CN1907029A - Rare earth composite silicasol capable of repressing rice absorbing high-density metal - Google Patents
Rare earth composite silicasol capable of repressing rice absorbing high-density metal Download PDFInfo
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- CN1907029A CN1907029A CNA2006100369948A CN200610036994A CN1907029A CN 1907029 A CN1907029 A CN 1907029A CN A2006100369948 A CNA2006100369948 A CN A2006100369948A CN 200610036994 A CN200610036994 A CN 200610036994A CN 1907029 A CN1907029 A CN 1907029A
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Abstract
The invention discloses a nano composite silicasol doped with rare-earth element, which comprises nano silicon dioxde collosol and rare-earth oxide collosol, wherein the content of the rare-earth elements is 0.01-1 wt%. The nano composite silicasol can be synthesized under rather low temperature and normal pressure.
Description
Technical field
The present invention relates to a kind of Nano silica sol, specifically, relate to a kind of nano combined Ludox of doped with rare-earth elements.
Background technology
Silicon dioxide gel just is widely used in the multiple product of all conglomeraties such as papermaking, coating, catalyzer, anti-skidding product, polymer composite, electronic package material, high technology ceramics material, rubber, plastics, fiberglass, binding agent, wafer polishing, high-grade filler, fluid sealant, coating, optical fiber, hot investment casting once discovery, nano silicon is as a kind of emerging material, and it is in fields such as aerospace flight technology, electronics, metallurgy, chemistry, biology and medical science demonstration elegance.And intersecting, merging of inorganic chemistry, Environmental Chemistry and material science and life science forming a new research direction, utilize the research on environmentally conscious materials and biological nano material raising disease-resistant crops ability, resistance and the extermination of disease and insect pest thereof, forming unique research field; And attempt in agriculture environmental protection and plant protection, directly using.
In recent years, developed country has developed some frontiers that nano silicon is used, and as in agricultural, applying nano made of silicon dioxide agricultural seed inorganic agent can make vegetables, cotton, corn, wheat improve output, ripen in advance.Can also to be applied to vegetable and fruit fresh-keeping for nano silicon in addition, also has sterilizing function etc.Recent study shows that silicon can improve the resistance of plant to heavy metallic poison, and it is convenient and cheap to utilize, and has caused people's great attention.Execute silicon and can obviously alleviate the paddy rice heavy metallic poison, on cadmium pollution soil, use the blast furnace slag that is rich in silicon to biological yield and the yield of brown rice of paddy rice and do not make significant difference, but the content of cadmium significantly descends in the rice, drop to the 7.7-8.5% of contrast, handle ratio with liming, the rice cadmium content reduces 6-8 doubly.Silicon can be alleviated the plant aluminum poison as the plant beneficial element and also be confirmed on Chinese sorghum, barley and Soybean and Other Crops.And rare earth mixing with nano silica is directly sprayed in corps leaf surface, the absorption raising quality of agricultural product that improve crops preventing from heavy metal performance, reduces to heavy metal still is a brand-new application.
The preparation silicon dioxide gel has two kinds of preparation methods with regard to principle: a kind of growth of chemical reaction generation silica ultra micron, nucleation of utilizing in the solution, and the method that makes Ludox is a coacervation; Utilize machinery that silicon dioxide microparticle is scattered in the method that makes Ludox in the water under given conditions and be dispersion method.Methods such as elemental silicon dissolution method, ion-exchange, electrolytic electro-dialysis method, peptisation, sour neutralisation and dispersion method are arranged with regard to preparation technology.What the preparation method of nano silicon was studied both at home and abroad at present is more.USP3714064 describes the method for water glass preparation particle diameter Ludox between 2-5nm, but will cool off ion exchange resin in manufacturing process, and wants volume inconvenience during si-enriched colloidal sol, the operation more complicated; USP4806665 and USP4915870 have narrated the method for preparing particle diameter Ludox between 2-5nm with short-chain alkyl hydramine and potassium hydroxide, but all do not mention the stability of this class colloidal sol; USP6372806 has described with silicic acid and waterglass and has prepared the method for particle diameter less than the 4nm Ludox, but the content of its silica does not all have to surpass 20%, and only be 30 days stationary phase; CN00814361.7 has announced that a kind of utilization adds the phosphonate group complexing agent in containing the solution of silicic acid, prepare the method for high-purity silicon dioxide colloidal sol, but grain size is relatively large; CN96100907.1 has described the manufacture method of the large granular silicon dioxide gel of a kind of high-purity, high concentration, the distribution of high single-size; CN200410014611.8 has proposed a kind of manufacture method of paper grade (stock) nano silicon dioxide sol, but technology is comparatively complicated; CN200410077963.8 discloses a kind of production method of acid silicon dioxide sol; CN200410091123.7 has introduced a kind of dioxide/silica gel preparation of carrying nano silver.Also be not exclusively used at present the rare earth mixing with nano silicon dioxide gel preparation method's who suppresses the absorption of crops heavy metal report.
Summary of the invention
The object of the present invention is to provide a kind of rare earth comprehensive silicon colloidal sol that crops absorb heavy metal that can be used to suppress.
