CN109777428A - Composite modified diatomite heavy metal deactivator and its application - Google Patents
Composite modified diatomite heavy metal deactivator and its application Download PDFInfo
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- CN109777428A CN109777428A CN201910187265.XA CN201910187265A CN109777428A CN 109777428 A CN109777428 A CN 109777428A CN 201910187265 A CN201910187265 A CN 201910187265A CN 109777428 A CN109777428 A CN 109777428A
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Abstract
The present invention discloses a kind of composite modified diatomite heavy metal deactivator, and the raw material including following mass fraction is prepared: 20-115 parts of straw biological powdered carbon, CaCO310-20 parts of modification infusorial earth, Mg (OH)25-10 parts of modification infusorial earth, Fe3O42-5 parts of modification infusorial earth.Invention additionally discloses a kind of applications of composite modified diatomite heavy metal deactivator.The advantages of present invention has remediation efficiency high and reduces secondary pollution, the target for realizing and reducing agricultural product Accumulation of heavy metals amount, improve quality of agricultural product, provides safeguard for agricultural products in China safety in production.
Description
Technical field
The present invention relates to heavy metal deactivator technical field more particularly to composite modified diatomite heavy metal deactivator and its
Using.
Background technique
Heavy metal is the nonessential element of animal and plant growth, will be by plant after heavy metal enters agricultural land soil
Body is absorbed, is accumulated, and enters human body by food chain approach, is threatened to the health of the mankind.
2014, former Environmental Protection Department and Ministry of Land and Resources combined " the national Soil Pollution Investigation bulletin " issued and show
Show, for China's arable soil point exceeding standard rate up to 19.4%, major pollutants are cadmium (Cd), nickel (Ni), copper (Cu), arsenic (As), mercury
(Hg), lead (Pb) etc..And the Ministry of Agriculture finds the investigation in 1,400,000 hectares of China sewage irrigation region, the exceeded face of heavy metal-polluted soil
Product accounts for 64.8%.
For heavy metal pollution agricultural land soil, restorative procedure mainly has restoration of the ecosystem, phytoremediation, stabilisation/immobilization
The methods of repair.In view of rehabilitation cost, remediation efficiency and possible secondary pollution problems, in-situ passivation restorative procedure is more
With reparation superiority, and heavy metal deactivator is the key that soil in-situ recovery technique application success or failure.
It administers, need to solve the problems, such as follows: 1., admittedly currently, carrying out the in situ of contaminated soil using traditional heavy metal deactivator
Determine low efficiency；2., over time, the heavy metal being immobilized may be again converted into biologically effective state and be present in
In soil.
It therefore, how to be efficiently that in-situ passivation restorative procedure is badly in need of solving with stable fixation by the heavy metal contaminants in soil
One of certainly the problem of.
Summary of the invention
Technical problem to be solved by the present invention lies in how to be applied by the preparation of novel heavy metal passivator, passivator
With method, solution prior art remediation efficiency is low and leads to secondary pollution problems, and realizing reduces agricultural product heavy metal product
Tired amount, the target for improving quality of agricultural product, provide safeguard for agricultural products in China safety in production.
The present invention is to solve above-mentioned technical problem by following technological means: a kind of composite modified diatomite heavy metal is blunt
Agent, the raw material including following mass fraction are prepared: 30-115 parts of straw biological powdered carbon, CaCO3Modification infusorial earth 10-20
Part, Mg (OH)28-10 parts of modification infusorial earth, Fe3O42-5 parts of modification infusorial earth.
Preferably, the straw biological powdered carbon includes that the raw material of following mass fraction is prepared: wheat straw biologic charcoal
0-30 parts of powder, 0-35 parts of rape stalk biology powdered carbon, 20-30 parts of cornstalk biological powdered carbon, rice straw biology powdered carbon 10-20
Part.
Straw charring process: by one of crop material (wheat stalk, rape stalk, corn stover, rice straw)
Or it is several, removal impurity cleans up, and drying crushes afterwards for 24 hours, places it in vacuum heat treatment furnace, hot at 300-600 DEG C
2-6h is solved, that is, completes the carbonization process of stalk.
Preferably, the CaCO3Modification infusorial earth, which includes the following steps, to be prepared:
(1) by diatomite and combined, washing to pH is neutrality, and drying sieving obtains pretreated silicon
Diatomaceous earth；
(2) by pretreated diatomite and Na2CO3Aqueous solution mixing, is added CaCl2Aqueous solution, after oscillation, washing is extremely
PH is neutrality, dries, is ground up, sieved, obtains CaCO3Modification infusorial earth.
Preferably, the CaCO3Modification infusorial earth, which includes the following steps, to be prepared:
(1) ratio for being 1g/5mL-1g/8mL in solid-to-liquid ratio, the hydrochloric acid for being 1mol/L-2mol/L by diatomite and concentration
Aqueous solution mixes, and after ultrasonic disperse 30-60min, washs diatomite until filtrate pH is neutral, baking with ethyl alcohol and deionized water
It does to constant weight, crosses 60 mesh standard sieves, obtain pretreated diatomite；
(2) pretreated diatomite and concentration are 0.5mol/L by the ratio for being 1g/5mL-1g/10mL in solid-to-liquid ratio
Na2CO3Aqueous solution mixing, under the conditions of 25 DEG C -30 DEG C after constant temperature oscillation 1h-2h, is added the CaCl of 4mol/L2Aqueous solution
(Na2CO3Aqueous solution and CaCl2The volume ratio of aqueous solution is 5:1-10:1), then after 30 DEG C of constant temperature oscillation 30min, washed with distillation
Washing product to filtrate is after neutrality, and 105 DEG C of constant temperature dryings, grinding crosses 200 mesh standard sieves, obtains CaCO3Modification infusorial earth.
Preferably, the Mg (OH)2Modification infusorial earth, which includes the following steps, to be prepared:
(1) dry by diatomite roast, the diatomite after being roasted；
(2) diatomite, magnesium chloride, the sodium hydroxide after roasting are mixed, after mix products are stood, after washing, filtering,
It dries, be ground up, sieved, obtain Mg (OH)2Modification infusorial earth.
Preferably, the Mg (OH)2Modification infusorial earth, which includes the following steps, to be prepared:
(1) by diatomite under the conditions of 450 DEG C roast 2-3h, the diatomite after being roasted；
(2) spare by 100 DEG C of freeze-day with constant temperature of magnesium chloride；
It (3) is in mass ratio the ratio of 1:1:1/2-2/3, the magnesium chloride and hydrogen after diatomite, drying after weighing roasting
Sodium oxide molybdena；It first will be after diatomite and magnesium chloride co-ground 5-10min；Hydrogen is added in diatomite-magnesium chloride system
Sodium oxide molybdena solid, being ground to reaction terminates, and mix products are statically placed in air after 3-5h, is washed, is filtered repeatedly with aquae destillata
Afterwards, by after 110 DEG C of constant temperature drying 9-12h of mix products, grinding crosses 200 the polished standard screens, obtains Mg (OH)2Modification infusorial earth.
Preferably, the Fe3O4Modification infusorial earth, which includes the following steps, to be prepared:
(1) it by after diatomite roast, mills, be sieved, the diatomite after obtaining pre- roast sieving；
(2) diatomite aqueous solution is configured with the diatomite after the sieving of pre- roast, by diatomite suspension and Fe3O4Aqueous solution
Mixing is added into chitosan-acetic acid-aqueous solution of pH=6, reaction；
(3) to after the reaction was completed, wash and be precipitated to neutrality, constant temperature drying precipitating, grinding precipitating is sieved, obtains Fe3O4It is modified
Diatomite.
Preferably, the Fe3O4Modification infusorial earth, which includes the following steps, to be prepared:
(1) diatomite after roast 2-4h, is milled under the conditions of 450 DEG C and crosses 60 mesh standard sieves, obtain pre- roast sieving
Diatomite afterwards；
(2) ratio for being 1g/10mL-1g/15mL in solid-to-liquid ratio mixes the diatomite after the sieving of pre- roast with distilled water
It closes, obtains diatomite suspension；
The ratio for being 1g/40mL-1g/50mL in solid-to-liquid ratio, by 28kHz ultrasonic disperse 25min by Fe3O4It is completely dissolved
In distilled water, Fe is obtained3O4Aqueous solution；
By 1g chitosan (Deacetylation degree: 85%) being dissolved in the acetic acid aqueous solution of 400mL1%, after complete stirring and dissolving,
Adjust pH to 6；
(3) by Fe3O4Aqueous solution pours into diatomite suspension, and after stirring, chitosan-acetic acid-aqueous solution is added,
(Fe3O4Aqueous solution, diatomite suspension, chitosan-acetic acid-aqueous solution three volume ratio are 2:20:3), in 60 DEG C -70 DEG C
Water-bath 3-5h；It is precipitated to neutrality to after the reaction was completed, be washed with distilled water, after 70 DEG C of constant temperature drying precipitating 8-10h, grinding
Precipitating crosses 60 mesh standard sieves, obtains Fe3O4Modification infusorial earth.
