WO2015096533A1 - 一种可以抑制水稻重金属吸收积累生产富硒稻米的硒掺杂纳米硅溶胶及其制备方法 - Google Patents
一种可以抑制水稻重金属吸收积累生产富硒稻米的硒掺杂纳米硅溶胶及其制备方法 Download PDFInfo
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- WO2015096533A1 WO2015096533A1 PCT/CN2014/088288 CN2014088288W WO2015096533A1 WO 2015096533 A1 WO2015096533 A1 WO 2015096533A1 CN 2014088288 W CN2014088288 W CN 2014088288W WO 2015096533 A1 WO2015096533 A1 WO 2015096533A1
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
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- the invention belongs to the field of soil and fertilizer, and particularly relates to a selenium-doped nano-silica sol which can inhibit the absorption and accumulation of heavy metals in rice to produce selenium-enriched rice and a preparation method thereof.
- Selenium is an essential trace element in animals and human body. It is a component of glutathione peroxidase and has an antioxidant effect. In 1973, the World Health Organization (WHO) announced that selenium is an essential nutrient for the human body; in 1988, the Chinese Nutrition Society listed selenium as a necessary nutrient for humans. Selenium has many physiological functions in humans and animals: selenium has anti-cancer, anti-tumor and anti-aging effects.
- Endemic diseases in China such as Keshan disease and Kashin-Beck disease, are closely related to selenium deficiency in the environment. Therefore, selenium plays an important role in human health.
- the selenium required by the human body must be obtained from the diet.
- the International Selenium Society recommends that the daily intake of selenium in humans is 60-400 ⁇ g, and the recommended daily intake of the Chinese Nutrition Society is 50-200 ⁇ g.
- the China Nutrition Society survey shows that the average daily selenium intake of Chinese residents is only 26-32 ⁇ g; the number of selenium-deficient provinces in China is as high as 22, and the selenium-deficient area accounts for about 72% of the country's land area.
- selenium-enriched fertilizers By increasing the resistance of rice to selenium nutrition to heavy metals, it can not only reduce the absorption and accumulation of heavy metals in rice, but also increase the level of selenium enrichment in rice. Therefore, the development and application of selenium-enriched fertilizers have received extensive attention.
- the selenium-enriched fertilizers at home and abroad mainly include water-soluble foliar selenium-enriched fertilizer, inorganic organic selenium-rich compound fertilizer, and selenium-enriched slow-release fertilizer.
- selenium-enriched fertilizers Although there are many patents for the preparation of selenium-enriched fertilizers, most of them are simply prepared by simply mixing inorganic selenite with livestock manure or agricultural waste or by microbial fermentation.
- Fertilizers prepared by these methods have a low selenium content and often contain less than 0.1% selenium, and the inorganic selenite itself is biologically toxic. The applied dose is too large to cause damage to the crop, and the application safety is poor.
- the preparation of high-activity, safe and efficient selenium-enriched foliar silicon fertilizer with nano-silica sol as a carrier has not been reported. Silicon is a special beneficial element. Regulating the silicon nutrition of rice can increase the heavy metal resistance of crops and inhibit the absorption of crops. metal.
- selenium-doped foliar silicon fertilizer will inevitably improve the absorption performance of heavy metal in crops, and at the same time produce selenium-enriched agricultural products; it not only meets the demand for selenium-enriched agricultural products, but also provides for the treatment of heavy metals in farmland soils in China. A new way out.
- the object of the present invention is to provide a safe and efficient selenium-doped nano-silica sol which can inhibit the absorption and accumulation of heavy metals in rice and can produce selenium-enriched rice, can inhibit the absorption and accumulation of heavy metals in rice, and produce a selenium-enriched rice, and a preparation method thereof.
- the preparation method has the advantages of simple process and low production cost, and the prepared selenium-doped nano-silica sol product capable of inhibiting the absorption and accumulation of heavy metals in rice to produce selenium-enriched rice has stable performance, a particle size of less than 50 nm and uniform distribution, and the product is a uniform transparent sol, pH. Close to neutral, it can be widely used to inhibit the absorption and accumulation of heavy metals by crops, and at the same time produce selenium-enriched rice.
- the selenium-doped nano-silica sol which can inhibit the absorption and accumulation of heavy metals in rice and produce selenium-enriched rice mainly uses nano silica sol as a carrier, sodium selenite as a raw material, vitamin C as a reducing agent, polyvinylpyrrolidone, etc.
