CN108865149A - A kind of heavy metal-polluted soil stabilizer and preparation method thereof based on natural polymer - Google Patents
A kind of heavy metal-polluted soil stabilizer and preparation method thereof based on natural polymer Download PDFInfo
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- CN108865149A CN108865149A CN201810420023.6A CN201810420023A CN108865149A CN 108865149 A CN108865149 A CN 108865149A CN 201810420023 A CN201810420023 A CN 201810420023A CN 108865149 A CN108865149 A CN 108865149A
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- lignin
- heavy metal
- chitosan
- humic acid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention discloses a kind of heavy metal-polluted soil stabilizer and preparation method thereof based on natural polymer.The chitosan for being 70%~90% using deacetylation and be dissolved in pH more than or equal in 10 aqueous solutions humic acid and lignin as raw material, be crosslinked by glutaraldehyde substep and intermolecular latex interpenetrating polymerization is made, wherein the mass ratio of various amounts of components is chitosan：Humic acid：Lignin or lignosulfonates：Glutaraldehyde=1~6：1~3：0~6：0.5~1.0.The preparation method, easy to operate, safe operating environment, gained natural polymer heavy metal-polluted soil stabilizer are significantly improved in stable soil heavy metal aspect of performance.
Description
Technical field
The invention belongs to a kind of heavy metal-polluted soil stabilizer, an a kind of specifically soil huge sum of money based on natural polymer
Belong to PbAnd CdStabilizer and preparation method thereof.
Background technique
With the acceleration of industrialization and urbanization process, heavy metal pollution of soil environmental problem is especially prominent.Wherein, lead
(Pb) it is a kind of polyaffinity heavy metal, belong to persistent pollutant in the soil, mainly accumulated by crop kernels, passes through food
Object chain jeopardizes human health.PbOnce can cause brain tissue impairment into body by encroaching on cerebral nerve tissue, can cause to locate
In developmentally retarded children, the more dynamic, feeblemindedness etc. of growth and development stage.Compared to PbFor, the cadmium (C in soild) it is easier to leaching,
It is not only to cause the arch-criminal of public hazards " pain pain ", and the liver of human body, kidney organ's damage can also be caused.It is reported that China CdIt is dirty
About 1.3 ten thousand hm of dye arable land2, it is related to 25 areas of 11 provinces and cities；It containing the place of production that Pb is more than 1.0mg/kg has been more than 11 in grain
It is a, P in soilbContent is up to 1143mg/kg.Therefore, P in soil is scientificlly and effectively controlledbAnd CdRelease and transfer, have become
For the realistic problem urgently solved.
There are the certain growth periods for crops.By taking rice as an example, breeding time is generally 150~180d, and it is raw to be divided into nutrition
Long and two stages of reproductive growth.Some researches show that, crop mainly appears on metabolism active period to the absorption and transhipment of heavy metal,
The pustulation period of usual rice reproductive growth and heading stage outline are higher than the tillering stage of nutrient growth.As long as this purpose, by plant root
Heavy metal in soil environment is effectively stable in the progress of crop growth phase, can reduce heavy metal and is absorbed by crop root
Cauline leaf or seed accumulation, so that cutting off heavy metal is entered the approach for generating harm caused by human body to human health as food chain.
Summary of the invention
The preparation method of it is an object of that present invention to provide a kind of heavy metal-polluted soil stabilizer based on natural polymer, the party
Method is easy to operate, safe operating environment, and the heavy metal-polluted soil stabilizer of preparation shows good stabilization to Pb in soil and Cd
Effect, the characteristic that the raw material used also has improvement soil, even can promote plant growth.
Another object of the present invention is to provide the soil weights with " stablizing in limited time " characteristic using above method preparation
Metallic stabilizer is crosslinked and intermolecular interpenetrating net using chitosan and humic acid and lignin as raw material by glutaraldehyde substep
Network polymerization is made.