Above-mentioned composite modified diatomite heavy metal deactivator is applied to rain fed crop farmland invention additionally discloses a kind of
Method, comprising the following steps:
(1) the heavy metal risk class for selecting crop planting plot soil is low-risk, wherein 1 < Pi≤2,1 <
Pimax≤2；Or, moderate risk, wherein 2 < Pi≤3,2 Pimax≤3 <；
(2) after high temperature impregnates soil 3-5 days, water is discharged, is exposed to the sun 2-3 days；
(3) while deep ploughing polluted agricultural land, by rice straw, corn stover, wheat stalk, the rape stalk after compost
One or more of mix well with the soil, compost stalk additive amount is 110-260kg/ mus, then spreads fertilizer over the fields composite modified diatomite weight
Matal deactivator, additive amount are 150-200kg/ mus；
(4) mulch is covered on the soil after deep ploughing, and be exposed to the sun 8-10 days；Later, it opens mulch and continues the 5- that divulges information, is exposed to the sun
10 days；Rain drop erosion is avoided during being exposed to the sun；
(5) crops are planted on the agricultural land soil of Passivation Treatment in situ.
Invention additionally discloses a kind of method that above-mentioned composite modified diatomite heavy metal deactivator is applied to paddy field, packets
Include following steps:
(1) the heavy metal risk class for selecting paddy field is low-risk, wherein 1 < Pi≤2,1 Pimax≤2 <；In or,
Spend risk, wherein 2 < Pi≤3,2 Pimax≤3 <；
(2) it pours water and impregnates soil 12h or more, after soil is soft, when mud foot depth is 0.1-0.2m, water is discharged；
(3) rice straw after compost is equably sprinkling upon field, the amount of spreading fertilizer over the fields is 200-300kg/ mus；In compost rice straw
On stalk, the composite modified diatomite heavy metal deactivator of preparation is spread fertilizer over the fields, the amount of spreading fertilizer over the fields is 100-200kg/ mus；
(4) pollution paddy field is turned over；
(5) it pouring water in the paddy field after deep ploughing, depth 1-3cm maintains the soaking state in paddy field, and the time is 15-20 days,
Period avoids rain drop erosion；
(6) soak period nearly at the end of, stop adding irrigation water into paddy field, steam the earth's surface water layer in paddy field naturally
It is dry, and maintain the moisture state of paddy field soil；
(7) in situ after Passivation Treatment paddy field soil in transplanting rice seedling.
The present invention has the advantages that
(1) the composite modified diatomite heavy metal deactivator prepared by the present invention is obvious to the passivation effect of heavy metal, holds
The continuous time is long, used raw material sources are extensive, it is cheap, secondary pollution will not be generated to soil；Utilize institute of the present invention
The heavy metal deactivator preparation method and formula of offer can make the soil after repairing preferably meet the growth need of crops
It asks, reduces the accumulation of heavy metal in agricultural product, improve quality of agricultural product；Heavy metal in-situ passivation method proposed by the invention
It is easy to operate it is easy to learn, be easy to that large-scale promotion, cost is relatively low.
To produce the agricultural product for being lower than " pollutants in food limitation " (GB2762-2005), and formed propagable heavy
Metal is passivated the purpose of technical system, modification passivator of the invention include 1., high reaction activity, high adsorption, high structure it is steady
Qualitative and passivation persistence；2., raw material sources are abundant, inexpensive safety, the performances such as without secondary pollution.On the other hand, pass through height
Effect, propagable heavy metal deactivator application technique reduce absorption and accumulation of the crops to heavy metal.
(2) the suitable heavy metal risk class of the present invention is the farmland of low-risk or moderate risk, including crop field and facility agriculture
Field；Experimental method is scientific and reasonable, and all indexs meet National Standard of the People's Republic of China and People's Republic of China's agricultural agriculture
The relevant regulations in portion, village；The content of beary metal of agricultural product can be reduced from source, ensures agricultural product security, ensure the people
Health, be of great immediate significance and wide application prospect.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is of the invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
It should be noted that it can directly on the other element when element is referred to as " being fixed on " another element
Or there may also be elements placed in the middle.When an element is considered as " connection " another element, it, which can be, is directly connected to
To another element or it may be simultaneously present centering elements.
Embodiment 1
Selection target planting site (heavy-metal contaminated soil i.e. to be repaired).The content of beary metal of the agricultural land soil is measured,
As a result as shown in table 1.According to National Standard of the People's Republic of China " standard of soil environment quality " (GB15618-1995), in
Magnificent people's republic's national standard " Cadmium in Soil, lead, chromium, mercury, the arsenic secure threshold of Rice Production " (GB/T36869-2018) and
" national rapid test paper heavy metal-polluted soil safety assessment technique regulation " (2015), the heavy metal risk class of selected paddy field
For low-risk (1 < Pi≤2,1 Pimax≤2 <).
The heavy metal content in soil of the sampling of table 1 plot I
| Heavy metal content in soil | Cd(mg/kg) |
| Sample plot I | 0.24 |
| GB15618-1995 primary standard | 0.20 |
| GB15618-1995 secondary standard | 0.30 |
| GB15618-1995 grade III Standard | 1.00 |
1. in-situ passivation method of the invention
(1) a kind of preparation method of composite modified diatomite heavy metal deactivator, includes the following steps:
CaCO3The preparation of modification infusorial earth:
1. the ratio for being 1g/5mL in solid-to-liquid ratio mixes the aqueous hydrochloric acid solution that diatomite original soil and concentration are 2mol/L,
Be placed in ultrasonic disperse instrument, disperse 30min after, will precipitating filtering, and with ethyl alcohol and deionized water repeatedly wash precipitate until
Filtrate pH is neutrality.Diatomite is dried to constant weight, 60 mesh standard sieves is crossed, obtains pretreated diatomite.
2. the ratio for being 1g/5mL in solid-to-liquid ratio, the Na for being 0.5mol/L by pretreated diatomite and concentration2CO3Water
Solution mixes, and after 30 DEG C of constant temperature oscillation 1h, the CaCl of 4mol/L is added2Aqueous solution (Na2CO3Aqueous solution and CaCl2Aqueous solution
Volume ratio is 10:1) after, then after 30 DEG C of constant temperature oscillation 30min, supernatant is removed, after being washed with distilled water to filtrate as neutrality,
105 DEG C of constant temperature drying precipitatings, are fully ground, cross 200 mesh standard sieves, obtain CaCO3Modification infusorial earth.
Mg(OH)2The preparation of modification infusorial earth:
1. diatomite original soil is put into Muffle furnace, in 450 DEG C of roast 2h.At the same time, magnesium chloride constant temperature is put into do
In dry case, 100 DEG C of dryings are for 24 hours, spare.
2. it is in mass ratio the ratio of 1:1:2/3, the magnesium chloride and hydroxide after diatomite, drying after weighing roasting
Sodium.Diatomite and magnesium chloride are put into same mortar, after being fully ground 10min, in diatomite-magnesium chloride system again
Sodium hydrate solid is added, after being ground to the generation of yellow lump, continues to be ground to the disappearance of yellow lump；Mixture is statically placed in
In air after 5h, after distilled water washing, by product at 110 DEG C constant temperature drying 9h, be fully ground, cross 200 mesh standard sieves, obtain
Mg(OH)2Modification infusorial earth.
Fe3O4The preparation of modification infusorial earth:
1. diatomite original soil is put into Muffle furnace, it is spare after milling and crossing 60 mesh standard sieves after 450 DEG C of roast 3h.
2. the ratio for being 1g/13mL in solid-to-liquid ratio mixes pretreated diatomite and distilled water, it is outstanding to obtain diatomite
Supernatant liquid.The ratio for being 1g/40mL in solid-to-liquid ratio, by Fe3O4It is dissolved in distilled water, 28kHz ultrasonic disperse 25min obtains Fe3O4
Aqueous solution.By 1g chitosan (Deacetylation degree: 85%) being dissolved in the acetic acid aqueous solution of 400mL1%, after complete stirring and dissolving,
PH to 6 is adjusted, chitosan-acetic acid-aqueous solution is obtained.
