CN109777439A - Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount - Google Patents
Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount Download PDFInfo
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Abstract
The present invention discloses a kind of soil heavy metal passivant, including polyfunctional group cellulose passivator.The soil heavy metal passivant can efficiently reduce Accumulation of heavy metals amount in tomato, it is made to meet relevant criterion/requirement.Meanwhile the invention also discloses the preparation method of the soil heavy metal passivant and it reduce tomato Accumulation of heavy metals amount in application.
Description
Technical field
The invention belongs to technical field of land improvement, and in particular to a kind of soil heavy metal passivant and its reduce tomato
Application in Accumulation of heavy metals amount.
Background technique
Heavy metal is the non-essential element of animal and plant growth.It, can be by plant after heavy metal enters agricultural land soil
It absorbs, accumulation, and human body is entered by food chain.Heavy metal will affect the active and micro member of the metabolism of amino acid, enzyme system
The metabolism of element, threatens to human health.
" national Soil Pollution Investigation bulletin " display of Environmental Protection Departments in 2014 and Ministry of Land and Resources's joint publication,
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..The Ministry of Agriculture accounts for the sewage irrigation Regional survey discovery of 1,400,000 hectares of China, the exceeded area of heavy metal-polluted soil
64.8%.
Tomato is susceptible to the crops of heavy metal pollution.Studies have shown that is 0.97mg/kg in agricultural land soil cadmium content
Under conditions of (national standard " standard of soil environment quality ", GB15618-1995, III Standard value 1.0mg/kg)), have
The fruit Cd content of 95.3% experimental cultivar be more than national standard " pollutants in food limitation " (GB2762-2005 ,≤
0.05mg/kg FW), and most kinds are more than 1 times or so of this limit value.For heavy metal pollution farmland, exploitation is high
Effect, easy to operate, the propagable method for reducing Accumulation of heavy metals amount in tamato fruit have important application value and wide
Market prospects.
Meet " pollutants in food limitation " (GB2762-2005, solanaceous vegetables Cd content≤0.05mg/ to reach to produce
Kg FW) agricultural product purpose, on the one hand to make great efforts contaminated soil administer by the method for physics, chemistry and biology and
It repairs, reduces the content of soil available heavy metal；On the other hand, it to be dropped by efficient, propagable agrotechnical measure
Absorption and accumulation of the low tomato to heavy metal.Both methods is to reduce content of beary metal in tomato, solve agricultural products in China
The important means of safety problem.
Summary of the invention
The purpose of the present invention, which essentially consists in, to be provided a kind of soil heavy metal passivant and its is reducing tomato Accumulation of heavy metals
Application in amount, the soil heavy metal passivant can efficiently reduce Accumulation of heavy metals amount in tomato, make its meet relevant criterion/
It is required that being provided a strong guarantee for tomato in China safety in production.
Specifically, soil heavy metal passivant of the invention, including polyfunctional group cellulose passivator, it is described multifunctional
Group's cellulose passivator is made via the following steps:
(1) plant fiber is crushed, is sieved, obtains fiber dust；
(2) by solid-to-liquid ratio 1g/10mL-1g/20mL by fiber dust be 1-5% with mass fraction NaOH solution in 50-
3-5h is pre-processed under the conditions of 70 DEG C, filters out pretreated fiber dust, it is dry after washing to neutrality；
It (3) is 30-35%'s with mass fraction by the fiber dust after above-mentioned drying by solid-to-liquid ratio 1g/10mL-1g/15mL
The mixed liquor stirring hydrolysis 2-5h for the sulfuric acid that hydrochloric acid and mass fraction are 29-56%, hydrolysis temperature is 50-70 DEG C, is then added
Deionized water terminates hydrolysis；Suspension is separated, spent acid and cellulose dope are collected；
(4) 0.5-1 times of deionized water is added in cellulose dope, is neutralized to neutrality with NaOH solution, point
It is dry from, washing, obtain cellulose；
(5) above-mentioned cellulose is put into container, n,N-Dimethylformamide is added, be swollen 0.5-3h；Then by hydrogen-oxygen
Change one or more of sodium, mercaptoethanol, thiocarbamide, iminodiacetic acid to be added thereto, through first time back flow reaction 12-48h
Afterwards, be cooled to room temperature, filter, washing product until filtrate be neutrality, then use ethanol washing, drying；Then by product and
The methanol aqueous solution of 1500mL mass concentration 50% is added to the container, and after second of back flow reaction 2-6h, is cooled to room temperature, mistake
Filter, is successively washed with deionized water, methanol, is dried in vacuo 8-12h, is obtained polyfunctional group cellulose passivator.