To achieve the goals above, the present invention provides a kind of preparation side based on natural polymer heavy metal-polluted soil stabilizer
Method includes the following steps：
(1) chitosan that deacetylation is 70%~90% is placed in 1vt%~3vt% acetum, chitosan exists
Mass concentration in acetum is 1wt%~3wt%, and 0.5~1.5h, mixing speed 80-100rpm make under stirring at room temperature
Chitosan is sufficiently swollen；
(2) humic acid and lignin or lignosulfonates are dissolved in water of the pH more than or equal to 10, are filtered to remove not
Molten object, wherein humic acid mass concentration is 0.5wt%~1.5wt%, lignin or lignosulfonates mass concentration are 0wt%
~3wt%；
Since humic acid and lignin or lignosulfonates are insoluble in acid or neutral water, alkaline water can only be dissolved in
In, therefore water dissolution humic acid and lignin or lignosulfonates using pH more than or equal to 10.
(3) by the chitosan solution through being sufficiently swollen in step (1), in the case where revolving speed is 80-100rpm stirring, water-bath is heated to
65 DEG C~85 DEG C, 20~30min of glutaraldehyde solution that mass concentration is 10vt% is added dropwise, then the corruption of a dropping step (2) preparation
Acid and lignin or lignin sulfonic acid 5~10min of saline solution are grown, then it is 10vt% glutaraldehyde solution that mass concentration, which is added dropwise, it is preceding
The 10vt% glutaraldehyde solution volume being added dropwise twice afterwards is equal, is stirred to react 4 under the conditions of being kept for 65 DEG C~85 DEG C after being added dropwise
Go out slurry after~8h；
First plus glutaraldehyde be first to chitosan carry out precrosslink formed gel skeleton, afterwards plus glutaraldehyde be by humic
Crosslinking is re-formed between acid, lignin and chitosan.
Since chitosan dissolves in acid condition (acetum), and (pH is more than or equal to lignin under alkaline condition
In 10 water) dissolution, and dissolution pH wider range of humic acid, the humic acid and lignin alkaline solution that the later period is added can cause
Reaction system pH is increased, and part chitosan will become gel, carries out the heterogeneous crosslinking in part with lignin, and partial solubility is rotten
Interpenetrating networks crosslinking will be occurred by growing acid molecule and chitosan and lignin.
(4) slurry prepared by step (3) is added to 1~2h of alcohol solution dipping of same volume 1vt%~3vt% acetic acid, mistake
Filter repetitive operation 3~4 times, is then washed with deionized to neutrality, filtering, then add standby slurry same volume unsaturated carbonate
Hydrogen sodium solution soaked overnight, filtering are washed with deionized to neutrality, dry to constant weight at 70-90 DEG C after filtering.
Wherein, chitosan, humic acid, lignin or lignosulfonates, glutaraldehyde mass ratio be：Chitosan：Humic
Acid：Lignin or lignosulfonates：Glutaraldehyde=1~6：1~3：0~6：0.5~1.0.
Preferably, the lignosulfonates are sodium lignin sulfonate.
The present invention also provides a kind of natural polymer heavy metal-polluted soil stabilizers prepared using the above method.
Heavy metal-polluted soil stabilizer provided by the invention based on natural polymer, first with glutaraldehyde to deacetylation
Tentatively be crosslinked for 70%~90% chitosan, then continue to be crosslinked with humic acid and lignin, by intermolecular cross-linking and
Interpenetrating networks method obtains a kind of polymer based on natural polymer.
Chitosan is the product after the chitin deacetylation in shrimp, crab and insect shell, not only has good give birth to
Object degradability, moreover it is possible to promote plant growth, because being rich in active amino and hydroxyl in structure, stronger absorption is shown to heavy metal
Performance, while chitosan also possesses certain antagonistic property.