3. by Fe3O4Aqueous solution pours into diatomite suspension, after mixing evenly, chitosan-acetic acid-aqueous solution is added,
(Fe3O4Aqueous solution, diatomite suspension, chitosan-acetic acid-aqueous solution three volume ratio are 2:20:3), it is anti-in 65 DEG C of water-baths
Answer 4h；To after the reaction was completed, washed repeatedly with distilled water be precipitated to filtrate be it is neutral, then by product at 70 DEG C constant temperature drying
It after 9h, is fully ground, crosses 60 mesh standard sieves, obtain Fe3O4Modification infusorial earth.
(2) a kind of design of composite modified diatomite heavy metal deactivator formula is as follows:
Preferably, diatomite passivator formula are as follows: 35 parts of rape stalk biology powdered carbon, 20 parts of cornstalk biological powdered carbon,
20 parts of rice straw biology powdered carbon, CaCO310 parts of modification infusorial earth, Mg (OH)210 parts of modification infusorial earth, Fe3O4Modification infusorial earth
5 parts.
Straw biological powdered carbon in each embodiment of the present invention is respectively to remove rape stalk, corn stover, rice straw
It except impurity, cleans up, drying crushes afterwards for 24 hours, places it in vacuum heat treatment furnace, 6h is pyrolyzed at 300 DEG C, is i.e. completion straw
The carbonization process of stalk.(3) present invention is by providing a kind of method of administration of composite modified diatomite heavy metal deactivator, to reduce
The content of biologically effective state heavy metal in water paddy soil, comprising the following steps:
1., pour water and impregnate soil 12h, when mud foot depth be 0.15m when, water is discharged.2., by the rice straw after compost
Stalk is equably sprinkling upon field, and the amount of spreading fertilizer over the fields is 260kg/ mus.3., on rice straw, spread fertilizer over the fields compound prepared by embodiment 1 change
Property diatomite heavy metal deactivator, the amount of spreading fertilizer over the fields be 150kg/ mus.4., turn over pollution paddy field, preferred depth 0.3m.Select stalk
Chopper turns over paddy field, disposable to complete to turn over, the crushing of straw biological charcoal, play the processes such as slurry, smooth, enables soil
Fully mixed with stalk, composite modified diatomite heavy metal deactivator.5., pour water in the paddy field after turning over, depth is
3cm maintains the soaking state in paddy field, and the time is 20 days, during which avoids rain drop erosion.Soak period nearly at the end of, stop to
Water is added in paddy field, is evaporated the earth's surface water layer in paddy field naturally, and maintain the moisture state of paddy field soil.6., it is blunt in situ
Change transplanting rice seedling in treated paddy field.7., the Cultivate administration measure of rice is according to People's Republic of China's agricultural industry
Regulation in standard " pollution-free food Rice Production technical regulation " (NY/T5117-2002) executes.
2. non-in-situ passivation processing
1., select straw counters-field set to turn over paddy field, it is disposable to complete to turn over, play the processes such as slurry, smooth, turn over depth
Degree is 0.3m.2., the transplanting rice seedling in the paddy field after turning over, being smooth.3., the Cultivate administration measure of rice is according to middle Chinese
Regulation in people republic agricultural industry criteria " pollution-free food Rice Production technical regulation " (NY/T5117-2002) executes.
3. comparative example: carrying out repairing test to the soil in same 3 plot respectively using 3 kinds of modification infusorial earths.Specifically
Process is as follows.
The preparation method of 3 kinds of composite modified diatomite heavy metal deactivators: with " 1. original positions of the invention of above-described embodiment 1
Passivating method." in step (1) it is identical.
The Cultivate administration measure of 3 kinds of composite modified diatomite heavy metal deactivator method of administration, rice: 1., spread fertilizer over the fields it is compound
The amount of application of modification infusorial earth heavy metal deactivator, 3 kinds of composite modified diatomite heavy metal deactivators is respectively as follows: CaCO3It is modified
15kg/ mus of diatomite, Mg (OH)215kg/ mus of modification infusorial earth, Fe3O47.5kg/ mus of modification infusorial earth.2., paddy field turned over
It ploughs, ploughed depth 0.3m enables soil fully to mix with composite modified diatomite heavy metal deactivator.3., in situ
Transplanting rice seedling in paddy field after Passivation Treatment.4., the Cultivate administration measure of rice is according to People's Republic of China's agricultural row
Regulation in industry standard " pollution-free food Rice Production technical regulation " (NY/T5117-2002) executes.
4. verifying example: using composite modified diatomite heavy metal deactivator, it may be assumed that the mixture of 3 kinds of modification infusorial earths, to same
The plot of sample carries out repairing test.Detailed process is as follows.
A kind of preparation method of NEW TYPE OF COMPOSITE modification infusorial earth heavy metal deactivator: " 1. is of the invention with above-described embodiment 1
In-situ passivation method." in step (1) it is identical.
Composite modified diatomite heavy metal deactivator: the mixture of 3 kinds of composite modified diatomite heavy metal deactivators.
CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth, Fe3O4The mass ratio of modification infusorial earth is 2:2:1.
A kind of Cultivate administration measure of the passivator method of administration of optimization, rice: 1., a composite modified diatomite huge sum of money is spread fertilizer over the fields
Belong to passivator, the amount of spreading fertilizer over the fields is 37.5kg/ mus.2., paddy field is turned over, ploughed depth 0.3m enables soil fully
It is mixed with composite modified diatomite heavy metal deactivator.3., transplanting rice seedling in the paddy field after Passivation Treatment in situ.④,
The Cultivate administration measure of rice is according to People's Republic of China's agricultural industry criteria " pollution-free food Rice Production technical regulation "
(NY/T5117-2002) regulation in executes.
5. soil remediation effect
Content of beary metal in the I soil of plot is detected, as a result as shown in table 2.Method is to soil shown in the present invention
The remediation efficiency of available state Cd is 55.56% in earth.In comparison, method shown in example is verified to imitate the reparation of available state Cd in earth
Rate is 44.44%.Illustrate, using passivator method of administration provided by the invention, passivator can be improved to Cd in contaminated soil
Passivation/fixed efficiency.
Compared with the Cd remediation efficiency (44.44%) for verifying method shown in example, through CaCO3Modification infusorial earth, Mg (OH)2Change
Property diatomite, Fe3O4After the independent Passivation Treatment of modification infusorial earth, the remediation efficiency of soil available cadmium is respectively 11.11%,
16.67% and 11.11%.Illustrate, by CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth and Fe3O4Modification infusorial earth carries out
After compounding, remediation efficiency is higher than the sum of the remediation efficiency that 3 kinds of diatomite passivator are administered alone, 3 kinds of composite modified diatomite
Heavy metal deactivator is to the passivation of Cd in contaminated soil/be fixed with synergistic effect.
The changes of contents of plot I heavy metal-polluted soil Cd after the reparation of table 2
It applies the reason of remediation efficiency can be enhanced in composite modified diatomite heavy metal deactivator to be: modification infusorial earth pair
Absorption/fixed performance of heavy metal ion, construction, functional group, the distribution of layer charge, electricity price and ionic radius with itself etc.
Factor is related.Functional group entrained by different modification infusorial earths and relevant ionic radius, the distribution of layer charge, electricity price are not
Together, cause the construction of different modification infusorial earths also different.Relative to the modification infusorial earth of application single kind, composite modified diatom
Soil increases for quantity, the type of adsorption site provided by heavy metal ion, and the repulsive force between a variety of functional groups weakens, right
The absorption of heavy metal ion and crystallized ability enhance, and improve the validity and long-term effect to immobilization of heavy metals.
6. repairing effect further confirms that
To further confirm that repairing effect of the invention and technical advantage compared with the existing technology, on same plot point
It Xuan Qu not be without the cell plantation shown in repair process, verifying example after method repair process, after method repair process shown in the present invention
Fragrant glutinous rice, kind are a surname round-grained rice glutinous No. 1.
Rice in cell after method repair process shown in method shown in no repair process, verifying example, the present invention is produced
Amount and its constituent element are counted, as a result as shown in table 3, compared with the processing of non-in-situ passivation, using shown in the present invention
After method shown in method and comparative example handles agricultural land soil, the number of productive ear of the fragrant glutinous rice planted, grain number per spike, setting percentage,
Thousand quality and actual production all obviously increase.