- An emulsifier that selenium is doped in a specific ratio and dispersed into a silica sol to form a selenium-doped nanosilica sol having a special structure and function capable of inhibiting absorption and accumulation of heavy metals in rice to produce selenium-enriched rice.
- the selenium-doped nano-silica sol of the invention capable of inhibiting the absorption of heavy metals in rice to produce selenium-enriched rice is prepared by the following method, and the preparation method comprises the following steps:
- metal silicate solution metal silicon powder or metal silicate is added to an alkaline solution having a concentration of 0.1 to 5 M under stirring to prepare a metal silicate solution containing metal silicon powder or The concentration of the metal silicate is 5% by weight to saturation, and the pH is 10-13; the metal silicate is Na 2 SiO 3 , K 2 SiO 3 or Li 2 SiO 3 ;
- emulsified selenium doping solution under stirring, the emulsifier is added to the acidic selenium doping solution of step (3), and the mass percentage of the final emulsifier is controlled at 0.05 to 5%, thereby obtaining emulsified selenium doping.
- the emulsifier is polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Tween series or Span series;
- preparing a selenium-doped acidic silica sol precursor the emulsified selenium doping solution of the step (4) is added to the acidic silica sol precursor of the step (2) under stirring to obtain a selenium-doped acidic silica sol precursor.
- the mass percentage of silicon:selen in the selenium-doped acidic silica sol precursor is 3 to 200:1;
- the alkaline solution of the step (1) is prepared by using sodium hydroxide, potassium hydroxide or ammonia water, preferably at a concentration of 0.1 to 2M.
- the pH of the collected liquid in the step (2) is preferably 2 to 3.5, and the heating temperature of the collecting liquid is preferably 45 to 55 °C.
- the dilute acid solution of the step (3) may be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or the like, preferably hydrochloric acid; the acid selenium doping liquid preferably has a selenium content mass percentage of 2 to 7.6%; The pH of the liquid is preferably controlled to be 1-2.
- the emulsifier described in the step (4) is preferably tempered, and the final emulsifier mass percentage is preferably controlled to 0.5 to 2%.
- the mass percentage of silicon:selenium in the selenium-doped acidic silica sol precursor of the step (5) is preferably from 9 to 20:1.
- the temperature of the alkaline solution prepared by the alkaline catalyst of the step (6) is preferably controlled at 45 ° C to 85 ° C, and the stirring reaction is continued for 30 to 60 min.
- the reducing agent of the step (7) is preferably ascorbic acid (Vc), and the temperature of the solution is preferably controlled to be 50 ° C to 85 ° C.
- the selenium-doped nano-silica sol prepared by the invention can inhibit the absorption and accumulation of heavy metals in rice to produce selenium-enriched rice, has high stability, high concentration and uniform transparency, and has the following advantages compared with the prior art:
- the selenium-doped nano-silica sol prepared by the method of the invention has a silica content of more than 20%, a selenium content of more than 1%, and a low impurity content.
- the pH of the selenium-doped nano-silica sol of the present invention is close to neutral, and the selenium is dispersed in the middle of the silica colloid with the nano-particles, and the colloidal particle size is less than 50 nm. After spraying on the foliar surface, the growth of the crop can be significantly promoted and inhibited. The absorption of arsenic by crops accumulates, and the selenium content of crops is increased, and there is no toxic side effect on crops, and the application is safe.
- the preparation method of the present invention is carried out at a lower temperature and a normal pressure, the conditions are mild, the process is simple, and the operation is easy, so that mass production is easy. And its raw materials are widely sourced, the cost is lower and the output is larger, which is conducive to promotion.
- Example 1 is a scanning electron micrograph of a 1% selenium doped silica sol of Example 1;
- Example 2 is a particle size distribution of a 1% selenium doped silica sol of Example 1;
- Figure 3 is a diagram showing the effect of spraying different fertilizers on the dry weight of rice grains in the pot experiment of Example 4.
- Figure 4 is a diagram showing the effect of spraying different fertilizers on the arsenic content of rice in the pot experiment of Example 4;
- Figure 5 is a diagram showing the effect of spraying different fertilizers on the selenium content of rice in the pot experiment of Example 4;
- 6 is a graph showing the effect of spraying different concentrations of selenium-doped silica sol on the arsenic content of arsenic-contaminated rice in Yanhong Town;
- Figure 8 is a graph showing the effect of spraying different concentrations of selenium-doped silica sol on the cadmium content of cadmium-contaminated farmland in Handan City;
- Figure 9 is a graph showing the effect of spraying different concentrations of selenium-doped silica sol on the selenium content of rice in cadmium-contaminated farmland in Handan City.