The present invention selects chitosan of the deacetylation 70%~90%, is the chitosan due to deacetylation less than 70%
Middle active group amino content is less, and glutaraldehyde cross-linking is difficult, the chitosan greater than 90%, amino content mistake in molecular structure
Height can generate serious self-crosslinking phenomenon, influence the cross-linking machine meeting of chitosan and glutaraldehyde and humic acid and lignin.
Main component of the humic acid as the soil organism has loose " cavernous body " structure and carboxyl, phenolic hydroxyl group, aldehyde
A variety of functional groups such as base mostly use as fertilizer and soil conditioner.
Lignin is a kind of poly phenols macromolecule being widely present in plant cell wall, and content is only second to fiber
Element accounts for about the 20% of plant total amount.Alkali lignin is the Main By product with timber, bamboo, grass etc. for paper making raw material, because of its structure
In containing a large amount of methoxyl groups, hydroxyl and carbonyl etc. can with the functional group in conjunction with heavy metal, and abundance, heavy metal adsorption,
Stablize the great Development volue of aspect.
It is provided by the invention a kind of based on natural polymer heavy metal-polluted soil stabilizer, with deacetylation 70%~90%
Chitosan and be dissolved in pH more than or equal in 10 water humic acid and lignin be that basic material carries out cross-linked polymeric, it is on the one hand logical
Multiple active adsorption sites and space structure are crossed to realize while all have higher stabilizing power to various heavy, is mainly used
Pb and Cd heavy metal in stable soil；Another party can keep macromolecule steady using the antagonistic property of cross-linking reaction and chitosan
The stabilization time of agent in the soil is determined, to prevent in a short time by the various microbial degradations in soil.
The natural polymer heavy metal-polluted soil stabilizer that this preparation method obtains, due to introducing the heavy metal of different structure
Active adsorption sites simultaneously have certain space network structure, while showing preferable stablize to various heavy in soil and imitating
Fruit, especially to P in soilbAnd CdStabilization efficiency improve nearly 1 times, and stablize the time and improve nearly 5 times.In addition, the soil of preparation
Earth heavy metal stabilizer not only will not bring secondary pollution to environment after environment degradable, can also become soil and fertilizer or plant
Object positive growth factor.
The natural polymer heavy metal-polluted soil stabilizer preparation method provided in the present invention, easy to operate, operating environment peace
Entirely, gained natural polymers are obviously improved in terms of heavy metal-polluted soil stability.
Detailed description of the invention
Figure 1A is the electron-microscope scanning figure (× 10.00K) of humic acid.
Figure 1B is the electron-microscope scanning figure (× 10.00K) of chitosan.
Fig. 1 C is the electron-microscope scanning figure (× 10.00K) of lignin.
Fig. 1 D be the heavy metal-polluted soil stabilizer prepared by the present invention based on natural polymer electron-microscope scanning figure (×
10.00K)。
Fig. 2 is that humic acid, chitosan, lignin and the heavy metal-polluted soil prepared by the present invention based on natural polymer are stablized
The infrared spectrogram of agent.
Specific embodiment
Embodiment 1
1.0g humic acid is added to the water, with 1wt%NaOH aqueous solution tune pH to 11.5, stirring and dissolving makes humic acid
Concentration is 1wt%；Continue that 2.0g lignin stirring and dissolving is added into humic acid solution, makes the concentration 1wt% of lignin, mistake
It is spare after filter.
The chitosan oligomer that 2.0g deacetylation is 80% is dissolved in 4vt% acetum, the concentration of chitosan is made
It for 2wt%, is placed in the three-neck flask equipped with blender and is uniformly mixed, stir 80rpm, be swollen 1.0h.Heating water bath to 80 DEG C,
Stirring is lower to be added dropwise 10vt% glutaraldehyde solution 7.5ml, and the humic acid and lignin liquor of preparation is added dropwise, after being added dropwise to complete 10min,
10vt% glutaraldehyde solution 7.5ml is added dropwise again, constant temperature stirring is lower at 80 DEG C reacts 5h.