Table 3 is planted in in-situ passivation treated the fragrant glutinous rice Yield and its components factor on the I of plot
| Processing | Number of productive ear/m2 | Grain number per spike | Setting percentage (%) | Thousand quality (g) | Actual production (kg/ mus) |
| Non- in-situ passivation processing | 252.0 | 121.5 | 77.6 | 26.17 | 651.5 |
| Verify method shown in example | 289.0 | 149.8 | 89.3 | 26.83 | 719.8 |
| Method shown in the present invention | 293.0 | 153.9 | 92.4 | 26.96 | 742.6 |
Content of beary metal measurement.Rice is harvested in rice harves period, and measures the content of wherein heavy metal, detection method
According to National Standard of the People's Republic of China " sodium in grain and oil detection Grain and its product, magnesium, potassium, calcium, chromium, manganese, iron, copper, zinc,
Arsenic, selenium, cadmium and lead measurement inductively coupled plasma mass spectrometry " regulation in (GB/T35876-2018) carries out.
As shown in table 4, under without in-situ passivation treatment conditions, the Cd content in aromatic glutinous rice is higher than national standard " food
Middle pollutant limitation " specified value (that is: Cd≤0.2mg/kgFW) in (GB2762-2017).By original shown in the present invention
Position passivating method processing and verifying example shown in method processing after, the Cd content in aromatic glutinous rice be down to respectively 0.08mg/kg and
0.13mg/kg meets the requirement of national standard " pollutants in food limitation " (GB2762-2017).With the processing of non-in-situ passivation
It compares, method shown in the processing of in-situ passivation shown in the present invention and verifying example handles the Cd reduced in aromatic glutinous rice significantly and contains
Amount, fall is 61.90% and 39.00% respectively.Illustrate, using passivator method of administration provided by the invention, Ke Yigeng
Effectively reduce the Accumulation of heavy metals amount in rice.
Content of beary metal changes in the aromatic glutinous rice of 4 in-situ passivation of table before and after the processing
As shown in table 5, compared with the processing of non-in-situ passivation, method shown in application verification example and the processing of method shown in the present invention
After agricultural land soil, Ca, Mg, Mn, Zn, Cu, Fe content for the aromatic glutinous rice planted all are obviously increased.
The variation of Accumulation of nutrient element in the aromatic glutinous rice of 5 in-situ passivation of table before and after the processing
As shown in table 6, compared with the processing of non-in-situ passivation, method shown in application verification example and the processing of method shown in the present invention
After agricultural land soil, Coarse Rice Rate, polished rice rate, head rice rate, the amylopectin content for the fragrant glutinous rice planted have different amplitudes
Increase.
The variation (i) of the aromatic glutinous rice quality of 6 in-situ passivation of table before and after the processing
As shown in table 7, compared with the processing of non-in-situ passivation, method shown in application verification example and the processing of method shown in the present invention
After agricultural land soil, protein content, the essential amino acid for the fragrant glutinous rice planted account for the ratio of total amino acid content, people
The ratio of body essential amino acid and non-human essential amino acid, crude fat content, VB2Content has different amplitudes to increase.
The variation (ii) of the aromatic glutinous rice quality of 7 in-situ passivation of table before and after the processing
As shown in table 8, it compared with the processing of non-in-situ passivation, is produced using the aromatic glutinous rice of the plantation of method shown in the present invention
11 kinds of new volatile materials；The aromatic glutinous rice that method shown in Comparison study example is planted produces 8 kinds of new volatile materials.It is former
There is the percentage composition of volatile materials to show different degrees of ascendant trend；Cause the characteristic perfume of aromatic glutinous rice more bright
It is aobvious.
The variation of the composition of volatile materials in the aromatic glutinous rice of 8 in-situ passivation of table before and after the processing
The beneficial effect that the present embodiment has is: the composite modified diatomite heavy metal deactivator being prepared for, to heavy metal
Passivation effect it is obvious, used raw material will not to soil generate secondary pollution；Utilize a huge sum of money provided by the present invention
Belong to passivator preparation method, formula and passivator method of administration, the paddy field after repairing can be made preferably to meet the life of rice
Long demand reduces the accumulation of heavy metal in rice, improves the quality of rice.
Embodiment 2
Selection target planting site (heavy-metal contaminated soil i.e. to be repaired).Heavy metal content in soil is measured, as a result such as table 9
Shown in.According to National Standard of the People's Republic of China " standard of soil environment quality " (GB15618-1995), " national agricultural product
Producing Area Soil heavy metal safety assessment technique regulation " (2015), the heavy metal risk etc. of selected crop planting plot soil
Grade is moderate risk (2 < Pi≤3,2 Pimax≤3 <).
The heavy metal content in soil of the sampling of table 9 plot II
1. in-situ passivation method of the invention
(1) a kind of preparation method of modification infusorial earth heavy metal deactivator, includes the following steps:
CaCO3The preparation of modification infusorial earth:
1. the ratio for being 1g/8mL in solid-to-liquid ratio mixes the aqueous hydrochloric acid solution that diatomite original soil and concentration are 1mol/L,
Be placed in ultrasonic disperse instrument, disperse 60min after, will precipitating filtering, and with ethyl alcohol and deionized water repeatedly wash precipitate until
Filtrate pH is neutrality.Diatomite is dried to constant weight, 60 mesh standard sieves is crossed, obtains pretreated diatomite.
2. the ratio for being 1g/10mL in solid-to-liquid ratio, the Na for being 0.5mol/L by pretreated diatomite and concentration2CO3Water
Solution mixes, and after vibrating 2h at 25 DEG C, the CaCl of 4mol/L is added2Aqueous solution (Na2CO3Aqueous solution and CaCl2The body of aqueous solution
Ratio is accumulated as 5:1), after 30 DEG C of constant temperature oscillation 30min, removes supernatant.Then it is washed with distilled water after product is neutral to filtrate,
Constant temperature drying at 105 DEG C, is fully ground, and crosses 200 the polished standard screens.Obtain CaCO3Modification infusorial earth.
Mg(OH)2The preparation of modification infusorial earth:
1. diatomite original soil is put into Muffle furnace, in 450 DEG C of roast 3h.At the same time, magnesium chloride constant temperature is put into do
In dry case, 100 DEG C of dryings are for 24 hours, spare.
2. it is in mass ratio the ratio of 1:1:1/2, the magnesium chloride and hydroxide after diatomite, drying after weighing roasting
Sodium.Diatomite and magnesium chloride are put into same mortar, 5min is fully ground；Add again in diatomite-magnesium chloride system
Enter sodium hydrate solid, after being ground to the generation of yellow lump, continues to be ground to the disappearance of yellow lump；Mixture is statically placed in sky
In gas after 3h, it is filtered with distilled water washing, then by mixture.After filtering, constant temperature drying at 110 DEG C will be deposited in
12h, it is fully ground, crosses 200 the polished standard screens, obtain Mg (OH)2Modification infusorial earth.
Fe3O4The preparation of modification infusorial earth:
1. diatomite original soil is put into Muffle furnace, it is spare after milling and crossing 60 mesh standard sieves after 450 DEG C of roast 2h.
2. the ratio for being 1g/15mL in solid-to-liquid ratio mixes pretreated diatomite and distilled water, it is outstanding to obtain diatomite
Supernatant liquid.The ratio for being 1g/50mL in solid-to-liquid ratio, by Fe3O4It is dissolved in distilled water, 28kHz ultrasonic disperse 25min obtains Fe3O4
Aqueous solution.By 1g chitosan (Deacetylation degree: 85%) being dissolved in the acetic acid aqueous solution of 400mL1%, after complete stirring and dissolving,
PH to 6 is adjusted, chitosan-acetic acid-aqueous solution is obtained.
3. by Fe3O4Aqueous solution pours into diatomite suspension, after mixing evenly, chitosan-acetic acid-aqueous solution is added,
(Fe3O4Aqueous solution, diatomite suspension, chitosan-acetic acid-aqueous solution three volume ratio are 2:20:3), it is anti-in 60 DEG C of water-baths
Answer 5h；To which after the reaction was completed, with distilled water, repeatedly then washed product will be deposited in constant temperature drying 8h at 70 DEG C to neutrality.It fills
Divide grinding, crosses 60 mesh standard sieves, obtain Fe3O4Modification infusorial earth.
(2) a kind of design of composite modified diatomite heavy metal deactivator formula is as follows:
Preferably, diatomite passivator formula are as follows: 30 parts of wheat straw biologic powdered carbon, 25 parts of cornstalk biological powdered carbon,
10 parts of rice straw biology powdered carbon, CaCO315 parts of modification infusorial earth, Mg (OH)210 parts of modification infusorial earth, Fe3O4Modification infusorial earth
3 parts.