- Example 1 Preparation of selenium-doped nanosilica sol which can inhibit the absorption and accumulation of heavy metals in rice and produce selenium-enriched rice
- the selenium-doped acidic silica sol precursor is slowly added to 20 ml of 25-28% ammonia water, stirred while stirring, and kept at a temperature of 45 ° C. After the addition is completed, the pH is 7-7. Between 9 and further, the reaction was stirred at 45 ° C for 30 min to obtain a selenium-doped silica sol precursor.
- the selenium-doped silica sol precursor liquid is slowly added to 50 mL of 0.1 M ascorbic acid (Vc) heated to 50 ° C by microwave (or water bath), and added dropwise, until the sol red color is no longer deepened, and the selenium is sufficiently reduced. Stirring was continued for more than 2 hours to obtain a sol.
- the prepared sol was subjected to two dialysis and concentrated to 200 mL by evaporation to obtain a uniformly stable and translucent high-purity selenium-doped nanosilica sol, which was inhibited in this example.
- Heavy metal absorption in rice accumulates and produces selenium-doped nano-silica sols for selenium-enriched rice.
- the prepared high-purity selenium-doped nano-silica sol has a silica content of 20% and a selenium content of 0.1%, 0.5%, 1% and 2%, respectively.
- Figure 1 is a scanning electron micrograph of a selenium-doped nanosilica sol having a selenium content of 1%
- Fig. 2 is a particle size distribution of a selenium-doped nanosilica sol having a selenium content of 1%.
- Example 2 Preparation of selenium-doped nanosilica sol which can inhibit the absorption and accumulation of heavy metals in rice and produce selenium-enriched rice
- the above metal silicate solution is passed through a 100 mL (wet volume) hydrogen type strong acid cation multi-stage resin exchange column at a rate of 5 mL/min, and the pH of the outlet of the control column is between 2.5 and 3.5, and the collected liquid is microwaved. (or water bath) stirring and heating to 90 ° C, static cooling and aging for 30 min, the acidic silica sol precursor is obtained, ready for use.
- the above emulsified selenium doping solution is added dropwise to the above-mentioned selenium-doped acidic silica sol precursor, and stirred while maintaining the temperature at 85 ° C; after the addition, stirring is continued for 90 min to obtain Selenium doped acidic silica sol precursor. Then, the selenium-doped acidic silica sol precursor is slowly added to 20 ml of sodium hydroxide having a concentration of 0.5-1.2 M, and stirred while maintaining the temperature at 85 ° C. After the completion of the dropwise addition, the pH is at Between 7 and 9, the reaction was further stirred at 85 ° C for 30 min to obtain a selenium-doped silica sol precursor.
- the selenium-doped silica sol precursor solution is slowly added to 50 mL of 0.5 M glutathione heated to 85 ° C by microwave (or water bath), and added dropwise until the sol red color is no longer deepened, and the selenium is sufficiently reduced. Stirring was continued for more than 2 hours to obtain a sol.
- the prepared sol was subjected to two dialysis and concentrated to 200 mL by evaporation to obtain a uniformly stable and translucent high-purity selenium-doped nanosilica sol, which was inhibited in this example. Heavy metal absorption in rice accumulates and produces selenium-doped nano-silica sols for selenium-enriched rice.
- the prepared high-purity selenium-doped nano-silica sol has a silica content of 15% and a selenium content of 0.12%, 0.58%, 1.5% and 2.3%, respectively.
- Example 3 Preparation of selenium-doped nanosilica sol which can inhibit the absorption and accumulation of heavy metals in rice and produce selenium-enriched rice
- the salt has a mass fraction of 20%.
- the above metal silicate solution is passed through a 100 mL (wet volume) hydrogen type strong acid cation multi-stage resin exchange column at a rate of 5 mL/min, and the pH of the outlet of the control column is between 2.5 and 3.5, and the collected liquid is microwaved. (or water bath) stirring and heating to 35 ° C, static cooling and aging for 30 min, the acidic silica sol precursor is obtained, ready for use.
- the emulsified selenium doping solution is added dropwise to the selenium-doped acidic silica sol precursor, and stirred while maintaining the temperature at 35 ° C; after the addition, stirring is continued for 30 min to obtain a selenium-doped acidic silica sol precursor. . Then, the selenium-doped acidic silica sol precursor is slowly added to 20 ml of potassium hydroxide having a concentration of 0.1-0.5 M, and stirred while maintaining the temperature at 35 ° C. After the dropwise addition, the pH is at Between 7 and 9, the reaction was further stirred at 35 ° C for 60 min to obtain a selenium-doped silica sol precursor.