Another object of the present invention provides the preparation method of above-mentioned rare earth comprehensive silicon colloidal sol.
To achieve these goals, the present invention adopts following technical scheme:
A kind of rare earth comprehensive silicon colloidal sol that suppresses paddy rice absorption heavy metal is made up of nano silicon dioxide sol and rare earth oxide colloidal sol, and the content of rare earth element is 0.01%～1 weight %.
The preparation method of above-mentioned rare earth comprehensive silicon colloidal sol is: after nano silicon dioxide sol and the dialysis of rare earth oxide colloidal sol difference, transferring pH is 7, mixes, and makes rare earth comprehensive silicon colloidal sol.Gained rare earth comprehensive silicon colloidal sol outward appearance clarification, transparent, light blue, sol system pH value about 7, particle diameter generally below 15nm, SiO in the colloid
2Content is 5%～10%, and rare earth ion content is below 1%.
Above-mentioned rare earth oxide is the oxide of cerium, lanthanum, neodymium, europium or gallium, and described nano silicon dioxide sol is inorganic nano silicon dioxide gel or organic nano silicon dioxide gel.
Above-mentioned rare earth oxide colloidal sol can be prepared from by following method: be raw material with the nitrate of rare earth element, alkali lye is as precipitating reagent, the water cyclic washing to neutrality, filtering-depositing; In the precipitation that obtains, add inorganic acid, regulating pH is 0.3～2.0, and constantly stirs, and at room temperature continues then to stir more than 2 hours, in 40 ℃～90 ℃ water-baths heating and stir more than 3～50 hours, obtain stable homogeneous and translucent high purity rare earth oxides colloidal sol.
Above-mentioned inorganic nano silicon dioxide gel can be prepared from by following method:
(1) precursor liquid preparation and activation: the metal silicate solution of preparation 5～20 weight %, preferentially choose 5%～10%, concentration is too high reunites in acidization easily; SiO in the solution
2/ M
2The mol ratio of O (M is Na, K or Li) is 1～5, preferentially chooses 2～4, and under vigorous stirring, in 25 ℃～30 ℃ temperature microwave activations 2～3 hours, cold filtration obtained reaction precursor liquid, and the pH value is generally about 13.Metal silicate solution is water white transparency, impure few preferably, and metal silicate can be selected Na
2SiO
3, K
2SiO
3Or Li
2SiO
3, preferentially choose Na
2SiO
3
(2) preparation of active silicic acid: the precursor liquid that step (1) is obtained will carry out acidification, to make active silicic acid solution.Acidifying can be adopted and add inorganic, ammonium salt or organic acid is handled, and also available hydro-strong acidic cation exchange resin is handled.When adding acid and carrying out acidification, at first the finite concentration acid solution is added drop-wise to certain speed in step (1) precursor liquid of vigorous stirring, between control pH value to 9～10, stops to drip, and continues to stir to obtain intermediate solution in 1 hour; Then intermediate solution is added drop-wise to same speed in the acid solution of same concentrations of vigorous stirring, control pH value to 1～4 preferentially are controlled between 1.5～3, can obtain active silicic acid solution; Selected acid can be inorganic acid, ammonium salt or organic acid.Acidifying also can be carried out with hydro-strong acidic cation exchange resin, the precursor liquid that step (1) is obtained passes through multistage resin-column with given pace, the control column outlet is collected liquid pH value between 1～4, preferably controls to 1.5～3, can obtain active silicic acid solution.Behind active silicic acid solution microwave (or water-bath) the heating 15min of preparation, static cooling and aging 60min is standby.
(3) add catalyzer and carry out the active silicic acid polymerisation: the preparation aqueous slkali is as catalyzer, microwave or water-bath are heated to 45 ℃～75 ℃, step (2) gained active silicic acid solution is splashed into wherein, till pH value to 7～9, keep temperature to continue stirring reaction 45～90min, can obtain the subalkaline high-purity nm silicon dioxide gel of a kind of stable transparent.Vacuum evaporation dehydration or hyperconcetration also can obtain the higher silicon dioxide gel of concentration.Described aqueous slkali is sodium hydroxide, potassium hydroxide, urea, weak aqua ammonia or sodium silicate solution.
Above-mentioned organic nano silicon dioxide gel can be prepared from by following method: ethanol, ammoniacal liquor, water, ethyl orthosilicate were mixed in 120: 10 by volume～15: 10～100: 1,40 ℃ are continued heated and stirred reaction 5～24h, products therefrom dilutes with high purity water, dialysis obtained the organic nano silicon dioxide gel to neutral after the decompression distillation rotary evaporation was removed ethanol.
Above-mentioned organic nano silicon dioxide gel also can be prepared from by following method: with the OP emulsifier is surfactant, n-amyl alcohol is a cosurfactant, rare nitric acid is water, cyclohexane is that oil phase prepares microemulsion, add nitrate of rare earth element solution, stir, stir adding ethyl orthosilicate (TEOS) at last, room temperature reaction 10～24h makes rear-earth-doped organic nano silicon dioxide gel.