(3) the straw biological powdered carbon in each embodiment of the present invention is respectively by wheat stalk, corn stover, rice straw
Stalk, removal impurity clean up, and drying crushes afterwards for 24 hours, places it in vacuum heat treatment furnace, 2h is pyrolyzed at 600 DEG C, i.e.,
Complete the carbonization process of stalk.The present invention is dropped by providing a kind of method of administration of composite modified diatomite heavy metal deactivator
The content of biologically effective state heavy metal in low soil, comprising the following steps:
1., high temperature impregnate soil 5 days after, water is discharged, is exposed to the sun 2 days.2., the rice straw by after compost, corn
One or more of stalk, wheat stalk, rape stalk are equably sprinkling upon field, and the amount of spreading fertilizer over the fields is 260kg/ mus.3., in stalk
On, composite modified diatomite heavy metal deactivator prepared by embodiment 2 is spread fertilizer over the fields, the amount of spreading fertilizer over the fields is 200kg/ mus.Select stalk
Chopper turns over farmland, disposably completes rotary tillage, straw biological charcoal crushes, the processes such as smooth, by compost stalk, compound
Modification infusorial earth heavy metal deactivator mixes well withs the soil, and preferred depth of deep ploughing is 0.3m.4., cover on the soil after deep ploughing
Mulch, and be exposed to the sun 8 days；Later, mulch is opened to continue to divulge information, be exposed to the sun 10 days；It keeps agricultural land soil wet during being exposed to the sun, but avoids
Rain drop erosion.5., plant tomato on the agricultural land soil of Passivation Treatment in situ.6., the Cultivate administration measure of tomato is according to China
Rule in people's republic's agricultural industry criteria " pollution-free food tomato Protected production technical regulation " (NY/T5007-2001)
It is fixed to execute.
2. non-in-situ passivation processing
1., select rotary cultivator farmland is turned over, depth 0.3m.2., in the farmland after rotary tillage, smooth plantation kind
Eggplant.3., " pollution-free food tomato protecting field is raw according to People's Republic of China's agricultural industry criteria for the Cultivate administration measure of tomato
Producing technical regulation " regulation in (NY/T5007-2001) executes.
3. comparative example: carrying out repairing test to the soil in same 3 plot respectively using 3 kinds of modification infusorial earths.Specifically
Process is as follows.
The preparation method of 3 kinds of composite modified diatomite heavy metal deactivators: with " 1. original positions of the invention of above-described embodiment 2
Passivating method." in step (1) it is identical.
The Cultivate administration measure of 3 kinds of composite modified diatomite heavy metal deactivator method of administration, rice: 1., spread fertilizer over the fields it is compound
The amount of application of modification infusorial earth heavy metal deactivator, 3 kinds of composite modified diatomite heavy metal deactivators is respectively as follows: CaCO3It is modified
30kg/ mus of diatomite, Mg (OH)220kg/ mus of modification infusorial earth, Fe3O410kg/ mus of modification infusorial earth.2., carry out farmland turn over,
Ploughed depth is 0.3m, and soil is enable fully to mix with composite modified diatomite heavy metal deactivator.3., the plantation of tomato
Management measure is according to People's Republic of China's agricultural industry criteria " pollution-free food tomato Protected production technical regulation " (NY/
T5007-2001 the regulation in) executes.
4. verifying example: using composite modified diatomite heavy metal deactivator, it may be assumed that the mixture of 3 kinds of modification infusorial earths, to same
The plot of sample carries out repairing test.Detailed process is as follows.
A kind of preparation method of NEW TYPE OF COMPOSITE modification infusorial earth heavy metal deactivator: " 1. is of the invention with above-described embodiment 2
In-situ passivation method." in step (1) it is identical.
Composite modified diatomite heavy metal deactivator: the mixture of 3 kinds of composite modified diatomite heavy metal deactivators.
CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth, Fe3O4The mass ratio of modification infusorial earth is 3:2:1.
A kind of Cultivate administration measure of the passivator method of administration of optimization, tomato: 1., a composite modified diatomite huge sum of money is spread fertilizer over the fields
Belong to passivator, the amount of spreading fertilizer over the fields is 60kg/ mus.2., farmland is turned over, ploughed depth 0.3m, enable soil fully with
Composite modified diatomite heavy metal deactivator mixing.3., the Cultivate administration measure of tomato is according to People's Republic of China's agricultural row
Regulation in industry standard " pollution-free food tomato Protected production technical regulation " (NY/T5007-2001) executes.
5. soil remediation effect
Content of beary metal in the II soil of plot is detected, as a result as shown in table 10.Method pair shown in the present invention
The remediation efficiency of soil available Pb is 41.40%.In comparison, reparation of the method to available state Pb in earth shown in example is verified
Efficiency is 33.33%.Illustrate, using passivator method of administration provided by the invention, passivator can be improved in contaminated soil
Passivation/fixed efficiency of Pb.
Compared with the Pb remediation efficiency (33.33%) for verifying method shown in example, through CaCO3Modification infusorial earth, Mg (OH)2Change
Property diatomite, Fe3O4After the independent Passivation Treatment of modification infusorial earth, the remediation efficiency of soil available Pb is respectively 8.60%,
9.13% and 9.68%.Illustrate, by CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth and Fe3O4Modification infusorial earth is answered
With later, remediation efficiency is higher than the sum of the remediation efficiency that 3 kinds of diatomite passivator are administered alone, 3 kinds of composite modified diatomite weights
Matal deactivator is to the passivation of Pb in contaminated soil/be fixed with synergistic effect.
The changes of contents of plot II heavy metal-polluted soil Pb after the reparation of table 10
Content of beary metal in the II soil of plot is detected, as a result as shown in table 11.Method pair shown in the present invention
The remediation efficiency of soil available Cd is 45.16%.In comparison, reparation of the method to available state Cd in earth shown in example is verified
Efficiency is 38.71%.Illustrate, using passivator method of administration provided by the invention, passivator can be improved in contaminated soil
Passivation/fixed efficiency of Cd.
Compared with the Cd remediation efficiency (33.33%) for verifying method shown in example, through CaCO3Modification infusorial earth, Mg (OH)2Change
Property diatomite, Fe3O4After the independent Passivation Treatment of modification infusorial earth, the remediation efficiency of soil available cadmium is respectively 12.9%,
6.45% and 9.68%.Illustrate, by CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth and Fe3O4Modification infusorial earth is answered
With later, remediation efficiency is higher than the sum of the remediation efficiency that 3 kinds of diatomite passivator are administered alone.
The changes of contents of plot II heavy metal-polluted soil Cd after the reparation of table 11
6. repairing effect further confirms that
To further confirm that repairing effect of the invention and technical advantage compared with the existing technology, on same plot point
It Xuan Qu not be without the cell plantation shown in repair process, verifying example after method repair process, after method repair process shown in the present invention
Tomato, kind are Anhui miscellaneous 21 and Sufen No.8.
To the cell shown in no repair process, verifying example after method repair process, after method repair process shown in the present invention
On tamato fruit trait data counted, as a result as shown in Table 12, with non-in-situ passivation processing compared with, application verification
After method shown in example handles agricultural land soil with method shown in the present invention, the fruit yield of the Anhui planted miscellaneous 21 and Sufen No.8,
The hardness of fruit, Dan Xianguo mass all obviously increase.
Table 12 is planted in in-situ passivation treated the tamato fruit character on the II of plot
Content of beary metal measurement.Its fruit is harvested in tomato water content in harvest, and measures the content of heavy metal in tamato fruit,
Detection method is according to " measurement of national food safety standard Pb in food " (GB5009.12-2017) and " food safety country marks
The measurement of quasi- cadmium in foods " regulation in (GB5009.15-2014) carries out.