- the selenium-doped silica sol precursor liquid is slowly added to 50 mL of 0.1 M glucose heated to 35 ° C by microwave (or water bath), dropwise, until the sol is reddish, the selenium is fully reduced, and stirring is continued. After 2 hours or more, the sol is obtained, and the prepared sol is subjected to two dialysis and concentrated to 200 mL by evaporation to obtain a uniformly stable and translucent high-purity selenium-doped nano-silica sol, which can inhibit the absorption of heavy metals in rice. Accumulate selenium-doped nano-silica sol for producing selenium-enriched rice.
- the prepared high-purity selenium-doped nano-silica sol has a silica content of 10% and a selenium content of 0.1%, 0.2%, 0.4%, and 0.8%, respectively.
- Example 4 Effect of foliar application of selenium-doped nano-silica sol on mitigation of heavy metals in rice
- the tested soil was collected from an arsenic-contaminated paddy field in Yanhong Town, Chenghai District, Shantou City, Guangdong province.
- the soil was taken from the surface of the paddy field (0-10 cm). After air drying, it was sieved, and 10 kg of soil was placed in the barrel.
- the soil was basically physical and chemical. The properties are as follows: pH 6.12, organic matter 2.73%, total nitrogen 1.5g/kg, total phosphorus 1.02g/kg, total potassium 11.3g/kg, CEC 8.75cmol/kg, total arsenic 93.6mg/kg, total selenium 0.879mg/ Kg.
- Rice cultivation and treatment The rice variety is Youyou 128.
- the surface of rice seeds was sterilized with 5% sodium hypochlorite solution for 15 minutes. After rinsing with tap water, germination and seedlings were planted, and uniform seedlings were selected for transplanting.
- foliar application of silica sol or the 1% selenium-doped nanosilica sol of Example 1 can significantly promote rice growth, and the dry weight of rice grains increased by 20.2% compared with the control. 43.8%; compared with foliar application of silica sol, foliar application of 1% selenium-doped nano-silica sol promoted the growth of rice more significantly.
- the aqueous solution prepared by spraying 1% sodium selenite on the foliar surface had an inhibitory effect on rice growth; the dry weight of rice grain decreased by 13.1% compared with the control.
- Foliar application of selenium-doped nano-silica sol can not only promote rice growth, but also inhibit the accumulation of arsenic in rice and increase the selenium content of rice.
- the arsenic content of rice decreased by 46% after spraying 1% selenium-doped nano-silica sol, while the arsenic content of rice decreased by 28% after spraying pure silica sol, and 1% sodium selenite was sprayed. After the aqueous solution, the arsenic content of rice decreased by 19%.
- the selenium content of rice increased from 0.050 mg/kg to 0.272 mg/kg; the selenium-enriched rice standard was reached.
- the selenium content of the rice prepared by spraying 1% sodium selenite on the foliar surface was 0.180 mg/kg; only 66% of the 1% selenium-doped nano-silica sol rice was sprayed on the foliar surface.
- Example 5 Foliar application of selenium-doped nano-silica sol to reduce the effect of heavy metal arsenic absorption in rice field
- Spraying time During the rice tillering period (about 60 days), spray at about 4 o'clock in the afternoon when sunny or cloudy weather is selected; if it rains within 24 hours after spraying, it will be sprayed once.
- the series concentration gradient of selenium-doped nano-silica sol produced in Example 1 has a silicon content of 20% and a selenium content of 0.1%, 0.5%, 1% and 2%, about 1L per acre, foliar spray with 100L of water; spray the same amount of clean water as control; respectively recorded as 0.1% Se-Si, 0.5% Se-Si, 1% Se-Si, 2 %Se-Si, CK.
- Each of the 4 cells is processed, and the random blocks are arranged.
- the selenium doping concentration reaches 0.5%
- the arsenic content of rice meets the national food safety standards (inorganic arsenic ⁇ 0.2mg/kg GB2762-2012); and when the selenium doping amount is 0.1% and 0.5%, the selenium in rice The contents are 0.12 mg/kg and 0.26 mg/kg, respectively, in line with the selenium-enriched rice standard. Therefore, in Yanhong Town, 90% selenium-doped nano-silica sol can be sprayed on the arsenic-contaminated farmland to produce selenium-enriched rice with arsenic content up to standard.
