CN106367076A - Preparation method of organic-inorganic composite heavy metal contaminated soil passivator - Google Patents
Preparation method of organic-inorganic composite heavy metal contaminated soil passivator Download PDFInfo
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- CN106367076A CN106367076A CN201610753001.2A CN201610753001A CN106367076A CN 106367076 A CN106367076 A CN 106367076A CN 201610753001 A CN201610753001 A CN 201610753001A CN 106367076 A CN106367076 A CN 106367076A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
Abstract
The invention discloses a preparation method of an organic-inorganic composite heavy metal contaminated soil passivator. The preparation method includes the following steps that 1, bentonite is put into a drying oven and dried for 10 hours at the temperature of 105 DEG C for usage; 2, the dried bentonite is weighed, water is added into the dried bentonite so that turbid liquid can be prepared, wherein the ratio of liquid to solid is 100 mL:2-10 g, and stirring is carried out for 0.5 hour; 3, sodium carbonate is added into the turbid liquid, and the mixture is subjected to a stirring reaction for 2 hours at the temperature of 70 DEG C; 4, a modifier is added, and the mixture continues to be subjected to a stirring reaction for 1-10 hours at the temperature of 30-90 DEG C; 5, after the reaction is ended, the mixture is cooled to room temperature, subjected to suction filtration and washed with deionized water till the pH value is 7.0, drying is carried out for 24 hours at the temperature of 60 DEG C, and the passivator finished product is obtained after grinding and 100-mesh sieving. The passivator has the advantages that the source of raw materials is wide, and the passivator is low in price, natural and free of contamination; the preparation method is simple, reaction conditions are mild, product performance is stable, and the passivator has a good effect on passivated repair of heavy metal contaminated soil and can be applied to repairing of large-area composite heavy metal contaminated soil.
Description
Technical field
The present invention relates to a kind of preparation method of heavy-metal contaminated soil passivator, belong to heavy metal-polluted soil in environmental conservation
Pollution control field, specifically a kind of preparation method of organic-inorganic compoiste heavy-metal contaminated soil passivator.
Background technology
But the development with industrial or agricultural, soil contamination problem is increasingly serious, has a strong impact on the development of national economy.Data sheet
Bright, farm land area about 25,000,000 m of China's heavy metal pollution2, contaminated by heavy metals every year grain up to 12,000,000 t,
Lead to grain drop in production to be up to more than 1,000 ten thousand t, at least 20,000,000,000 yuan of total economic loss because of heavy metal pollution.Meanwhile, huge sum of money accessory
There is non-biodegradable, not only the yield to crops and quality produce larger harm, and are constantly enriched with by the transmission of food chain,
Finally in people's body accumulation health risk.Therefore, strengthen heavy metal-polluted soil reparation extremely urgent.Soil restoring technology can be divided into
Physical technique, chemical technology and biotechnology: peripheral doses technology includes intercepting landfill, thermal desorption, electro reclamation etc., and chemistry is repaiied
Recovering technology includes passivation, elution technique etc., and biotechnology includes microorganism remediation, phytoremediation and animal reparation technology etc..Its
In, passivating technique has simple to operate, cycle is short, low cost, the advantage such as applied widely, is large area heavy-metal contaminated soil
More preferably the selecting of reparation, the actual demand that current China heavy-metal contaminated soil is repaired can be met well.
Passivating technique refers to, by applying passivator toward in soil, heavy metal is changed on physics and chemical property more
Stable material, reduces the dissolubility of heavy metal, reduces to the impact caused by environment.Thus, the key of passivating technique application
It is passivator.At present, Compound Heavy Metals soil gets more and more, the mark that single passivator difficult to reach reparation is applied
Accurate, then the respective feature of passivator not of the same race by number of different types passivator compound use, can be played, strengthen passivation and repair
Reactivation power, reaches the purpose of the soil of repairing heavy metal pollution.Accordingly, it is considered to by organic carry out with inorganic passivant composite modified
Prepare passivator, the possible ph change that on the one hand organic available buffer chemical inactivators are brought, on the other hand, organic matter
Complex can be combined to form with these inorganic passivant, play the effect preventing organic rapid degraded to a certain extent, because
And can overcome the disadvantages that the risk brought because of organic matter decomposition, reach collaborative and complementary effect.
