印楝素的罐组式逆流提取方法 Azadirachtin pot groups countercurrent extraction method

技术领域 Technical Field

[0001] 本发明涉及一种从植物中提取杀虫剂的方法，具体涉及一种从印楝种子中罐组式逆流提取印楝素的方法。 [0001] The present invention relates to a method for extracting pesticides from plants, specifically relates to a method from neem seeds pot groups countercurrent extraction azadirachtin.

背景技术 Background

[0002] 印楝素类杀虫剂具有广谱、高效、低毒、无残留、对人畜无毒副作用、对害虫天敌安全及不易产生抗药性等特点，是目前国内外研究和应用最为广泛的生物农药之一，已被国务院绿色食品办公室列为绿色食品生产重点推介的无公害农药。 [0002] azadirachtin insecticides with broad-spectrum, high efficiency, low toxicity, no residue, non-toxic to humans and animals side effects, safety and easy for natural enemies of pests resistant features, is currently at home and abroad and the most widely used research One of bio-pesticides, has been Green Food Office of the State Council as a green food production highlights of pollution-free pesticides.

[0003] 从印楝种子中提取印楝素，是印楝素类杀虫剂生产的首要环节和重要操作单元。 [0003] The extract azadirachtin from neem seeds, insecticides azadirachtin production is the first link and important operating units. 印楝种子中印楝素含量很低（一般为0. 3%〜0. 4%，高的可达0. 6% )，印楝素提取较为困难，其提取工艺技术的优劣直接影响到企业的经济效益。 Azadirachtin from neem seeds content is very low (typically 0.3% ~ 0. 4%, high up 0.6%), azadirachtin is more difficult to extract, the extract process technology will directly affect the economic efficiency of enterprises. 印楝种子中含有20%〜30% 油脂，直接机械粉碎难以细碎，影响印楝素的浸出，其原料预处理方式目前大多采用去壳、 压榨脱脂（如中国专利CN1158928C、CN1184222C、CN1362020A、CN1423938A、CN1423939A、 CN1524858A、CN101440099A)，但印楝素的热稳定性差，大于35°C时印楝素的降解速率明显增大，65°C时印楝素的降解速率最大，因此在压榨脱脂过程由于高温即有40%左右印楝素被降解，导致印楝素产率下降；亦有采用溶剂或超临界C02脱脂（如中国专利CN1049091C、 CN1199980C、CN101029276A、CN1116394C)，虽可减少印楝素的损失，但增加了加工时间及成本。 Neem seeds contain 20% ~ 30% oil, direct mechanical crushing difficult crushing, leaching effect azadirachtin, the raw material pretreatment is currently mostly used shell, press skimmed (such as Chinese patent CN1158928C, CN1184222C, CN1362020A, CN1423938A, CN1423939A, CN1524858A, CN101440099A), but the difference in thermal stability of azadirachtin, significantly increased the rate of degradation of azadirachtin greater than 35 ° C, 65 ° C when the maximum rate of degradation of azadirachtin, so press the degreasing process due to high temperatures that is about 40% azadirachtin is degraded, resulting in decreased yield of azadirachtin; also with a solvent or supercritical C02 skimmed (such as Chinese patent CN1049091C, CN1199980C, CN101029276A, CN1116394C), although can reduce the loss of azadirachtin, but increased processing time and costs. 中国专利CN100448871C印楝种子只需去壳，不经脱脂即用高速刀片切削搅拌粉碎提取，使物料及溶剂具有较好的流动性，印楝素产率较高，但印楝种仁需用3〜5倍极性有机溶剂预浸6〜12小时，提取时间为3〜5小时/次，再重复2〜5次，完成一个提取周期至少需15小时，最少需9倍溶剂提取，且高速搅拌粉碎易过热，提取温度难控，需采用夹套或盘管冷却以减少印楝素降解，使能耗增加。 China Patent CN100448871C neem seed just shelled, without the skimmed-use high-speed stirring and crushing blade cutting extraction solvent so that the material and has good liquidity, high yield azadirachtin, but neem seeds required 3 ~ 5 times prepreg 6~12 hours a polar organic solvent, extraction time is 3 to 5 hours / times, then repeated 2~5 times to complete at least one extraction cycle takes 15 hours to take at least nine times, solvent extraction, and high-speed agitation smash overheat, temperature difficult to control, requires the use of a cooling jacket or coil to reduce the degradation of azadirachtin, increase energy consumption.

