储存方法。
为实现上述发明目的，本发明采用如下技术方案；
一种粮食储存方法，包括如下操作：在室温至40℃环境下，将熏蒸剂放置在粮堆的下方或/和四周；所述的熏蒸剂为硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物。
作为优选方案，在室温下，将熏蒸剂放置在密闭环境中的粮堆的下方或/和四周。
作为优选方案，将所述熏蒸剂负载在具有吸附作用的载体材料上，所述的载体材料可以为滤纸、硅胶、糊精、滤膜、棉花、海绵或布等。
作为优选方案，将负载有熏蒸剂的载体材料放置在具有向外扩散的口或网孔面的中空装置中，所述的中空装置可以是箱式结构、盒式结构、笼式结构、袋子等。
作为进一步优选方案，所述中空装置具有风扇和调速功能。
作为进一步优选方案，所述中空装置具有自加热和调温功能。
作为优选方案，所述熏蒸剂是由硫代亚磺酸酯类化合物与硫代磺酸酯类化合物按体积比为1：1～1：5的复配物。
作为优选方案，所述的硫代亚磺酸酯类化合物是具有如下结构通式：
Figure PCTCN2016087974-appb-000001
的化合物，其中：R1与R2相同或不同，且均选自C1-C4的烷烃基(例如：甲基、乙基、丙基、丁基)或C2-C4的烯烃基(例如：烯丙基)。
作为进一步优选方案，R1与R2相同。
作为优选方案，所述的硫代磺酸酯类化合物是具有如下结构通式：
Figure PCTCN2016087974-appb-000002
的化合物，其中：R3与R4相同或不同，且均选自C1-C4的烷烃基(例如：甲基、乙基、丙基、丁基)或C2-C4的烯烃基(例如：烯丙基)。
作为进一步优选方案，R3与R4相同。
与现有技术相比，本发明具有如下有益效果：
本发明通过选用硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物作为熏蒸剂，不仅实现了对粮食的安全有效杀菌消毒，而且对环境的污染最低，没有熏蒸剂残留问题，不影响粮食本身和人体健康，具有绿色环保的优点；尤其是，本发明可实现在同一熏蒸环境下对多种粮食和各种细菌霉菌进行一次性处理，并且经过本发明熏蒸处理后的粮食，能在粮仓环境或运输条件下放置至少半年以上不再复生细菌霉菌；另外，本发明方法还具有操作简单，成本低，适用的粮食品种和细菌霉菌范围广等优点，对储粮的安全长久保存具有重要价值和深远意义。
具体实施方式
下面通过实施例对本发明的技术方案做进一步详细说明。
实施例1：熏蒸剂的制备
1、甲基硫代亚磺酸甲酯与乙基硫代磺酸乙酯的复配物：
将甲基硫代亚磺酸甲酯与乙基硫代磺酸乙酯按体积比1:3在室温下搅拌混合均匀；简记为熏蒸剂A；测定小鼠经口LD50>500mg/Kg，属于低毒。
2、乙基硫代亚磺酸乙酯与甲基硫代磺酸甲酯的复配物：
将乙基硫代亚磺酸乙酯与甲基硫代磺酸甲酯按体积比1:2在室温下搅拌混合均匀；简记为熏蒸剂B；测定小鼠经口LD50>500mg/Kg，属于低毒。
3、乙基硫代亚磺酸乙酯与乙基硫代磺酸乙酯的复配物：
将乙基硫代亚磺酸乙酯与乙基硫代磺酸乙酯按体积比1:1在室温下搅拌混合均匀；简记 为熏蒸剂C；测定小鼠经口LD50>500mg/Kg，属于低毒。
4、甲基硫代亚磺酸甲酯与甲基硫代磺酸甲酯的复配物：
将甲基硫代亚磺酸甲酯与甲基硫代磺酸甲酯按体积比1:1.5在室温下搅拌混合均匀；简记为熏蒸剂D；测定小鼠经口LD50>500mg/Kg，属于低毒。
5、丙基硫代亚磺酸丙酯与乙基硫代磺酸乙酯的复配物：
将丙基硫代亚磺酸丙酯与乙基硫代磺酸乙酯按体积比1:2.5在室温下搅拌混合均匀；简记为熏蒸剂E；测定小鼠经口LD50>500mg/Kg，属于低毒。
6、丙基硫代亚磺酸丙酯与烯丙基硫代磺酸烯丙酯的复配物：
将丙基硫代亚磺酸丙酯与烯丙基硫代磺酸烯丙酯按体积比1:4在室温下搅拌混合均匀；简记为熏蒸剂F；测定小鼠经口LD50>500mg/Kg，属于低毒。
7、乙基硫代亚磺酸乙酯与丁基硫代磺酸丁酯的复配物：
将乙基硫代亚磺酸乙酯与丁基硫代磺酸丁酯按体积比1:5在室温下搅拌混合均匀；简记为熏蒸剂G；测定小鼠经口LD50>500mg/Kg，属于低毒。
8、甲基硫代亚磺酸乙酯与乙基硫代磺酸甲酯的复配物：
将甲基硫代亚磺酸乙酯与乙基硫代磺酸甲酯按体积比1:3在室温下搅拌混合均匀；简记为熏蒸剂H；测定小鼠经口LD50>500mg/Kg，属于低毒。
9、烯丙基硫代亚磺酸烯丙酯与甲基硫代磺酸烯丙酯的复配物：
将烯丙基硫代亚磺酸烯丙酯与甲基硫代磺酸烯丙酯按体积比1:2.5在室温下搅拌混合均匀；简记为熏蒸剂I；测定小鼠经口LD50>500mg/Kg，属于低毒。
实施例2：粮食熏蒸实验
粮食品种：玉米
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
熏蒸方法：
先将熏蒸剂C负载在滤纸上，然后将玉米样品放置在滤纸的上方(可通过设置固定框架予以实现)，在室温下熏蒸。
经取样监测得知：当熏蒸36小时后，经上述熏蒸处理后的玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的玉米样品放置在室温环境中，定期进行霉菌跟踪检测， 检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的玉米样品的颜色没有发生明显变化。
实施例3-1：粮食熏蒸实验
粮食品种：稻谷
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，再将稻谷样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的稻谷样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的稻谷样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的稻谷样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的稻谷样品的颜色没有发生明显变化。
实施例3-2：粮食熏蒸实验
粮食品种：稻谷
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在表面具有网孔、自带有风扇和调速功能的中空盒体中，再将该盒体放置在玻璃缸的底部，将稻谷样品放置在该盒体的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下打开风扇(风速设定为中速)进行熏蒸。