As shown in table 13, Pb, Cd content of Anhui miscellaneous 21 and Sufen No.8 are respectively higher than under without in-situ passivation treatment conditions
In national standard " pollutants in food limitation " (GB2762-2017) specified value (that is: Pb≤0.1mg/kgFW, Cd≤
0.05mg/kgFW), after the processing of the in-situ passivation method shown in the present invention, Pb, Cd in above-mentioned 2 kind fruits contain
Amount is respectively lower than 0.1mg/kg, 0.05mg/kg, meets national standard " pollutants in food limitation " (GB2762-2017) and wants
It asks.Compared with the processing of non-in-situ passivation, method shown in example of verifying significantly reduces that Anhui is miscellaneous 21, the Pb content in Sufen No.8 fruit,
Fall is 52.63% and 50.00% respectively；Significantly reduce that Anhui is miscellaneous 21, the Cd content in Sufen No.8 fruit, the lower range of decrease
Degree is 68.75% and 53.84% respectively.Compared with the processing of non-in-situ passivation, method shown in the present invention significantly reduce Anhui it is miscellaneous 21,
Pb content in Sufen No.8 fruit, fall are 63.16% and 65.38% respectively；Significantly reduce that Anhui is miscellaneous 21, Sufen No.8
Cd content in fruit, fall are 75.00% and 61.54% respectively.Illustrate, is applied using passivator provided by the invention
Method can more effectively reduce the Accumulation of heavy metals amount in tamato fruit.
The changes of contents of heavy metal in the tamato fruit of 13 in-situ passivation of table before and after the processing
As shown in table 14, compared with the processing of non-in-situ passivation, through treated the farmland soil of in-situ passivation shown in the present invention
Earth, the Anhui planted is miscellaneous 21, the soluble protein content of Sufen No.8 fruit, soluble solid content, dry matter content, dimension
Raw element C content, soluble sugar content and sugar-acid ratio all obviously increase, and Quality of Tomato Fruit is obviously improved.
Table 14 is planted in in-situ passivation treated the Quality of Tomato Fruit on the II of plot
The beneficial effect that the present embodiment has is: the composite modified diatomite heavy metal deactivator being prepared for, to heavy metal
Passivation effect it is obvious, used raw material will not to soil generate secondary pollution；Utilize a huge sum of money provided by the present invention
Belong to passivator formula and passivator method of administration, the soil after repairing can be made preferably to meet the growth demand of tomato, reduced
The accumulation of heavy metal, improves the quality of tomato in tamato fruit.
Embodiment 3
Selection target planting site (heavy-metal contaminated soil i.e. to be repaired).Heavy metal content in soil is measured, as a result such as table
Shown in 15.According to National Standard of the People's Republic of China " standard of soil environment quality " (GB15618-1995), the Chinese people
Republic's national standard " dryland soil cadmium, lead, chromium, mercury, the arsenic secure threshold of plantation rhizome vegetable " (GB/T36783-
2018), " national rapid test paper heavy metal-polluted soil safety assessment technique regulation " (2015), selected crop planting plot soil
The heavy metal risk class of earth is moderate risk (2 < Pi≤3,2 Pimax≤3 <).
The heavy metal content in soil of the sampling of table 15 plot III
1. in-situ passivation method of the invention
(1) a kind of preparation method of modification infusorial earth heavy metal deactivator, includes the following steps:
CaCO3The preparation of modification infusorial earth:
1. the ratio for being 1g/6mL in solid-to-liquid ratio mixes the aqueous hydrochloric acid solution that diatomite original soil and concentration are 1.5mol/L
It is even, it is placed in ultrasonic disperse instrument, disperses after 45min, precipitating is filtered, and washed product is straight repeatedly with ethyl alcohol and deionized water
It is neutrality to pH.Drying is precipitated to constant weight, crosses 60 mesh standard sieves, obtains pretreated diatomite.
2. the ratio for being 1g/8mL in solid-to-liquid ratio, the Na for being 0.5mol/L by pretreated diatomite and concentration2CO3Water
Solution mixes, and after vibrating 1.5h at 26 DEG C, the CaCl of 4mol/L is added2Aqueous solution (Na2CO3Aqueous solution and CaCl2Aqueous solution
Volume ratio is 7:1), after 30 DEG C of constant temperature oscillation 30min, remove supernatant.Then it is washed with distilled water and is precipitated to filtrate as neutrality
Afterwards, constant temperature drying at 105 DEG C, is fully ground, and crosses 200 the polished standard screens.Obtain CaCO3Modification infusorial earth.
Mg(OH)2The preparation of modification infusorial earth:
1. diatomite original soil is put into Muffle furnace, in 450 DEG C of roast 2.5h.At the same time, magnesium chloride is put into constant temperature
In drying box, 100 DEG C of dryings are for 24 hours, spare.
2. it is in mass ratio the ratio of 1:1:4/7, the magnesium chloride and hydroxide after diatomite, drying after weighing roasting
Sodium.Diatomite and magnesium chloride are put into same mortar, 7min is fully ground；Add again in diatomite-magnesium chloride system
Enter sodium hydrate solid, after being ground to the generation of yellow lump, continues to be ground to the disappearance of yellow lump；Mixture is statically placed in sky
In gas after 4h, it is filtered with distilled water washing, then by mixture.After filtering, constant temperature drying at 110 DEG C will be deposited in
10h, it is fully ground, crosses 200 the polished standard screens.It obtains Mg (OH)2Modification infusorial earth.
Fe3O4The preparation of modification infusorial earth:
1. diatomite original soil is put into Muffle furnace, it is spare after milling and crossing 60 mesh standard sieves after 450 DEG C of roast 4h.
2. the ratio for being 1g/10mL in solid-to-liquid ratio mixes pretreated diatomite and distilled water, it is outstanding to obtain diatomite
Supernatant liquid.The ratio for being 1g/45mL in solid-to-liquid ratio, by Fe3O4It is dissolved in distilled water, 28kHz ultrasonic disperse 25min obtains Fe3O4
Aqueous solution.By 1g chitosan (Deacetylation degree: 85%) being dissolved in the acetic acid aqueous solution of 400mL1%, after complete stirring and dissolving,
PH to 6 is adjusted, chitosan-acetic acid-aqueous solution is obtained.
3. by Fe3O4Aqueous solution pours into diatomite suspension, after mixing evenly, chitosan-acetic acid-aqueous solution is added,
(Fe3O4Aqueous solution, diatomite suspension, chitosan-acetic acid-aqueous solution three volume ratio are 2:20:3), it is anti-in 70 DEG C of water-baths
Answer 3h；To after the reaction was completed, with distilled water repeatedly washed product to neutrality, then by product at 70 DEG C constant temperature drying 10h.It fills
Divide grinding, crosses 60 mesh standard sieves, obtain Fe3O4Modification infusorial earth.
(2) a kind of design of composite modified diatomite heavy metal deactivator formula is as follows:
Preferably, diatomite passivator formula are as follows: 20 parts of wheat straw biologic powdered carbon, 15 parts of rape stalk biology powdered carbon,
30 parts of cornstalk biological powdered carbon, 15 parts of rice straw biology powdered carbon, CaCO320 parts of modification infusorial earth, Mg (OH)2Modified diatom
8 parts of soil, Fe3O42 parts of modification infusorial earth.
Straw biological powdered carbon in each embodiment of the present invention is respectively to go wheat stalk, rape stalk, corn stover
It except impurity, cleans up, drying crushes afterwards for 24 hours, places it in vacuum heat treatment furnace, 4h is pyrolyzed at 450 DEG C, is i.e. completion straw
The carbonization process of stalk.
(3) present invention is reduced in soil by providing a kind of method of administration of composite modified diatomite heavy metal deactivator
Biologically effective state heavy metal content, comprising the following steps:
1., high temperature impregnate soil 4 days after, water is discharged, is exposed to the sun 3 days.2., the rice straw by after compost, corn
One or more of stalk, wheat stalk, rape stalk are equably sprinkling upon field, and the amount of spreading fertilizer over the fields is 110kg/ mus.3., in stalk
On, composite modified diatomite heavy metal deactivator prepared by embodiment 3 is spread fertilizer over the fields, the amount of spreading fertilizer over the fields is 150kg/ mus.Select stalk
Chopper turns over farmland, disposably completes rotary tillage, straw biological charcoal crushes, the processes such as smooth, by compost stalk, compound
Modification infusorial earth heavy metal deactivator mixes well withs the soil, and preferred depth of deep ploughing is 0.4m.4., cover on the soil after deep ploughing
Mulch, and be exposed to the sun 10 days；Later, mulch is opened to continue to divulge information, be exposed to the sun 5 days；Ground moistening is kept during being exposed to the sun, but avoids rainwater
It washes away.5., plant ginger on the agricultural land soil of Passivation Treatment in situ.6., the Cultivate administration measure of ginger is according to the Chinese people
Regulation in republic's national standardization technical guide " ginger production specifications " (GB/Z26584-2011) executes.
2. non-in-situ passivation processing
1., select rotary cultivator farmland is turned over, ploughed depth 0.4m.2., plant in the farmland after turning over, being smooth
Plant ginger.3., " ginger is raw according to National Standard of the People's Republic of Chinaization technical guide for the Cultivate administration measure of ginger
Producing technical specification " regulation in (GB/Z26584-2011) executes.