发明内容 DISCLOSURE

[0004] 本发明的目的在于克服现有印楝素提取工艺技术中存在的缺点，提供一种印楝素的罐组式逆流提取方法，以简化工艺流程、缩短提取周期、提高印楝素产率、降低能耗、节省溶剂、利于工业化生产。 [0004] The object of the present invention is to overcome the disadvantages of the prior art that azadirachtin extraction process, providing pot groups countercurrent extraction method azadirachtin to simplify the process and shorten the extraction cycle, increase azadirachtin production rate, reduce energy consumption, save solvent, suitable for industrial production.

[0005] 本发明的技术方案是：印楝素的罐组式逆流提取方法，其步骤如下： [0005] The aspect of the present invention are: azadirachtin pot groups countercurrent extraction method comprises the following steps:

[0006] A、将印楝种子破碎成1〜4mm颗粒； [0006] A, will be broken into 1~4mm neem seed particles;

[0007] B、取印楝种子粉置于罐组式逆流提取装置中，提取温度为10〜60°C，以数罐为一组，泵入1 ： 1〜5W/V的溶剂，动态逆流提取20〜50min/罐； [0007] B, taken neem seed meal disposed pot groups countercurrent extraction apparatus, the extraction temperature is 10~60 ° C, to the number of cans as a group, pumped into 1: 1~5W / V solvent, countercurrent dynamic Extraction 20~50min / cans;

[0008] C、收集提取液于45°C减压浓缩，回收溶剂得含印楝素的固态提取物。 [0008] C, collect the extract was concentrated under reduced pressure at 45 ° C, the solid was recovered solvent extract containing azadirachtin.

[0009] 所述的罐组为每组1〜9个提取罐串联或并联或串并联合用。 [0009] The tank group for each group of 1~9 an extraction tank in series or in parallel or series and joint use.

[0010] 上述提取溶剂为水、醇、酮、酯、取代烃、醚、腈中的一种或它们的混合物，混合物的配比为任意配比，如水、甲醇、乙醇、异丙醇、丙酮、丁酮、乙酸乙酯、乙酸甲酯、二氯甲烷、三氯甲烷、甲基叔丁基醚、乙腈等或其混合物。 [0010] said extraction solvent is water, an alcohol, a ketone, an ester, substituted hydrocarbons, ethers, nitriles or a mixture thereof, the ratio of the mixture of any ratio, such as water, methanol, ethanol, isopropanol, acetone , methyl ethyl ketone, ethyl acetate, methyl acetate, methylene chloride, chloroform, methyl tert-butyl ether, acetonitrile and the like or mixtures thereof. [0011] 本发明与现有工艺技术比较具有下列优点和效果： [0011] The present invention and the prior comparative technology has the following advantages and effects:

[0012] 1.无需进行种子去壳、脱脂，种子粗碎即可，简化了原料预处理，省工省力，避免了种子去壳脱脂步骤印楝素的损失； [0012] 1 seed without shell, degreasing, seed crushing to simplify the pretreatment of raw materials, saving labor, seed, shelled degreasing step to avoid loss of azadirachtin;

[0013] 2.采用罐组式动态逆流提取替代单罐式多次提取，将多个提取单元科学组合，单元之间形成浓度梯度，增大传质动力，提高了印楝素浸出效率，每罐提取时间在50min以内，大大缩短了提取周期； [0013] 2. Using pot groups dynamic countercurrent extraction, multiple extractions instead of a single tank, a plurality of extraction means science combined to form a concentration gradient between the cells, increasing the mass transfer power to improve the extraction efficiency azadirachtin per tank extraction time in less than 50min, greatly reducing the extraction cycle;

[0014] 3.可常温或适当加温（< 35°C )提取，减少印楝素降解，使印楝素提取充分，提高印楝素产率8. 88%~ 26. 97% ； [0014] 3. Can be normal or proper heating (<35 ° C) to extract, to reduce the degradation of azadirachtin that azadirachtin extract sufficient to improve the yield of 8.88% azadirachtin ~ 26.97%;

[0015] 4.溶剂反复利用，溶剂用量少（1 ： 2〜3. 33W/V)，后续浓缩能耗低； [0016] 5.罐组式逆流提取设备参数易控，操作便捷、安全，处理量大，易于工业化生产。 [0015] The solvent repeated use, less solvent (1: 2~3 33W / V.), Low energy consumption and the subsequent enrichment; [0016] 5. The pot groups countercurrent extraction device parameters easy to control, easy operation, safety , large capacity, easy to industrial production.