经取样监测得知：当熏蒸18小时后，经上述熏蒸处理后的稻谷样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的稻谷样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的稻谷样品放置在室温环境中，定期进行霉菌跟踪检测， 检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的稻谷样品的颜色没有发生明显变化。
实施例3-3：粮食熏蒸实验
粮食品种：稻谷
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在表面具有网孔、自带有加热和调温功能的中空盒体中，再将该盒体放置在玻璃缸的底部，将稻谷样品放置在该盒体的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，调节盒体的温度为30℃下进行熏蒸。
经取样监测得知：当熏蒸20小时后，经上述熏蒸处理后的稻谷样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的稻谷样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的稻谷样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的稻谷样品的颜色没有发生明显变化。
实施例3-4：粮食熏蒸实验
粮食品种：稻谷
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在表面具有网孔、自带有加热调温功能的中空盒体中，再将该盒体放置在玻璃缸的底部，将稻谷样品放置在该盒体的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，调节盒体的温度为40℃下进行熏蒸。
经取样监测得知：当熏蒸10小时后，经上述熏蒸处理后的稻谷样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的稻谷样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的稻谷样品放置在室温环境中，定期进行霉菌跟踪检测， 检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的稻谷样品的颜色没有发生明显变化。
实施例3-5：粮食熏蒸实验
粮食品种：稻谷
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在表面具有网孔、自带有风扇和调温功能的中空盒体中，再将该盒体放置在玻璃缸的底部，将稻谷样品放置在该盒体的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，调节盒体的温度为30℃,同时打开风扇(风速设定为低速)下进行熏蒸。
经取样监测得知：当熏蒸8小时后，经上述熏蒸处理后的稻谷样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的稻谷样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的稻谷样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的稻谷样品的颜色没有发生明显变化。
由实施例3-1至3-5的实验结果可见：密闭环境及风扇的风力和适当的加温均有利于熏蒸效果，在达到相同熏蒸效果下可明显缩短熏蒸时间。
实施例4：粮食熏蒸实验
粮食品种：大豆等豆类
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
熏蒸方法：
先将熏蒸剂C负载在硅胶颗粒上，然后将硅胶颗粒装置在表面具有网孔的袋子中，再将该袋子放置在玻璃缸的底部，将豆类样品放置在该袋子的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸36小时后，经上述熏蒸处理后的豆类样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的豆类样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的大豆等豆类样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的大豆等豆类样品的颜色没有发生明显变化。
实施例5：粮食熏蒸实验
粮食品种：马铃薯、番薯等薯类
病害：蜡叶芽枝霉、根霉和木霉等
熏蒸剂：熏蒸剂C
熏蒸方法：
先将熏蒸剂C负载在环糊精上，然后将环糊精装置在表面具有网孔的袋子中，再将该袋子放置在玻璃缸的底部，将马铃薯、番薯等薯类样品放置在该袋子的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸30小时后，经上述熏蒸处理后的薯类样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的薯类样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的马铃薯、番薯等薯类样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的马铃薯、番薯等薯类样品的颜色没有发生明显变化。
实施例6：粮食熏蒸实验
粮食品种：小麦、大麦等麦类
病害：曲霉、毛壳霉和木霉等
熏蒸剂：熏蒸剂C
熏蒸方法：
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、大麦等麦类样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的麦类样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的麦类样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的麦类样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的麦类样品的颜色没有发生明显变化。
实施例7-1：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂C
熏蒸方法：
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-2：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂A