Bentonite is the nonmetallic ore with montmorillonite as essential mineral.Smectite structure is to press from both sides one by two silicon-oxy tetrahedrons
The 2:1 type layer structure of layer alumina octahedral composition, has stronger cation exchange capacity (CEC) because of its negatively charged.Due to ore deposit
The surface adsorption effect of thing, the exchange interaction of interlayer cation, the filtration in duct and special two-dimensional nanostructure effect
Deng so that bentonite becomes rare passivator in heavy-metal contaminated soil reparation application.The layer structure of montmorillonite and
Strong ion-exchange capacity makes Organic substance may be adsorbed between montmorillonite lamella, becomes bentonite modified and prepares organic and inorganic again
Fit theoretical basiss.Lot of documents shows: at normal temperatures and pressures, ion, water and salt and nearly all Organic substance, can
Enough pass in and out the interlayer of montmorillonite mineral, form complicated montmorillonite inorganic complex or organic complex.Therefore, can be by having
Machine thing monomer molecule or polymer long-chain are inserted into the piece interlayer of montmorillonite stratiform or are connected to montmorillonite surface, have prepared
Machine-inorganic composite type passivating material.Not only introduce heavy metal high adsorption capacity group, also increase montmorillonite intergranular away from,
So that montmorillonite is defined and there is the big porous active material of microporous network structure, specific surface area, further enhance bentonitic suction
Attached and ion-exchange performance, reaches the purpose improving bentonite passivation effect.
Content of the invention
The technical problem to be solved is to provide a kind of system of organic-inorganic compoiste heavy metal soil passivator
Preparation Method, it is to prepare heavy-metal contaminated soil passivator with composite modified bentonite for raw material, and the method has raw material
Source is extensive, cheap, good passivation effect, the advantages of do not result in secondary pollution.
For solving above-mentioned technical problem, the present invention employs the following technical solutions:
The preparation method of organic-inorganic compoiste heavy metal soil passivator of the present invention, including following operating procedure:
The first step, the bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, and sealing after drying is protected
Deposit, standby,
Second step, weighs the bentonite of a certain amount of drying, adds water and is made into the suspension that liquid-solid ratio is 100ml:2-10g,
Stirring 0.5 hour,
3rd step, the addition sodium carbonate in above-mentioned suspension, stirring reaction 2 hours at 70 DEG C,
4th step, the appropriate modifying agent of addition, continuously stirred reaction 1-10 hour at 30-90 DEG C,
5th step, after reaction terminates, is cooled to room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product organic-inorganic compoiste heavy-metal contaminated soil passivator finished product.
In 3rd step, the sodium carbonate of addition and the bentonite dried are 0.05:1 in mass ratio.
In 4th step, the modifying agent of addition and the bentonite dried are 1-20:100 in mass ratio.
In 4th step, described modifying agent be one of lignin, aminated lignin or sodium humate or more than one
Mixing.
Described lignin and aminated lignin are respectively derived from finished product and its amine that pulping and paper-making waste liquid acid adding precipitation filters
Change product.
The preparation method of organic-inorganic compoiste heavy metal soil passivator of the present invention, compared with prior art, have with
Lower advantage:
(1) passivator of the present invention is made using natural substance modified, does not destroy Soil structure, does not produce secondary pollution, and
And it is cheap；
(2) lignin and sodium humate are connected to montmorillonite surface by intercalation or ion-exchange reactionss by the present invention
And it is inserted into the piece interlayer of stratiform, introduce the strong group of heavy metal adsorption, increase the interlamellar spacing of montmorillonite simultaneously, so that illiteracy is taken off
Stone defines has the big porous active material of microporous network structure, specific surface area, further enhance bentonitic absorption and from
Sub- switching performance, forms organic-inorganic compoiste passivator, is applied in soil, can significantly improve bentonite heavy metal soil
The passivation repairing effect of earth, particularly has good passivation repairing effect to Compound Heavy Metals soil；
(3) the heavy-metal contaminated soil passivator prepared by the inventive method is neutrality, soil is had no toxic side effect, is ring
Border friendly passivator；
(4) the inventive method preparation process is simple, reaction condition is gentle, and properties of product are stable, workable.