In the preparation of above-mentioned polyfunctional group cellulose passivator, the plant fiber in step (1) can be rice straw,
Corn stover, wheat stalk, rape stalk etc..Preferably, plant fiber is crushed, crosses 30 mesh and 120 meshes, leaves and takes middle part
The fiber dust divided.
In step (2), pretreated purpose is to wash away impurity and dissolved lignin, impurity and lignin counterweight metallic blunt
Change does not help, and there is the risk for bringing counter productive.
In step (3), the volume ratio of hydrochloric acid and sulfuric acid is preferably 1:3-1:4 in mixed liquor.It can be by the way that deionized water be added
To terminate hydrolysis, specific amount of water is that easy determining routine techniques illustratively can to those skilled in the art
To be 1-3 times of deionized water.
In step (4), cellulose obtained is corynebacterium, and 50 μm of partial size <, yield is good dispersion, steady up to 65-75%
Qualitative height.
In step (5), before back flow reaction, one of sodium hydroxide, mercaptoethanol, thiocarbamide, iminodiacetic acid is added
Or it is several.Preferably, the mass ratio of cellulose and sodium hydroxide, mercaptoethanol, thiocarbamide and iminodiacetic acid is respectively 100:
0-2,100:0-10,100:0-5 and 100:0-20, more preferable 100:0-1,100:0-5,100:0-2.5 and 100:0-10.It is logical
Cross first time back flow reaction, can accelerating fibers element surface functional group generating rate.It is washed with after ethanol washing, can effectively be gone
Except most of soluble large molecule impurity of material surface；By second of back flow reaction, then can remove in material duct or
Impurity in lamella.Finally, the higher polyfunctional group cellulose passivator product of purity is obtained.
Correspondingly, the invention further relates to the preparation method of above-mentioned polyfunctional group cellulose passivator, including it is as described above
The step of (1)-(5).
Soil heavy metal passivant of the invention can be only made of above-mentioned polyfunctional group cellulose passivator.By above-mentioned
Polyfunctional group cellulose passivator made from step has the selective absorption performance to heavy metal, to the passivation efficiency of heavy metal
The Accumulation of heavy metals amount in agricultural product can be effectively reduced in height.
In addition to above-mentioned polyfunctional group cellulose passivator, from the angle of performance optimization, it is preferable that soil of the invention
Heavy metal deactivator also contains carbonate mineral and crop material.When preparation, each component is uniformly mixed.Be readily appreciated that and
It is well established that carbonate mineral and crop material are all with powdered use.
Carbonate mineral pH with higher, consumption H+The characteristics of, the pH of soil system can be improved, it is lasting to reduce a huge sum of money
The validity of category.Crop material has preferable water conservation, fertilizer conservation performance, can be avoided soil hardening, reduces cost.Practical application
Show that suitable carbonate mineral, crop material and polyfunctional group cellulose passivator are used cooperatively, can mention more significantly
Tomato Quality is risen, the accumulation of heavy metal in tamato fruit is reduced.
The carbonate mineral can be calcite powder, dolomite powder, magnesite powder, one in limestone powder
Kind is several.The crop material can be one or more of rice straw, corn stover, wheat stalk, rape stalk.
It is further preferred that soil heavy metal passivant of the invention includes following component:
0-15 parts of calcite powder, 0-10 parts of dolomite powder, 0-10 parts of magnesite powder, 0-20 parts of limestone powder,
0-35 parts of rice straw, 0-30 parts of corn stover, 0-35 parts of wheat stalk, 0-30 parts of rape stalk, polyfunctional group cellulose is blunt
5-15 parts of agent.