[0017] 本发明所述印楝素的罐组式逆流提取方法可明显提高印楝素产率，减少工艺设备的投入，缩短提取周期，节能节溶剂，生产成本低，易于实现工业化生产，经济效益及社会效益好。 [0017] The present invention pot groups countercurrent extraction azadirachtin azadirachtin can significantly improve the yield and reduce the investment process equipment, shorten the extraction cycle, saving energy and solvents, low production cost, easy to implement industrial production, economy benefits and social good.

具体实施方式 DETAILED DESCRIPTION

[0018] 下面结合具体实施例进一步阐述本发明，但本发明的保护范围并不仅限于此。 [0018] In the following with reference to specific examples further illustrate the invention, but the scope of the present invention is not limited thereto.

[0019] 实施例1 [0019] Example 1

[0020] 以单罐为一组，取印楝种子粉1500g置于提取罐中，设提取温度为32°C，泵入5 倍甲醇动态逆流循环提取49min，溶剂用量为1 ： 5W/V，收集提取液于45°C减压浓缩，回收甲醇得含10. 89%印楝素的黄绿色固态提取物（高效液相色谱法测定），印楝素产率为0. 304%。 [0020] In a single tank as a group, taking into 1500g neem seed meal extraction tank, set extraction temperature 32 ° C, was pumped into the cycle 5 times methanol dynamic countercurrent extraction 49min, the solvent in an amount of 1: 5W / V, The extract was collected at 45 ° C and concentrated under reduced pressure to recover the solid yellow-green extract containing methanol to obtain 10.89% of azadirachtin (high performance liquid chromatography), azadirachtin yield of 0.304%.

[0021] 实施例2 [0021] Example 2

[0022] 以3罐为一组，每罐装入印楝种子粉1500g，设提取温度为32°C，第一罐用5倍甲醇动态逆流循环提取39min，第二罐以前一单元提取液补充3倍甲醇动态逆流循环提取39min，第三罐以前一单元提取液补充2倍甲醇动态逆流循环提取39min，溶剂用量为1 ： 3. 33W/V，收集提取液于45°C减压浓缩，回收甲醇得含10. 46%印楝素的黄绿色固态提取物（高效液相色谱法测定），印楝素产率为0. 331 %。 [0022] In a group of cans 3, neem seed meal into each canned 1500g, set extraction temperature 32 ° C, 5 times with methanol first tank countercurrent circulation dynamic extraction 39min, before a second tank means extract added 3 times methanol dynamic countercurrent extraction cycle 39min, the third tank before a cell extract supplemented with 2 fold methanol dynamic countercurrent extraction cycle 39min, the solvent in an amount of 1: 3. 33W / V, collect the extract was concentrated under reduced pressure at 45 ° C, recycling yellow-green solid-state methanol extracts obtained containing 10.46% of azadirachtin (high performance liquid chromatography), azadirachtin yield of 0.331%.

[0023] 实施例3 [0023] Example 3

[0024] 以4罐为一组，每罐装入印楝种子粉1500g，设提取温度为32°C，第一罐用5倍甲醇动态逆流循环提取34min，第二罐以前一单元提取液补充2. 5倍甲醇动态逆流循环提取34min，第三罐以前一单元提取液补充1. 5倍甲醇动态逆流循环提取34min，第四罐以前一单元提取液补充1倍甲醇动态逆流循环提取34min，溶剂用量为1 ： 2. 5W/V，收集提取液于45°C减压浓缩，回收甲醇得含10. 62%印楝素的黄绿色固态提取物（高效液相色谱法测定），印楝素产率为0. 386%。 [0024] In a group of cans 4, neem seed meal into each canned 1500g, set extraction temperature 32 ° C, 5 times with methanol first tank countercurrent circulation dynamic extraction 34min, before a second tank means extract added 2.5 times the methanol loop dynamic countercurrent extraction 34min, before a third tank unit extract supplement 1.5 times methanol dynamic countercurrent extraction cycle 34min, before a fourth tank unit 1x methanol extract supplement dynamic countercurrent extraction cycle 34min, solvent The amount of 1: 2. 5W / V, collect the extract was concentrated under reduced pressure at 45 ° C, the solid yellow-green recycle methanol extract was containing 10.62% of azadirachtin (high performance liquid chromatography), azadirachtin The yield was 0.386%.