Compared with prior art, the present invention has following beneficial effect:
(1) the concentration height of Fa Ming rare earth comprehensive silicon colloidal sol, homogeneous is bright, and good stability flocculent deposit can not occur behind placement or the dilute with water for a long time, and specific surface area obvious decline can not occur yet.
(2) rare earth comprehensive silicon colloidal sol particle diameter is little, is generally less than 15nm, and particle diameter is single, and specific surface area is big, and light transmission is good.
(3) doping of rare earth element has strengthened the resistant function of plant to heavy metal, strides film and enters in the plant cell because its high-specific surface area and strong adsorption ability obviously suppress heavy metal.
(4) preparation process of colloid is carried out under lower temperature and normal pressure, mild condition, and technology is simple, is convenient to operation, thereby is easy to carry out large-scale production.
(5) raw material sources of this colloidal sol preparation are extensive, cheap, pollute for a short time, help carrying out cleaner production.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of inorganic, organic silicon sol and cerium colloidal sol;
Fig. 2 is the light transmittance spectrogram of inorganic, organic silicon sol and cerium colloidal sol;
Fig. 3 is the light transmittance spectrogram of different cerium doping inorganic nano silicon dioxide gels;
Fig. 4 is a particle size distribution figure of mixing the decorations silicon dioxide gel;
Fig. 5 is the light transmittance spectrogram of different cerium doping organic nano silicon dioxide gels;
Fig. 6 is inorganic, organic and cerium doped silicon colloidal sol XRD spectra;
Fig. 7 is the infrared spectrum analysis of inorganic organic silicon sol;
Fig. 8 is the infrared spectrum analysis of mixing the decorations Ludox.
Embodiment
Choose SiO
2/ Na
2The O mol ratio is 3 sodium silicate, is mixed with concentration and is 10% sodium silicate solution 400ml, and 30 ℃ of temperature lower magnetic forces stir 2h.
Measure 10% hydrochloric acid 130ml and progressively drip wherein in separatory funnel, after dropwising, the pH value of solution is 9.5; Then with the sodium silicate solution of 530ml pH value=9.5, counter dripping in 70ml 10% hydrochloric acid under stirring condition can obtain the pH value and be 2 active silicic acid solution.
Compound concentration be 2% potassium hydroxide solution as catalyzer, microwave is stirred and heated to 70 ℃, active silicic acid at the uniform velocity to drip wherein, control pH value is 8, stop to drip, continue stirring reaction 75min, obtain the subalkaline high-purity nm silicon dioxide gel of a kind of stable transparent after finishing processing.
With the 50g cerous nitrate be dissolved in 500ml go dried up in mixing, stir fully dissolving, after the cooling, to drip concentration again be the ammoniacal liquor 950ml of 1M and control its adding speed, regulate make its abundant hydrolytic precipitation more than the pH to 10 after, stirred 4 hours; Filtration washing to pH be between 8, then filter cake is added the water mixing, add the nitric acid of concentration 10%, regulating pH is 1.0, normal temperature stirred 4 hours down, heated and stirred 24 hours in 60 ℃ of water-baths obtains the pale blue transparent ceric oxide sol of yellow partially then.
After silicon dioxide gel and ceric oxide sol dialysis, adjusting colloidal sol pH is 7, extract solid content respectively and be 0.2% silicon dioxide gel and solid content and be 0.2% ceric oxide sol, dissolved mutually, mix and adsorb in 1: 1,2: 1,3: 1,5: 3,5: 4 with volume ratio, and the cerium doping inorganic nano silicon dioxide gel of formation different levels of doping.
Adopt the sodium silicate solution 100ml of the method preparation 10% of embodiment 1, at the uniform velocity by the multistage resin-column of 50ml (humid volume) hydrogen type strong acid cation, the control column outlet is collected liquid pH value 3, can obtain active silicic acid solution.
Compound concentration is that 2% potassium hydroxide solution is as catalyzer, stirring in water bath is heated to 70 ℃, active silicic acid is at the uniform velocity dripped wherein with the speed that is fit to, control pH value is 8, stop to drip, continue stirring reaction 75min, finish to handle obtaining the subalkaline high-purity nm silicon dioxide gel of a kind of stable transparent.
According to step hydrolytic precipitation, the filtration washing of embodiment 1, then filter cake is added the water mixing, add the nitric acid of concentration 10%, regulating pH is 1.0, normal temperature stirred 4 hours down, and heated and stirred promptly obtained the yellow partially transparent ceric oxide sol of pale blue more than 24 hours in 60 ℃ of water-baths then.
After silicon dioxide gel and ceric oxide sol dialysis, adjusting colloidal sol pH is 7, extract solid content respectively and be 0.2% silicon dioxide gel and solid content and be 0.2% ceric oxide sol, dissolved mutually, mix and adsorb in 1: 1,2: 1,3: 1,5: 3,5: 4 with volume ratio, and the cerium doping inorganic nano silicon dioxide gel of formation different levels of doping.