The present invention does not do specific limitation to the method for administration of soil heavy metal passivant, and heavy-metal contaminated soil can be used and change
The conventional application method of soil conditioner in good field.But based on giving full play to above-mentioned soil heavy metal passivant effect, as far as possible
Reduce the purpose of biologically effective state content of beary metal in soil, it is preferred to use a kind of method of administration of optimization, including the following steps:
(1) tomato planting plot soil is selected；Preferably, according to " national rapid test paper heavy metal-polluted soil security evaluation
Technical stipulation " heavy metal-polluted soil safety status classification standard, the heavy metal risk class of selected plot soil is low-risk
(1 < Pi≤ 2,1 < Pimax≤ 2) or moderate risk (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) deep ploughing farmland, while passivator being mixed well withed the soil, the additive amount of passivator is 10-30kg per acre；It is preferred that
Ground, deep ploughing depth are 0.2-0.4m, are effectively turned over to the soil of the depth, and soil and passivator can be made sufficiently mixed
It closes, the demand that the soil horizon after making passivation can satisfy crop root part to growing space enhances the gas permeability of soil, makes crop
Growing way is more preferable；
(4) mulch is covered on the soil after deep ploughing, be exposed to the sun 5-10 days, opened mulch later and continue the 5-10 that divulges information, is exposed to the sun
It, avoids rainwater alluviation during being exposed to the sun.
After carrying out above-mentioned processing to agricultural land soil using soil heavy metal passivant of the invention, planting facility crop kind
Eggplant.Without limitation, the Cultivate administration measure of tomato may include following aspect:
(1) variety selection and plantation: selection is disease-resistant, high-quality, high yield, storage tolerance, commodity is good, adapts to the kind in market；
The tomato variety of screening is planted in the plot for having already passed through Passivation Treatment, it is long according to breediness, training type, growth period
Short and cultivation habit, preferably makes planting density reach 3000-4000 plants/667m2；
(2) Cultivate administration: the Cultivate administration measure of tomato is according to People's Republic of China's agricultural industry criteria " nuisanceless food
Product tomato Protected production technical regulation " regulation in (NY/T 5007-2001) executes；Preferably, using timing rhizosphere part
Trickle irrigation method carries out top dressing, and the efficiency of heavy metallic activation can be effectively reduced in trickle irrigation, reduces the murder by poisoning of heavy metal on plants, reduces and makees
Accumulation of the object to heavy metal；
(3) prevention and control of plant diseases, pest control: the application method and dosage of all pesticides are according to National Standard of the People's Republic of China's " agriculture
Medicine reasonable application " relevant regulations in (GB/T 8321) execute.
Compared with the prior art, technical solution of the present invention has the advantage that
1. the polyfunctional group cellulose passivator prepared is obvious to the passivation effect of heavy metal, the duration is long, and uses
Raw material will not to soil generate secondary pollution.In conjunction with soil heavy metal passivant and method of administration of the invention, can make
Soil after reparation preferably meets the growth demand of crops, reduces the accumulation of heavy metal in tamato fruit, improves tomato
Quality；It is easy to operate it is easy to learn, be easy to that large-scale promotion, cost is relatively low.
2. the present invention can apply on the soil of all suitable tomato growths, the tomato including crop field and chamber planting；
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 rural area
The relevant regulations in portion；The content of beary metal of tomato can be reduced from source, ensure the quality safety of tomato and its processed goods, from
And ensure the health of the people.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, but should not be construed as to guarantor of the invention
Protect the limitation of range.
Embodiment one
1. the preparation of polyfunctional group cellulose passivator
Through the following steps, polyfunctional group cellulose passivator is prepared:
In mass ratio it is the ratio of 2:5:3, corn stover, wheat stalk, rape stalk is crushed with pulverizer, crosses 30 mesh
And 120 meshes, leave and take the fiber dust of middle section.
In solid-to-liquid ratio be 1g/10mL ratio, by fiber dust mass fraction be 5% NaOH solution in 50 DEG C of conditions
Lower pretreatment 3h filters out pretreated fiber dust, dry after washing to neutrality.
In solid-to-liquid ratio be 1g/15mL ratio, by pretreated fiber dust with hydrochloric acid (mass fraction 30%) with
Mixed liquor (volume ratio of hydrochloric acid and sulfuric acid is 1:3) stirring hydrolysis 2h of sulfuric acid (mass fraction 56%), hydrolysis temperature 70
DEG C, 2 times of deionized water is then added, terminates hydrolysis；Suspension is separated, spent acid and cellulose dope are collected.
0.5 times of deionized water is added in cellulose dope, then is neutralized to neutrality with NaOH solution, washes repeatedly
It washs, be centrifuged 3 times, it is dry, obtain cellulose.Cellulose is corynebacterium, and 50 μm of partial size <, yield is good dispersion, steady up to 66.8%
Qualitative height.