[0025] 实施例4 [0025] Example 4

[0026] 以4罐为一组，每罐装入印楝种子粉1500g，设提取温度为32°C，第一罐用5倍乙醇动态逆流循环提取34min，第二罐以前一单元提取液补充2. 5倍乙醇动态逆流循环提取34min，第三罐以前一单元提取液补充1. 5倍乙醇动态逆流循环提取34min，第四罐以前一单元提取液补充1倍乙醇动态逆流循环提取34min，溶剂用量为1 ： 2. 5W/V，收集提取液于45°C减压浓缩，回收乙醇得含13. 65%印楝素的绿色固态提取物（高效液相色谱法测定)， 印楝素产率为0. 337%。 [0026] In a group of cans 4, neem seed meal into each canned 1500g, set extraction temperature 32 ° C, 5 times with ethanol first tank countercurrent circulation dynamic extraction 34min, before a second tank means extract added 2.5 times more ethanol dynamic countercurrent extraction cycle 34min, the third tank before a supplementary unit extracts 1.5 times more ethanol dynamic countercurrent extraction cycle 34min, the fourth tank before a cell extract ethanol add a dynamic countercurrent extraction cycle times 34min, solvent The amount of 1: 2. 5W / V, collect the extract was concentrated under reduced pressure at 45 ° C, the solid green recycle ethanol extract was containing 13.65% of azadirachtin (high performance liquid chromatography), azadirachtin production rate of 0.337%.

[0027] 实施例5 [0027] Example 5

[0028] 以4罐为一组，每罐装入印楝种子粉1500g，设提取温度为32°C，第一罐用5倍乙酸乙酯动态逆流循环提取34min，第二罐以前一单元提取液补充2. 5倍乙酸乙酯动态逆流循环提取34min，第三罐以前一单元提取液补充1. 5倍乙酸乙酯动态逆流循环提取34min，第四罐以前一单元提取液补充1倍乙酸乙酯动态逆流循环提取34min，溶剂用量为1 ： 2. 5W/V，收集提取液于45°C减压浓缩，回收乙酸乙酯得含19. 34%印楝素的绿色固态提取物（高效液相色谱法测定），印楝素产率为0. 228%。 [0028] In 4 cans as a group, each filled into neem seed powder 1500g, set the extraction temperature is 32 ° C, the first tank with 5 ethyl acetate dynamic countercurrent extraction cycle 34min, a unit before extracting a second tank liquid supplement 2.5 times ethyl dynamic countercurrent extraction cycle 34min, the third tank before a supplementary unit extracts 1.5 times ethyl dynamic countercurrent extraction cycle 34min, before a fourth tank unit extract supplement 1x acetate ester dynamic countercurrent extraction cycle 34min, the amount of solvent is 1: 2. 5W / V, collect the extract was concentrated under reduced pressure at 45 ° C, ethyl acetate was recovered containing 19.34% of azadirachtin extract green solid-state (high performance liquid Phase Chromatography), azadirachtin yield of 0.228%.

[0029] 实施例6 [0029] Example 6

[0030] 以5罐为一组，每罐装入印楝种子粉1500g，设提取温度为32°C，第一罐用5倍甲醇动态逆流循环提取29min，第二罐以前一单元提取液补充2倍甲醇动态逆流循环提取29min，第三罐至第五罐均以前一单元提取液补充1倍甲醇动态逆流循环提取29min，溶剂用量为1 ： 2W/V，收集提取液于45°C减压浓缩，回收甲醇得含10. 18%印楝素的黄绿色固态提取物（高效液相色谱法测定），印楝素产率为0. 299%。 [0030] In the tank 5 as a group, each filled into neem seed powder 1500g, set extraction temperature 32 ° C, 5 times with methanol first tank countercurrent circulation dynamic extraction 29min, before a second tank means extract added 2x methanol dynamic countercurrent extraction cycle 29min, the third tank to the fifth tank was previously a unit of methanol extract supplement twice a dynamic countercurrent extraction cycle 29min, the solvent in an amount of 1: 2W / V, collect the extract at 45 ° C under reduced pressure concentrated, recycling yellow-green solid-state methanol extract was containing 10.18% of azadirachtin (high performance liquid chromatography), azadirachtin yield of 0.299%.