- Example 6 Foliar application of selenium-doped nano-silica sol to reduce the absorption of heavy metals, cadmium and arsenic in rice
- the selenium doping concentration reaches 1%
- the cadmium content of rice drops below 0.2mg/kg, which meets the national food safety standards (cadmium ⁇ 0.2mg/kg GB 2762-2012); and when the selenium doping amount is 0.5% and At 1%, the selenium content in rice was 0.16 mg/kg and 0.28 mg/kg, respectively; meeting the selenium-enriched rice standard. Therefore, in the town of Handan City, the selenium-enriched rice with cadmium content can be produced on the cadmium-contaminated farmland by spraying the 1% selenium-doped nano-silica sol on the leaf surface.
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- 一种可以抑制水稻重金属吸收积累生产富硒稻米的硒掺杂纳米硅溶胶的制备方法,其特征在于,包括以下步骤:(1)配制金属硅酸盐溶液:将金属硅粉或金属硅酸盐在搅拌条件加入到浓度为0.1~5M的碱性溶液中,配制成金属硅酸盐溶液,其中含的金属硅粉或金属硅酸盐的浓度为重量百分比5%至饱和,pH为10~13;所述的金属硅酸盐为Na2SiO3、K2SiO3或Li2SiO3;(2)制备酸性硅溶胶前驱物:将金属硅酸盐溶液经过阳离子交换处理,控制收集液pH为1~4,将收集液加热到35-90℃,再静止冷却陈化,得到酸性硅溶胶前驱物;(3)制备酸性硒掺杂液:将含硒化合物在搅拌条件下溶解到稀酸溶液中,制备硒含量质量百分比为0.1-10%的酸性硒掺杂液,酸性硒掺杂液的pH值控制为1~4;所述的含硒化合物为亚硒酸、亚硒酸钠、亚硒酸钾或者亚硒酸氢钠;(4)制备乳化硒掺杂液:在搅拌条件下,将乳化剂加入到步骤(3)的酸性硒掺杂液中,最终乳化剂质量百分数控制在0.05~5%,由此得到乳化硒掺杂液;所述的乳化剂为聚乙烯吡咯烷酮、聚乙烯醇、吐温系列或斯潘系列;(5)制备硒掺杂酸性硅溶胶前驱物:将步骤(4)的乳化硒掺杂液在搅拌条件下加入到步骤(2)的酸性硅溶胶前驱物中,得到硒掺杂酸性硅溶胶前驱物,其中硒掺杂酸性硅溶胶前驱物中的硅:硒的质量百分比为3~200:1;(6)将步骤(5)的硒掺杂酸性硅溶胶前驱物加入到30℃~90℃的碱性催化剂配制的碱溶液中,直至碱溶液的pH值到7~9之时停止加入,继续搅拌反应30~90min,得到硒掺杂硅溶胶前体;所述的碱性催化剂为氢氧化钠、氢氧化钾、尿素、氨水或者硅酸钠溶液;(7)将步骤(6)的硒掺杂硅溶胶前体加入到30℃~90℃的还原剂溶液中,直至溶胶淡 红色不再加深,硒充分还原后,继续搅拌反应2小时以上,然后再经2次以上渗析,即得到硒掺杂纳米硅溶胶;所述的还原剂为抗坏血酸、谷胱甘肽或还原性糖类。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(1)的碱性溶液是用氢氧化钠、氢氧化钾或氨水配制,浓度为0.1~2M。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(2)的收集液的pH为2~3.5,收集液加热到温度45-55℃。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(3)的稀酸溶液是稀盐酸、稀硝酸、稀硫酸或稀磷酸溶液;所述的酸性硒掺杂液硒含量质量百分比为2~7.6%;所述的酸性硒掺杂液的pH值控制为1~2。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(4)所述的乳化剂为吐温,最终乳化剂质量百分数控制在0.5~2%。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(5)的硒掺杂酸性硅溶胶前驱物中的硅:硒的质量百分比为9~20:1。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(6)的碱性催化剂配制的碱溶液的温度控制在45℃~85℃,继续搅拌反应的时间为30~60min。
- 根据权利要求1所述的制备方法,其特征在于,所述的步骤(7)的还原剂为抗坏血酸,溶液的温度控制为50℃~85℃。
- 一种根据权利要求1、2、3、4、5、6、7或8所述的制备方法制备得到的可以抑制水稻重金属吸收积累生产富硒稻米的硒掺杂纳米硅溶胶。
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US9919978B2 (en) | 2018-03-20 |
US20160289129A1 (en) | 2016-10-06 |
JP2016511232A (ja) | 2016-04-14 |
CN103789114B (zh) | 2015-08-26 |
JP6068679B2 (ja) | 2017-01-25 |
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