3. comparative example: carrying out repairing test to the soil in same 3 plot respectively using 3 kinds of modification infusorial earths.Specifically
Process is as follows.
The preparation method of 3 kinds of composite modified diatomite heavy metal deactivators: with " 1. original positions of the invention of above-described embodiment 3
Passivating method." in step (1) it is identical.
The Cultivate administration measure of 3 kinds of composite modified diatomite heavy metal deactivator method of administration, rice: 1., spread fertilizer over the fields it is compound
The amount of application of modification infusorial earth heavy metal deactivator, 3 kinds of composite modified diatomite heavy metal deactivators is respectively as follows: CaCO3It is modified
22.5kg/ mus of diatomite, Mg (OH)212kg/ mus of modification infusorial earth, Fe3O43kg/ mus of modification infusorial earth.2., farmland turned over
It ploughs, ploughed depth 0.4m enables soil fully to mix with composite modified diatomite heavy metal deactivator.3., ginger
Cultivate administration measure is according to National Standard of the People's Republic of Chinaization technical guide " ginger production specifications " (GB/
Z26584-2011 the regulation in) executes.
4. verifying example: using composite modified diatomite heavy metal deactivator, it may be assumed that the mixture of 3 kinds of modification infusorial earths, to same
The plot of sample carries out repairing test.Detailed process is as follows.
A kind of preparation method of NEW TYPE OF COMPOSITE modification infusorial earth heavy metal deactivator: " 1. is of the invention with above-described embodiment 3
In-situ passivation method." in step (1) it is identical.
Composite modified diatomite heavy metal deactivator: the mixture of 3 kinds of composite modified diatomite heavy metal deactivators.
CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth, Fe3O4The mass ratio of modification infusorial earth is 15:8:2.
A kind of Cultivate administration measure of the passivator method of administration of optimization, rice: 1., a composite modified diatomite huge sum of money is spread fertilizer over the fields
Belong to passivator, the amount of spreading fertilizer over the fields is 37.5kg/ mus.2., farmland is turned over, ploughed depth 0.4m enables soil fully
It is mixed with composite modified diatomite heavy metal deactivator.3., the Cultivate administration measure of ginger is according to country, the People's Republic of China (PRC)
Regulation in standardized directions technological document " ginger production specifications " (GB/Z26584-2011) executes.
5. soil remediation effect
Content of beary metal in the III soil of plot is detected, as a result as shown in table 16.Method pair shown in the present invention
The remediation efficiency of soil available Pb is 50.54%.In comparison, reparation of the method to available state Pb in earth shown in example is verified
Efficiency is 41.94%.Illustrate, using passivator method of administration provided by the invention, passivator can be improved in contaminated soil
Passivation/fixed efficiency of Pb.
Compared with the Pb remediation efficiency (41.94%) for verifying method shown in example, through CaCO3Modification infusorial earth, Mg (OH)2Change
Property diatomite, Fe3O4After the independent Passivation Treatment of modification infusorial earth, the remediation efficiency of soil available Pb is respectively 11.02%,
7.80% and 14.24%.Illustrate, by CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth and Fe3O4Modification infusorial earth carries out
After compounding, remediation efficiency is higher than the sum of the remediation efficiency that 3 kinds of diatomite passivator are administered alone.
The changes of contents of plot III heavy metal-polluted soil Pb after the reparation of table 16
Content of beary metal in the III soil of plot is detected, as a result as shown in Table 17.Method pair shown in the present invention
The remediation efficiency of soil available Cd is 52.63%.In comparison, reparation of the method to available state Cd in earth shown in example is verified
Efficiency is 31.58%.Illustrate, using passivator method of administration provided by the invention, passivator can be improved in contaminated soil
Passivation/fixed efficiency of Cd.
Compared with the Cd remediation efficiency (31.58%) for verifying method shown in example, through CaCO3Modification infusorial earth, Mg (OH)2Change
Property diatomite, Fe3O4After the independent Passivation Treatment of modification infusorial earth, the remediation efficiency of soil available cadmium is respectively 10.53%,
15.79% and 10.53%.Illustrate, by CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth and Fe3O4Modification infusorial earth carries out
After compounding, remediation efficiency is higher than the sum of the remediation efficiency that 3 kinds of diatomite passivator are administered alone.
The changes of contents of plot III heavy metal-polluted soil Cd after the reparation of table 17
Content of beary metal in the III soil of plot is detected, as a result as shown in Table 18.Method pair shown in the present invention
The remediation efficiency of soil available As is 48.74%.In comparison, reparation of the method to available state As in earth shown in example is verified
Efficiency is 27.36%.Illustrate, using passivator method of administration provided by the invention, passivator can be improved in contaminated soil
Passivation/fixed efficiency of As.
Compared with the As remediation efficiency (27.36%) for verifying method shown in example, through CaCO3Modification infusorial earth, Mg (OH)2Change
Property diatomite, Fe3O4After the independent Passivation Treatment of modification infusorial earth, the remediation efficiency of soil available As is respectively 7.59%,
8.28% and 8.97%.Illustrate, by CaCO3Modification infusorial earth, Mg (OH)2Modification infusorial earth and Fe3O4Modification infusorial earth is answered
With later, remediation efficiency is higher than the sum of the remediation efficiency that 3 kinds of diatomite passivator are administered alone.
The changes of contents of plot III heavy metal-polluted soil As after the reparation of table 18
6. repairing effect further confirms that
To further confirm that repairing effect of the invention and technical advantage compared with the existing technology, on same plot point
It Xuan Qu not be without the cell plantation shown in repair process, verifying example after method repair process, after method repair process shown in the present invention
Ginger, kind are the white ginger in Tongling.
To the cell after method repair process shown in no repair process, comparative example, after method repair process shown in the present invention
On ginger trait data counted, as a result as shown in Table 19, with non-in-situ passivation processing compared with, application verification example institute
After showing method processing agricultural land soil shown in method and the present invention, plant height, ginger block fresh weight, the ginger block length, ginger of the ginger planted
Block is wide all to be obviously increased.
Table 19 is planted in in-situ passivation treated the ginger character on the III of plot
Content of beary metal measurement.Its fruit is harvested in ginger water content in harvest, and measures the content of beary metal of ginger, detection side
Method is according to " measurement of national food safety standard Pb in food " (GB5009.12-2010), " national food safety standard food
Middle Cadmium detrmination " (GB5009.15-2014) and " measurement of national food safety standard total Arsenic in Food and inorganic arsenic "
(GB5009.11-2014) regulation in carries out.
As shown in table 20, under without in-situ passivation treatment conditions, Pb, Cd, As content of ginger are respectively higher than country's mark
Specified value (that is: Pb≤0.1mg/kgFW, Cd≤0.05mg/ in quasi- " pollutants in food limitation " (GB2762-2017)
KgFW, As≤0.5mg/kgFW), by in-situ passivation method processing shown in method processing shown in verifying example and the present invention
Afterwards, Pb, Cd, As content in ginger are respectively lower than 0.1mg/kg, 0.05mg/kg, 0.5mg/kg, meet national standard " food
Middle pollutant limitation " (GB2762-2017) requirement.Compared with the processing of non-in-situ passivation, verifying method shown in example reduces life
Pb, Cd, As content of ginger, fall are 30.77%, 44.44% and 26.15% respectively；Method shown in the present invention significantly drops
Low Pb, Cd, As content of ginger, fall are 46.15%, 55.56% and 43.08% respectively.Illustrate, using the present invention
The passivator method of administration of offer can more effectively reduce the Accumulation of heavy metals amount in ginger.
The changes of contents of the ginger heavy metal of 20 in-situ passivation of table before and after the processing
As shown in table 21, compared with the processing of non-in-situ passivation, through treated the farmland soil of in-situ passivation shown in the present invention
Earth, soluble sugar content, soluble protein content, the Vitamin C content of planted ginger all obviously increase, crude fiber content drop
Low, Quality of Ginger significantly improves.
Table 21 is planted in in-situ passivation treated the Quality of Ginger on the III of plot
The beneficial effect that the present embodiment has is: the composite modified diatomite heavy metal deactivator being prepared for, to heavy metal
Passivation effect it is obvious, used raw material will not to soil generate secondary pollution；Utilize a huge sum of money provided by the present invention
Belong to passivator formula and passivator method of administration, the soil after repairing can be made preferably to meet the growth demand of ginger, reduced
The accumulation of heavy metal, improves Quality of Ginger in ginger.