熏蒸方法：
先将熏蒸剂A负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-3：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂B
熏蒸方法：
先将熏蒸剂B负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-4：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂D
熏蒸方法：
先将熏蒸剂D负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-5：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂E
熏蒸方法：
先将熏蒸剂E负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上 也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-6：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂F
熏蒸方法：
先将熏蒸剂F负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-7：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂G
熏蒸方法：
先将熏蒸剂G负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉 米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-8：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂H
熏蒸方法：
先将熏蒸剂H负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例7-9：粮食熏蒸实验
粮食品种：小麦、稻谷、玉米
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂I
熏蒸方法：
先将熏蒸剂I负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将小麦、稻谷、玉米样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的小麦、稻谷、玉米样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的小麦、稻谷、玉米样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的小麦、稻谷、玉米样品放置在室温环境中，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的小麦、稻谷、玉米样品的颜色没有发生明显变化。
实施例8：粮食熏蒸实验
粮食品种：玉米、稻谷、小麦、大豆、黄豆、蚕豆、马铃薯、红薯等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂C
熏蒸方法：
先将熏蒸剂C负载在滤纸上，然后将该滤纸放置在玻璃缸的底部，将上述混合粮食样品放置在滤纸的上方(可通过在玻璃缸中设置固定框架予以实现)，密闭玻璃缸，在室温下进行熏蒸。
经取样监测得知：当熏蒸24小时后，经上述熏蒸处理后的上述混合粮食样品上已没有任何霉菌生长(由显微镜检测得知)，且经上述熏蒸处理后的上述混合粮食样品上也没有熏蒸剂残留(由气相色谱与质谱联用仪(GC-Ms)检测分析得知)。
将经过本实施例熏蒸处理后的上述混合粮食样品放置在室温环境中，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
通过色差仪观察经上述熏蒸处理后的混合粮食样品中各品种，如玉米、稻谷、小麦、大豆、黄豆、蚕豆、马铃薯、红薯等颜色没有发生明显变化。说明本发明方法可实现在同一熏蒸环境下对多品种粮食和各种细菌霉菌进行一次性处理。
最后有必要在此说明的是，以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。

Claims (9)

  1. 一种粮食储存方法，其特征在于，包括如下操作：在室温至40℃环境下，将熏蒸剂放置在粮堆的下方或/和四周；所述的熏蒸剂为硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物。
  2. 根据权利要求1所述的粮食储存方法，其特征在于：在室温下，将熏蒸剂放置在密闭环境中的粮堆的下方或/和四周。
  3. 根据权利要求1或2所述的粮食储存方法，其特征在于：将所述熏蒸剂负载在具有吸附作用的载体材料上。
  4. 根据权利要求3所述的粮食储存方法，其特征在于：将负载有熏蒸剂的载体材料放置在具有向外扩散的口或网孔面的中空装置中。
  5. 根据权利要求4所述的粮食储存方法，其特征在于：所述中空装置具有风扇和调速功能。
  6. 根据权利要求4或5所述的粮食储存方法，其特征在于：所述中空装置具有自加热和调温功能。
  7. 根据权利要求1或2所述的粮食储存方法，其特征在于：所述熏蒸剂是由硫代亚磺酸酯类化合物与硫代磺酸酯类化合物按体积比为1：1～1：5的复配物。
  8. 根据权利要求7所述的粮食储存方法，其特征在于：所述的硫代亚磺酸酯类化合物是具有如下结构通式：
    Figure PCTCN2016087974-appb-100001
    的化合物，其中：R1与R2相同或不同，且均选自C1-C4的烷烃基或C2-C4的烯烃基。
  9. 根据权利要求7所述的粮食储存方法，其特征在于：所述的硫代磺酸酯类化合物是具有如下结构通式：
    Figure PCTCN2016087974-appb-100002
    的化合物，其中：R3与R4相同或不同，且均选自C1-C4的烷烃基或C2-C4的烯烃基。
PCT/CN2016/087974 2015-07-19 2016-06-30 一种粮食储存方法 WO2017012457A1 (zh)

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