400g cellulose is put into 2000mL triangular flask, 1000mL n,N-Dimethylformamide is added, is swollen 1h；
Mercaptoethanol 8g, thiocarbamide 4g, iminodiacetic acid 16g are added in triangular flask, through first time back flow reaction for 24 hours after, it is cooling
To room temperature, filtering, it is neutrality that product to filtrate, which is washed with deionized, then with ethanol washing 3 times, dry.Then by product and
The methanol aqueous solution that 1500mL mass concentration is 50% is added in triangular flask, after second of back flow reaction 6h, is cooled to room temperature,
Filtering, then washed respectively 3 times with deionized water, methanol, 8 hours are dried in vacuo to get polyfunctional group cellulose passivator.
2. the preparation of soil heavy metal passivant
Soil heavy metal passivant A and B are prepared respectively.
Passivator A is made of polyfunctional group cellulose passivator obtained above.
Passivator B, contains: 10 parts of calcite powder, 5 parts of dolomite powder, and 20 parts of limestone powder, corn stover 15
Part, 30 parts of wheat stalk, 15 parts of rape stalk, 5 parts of polyfunctional group cellulose passivator.
3. application/soil Passivation Treatment of passivator
Application the following steps are included:
1. selecting soil, select Huainan City, Anhui Province coal mine periphery farmland for a target planting site (huge sum of money i.e. to be repaired
Belong to contaminated soil, be denoted as plot I).The content of beary metal of the agricultural land soil is measured, as a result as shown in table 1.According to the Chinese people
Republic's national standard " standard of soil environment quality " (GB 15618-1995) and " national rapid test paper heavy metal-polluted soil peace
Full assessment technology regulation " (2015), the heavy metal risk class of selected plot soil is low-risk (1 < Pi≤2,1 < Pimax
≤2)。
The heavy metal content in soil of 1 plot I of table
| Heavy metal content in soil | Pb(mg/kg) | Cd(mg/kg) |
| Plot I | 62.15 | 0.37 |
| GB 15618-1995 primary standard | 35.00 | 0.20 |
| GB 15618-1995 secondary standard | 300.00 | 0.30 |
| GB 15618-1995 grade III Standard | 500.00 | 1.00 |
2. high temperature impregnates soil 3 days, then water is discharged, is exposed to the sun 2 days.
3. polluted agricultural land of deep ploughing, while passivator being mixed well withed the soil, the additive amount of passivator is 10kg per acre, deep ploughing
Depth is 0.25m.
4. covering mulch on the soil after deep ploughing, and it is exposed to the sun 5 days；Later, mulch is opened to continue to divulge information, be exposed to the sun 6 days；Cruelly
Rainwater alluviation is avoided during solarization.
4. the Cultivate administration measure of tomato
Anhui miscellaneous 15, red big precious tomato, red cherry, red No. 7 of Anhui totally 4 tomato varieties are selected, are planted respectively in through transpassivation
In the plot of processing, planting density is 3000 plants/667m2.The Cultivate administration measure of tomato is according to People's Republic of China's agricultural
Regulation in professional standard " pollution-free food tomato Protected production technical regulation " (NY/T 5007-2001) executes, by fixed
The mode of Shi Genji Drip irrigation partly carries out top dressing.
5. passivation effect detects
The indexs such as fruit properties, content of beary metal, fruit quality to obtained tomato in plot after Passivation Treatment carry out
Detection.
As a comparison, the same plot of non-Passivation Treatment is set, specifically: referring to above-mentioned " application/soil of 3. passivator
Passivation Treatment " and " the Cultivate administration measures of 4. tomatoes " implement, difference is without using passivator.
As shown in table 2, compared with non-Passivation Treatment, after application passivator A and B processing agricultural land soil, the Anhui planted is miscellaneous
15, red big precious tomato, red cherry, red No. 7 fruits in Anhui yield, the hardness of fruit, Dan Xianguo mass all obviously increase.
2 tamato fruit character of table
Content of beary metal measurement: harvesting its fruit in tomato water content in harvest, and measure the content of heavy metal in tamato fruit,
Detection method is according to " measurement of national food safety standard Pb in food " (GB 5009.12-2017) and " food safety country
Cadmium detrmination in standard food " regulation in (GB 5009.15-2014) carries out.
In national standard " pollutants in food limitation " (GB2762-2017), the specified value of Pb, Cd content be respectively Pb≤
0.1mg/kg FW,Cd≤0.05mg/kg FW.As shown in table 3, compared with non-Passivation Treatment, application passivator A and B handle agriculture
Field soil can significantly reduce Pb, Cd content in each kind tomato；Wherein, passivator B is passivated improved effect more preferably, gained
Pb, Cd contents level meet the requirement of GB2762-2017 in tamato fruit.