Embodiment 3 prepares cerium organic nano silicon dioxide sol that mixes with tetraethoxysilance
The concentration of measuring 20 milliliters is 25-28% ammoniacal liquor, the ethanol of 10 milliliters high purity water and 500 milliliters adds in 1000 milliliters the self-control reactor, mixing and stirring is heated to 45 ℃ under water bath condition, then 15 milliliters ethyl orthosilicate is dripped one by one, stirred 3 hours after finishing, adding 10 milliliters of ethyl orthosilicates, continue reaction 3 hours, products obtained therefrom adds 1000 milliliters of high purity water dilutions, steam with decompression and to stay rotary evaporation to remove behind the ethanol with the dialysis of self-control dialysis device till the pH=7, make the organic nano silicon dioxide gel.
According to step hydrolytic precipitation, the filtration washing of embodiment 1, then filter cake is added the water mixing, add the nitric acid of concentration 10%, regulating pH is 1.0, normal temperature stirred 4 hours down, more than heated and stirred 10-24 hour, promptly obtained the yellow partially transparent ceric oxide sol of pale blue then in 60 ℃ of water-baths.
After silicon dioxide gel and ceric oxide sol dialysis, adjusting colloidal sol pH is 7, extract solid content respectively and be 0.2% silicon dioxide gel and solid content and be 0.2% ceric oxide sol, dissolved mutually, mix and adsorb in 1: 1,2: 1,3: 1,5: 3,5: 4 with volume ratio, and the cerium that forms different levels of doping organic nano silicon dioxide sol that mixes.
Embodiment 4 microemulsion methods prepare the organic nano Ludox
Will be with 1g Triton X-100 (OP emulsifier), the 50ml cyclohexane, the 10ml n-amyl alcohol, the rare nitric acid of 50ml joins in the 250ml round-bottomed flask, fully stir, make the micro emulsion inverse micellar solution, water-bath is heated to 40 ℃, add the 0.5g cerous nitrate solution then and continue mixing and stirring, stir adding 2.5ml ethyl orthosilicate at last, continue stirring reaction 24h, after the gained colloid stays rotary evaporation to remove organic additive with the decompression steaming, dialysis can obtain cerium organic nano silicon dioxide sol that mixes till the pH=7.
Adopting the method for embodiment 1 is that feedstock production goes out the subalkaline high-purity nm silicon dioxide gel of stable transparent with the sodium silicate.With the 100g lanthanum nitrate be dissolved in 1000ml go dried up in mixing, stir fully dissolving, after the cooling, to drip concentration again be the ammoniacal liquor 1950ml of 0.5M and control its adding speed, regulate make its abundant hydrolytic precipitation more than the pH to 10 after, stirred 4 hours; Filtration washing to pH be between 8, then filter cake is added the water mixing, add the nitric acid of concentration 10%, regulating pH is 1.0, normal temperature stirred 4 hours down, heated and stirred 24 hours in 60 ℃ of water-baths obtains nattier blue transparent titanium dioxide lanthanum colloidal sol then.
After Ludox and lanthanum diasolysis, adjusting colloidal sol pH is 7, extract solid content respectively and be 0.2% silicon dioxide gel and solid content and be 0.2% ceric oxide sol, dissolved mutually, mix and adsorb in 1: 1,2: 1,3: 1,5: 3,5: 4 with volume ratio, and the lanthanum doping inorganic nano silicon dioxide gel of formation different levels of doping.
Embodiment 6 preparation lanthanums organic nano silicon dioxide sol that mixes
Adopt the method for embodiment 3 to make the organic nano silicon dioxide gel to be prepared as raw material with tetraethoxysilance.With the 100g lanthanum nitrate be dissolved in 1000ml go dried up in mixing, stir fully dissolving, after the cooling, to drip concentration again be the ammoniacal liquor 1950ml of 0.5M and control its adding speed, regulate make its abundant hydrolytic precipitation more than the pH to 10 after, stirred 4 hours; Filtration washing to pH be between 8, then filter cake is added the water mixing, add the nitric acid of concentration 10%, regulating pH is 1.0, normal temperature stirred 4 hours down, heated and stirred 24 hours in 60 ℃ of water-baths obtains nattier blue transparent titanium dioxide lanthanum colloidal sol then.
After Ludox and lanthanum diasolysis, adjusting colloidal sol pH is 7, extract solid content respectively and be 0.2% silicon dioxide gel and solid content and be 0.2% ceric oxide sol, dissolved mutually, mix and adsorb in 1: 1,2: 1,3: 1,5: 3,5: 4 with volume ratio, and the lanthanum that forms different levels of doping organic nano silicon dioxide sol that mixes.