Specific embodiment
With reference to embodiment, the inventive method is further described:
Embodiment 1, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:5g, stirring 0.5 is little
When；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) add 0.5g lignin, continuously stirred reaction 3 hours at 75 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 2, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:2g, stir 0.5
Hour；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) 0.25g aminated lignin and 0.25g sodium humate are added, continuously stirred reaction 1 hour at 45 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 3, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:10g, stir 0.5
Hour；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) add 2g aminated lignin, continuously stirred reaction 7 hours at 90 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 4, its preparation method is:
(1) bentonite having been crossed 100 mesh sieves is placed in baking oven, dries 10 hours, sealing preserve after drying at 105 DEG C,
Standby；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:8g, stirring 0.5 is little
When；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) add 0.1g aminated lignin, continuously stirred reaction 5 hours at 90 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 5, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:5g, stir 0.5
Hour；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) 0.5g lignin and 0.5g sodium humate are added, continuously stirred reaction 10 hours at 30 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 6, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:5g, stirring 0.5 is little
When；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) add 0.4g sodium humate, continuously stirred reaction 3 hours at 75 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 7, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:8g, stirring 0.5 is little
When；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) 0.25g lignin and 0.5g sodium humate are added, continuously stirred reaction 5 hours at 60 DEG C；
(5), after reaction terminates, it is cooled to 25 DEG C of room temperature, sucking filtration, being washed with deionized to ph value is 7.0, at 60 DEG C
It is dried 24 hours, grinds, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 8, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:5g, stir 0.5
Hour；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) 0.06g aminated lignin and 0.04g sodium humate are added, continuously stirred reaction 4 hours at 45 DEG C；
(5) after reaction terminates, it is cooled to room temperature, sucking filtration, being washed with deionized to ph value is 7.0, be dried at 60 DEG C
24 hours, grind, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 9, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:10g, stir 0.5
Hour；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) 0.3g aminated lignin and 0.2g sodium humate are added, continuously stirred reaction 6 hours at 60 DEG C；
(5) after reaction terminates, it is cooled to room temperature, sucking filtration, being washed with deionized to ph value is 7.0, be dried at 60 DEG C
24 hours, grind, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Embodiment 10, its preparation method is:
(1) bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours at 105 DEG C, sealing preserve after drying, standby
With；
(2) take the bentonite of above-mentioned 10g drying, add water and be made into the suspension that liquid-solid ratio is 100ml:2g, stirring 0.5 is little
When；
(3) 0.5g sodium carbonate, stirring reaction 2 hours at 70 DEG C are added in above-mentioned suspension；
(4) 0.6g aminated lignin and 0.4g sodium humate are added, continuously stirred reaction 2 hours at 75 DEG C；
(5) after reaction terminates, it is cooled to room temperature, sucking filtration, being washed with deionized to ph value is 7.0, be dried at 60 DEG C
24 hours, grind, cross 100 mesh sieves, obtain final product product passivator of the present invention.
Test example 1
Adsorb heavy metal amount of capacity in simulation heavy metal wastewater thereby to pass judgment on the passivation of modified product heavy metal with modified product
Ability.The suction of the organic-inorganic compoiste heavy metal soil passivator heavy metal ion that table 1 prepares for the inventive method
Attached ability.
The absorbability of table 1 passivator heavy metal ion of the present invention
As shown in Table 1, the passivating agent products that the inventive method obtains can significantly improve bentonite to cu2+、pb2+、zn2+、
cd2+Adsorbance, respectively by original 25.65mg/g, 81.60mg/g, 26.55mg/g, 20.13mg/g bring up to maximum
53.18mg/g, 146.52mg/g, 66.98mg/g, 37.65mg/g, be respectively increased 107.3%, 79.6%, 152.3%,
87.0%.Meanwhile, the present invention synthesizes passivator preparing raw material bentonite, lignin and sodium humate are all natural goodses
Matter, and abundance, cheap and easy to get, therefore, the passivator preparing is with low cost, to environment non-secondary pollution, can simultaneously
Improve bentonitic added value, there is good economy, environmental benefit.