The changes of contents of heavy metal in 3 tamato fruit of table
As shown in table 4, compared with non-Passivation Treatment, after application passivator A and B processing agricultural land soil, the Anhui planted is miscellaneous
15, red big precious tomato, red No. 7 tamato fruits of red cherry and Anhui soluble protein content, soluble solid content, dry matter
Content, Vitamin C content, soluble sugar content and sugar-acid ratio all obviously increase, and Quality of Tomato Fruit is obviously improved.
4 Quality of Tomato Fruit of table
Embodiment two
1. the preparation of polyfunctional group cellulose passivator
Through the following steps, polyfunctional group cellulose passivator is prepared:
In mass ratio it is the ratio of 3:2, rice straw, rape stalk is crushed with pulverizer, crosses 30 mesh and 120 meshes,
Leave and take the fiber dust of middle section.
In solid-to-liquid ratio be 1g/15mL ratio, by fiber dust mass fraction be 3% NaOH solution in 60 DEG C of conditions
Lower pretreatment 4h filters out pretreated fiber dust, dry after washing to neutrality.
In solid-to-liquid ratio be 1g/13mL ratio, by pretreated fiber dust with hydrochloric acid (mass fraction 35%) with
Mixed liquor (volume ratio of hydrochloric acid and sulfuric acid is 2:7) stirring hydrolysis 3h of sulfuric acid (mass fraction 41%), hydrolysis temperature 60
DEG C, 1.5 times of deionized water is then added, terminates hydrolysis；Suspension is separated, spent acid and cellulose dope are collected.
0.75 times of deionized water is added in cellulose dope, then is neutralized to neutrality with NaOH solution, repeatedly
Washing, centrifugation 3 times, it is dry, obtain cellulose.Cellulose is corynebacterium, 50 μm of partial size <, yield up to 73.7%, good dispersion,
Stability is high.
400g cellulose is put into 2000mL triangular flask, 1000mL n,N-Dimethylformamide is added, is swollen 1h；
Thiocarbamide 6g, iminodiacetic acid 24g are added in triangular flask, through first time back flow reaction for 24 hours after, be cooled to room temperature, filter,
It is neutrality that product to filtrate, which is washed with deionized, then with ethanol washing 3 times, dry.Then product and 1500mL mass is dense
Degree is added in triangular flask for 50% methanol aqueous solution, after second of back flow reaction 4h, is cooled to room temperature, and filters, then spend
Ionized water, methanol wash 3 times respectively, are dried in vacuo 10 hours to get polyfunctional group cellulose passivator.
2. the preparation of soil heavy metal passivant
Soil heavy metal passivant A and B are prepared respectively.
Passivator A is made of polyfunctional group cellulose passivator obtained above.
Passivator B, contains: 10 parts of dolomite powder, 5 parts of magnesite powder, and 5 parts of limestone powder, 25 parts of rice straw,
25 parts of corn stover, 15 parts of wheat stalk, 15 parts of polyfunctional group cellulose passivator.
3. application/soil Passivation Treatment of passivator
Application the following steps are included:
1. selecting soil, select the reclaimed farmland on Tongling Anhui metallic ore periphery (i.e. to be repaired for target planting site
Multiple heavy-metal contaminated soil, is denoted as plot II).Heavy metal content in soil is measured, as a result as shown in table 5.According to middle Chinese
People republic national standard " standard of soil environment quality " (GB 15618-1995) and " national rapid test paper heavy metal-polluted soil
Safety assessment technique regulation " (2015), the heavy metal risk class of selected plot soil is moderate risk (2 < Pi≤3,2 <
Pimax≤3)。
The heavy metal content in soil of 5 plot II of table
| Heavy metal content in soil | Pb(mg/kg) | Cd(mg/kg) |
| Verify plot II | 60.54 | 0.58 |
| GB 15618-1995 primary standard | 35.00 | 0.20 |
| GB 15618-1995 secondary standard | 300.00 | 0.30 |
| GB 15618-1995 grade III Standard | 500.00 | 1.00 |
2. high temperature impregnates soil 5 days, then water is discharged, is exposed to the sun 3 days.
3. polluted agricultural land of deep ploughing, while passivator being mixed well withed the soil, the additive amount of passivator is 30kg per acre, deep ploughing
Depth is 0.3m.