Embodiment 7 is the contrast that the forerunner prepares colloidal sol with sodium silicate, ethyl orthosilicate
Respectively with sodium silicate for the forerunner prepare colloidal sol (embodiment 1 preparation), tetraethoxysilance for the forerunner prepare colloidal sol (embodiment 3 preparations) in 60 ℃ down oven dry in agate mortar, grind and obtain powder more than 12 hours, survey its XRD, as shown in Figure 6.Drawing from Fig. 6, is that organosilicon source, inorganic silicon source or the Ludox of rear-earth-doped preparation all do not have tangible crystal formation result, all is unformed silica.Shown in Fig. 1～3, the light transmittance spectrogram shows, with the organosilicon source be the colloidal sol light transmittance of feedstock production to be lower than with inorganic silicon source sodium silicate be the colloidal sol of feedstock production, this shows that latter's particle size is less than the former; Along with the raising of rare earth ion cerium doping ratio, the light transmittance spectrogram shows that its light transmission reduces, and considers the influence to photosynthesis of plant, and rare ratio that goes up doping is proper less than 0.1%.
Inorganic, the organic and infrared spectrum analysis of mixing the decorations Ludox of embodiment 8
Respectively sodium silicate for preparing colloidal sol (embodiment 1 preparation), tetraethoxysilance, the forerunner is prepared colloidal sol (embodiment 3 preparations) in 60 ℃ of oven dry more than 12 hours down for the forerunner, in agate mortar, grind and obtain powder, carry out the infared spectrum analysis, as Fig. 7, shown in Figure 8,1650～1600cm
-1, 1115cm
-1, 800cm
-1And 473cm
-1The absworption peak at place is the characteristic absorption peak of silica, and these peak values and gel silicas (unformed) standard spectrogram basically identical, the minute differences of spectrogram may be that the reason owing to impurity causes.Wherein, 800cm
-1And 473cm
-1Absworption peak illustrated that the elementary cell of its skeleton structure is the Si-O tetrahedron.1115cm
-1Be Si-O-Si antisymmetric stretching vibration absworption peak, 1650～1600cm
-1The H-O-H flexural vibrations of corresponding pore water and surperficial adsorbed water, 3442cm
-1Be the antisymmetry O-H stretching vibration absworption peak of silicon hydroxyl and combination water, 800cm
-1, 473cm
-1The symmetrical stretching vibration of corresponding very weak and stronger Si-O key shows that unformed silica is on the tetrahedral basis of Si-O in its this unit of its skeleton structure respectively, mainly exists with the poly-attitude form of height.
Embodiment 9 Ludox reduce the paddy rice heavy metal and absorb the potted plant experiment effect of earth culture
Soil processing: water intaking top layer, rice field mold (0-10cm), sieve after air-dry, claims 10 kilograms of native runnings into tank, apply 0.5,1.0 respectively, the 2.0mg/kg heavy metal cadmium, carry out pollutional condition and simulate.
Rice cultivating and processing:, wash back vernalization, grow seedlings rice paddy seed surface sterilization 15 minutes with 5% liquor natrii hypochloritis, select the seedling of uniformity to transplant with running water.Every basin 2 strains, in seedling stage (25-35 days), tillering stage (60-70 days), (80-90 days) foliage-spray in booting stage cerium doping prepared in accordance with the present invention inorganic nano silicon dioxide gel, cerium mix organic nano silicon dioxide sol and common Na
2SiO
3Deng silicon-agent, the colloidal sol si content all is adjusted to 20 μ mol L
-1Spray silicon and handle to divide a following scheme: spray separately 6 (1) three each period in period, sprayed 2 branches every one day and spray sooner or later, be sprayed onto that the globule appears in the blade face but till not dripping; All spray (2) three each periods in period, divides spray a period and spray altogether for 2 times 6 times.With the clear water is contrast, the same Routine Management of all the other field management.Results backs is Different Organs separately, with running water and deionized water clean, oven dry, ashing, acid be molten, mensuration Cd content.
Content of beary metal is measured: take by weighing about the levigate plant sample 0.500g of oven dry and be put in 150 milliliters of triangular flasks, add the pure HNO of top grade
325 milliliters, placement is spent the night, and covers little funnel, but at temperature adjustment heating 30min.Cooling adds the pure HClO of top grade
45 milliliters, low-temperature heat treats that a bottle words spoken by an actor from offstage cigarette disappears solution when being 2 milliliters of water white transparency residues, takes off cooling from electric furnace, washes 50 milliliters of volumetric flasks with hot water, and with distilled water constant volume, filtration, liquid to be measured is measured on atomic absorption spectrophotometer.