Test example 2
With laboratory simulation Compound Heavy Metals soil as experimental subject, its heavy metal concentration be cadmium 201.23mg/g,
Lead 1020.59mg/g, zinc 2024.68mg/g, copper 1021.76mg/g.Weigh 50g natural air drying, the simulation weight of ground 1mm sieve
Metallic pollution pedotheque is placed in 250ml beaker, and the dosage of passivator of the present invention is soil quality 1%, 3%, 5%, plus
Entering a certain amount of distilled water makes soil moisture content be maintained at 30% about, stirs, respectively maintenance 15 days.After 15 days, take and repair
Soil after multiple, to determine the effect of passivator using the leaching method of soil ph value and hj/300-2007, and with unmodified swollen
Profit soil carries out contrast experiment.Result is as shown in table 2.
The passivation repair ability to Compound Heavy Metals soil for table 2 passivator of the present invention
As shown in Table 2, the organic-inorganic compoiste heavy-metal contaminated soil passivator pair being prepared by the inventive method
Compound Heavy Metals soil has splendid passivation repairing effect, can be effectively improved soil ph value, and its passivation repair ability shows
Write and be better than unmodified bentonite.With the increase of passivator dosage, simulate the cu before and after soil passivation is repaired2+、pb2+、zn2+、
cd2+Leaching concentration is gradually lowered, and soil ph value then gradually rises；Under the conditions of same passivator dosage, organic-inorganic compoiste
The cu of soil after passivator reparation2+、pb2+、zn2+、cd2+Leaching concentration is below unmodified bentonite.Wherein it is passivated in the present invention
When the dosage of agent is 5%, the cu of soil after reparation2+、pb2+、zn2+、cd2+Leaching concentration be reduced to 0mg/l, 0.16mg/l,
2.69mg/l, 1.88mg/l, reduce ratio and reach 100%, 99.82%, 98.28%, 83.81% respectively.
Claims (5)
1. organic-inorganic compoiste heavy-metal contaminated soil passivator preparation method it is characterised in that the method include following
Operating procedure:
The first step, the bentonite crossing 100 mesh sieves is placed in baking oven, dries 10 hours, sealing preserve after drying at 105 DEG C, standby
With,
Second step, weighs the bentonite of a certain amount of drying, adds water and is made into the suspension that liquid-solid ratio is 100ml:2-10g, stirring
0.5 hour,
3rd step, the addition sodium carbonate in above-mentioned suspension, stirring reaction 2 hours at 70 DEG C,
4th step, the appropriate modifying agent of addition, continuously stirred reaction 1-10 hour at 30-90 DEG C,
5th step, after reaction terminates, is cooled to room temperature, sucking filtration, being washed with deionized to ph value is 7.0, is dried at 60 DEG C
24 hours, grind, cross 100 mesh sieves, that is, obtain organic-inorganic compoiste heavy-metal contaminated soil passivator finished product.
2. the preparation method of organic-inorganic compoiste heavy-metal contaminated soil passivator according to claim 1, its feature exists
In: in the 3rd step, the sodium carbonate of addition and the bentonite dried are 0.05:1 in mass ratio.
3. the preparation method of organic-inorganic compoiste heavy-metal contaminated soil passivator according to claim 1, its feature exists
In: in the 4th step, the modifying agent of addition and the bentonite dried are 1-20:100 in mass ratio.
4. according to claim 1 or 3 organic-inorganic compoiste heavy-metal contaminated soil passivator preparation method, it is special
Levy and be: in the 4th step, described modifying agent is one of lignin, aminated lignin or sodium humate or more than one is mixed
Close.
5. the preparation method of organic-inorganic compoiste heavy-metal contaminated soil passivator according to claim 4, its feature exists
In: described lignin and aminated lignin are respectively derived from finished product and its amination product that pulping and paper-making waste liquid acid adding precipitation filters
Product.
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| CN110467922A (en) * | 2019-07-12 | 2019-11-19 | 广东工业大学 | A kind of soil passivation modifying agent and its preparation method and application containing industrial lignin |
| CN111992258A (en) * | 2020-09-04 | 2020-11-27 | 广西大学 | Method for treating heavy metal pollution in sulfide ore tailings |
| CN113575007A (en) * | 2021-07-21 | 2021-11-02 | 广东禹兴建设工程有限公司 | Farmland reclamation method |
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