4. covering mulch on the soil after deep ploughing, and it is exposed to the sun 10 days；Later, mulch is opened to continue to divulge information, be exposed to the sun 6 days；
Rainwater alluviation is avoided during being exposed to the sun.
4. the Cultivate administration measure of tomato
Anhui miscellaneous 21, ruby, Huang Yingtao, Anhui powder 5 totally 4 tomato varieties are selected, are planted respectively in by Passivation Treatment
Plot in, planting density be 4000 plants/667m2.The Cultivate administration measure of tomato is according to People's Republic of China's agricultural industry
Regulation in standard " pollution-free food tomato Protected production technical regulation " (NY/T 5007-2001) executes, and passes through timing root
The mode of border Drip irrigation partly carries out top dressing.
5. passivation effect detects
The indexs such as fruit properties, content of beary metal, fruit quality to obtained tomato in plot after Passivation Treatment carry out
Detection.
As a comparison, the same plot of non-Passivation Treatment is set, specifically: referring to above-mentioned " application/soil of 3. passivator
Passivation Treatment " and " the Cultivate administration measures of 4. tomatoes " implement, difference is without using passivator.
As shown in table 6, compared with non-Passivation Treatment, after application passivator A and B processing agricultural land soil, the Anhui planted is miscellaneous
21, ruby, Huang Yingtao, Anhui powder 5 fruit yields, the hardness of fruit, Dan Xianguo mass all obviously increase.
6 tamato fruit character of table
Content of beary metal measurement: identical as the detection method recorded in embodiment one.
As shown in table 7, compared with non-Passivation Treatment, application passivator A and B handle agricultural land soil, can significantly reduce each
Pb, Cd content in kind tomato；Wherein, passivator B is passivated improved effect more preferably, Pb, Cd content water in gained tamato fruit
Averagely meet the requirement of GB2762-2017.
The changes of contents of heavy metal in 7 tamato fruit of table
As shown in table 8, compared with non-Passivation Treatment, after application passivator A and B processing agricultural land soil, the Anhui planted is miscellaneous
21, ruby, yellow No. 5 tamato fruits of cherry and Anhui powder soluble protein content, soluble solid content, dry matter contain
Amount, Vitamin C content, soluble sugar content and sugar-acid ratio all obviously increase, and Quality of Tomato Fruit is obviously improved.
8 Quality of Tomato Fruit of table
Embodiment three
1. the preparation of polyfunctional group cellulose passivator
Through the following steps, polyfunctional group cellulose passivator is prepared:
In mass ratio it is the ratio of 2:1:2, rice straw, corn stover, wheat stalk is crushed with pulverizer, crosses 30 mesh
And 120 meshes, leave and take the fiber dust of middle section.
In solid-to-liquid ratio be 1g/20mL ratio, by fiber dust mass fraction be 1% NaOH solution in 70 DEG C of conditions
Lower pretreatment 5h filters out pretreated fiber dust, dry after washing to neutrality.
In solid-to-liquid ratio be 1g/10mL ratio, by pretreated fiber dust with hydrochloric acid (mass fraction 35%) with
Mixed liquor (volume ratio of hydrochloric acid and sulfuric acid is 1:4) stirring hydrolysis 5h of sulfuric acid (mass fraction 29%), hydrolysis temperature 50
DEG C, 1 times of deionized water is then added, terminates hydrolysis；Suspension is separated, spent acid and cellulose dope are collected.
1 times of deionized water is added in cellulose dope, then is neutralized to neutrality with NaOH solution, washes repeatedly
It washs, be centrifuged 2 times, it is dry, obtain cellulose.Cellulose is corynebacterium, and 50 μm of partial size <, yield is good dispersion, steady up to 69.3%
Qualitative height.
400g cellulose is put into 2000mL triangular flask, 1000mL n,N-Dimethylformamide is added, is swollen 1h；
Sodium hydroxide 2g, mercaptoethanol 10g, thiocarbamide 5g, iminodiacetic acid 20g are added in triangular flask, first time is flowed back anti-
It after answering for 24 hours, is cooled to room temperature, filters, it is neutrality that product to filtrate, which is washed with deionized, then with ethanol washing 3 times, dry.
Then product and the methanol aqueous solution of 1500mL mass concentration 50% will be added in triangular flask, through second of back flow reaction 3h
Afterwards, it is cooled to room temperature, filters, then washed respectively 3 times with deionized water, methanol, be dried in vacuo 12 hours to get polyfunctional group fibre
Tie up plain passivator.