The result is shown in table 1, table 2, table 3, table 4, and experimental result shows, sprays silicon-agent and has deepened the rice leaf green, the tall and straight and mechanical force enhancing of blade; Do not apply the Exogenous Silicon material, raise with heavy metal concentration, the rice biological amount descends to some extent, the accumulation of heavy metal in paddy rice increases according to soil concentration, as 0.5,1.0, on the 2.0mg Cd/kg air dried soil level, in the root Cd content be respectively 13.1,15.9,29.6mg/kg (dw), also have identical trend to increase progressively in the seed.On same heavy metal level, the foliage-spray silicon matter, little to the influence of rice biological amount, content of beary metal all significantly descends in rice root, cauline leaf, each position of seed, and fall is followed successively by the inorganic Si colloidal sol of the organic Si colloidal sol＞Ce-of Ce-＞common Na in proper order
2SiO
30.5,1.0, during 2.0mgCd/kg air dried soil heavy metal level, all apply the organic Si colloidal sol of Ce-in three periods and make that Cd content drops to 24.33%, 20.34% and 16.20% of contrast respectively in the seed.When the heavy metal-polluted soil level is 2.0mg Cd/kg air dried soil, all applies the organic Si colloidal sol of Ce-in three periods and make that Cd content drops to 0.134mg/kg from 0.827 of contrast in the rice.It is also inequality to apply the organic Si colloidal sol of Ce-effect in the paddy rice different growing, wherein with in spraying effect the best in tillering stage, when the heavy metal-polluted soil level is 2.0mg Cd/kg air dried soil, all apply in seedling stage, tillering stage, booting stage, three periods the organic Si colloidal sol of Ce-make Cd content in the rice from the 0.827mg/kg of contrast drop to 0.167,0.101,0.146 respectively, 0.134mg/kg.In the national food hygienic standard, the rice cadmium content requires to be lower than 0.2mg/kg, applies silicon-agent by external source, effectively reduces cadmium content in the rice, is expected to pollute the qualified rice of production on the paddy soil at low-concentration heavy metal.
Table 1 three periods all sprays silicon-agent and handle down cadmium distribute (mg/kg) in the paddy rice body
| Contrast | Na 2SiO 3 | The inorganic Si colloidal sol of Ce- | The organic Si colloidal sol of Ce- | ||||||||||
| Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | ||
| Cadmium concentration | 0.5mg/kg | 13.1 | 2.7 | 0.045 | 8.79 | 2.08 | 0.043 | 4.9 | 0.25 | 0.023 | 2.85 | 0.189 | 0.011 |
| 1.0mg/kg | 15.9 | 4.3 | 0.327 | 13.8 | 3.41 | 0.215 | 8.5 | 2.41 | 0.104 | 6.14 | 1.23 | 0.067 | |
| 2.0mg/kg | 29.6 | 6.6 | 0.827 | 17.8 | 5.94 | 0.726 | 10.6 | 3.78 | 0.210 | 7.64 | 1.54 | 0.134 | |
Table 2 seedling spraying silicon-agent is handled down cadmium distribute (mg/kg) in the paddy rice body
| Contrast | Na 2SiO 3 | The inorganic Si colloidal sol of Ce- | The organic Si colloidal sol of Ce- | ||||||||||
| Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | ||
| Cadmium concentration | 0.5mg/kg | 13.1 | 3.1 | 0.051 | 9.31 | 2.21 | 0.052 | 5.2 | 0.31 | 0.031 | 2.97 | 0.235 | 0.022 |
| 1.0mg/kg | 15.9 | 5.2 | 0.401 | 15.1 | 3.65 | 0.324 | 9.2 | 2.67 | 0.131 | 6.68 | 1.48 | 0.095 | |
| 2.0mg/kg | 29.6 | 7.1 | 0.910 | 19.2 | 6.21 | 0.811 | 11.5 | 3.98 | 0.291 | 7.97 | 1.72 | 0.167 | |
Table 3 sprays silicon-agent tillering stage and handle down cadmium distribute (mg/kg) in the paddy rice body
| Contrast | Na 2SiO 3 | The inorganic Si colloidal sol of Ce- | The organic Si colloidal sol of Ce- | ||||||||||
| Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | ||
| Cadmium concentration | 0.5mg/kg | 13.1 | 2.5 | 0.041 | 8.51 | 1.98 | 0.034 | 4.0 | 0.21 | 0.019 | 2.61 | 0.151 | 0.008 |
| 1.0mg/kg | 15.9 | 4.0 | 0.301 | 12.9 | 3.10 | 0.195 | 7.4 | 2.21 | 0.091 | 5.87 | 1.12 | 0.059 | |
| 2.0mg/kg | 29.6 | 6.1 | 0.798 | 16.7 | 5.12 | 0.684 | 9.3 | 3.01 | 0.191 | 7.21 | 1.32 | 0.101 | |
Table 4 sprays silicon-agent booting stage and handle down cadmium distribute (mg/kg) in the paddy rice body
| Contrast | Na 2SiO 3 | The inorganic Si colloidal sol of Ce- | The organic Si colloidal sol of Ce- | ||||||||||
| Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | Root | Cauline leaf | Seed | ||
| Cadmium concentration | 0.5mg/kg | 13.1 | 2.6 | 0.043 | 8.63 | 2.10 | 0.037 | 4.7 | 0.27 | 0.027 | 2.78 | 0.165 | 0.019 |
| 1.0mg/kg | 15.9 | 4.1 | 0.312 | 12.8 | 3.21 | 0.221 | 8.3 | 2.51 | 0.125 | 6.51 | 1.20 | 0.083 | |
| 2.0mg/kg | 29.6 | 6.3 | 0.810 | 17.2 | 5.14 | 0.731 | 11.0 | 3.82 | 0.271 | 7.32 | 1.43 | 0.146 | |
Selected rice paddy seed with 5% sodium chlorate solution's surface sterilization 20 minutes, is rinsed well with running water, the 25 ℃ of vernalization after 24 hours of soaking seed, and the seed that will sprout is sowed at quartz sand.Be transplanted in 1/4 Kimura's nutrient solution when treating length and grow 2 liters of plastic basin, every basin 10 strains to 2 true leaves.Handle when treating length to 5 true leaves, cadmium is applied in the nutrient solution, spray Ce dopen Nano organic silicon sol of the present invention, divide every day morning, evening to spray twice, sprayed continuously three days, the water spray that does not spray nano-silicon is done contrast, observes the paddy growth situation.Processing scheme such as table 5.