It should be noted that, in this document, such as first and second or the like relational terms are used merely to one if it exists
A entity or operation with another entity or operate distinguish, without necessarily requiring or implying these entities or operation it
Between there are any actual relationship or orders.Moreover, the terms "include", "comprise" or its any other variant are intended to
Cover non-exclusive inclusion, so that the process, method, article or equipment for including a series of elements not only includes those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or setting
Standby intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in the process, method, article or apparatus that includes the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of composite modified diatomite heavy metal deactivator, which is characterized in that the preparation of raw material including following mass fraction and
At: 20-115 parts of straw biological powdered carbon, CaCO310-20 parts of modification infusorial earth, Mg (OH)25-10 parts of modification infusorial earth, Fe3O4Change
2-5 parts of diatomite of property.
2. composite modified diatomite heavy metal deactivator according to claim 1, which is characterized in that the straw biological charcoal
Powder includes that the raw material of following mass fraction is prepared: 0-30 parts of wheat straw biologic powdered carbon, rape stalk biology powdered carbon 0-35
Part, 10-30 parts of corn charcoal straw biological powdered carbon, 10-20 parts of straw biological powdered carbon of rice biological charcoal.
3. composite modified diatomite heavy metal deactivator according to claim 1, which is characterized in that the CaCO3Modified silicon
Diatomaceous earth, which includes the following steps, to be prepared:
(1) by diatomite and combined, washing to pH is neutrality, and drying sieving obtains pretreated diatomite；
(2) by pretreated diatomite and Na2CO3Aqueous solution mixing, is added CaCl2Aqueous solution, after oscillation, washing to pH is
Neutrality is dried, is ground up, sieved, obtains CaCO3Modification infusorial earth.
4. composite modified diatomite heavy metal deactivator according to claim 3, which is characterized in that the CaCO3Modified silicon
Diatomaceous earth, which includes the following steps, to be prepared:
(1) ratio for being 1g/5mL-1g/8mL in solid-to-liquid ratio, the hydrochloric acid for being 1mol/L-2mol/L by diatomite and concentration are water-soluble
Liquid mixing after ultrasonic disperse 30-60min, wash diatomite until filtrate pH is neutrality with ethyl alcohol and deionized water, is dried to
Constant weight, sieving, obtains pretreated diatomite；
(2) pretreated diatomite and concentration are 0.5mol/L's by the ratio for being 1g/5mL-1g/10mL in solid-to-liquid ratio
Na2CO3Aqueous solution mixing, under the conditions of 25 DEG C -30 DEG C after constant temperature oscillation, is added the CaCl of 4mol/L2Aqueous solution, then constant temperature vibration
After swinging 30min, being washed with distilled water product to filtrate is after neutrality, and 105 DEG C of constant temperature dryings, grinding is crossed 200 mesh standard sieves, obtained
CaCO3Modification infusorial earth.
5. composite modified diatomite heavy metal deactivator according to claim 1, which is characterized in that the Mg (OH)2It is modified
Diatomite, which includes the following steps, to be prepared:
(1) dry by diatomite roast, the diatomite after being roasted；
(2) by diatomite, magnesium chloride, the sodium hydroxide mixed grinding after roasting, after mix products are stood, after washing, filtering,
It dries, be ground up, sieved, obtain Mg (OH)2Modification infusorial earth.
6. composite modified diatomite heavy metal deactivator according to claim 5, which is characterized in that the Mg (OH)2It is modified
Diatomite, which includes the following steps, to be prepared:
(1) by diatomite under the conditions of 450 DEG C roast 2-3h, the diatomite after being roasted；
(2) spare by magnesium chloride freeze-day with constant temperature；
It (3) is in mass ratio the ratio of 1:1:1/2-2/3, the magnesium chloride and hydroxide after diatomite, drying after weighing roasting
Sodium；It first will be after diatomite and magnesium chloride co-ground 5-10min；Sodium hydrate solid is added in the reaction system, is ground to
Reaction terminates, and mix products are statically placed in air after 3-5h, after being washed, filtered repeatedly with aquae destillata, by 110 DEG C of mix products
After constant temperature drying 9-12h, grinding crosses 200 the polished standard screens, obtains Mg (OH)2Modification infusorial earth.
7. composite modified diatomite heavy metal deactivator according to claim 1, which is characterized in that the Fe3O4Modified silicon
Diatomaceous earth, which includes the following steps, to be prepared:
(1) it by after diatomite roast, mills, be sieved, the diatomite after obtaining pre- roast sieving；
(2) diatomite suspension is configured with the diatomite after the sieving of pre- roast, by diatomite suspension and Fe3O4Aqueous solution mixing,
It is added into chitosan-acetic acid-aqueous solution of pH=6, reaction；
(3) to after the reaction was completed, wash and be precipitated to neutrality, drying precipitating, grinding precipitating is sieved, obtains Fe3O4Modification infusorial earth.
8. composite modified diatomite heavy metal deactivator according to claim 7, which is characterized in that the Fe3O4Modified silicon
Diatomaceous earth, which includes the following steps, to be prepared:
(1) diatomite after roast 2-4h, is milled under the conditions of 450 DEG C and crosses 60 mesh standard sieves, after obtaining pre- roast sieving
Diatomite；
(2) diatomite after the sieving of pre- roast is mixed with distilled water, is obtained by the ratio for being 1g/10mL-1g/15mL in solid-to-liquid ratio
To diatomite suspension；
The ratio for being 1g/40mL-1g/50mL in solid-to-liquid ratio, by Fe3O4It is dissolved in distilled water, obtains Fe3O4Aqueous solution；
The ratio for being 1g/400mL in solid-to-liquid ratio, chitosan is dissolved in 1% acetic acid aqueous solution, after complete stirring and dissolving,
Adjust pH to 6；
(3) by the Fe after ultrasound3O4Aqueous solution pours into diatomite suspension, and after stirring, chitosan-acetic acid-aqueous solution is added,
In 60 DEG C of -70 DEG C of water-bath 3-5h；It is precipitated to neutrality to after the reaction was completed, be washed with distilled water, 70 DEG C of constant temperature drying precipitatings
After 8-10h, grinding precipitating crosses 60 mesh standard sieves, obtains Fe3O4Modification infusorial earth.
9. a kind of will be applied to rain fed crop such as the described in any item composite modified diatomite heavy metal deactivators of claim 1-8
The method in farmland, which comprises the following steps:
(1) the heavy metal risk class for selecting crop planting plot soil is low-risk, wherein 1 < Pi≤2,1 < Pimax
≤2；Or, moderate risk, wherein 2 < Pi≤3,2 Pimax≤3 <；
(2) after high temperature impregnates soil 3-5 days, water is discharged, is exposed to the sun 2-3 days；
(3) while deep ploughing polluted agricultural land, stalk, passivating material are mixed well withed the soil, stalk additive amount is 100-500kg/
Mu, the additive amount of composite modified diatomite heavy metal deactivator are 100-200kg/ mus；
(4) mulch is covered on the soil after deep ploughing, and be exposed to the sun 5-10 days；Later, it opens mulch and continues the 5-10 that divulges information, is exposed to the sun
It；Rain drop erosion is avoided during being exposed to the sun；
(5) crops are planted on the agricultural land soil of Passivation Treatment in situ.
10. a kind of will be applied to paddy field such as the described in any item composite modified diatomite heavy metal deactivators of claim 1-8
Method, which comprises the following steps:
(1) the heavy metal risk class for selecting paddy field is low-risk, wherein 1 < Pi≤2,1 Pimax≤2 <；Or, moderate wind
Danger, wherein 2 < Pi≤3,2 Pimax≤3 <；
(2) it pours water and impregnates soil 12h or more, after soil is soft, when mud foot depth is 0.1-0.2m, water is discharged；
(3) rice straw is equably sprinkling upon field, the amount of spreading fertilizer over the fields is 200-350kg/ mus；On rice straw, spread fertilizer over the fields compound
Modification infusorial earth heavy metal deactivator, the amount of spreading fertilizer over the fields are 100-200kg/ mus；
(4) pollution paddy field is turned over；
(5) it pours water in the paddy field after deep ploughing, depth 1-3cm maintains the soaking state in paddy field, and the time is 15-20 days, during which
Avoid rain drop erosion；
(6) soak period nearly at the end of, stop adding irrigation water into paddy field, be evaporated the earth's surface water layer in paddy field naturally,
And maintain the moisture state of paddy field soil；
(7) in situ after Passivation Treatment paddy field soil in transplanting rice seedling.
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