2. the preparation of soil heavy metal passivant
Soil heavy metal passivant A and B are prepared respectively.
Passivator A is made of polyfunctional group cellulose passivator obtained above.
Passivator B, contains: 15 parts of calcite powder, 10 parts of magnesite powder, and 10 parts of limestone powder, rice straw 25
Part, 30 parts of rape stalk, 10 parts of polyfunctional group cellulose passivator.
3. application/soil Passivation Treatment of passivator
Application the following steps are included:
1. selecting soil, selecting the former vegetable cultivation farmland on Tongling Anhui metallic ore library periphery is target planting site
(heavy-metal contaminated soil i.e. to be repaired, be denoted as plot III).Heavy metal content in soil is measured, as a result as shown in table 9.Root
According to National Standard of the People's Republic of China's " standard of soil environment quality " (GB 15618-1995) and " national rapid test paper soil
Earth heavy metal safety assessment technique regulation " (2015), the heavy metal risk class of selected plot soil is moderate risk (2 < Pi
≤ 3,2 Pimax≤3 <).
The heavy metal content in soil of 9 plot III of table
2. high temperature impregnates soil 4 days, then water is discharged, is exposed to the sun 3 days.
3. polluted agricultural land of deep ploughing, while passivator being mixed well withed the soil, the additive amount of passivator is 20kg per acre, deep ploughing
Depth is 0.4m.
4. covering mulch on the soil after deep ploughing, and it is exposed to the sun 7 days；Later, mulch is opened to continue to divulge information, be exposed to the sun 8 days；Cruelly
Rainwater alluviation is avoided during solarization.
4. the Cultivate administration measure of tomato
Anhui miscellaneous 20, anhydrous sodium sulphate teenage girl, powder cherry, Sufen No.8 totally 4 tomato varieties are selected, are planted respectively in through transpassivation
In the plot of processing, planting density is 3500 plants/667m2.The Cultivate administration measure of tomato is according to People's Republic of China's agricultural
Regulation in professional standard " pollution-free food tomato Protected production technical regulation " (NY/T 5007-2001) executes, by fixed
The mode of Shi Genji Drip irrigation partly carries out top dressing.
5. passivation effect detects
The indexs such as fruit properties, content of beary metal, fruit quality to obtained tomato in plot after Passivation Treatment carry out
Detection.
As a comparison, the same plot of non-Passivation Treatment is set, specifically: referring to above-mentioned " application/soil of 3. passivator
Passivation Treatment " and " the Cultivate administration measures of 4. tomatoes " implement, difference is without using passivator.
As shown in table 10, compared with non-Passivation Treatment, after application passivator A and B processing agricultural land soil, the Anhui planted is miscellaneous
20, anhydrous sodium sulphate teenage girl, powder cherry, the fruit yield of Sufen No.8, the hardness of fruit, Dan Xianguo mass all obviously increase.
10 tamato fruit character of table
Content of beary metal measurement: taking its fruit in tomato water content in harvest, and measure the content of heavy metal in tamato fruit,
Detection method is according to " measurement of national food safety standard total Arsenic in Food and inorganic arsenic " (GB 5009.11-2014) and " food
The measurement of the safe national standard cadmium in foods of product " regulation in (GB 5009.15-2014) carries out.
In national standard " pollutants in food limitation " (GB2762-2017), the specified value of Cd, As content be respectively Cd≤
0.05mg/kg FW,As≤0.5mg/kg FW.As shown in table 11, compared with non-Passivation Treatment, application passivator A and B handle agriculture
Field soil can significantly reduce Cd, As content in each kind tomato；Wherein, passivator B is passivated improved effect more preferably, gained
Cd, As contents level meet the requirement of GB2762-2017 in tamato fruit.
The changes of contents of heavy metal in 11 tamato fruit of table
As shown in table 12, compared with non-Passivation Treatment, after application passivator A and B processing agricultural land soil, the Anhui planted is miscellaneous
20, anhydrous sodium sulphate teenage girl, the soluble protein content of powder cherry and Sufen No.8 tamato fruit, soluble solid content, dry matter
Content, Vitamin C content, soluble sugar content and sugar-acid ratio all obviously increase, and Quality of Tomato Fruit is obviously improved.