Table 5 processing scheme and processing back rice biological amount and cadmium content distribution table
| Handle code | Cadmium concentration of treatment (mg/kg) | Spray Si concentration (μ mol L -1) | Ce doping (‰) | Biomass (g) | Root system cadmium content (mg/kg) | Cauline leaf cadmium content (mg/kg) |
| 0 | 10 | 0 | 0 | 5.17 | 109.2 | 19.12 |
| 1 | 10 | 5 | 0 | 5.23 | 81.2 | 13.45 |
| 2 | 10 | 10 | 0 | 5.61 | 72.6 | 10.12 |
| 3-0 | 10 | 20 | 0 | 5.82 | 60.2 | 4.02 |
| 3-1 | 10 | 20 | 0.1 | 5.78 | 53.1 | 3.86 |
| 3-2 | 10 | 20 | 0.2 | 5.89 | 48.2 | 3.84 |
| 3-3 | 10 | 20 | 0.4 | 6.15 | 40.1 | 2.13 |
| 3-4 | 10 | 20 | 0.6 | 6.71 | 35.4 | 2.01 |
| 3-5 | 10 | 20 | 0.8 | 6.01 | 44.2 | 2.24 |
| 3-6 | 10 | 20 | 1 | 5.74 | 55.4 | 3.01 |
| 4 | 10 | 30 | 0 | 5.64 | 58.4 | 3.87 |
| 5 | 10 | 40 | 0 | 5.54 | 48.7 | 3.76 |
| 6 | 10 | 50 | 0 | 5.61 | 41.0 | 4.04 |
Under the water planting condition paddy rice is carried out the foliage-spray Nano silica sol and can effectively suppress absorption and the accumulation of paddy rice to heavy metal cadmium, and have certain dose effect, the concentration that sprays silicon is at 20-40 μ mol L
-1The time best results; Ce mixes can further improve the resistance of paddy rice to cadmium, further reduces the accumulation of cadmium in the paddy rice body, and the doping content of Ce best results between 0.04～0.08%.
Embodiment 11 Ludox reduce the paddy rice heavy metal and absorb the field experiment effect
Implement the place: Shaoguan, Guangdong Province one dirty ore deposit polluted agricultural land, agricultural land soil physicochemical property such as table 6.
Table 6 soil basic physical and chemical
| The soil basic physical and chemical | |
| pH(CaCl 2) the total quick-acting K of K (%) available N (mg/kg) available P (mg/kg) (mg/kg) Pb (mg/kg) Cu (mg/kg) Zn (mg/kg) Cd (mg/kg) of the total P (%) of organic (%) total N (%) | 6.5 2.32 0.128 0.110 1.090 123.56 73.34 220 123.2 104.1 242.8 2.01 |
Field rice foliage-spray Ludox method:
(1) sprays the time:, select fine day or cloudy weather afternoon about 4, spray in rice plant of tillering stage (about about 60 days); As spray in back 24 hours and to rain, then fill spray once.
(2) concentration that sprays and dosage: with the Ce doping organic silicon sol silicon content 2mmol/L that the present invention produced, every mu of about 1L of consumption converts water 100L and carries out foliage-spray.
(3) field management: the same with the common rice field management.
Output and rice content of beary metal behind the table 7 field rice foliage-spray organic silicon sol
| Handle | Average per unit area yield (kilogram/mu) | 100-grain weight (g/100 grain) | Rice content of beary metal (mg/kg) | ||||
| Cu | Zn | Pb | Cd | ||||
| 9248 special B Guangdong, nine excellent 207 Peiza Shuangqi Zhejiang are fragrant sticking in excellent 128 | CK Si-B CK Si-A CK Si-A CK CK Si-A CK Si-A | 442.1 481.2 452.1 461.3 431.5 505.8 369 381 398.2 415.3 354.1 361.7 | 1.67 1.76 1.75 2.00 1.37 1.46 1.67 1.80 1.76 1.92 1.53 1.57 | 14.2 9.2 12.3 10.2 13.5 9.7 13.2 11.2 9.8 8.1 7.9 6.7 | 78.2 62.5 81.3 70.2 67.2 48.2 54.3 44.1 57.1 53.2 41.2 38.7 | 0.64 0.31 0.71 0.41 0.61 0.38 0.38 0.31 0.34 0.29 0.31 0.18 | 0.99±0.05 0.31±0.02 1.26±0.17 0.23±0.03 1.04±0.06 0.14±0.01 0.65±0.02 0.24±0.00 0.60±0.03 0.19±0.02 0.53±0.06 0.18±0.01 |
After the land for growing field crops sprays Ce doping organic silicon sol, can significantly improve rice yield and quality, obviously reduce the content of heavy metal Cu, Zn, Pb, Cd in the rice, wherein Cd content reduces the most remarkable, and training assorted two seven and in after nine excellent these two kinds spray organic silicon sol, the rice heavy metal descends the most obvious.After training assorted two seven and Guangdong perfume (or spice) were bonded at and spray organic silicon sol, its rice reached national food hygienic standard.