12 Quality of Tomato Fruit of table
Claims (10)
1. a kind of soil heavy metal passivant, including polyfunctional group cellulose passivator, the polyfunctional group cellulose passivator
It is made via the following steps:
(1) plant fiber is crushed, is sieved, obtains fiber dust；
(2) by solid-to-liquid ratio 1g/10mL-1g/20mL by fiber dust be 1-5% with mass fraction NaOH solution at 50-70 DEG C
Under the conditions of pre-process 3-5h, filter out pretreated fiber dust, it is dry after washing to neutrality；
(3) hydrochloric acid for being 30-35% with mass fraction by the fiber dust after above-mentioned drying by solid-to-liquid ratio 1g/10mL-1g/15mL
With mass fraction be 29-56% sulfuric acid mixed liquor stirring hydrolysis 2-5h, hydrolysis temperature be 50-70 DEG C, then be added go from
Sub- water terminates hydrolysis；Suspension is separated, spent acid and cellulose dope are collected；
(4) 0.5-1 times of deionized water is added in cellulose dope, is neutralized to neutrality with NaOH solution, separates, washes
It washs, it is dry, obtain cellulose；
(5) above-mentioned cellulose is put into container, n,N-Dimethylformamide is added, be swollen 0.5-3h；Then by sodium hydroxide,
One or more of mercaptoethanol, thiocarbamide, iminodiacetic acid are added thereto, cold after first time back flow reaction 12-48h
But to room temperature, filtering, washing product is until filtrate is neutrality, then uses ethanol washing, drying；Then by product and 1500mL mass
The methanol aqueous solution of concentration 50% is added to the container, and after second of back flow reaction 2-6h, is cooled to room temperature, and filtering is successively used
Deionized water, methanol washing, are dried in vacuo 8-12h, obtain polyfunctional group cellulose passivator.
2. soil heavy metal passivant according to claim 1, it is characterised in that: the plant fiber in step (1) is water
At least one of rice straw, corn stover, wheat stalk, rape stalk；Preferably, plant fiber is crushed, cross 30 mesh and
120 meshes leave and take the fiber dust of middle section.
3. soil heavy metal passivant according to claim 1, it is characterised in that: in step (3), the body of hydrochloric acid and sulfuric acid
Product is than being preferably 1:3-1:4.
4. soil heavy metal passivant according to claim 1, it is characterised in that: in step (5), cellulose and hydroxide
Sodium, mercaptoethanol, thiocarbamide and iminodiacetic acid mass ratio be respectively 100:0-2,100:0-10,100:0-5 and 100:0-
20, preferably 100:0-1,100:0-5,100:0-2.5 and 100:0-10.
5. soil heavy metal passivant described in any one of -4 according to claim 1, it is characterised in that: the heavy metal-polluted soil
Passivator is only made of polyfunctional group cellulose passivator.
6. soil heavy metal passivant described in any one of -4 according to claim 1, it is characterised in that: the heavy metal-polluted soil
Passivator also contains carbonate mineral and crop material；
Preferably, the carbonate mineral is calcite powder, dolomite powder, magnesite powder, one in limestone powder
Kind is several, and the crop material is one or more of rice straw, corn stover, wheat stalk, rape stalk.
7. soil heavy metal passivant according to claim 6, which is characterized in that the soil heavy metal passivant includes
Following component:
0-15 parts of calcite powder, 0-10 parts of dolomite powder, 0-10 parts of magnesite powder, 0-20 parts of limestone powder, rice
0-35 parts of stalk, 0-30 parts of corn stover, 0-35 parts of wheat stalk, 0-30 parts of rape stalk, polyfunctional group cellulose passivator
5-15 parts.
8. the preparation method of soil heavy metal passivant described in claim 1 includes the steps that (1)-described in claim 1
(5)。
9. soil heavy metal passivant of any of claims 1-7 is reducing answering in tomato Accumulation of heavy metals amount
With.
10. the method for administration of soil heavy metal passivant of any of claims 1-7, including the following steps:
(1) tomato planting plot soil is selected；
(2) after high temperature impregnates soil 3-5 days, water is discharged, is exposed to the sun 2-3 days；
(3) deep ploughing farmland, while passivator being mixed well withed the soil, the additive amount of passivator is 10-30kg per acre；Preferably,
Deep ploughing depth is 0.2-0.4m；
(4) mulch is covered on the soil after deep ploughing, be exposed to the sun 5-10 days, opened mulch later and continue to divulge information, be exposed to the sun 5-10 days, cruelly
Rainwater alluviation is avoided during solarization.
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