Claims (10)
1, a kind of rare earth comprehensive silicon colloidal sol that suppresses paddy rice absorption heavy metal is characterized in that being made up of nano silicon dioxide sol and rare earth oxide colloidal sol, and the content of rare earth element is 0.01%～1 weight %.
2, rare earth comprehensive silicon colloidal sol as claimed in claim 1 is characterized in that described rare earth oxide is the oxide of cerium, lanthanum, neodymium, europium or gallium.
3, rare earth comprehensive silicon colloidal sol as claimed in claim 1 or 2 is characterized in that described nano silicon dioxide sol is inorganic nano silicon dioxide gel or organic nano silicon dioxide gel.
4, the preparation method of the described rare earth comprehensive silicon of claim 1 colloidal sol is characterized in that comprising the steps: that transferring pH is 7, mixes, and makes the rare earth mixing with nano silicon dioxide gel with after nano silicon dioxide sol and the dialysis of rare earth oxide colloidal sol difference.
5, rare earth comprehensive silicon colloidal sol as claimed in claim 1 is characterized in that described rare earth oxide colloidal sol can be prepared from by following method:
(1) with the nitrate of rare earth element be raw material, alkali lye is as precipitating reagent, the water cyclic washing to neutrality, filtering-depositing; Add inorganic acid in the precipitation that obtains, regulating pH is 0.1～2.0, and constantly stirs;
(2) continue to stir under the room temperature 1～12 hour, preferred 2～3 hours, slurry 40 ℃～90 ℃ water-bath heating and stir more than 3～50 hours, is obtained rare earth oxide colloidal sol.
6, rare earth comprehensive silicon colloidal sol as claimed in claim 3 is characterized in that described inorganic nano silicon dioxide gel can be prepared from by following method:
(1) precursor liquid preparation and activation: preparation 1～30 weight %, the metal silicate solution of 5～20 weight %, SiO in the solution
2/ M
2The mol ratio of O is 1～5, under vigorous stirring, and in 20 ℃～100 ℃, preferred 25 ℃～30 ℃ temperature microwave activations 2～3 hours, cold filtration obtains precursor liquid; Described alkali silicate is Na
2SiO
3, K
2SiO
3Or Li
2SiO
3, M is Na, K or Li;
(2) preparation of active silicic acid: the precursor liquid that step (1) is obtained is through adding sour adjust pH to 8～10, counter again being added in the acid solution, and control pH value is between 1～4, and is preferred 1.5～3, obtains active silicic acid solution; Or the precursor liquid of step (1) gained handled with hydro-strong acidic cation exchange resin obtain active silicic acid solution;
(3) add catalyzer and carry out the active silicic acid polymerisation: the preparation aqueous slkali is as catalyzer, microwave or water-bath are heated to 30 ℃～100 ℃, preferred 45 ℃～75 ℃, step (2) gained active silicic acid solution is splashed into wherein, till pH value to 7～9, keep temperature to continue stirring reaction 30～120min, preferred 45～90min can obtain nano silicon dioxide sol.
7, rare earth comprehensive silicon colloidal sol as claimed in claim 3, it is characterized in that described organic nano silicon dioxide gel can be prepared from by following method: ethanol, ammoniacal liquor, water, ethyl orthosilicate were mixed in 120: 10 by volume～15: 10～100: 1,40 ℃ are continued heated and stirred reaction 5～24h, products therefrom dilutes with high purity water, dialysis obtained the organic nano silicon dioxide gel to neutral after the decompression distillation rotary evaporation was removed ethanol.
8, rare earth comprehensive silicon colloidal sol as claimed in claim 3, it is characterized in that described organic nano silicon dioxide gel can adopt microemulsion method to be prepared from: with the OP emulsifier is surfactant, n-amyl alcohol is a cosurfactant, rare nitric acid is water, and cyclohexane is that oil phase prepares microemulsion, adds nitrate of rare earth element solution, stir, stir the adding ethyl orthosilicate at last, room temperature reaction 10～24h makes rear-earth-doped organic nano silicon dioxide gel.
9, rare earth comprehensive silicon colloidal sol as claimed in claim 6 is characterized in that the described acid of step (2) can be inorganic acid, ammonium salt or organic acid.
10, rare earth comprehensive silicon colloidal sol as claimed in claim 6 is characterized in that the described aqueous slkali of step (3) is sodium hydroxide, potassium hydroxide, urea, weak aqua ammonia or sodium silicate solution.
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