Reaction paste filtering is taken out, trapped substance 1.53vt% acetum is impregnated, stirred and washed 3~4 times；Repeatedly
It is cleaned with deionized water to neutrality, filtering；Again with the saturated sodium bicarbonate solution soaked overnight for preparing slurry same volume, filtering
It is cleaned repeatedly with deionized water to neutrality afterwards, filtering is dried to constant weight under the conditions of 90 DEG C, obtains the soil based on natural polymer
Earth heavy metal stabilizer.
The chemical property of the measurement heavy metal-polluted soil stabilizer of embodiment 2
1, apparent structure
The heavy metal-polluted soil stabilizer based on natural polymer of humic acid, chitosan, lignin and preparation is carried out
Electron-microscope scanning, figure are shown in Figure 1A to Fig. 1 D.
The humic acid rough surface it can be seen from Figure 1A, it is loosely organized；It can be seen from Figure 1B and Fig. 1 C chitosan and
Lignin structure is finer and close, is in gel.It can be seen from Fig. 1 D compared with humic acid, the heavy metal-polluted soil of preparation is stablized
Agent structure is relatively uniform, integrality is good；And compared with chitosan and lignin, structure is obviously loose, and there are mesh-structured rich
Richness, specific area is big, and the adsorption capacity of heavy metal is big.
2, infrared spectroscopy structural characterization
Humic acid, chitosan, lignin and the heavy metal-polluted soil stabilizer prepared by the present invention based on natural polymer
Infrared spectrogram is as shown in Figure 2, it can be seen that：
3500~3300cm-1For the stretching vibration absworption peak of carboxyl, phenolic hydroxyl group and alcoholic extract hydroxyl group, amino, 1600cm-1For benzene
The characteristic peak of ring C=C, 2874cm-1For methylene C-H characteristic peak, 1367cm-1For-COOH characteristic peak, 1075cm-1For C-OH spy
Levy peak, 1645cm-1And 1599cm-1It is amino-N-H characteristic peak.Lignin, chitosan and humic acid it can be seen from Fig. 2
In addition to aromatic group, contain a large amount of carboxyl, hydroxyl or amino isopolarity group.
By the stabilizer obtained after glutaraldehyde cross-linking, compared with humic acid and lignin, in 1015cm-1The C-O at place is bright
It is aobvious to increase, and 3500~3300cm-1And 1075cm-1The C-OH characteristic peak at place becomes smaller.Illustrate glutaraldehyde and humic acid and lignin
In-OH react, generate C-O-C.Compared with chitosan, stabilizer is in 1599cm-1Amino-N-H the characteristic peak at place disappears
It loses, and in 1630cm-1The characteristic peak of left and right broadens, and illustrates that glutaraldehyde is reacted with amino in chitosan, produces certain
The C=N of amount, since limited amount is covered by C-N characteristic peak.As it can be seen that glutaraldehyde passes through lignin, chitosan and humic acid
Crosslinking and interpenetrating networks form polymer.
3, heavy metal-polluted soil stability is tested
For trying soil：It is derived from institute's garden with hundreds of grasses, after natural air drying, crosses 80 meshes.Repeatedly 0.3g/ is shone in spray in for examination soil
L plumbi nitras and nitric acid make the content of Pb and Cd in soil be each about 100mg/kg every solution, and after mixing plus water soaks, and make
Water content is 10%, and sealing, aging 15d, spare at 25~30 DEG C.
Stablize experiment：Added respectively in for examination soil chitosan, humic acid, lignin and preparation based on natural polymer
The heavy metal-polluted soil stabilizer of son, makes into 1.0g/kg, is uniformly mixed, and stablizes under the conditions of keeping moisture state, room temperature to be protected from light, one
Soil sampling 10g after fixing time is carried out, leaching toxicity test according to TCLP, using inductively coupled plasma spectrum generator
(Thermo iCAP 6300, ICP) measures the content of Pb and Cd in leachate, calculates its stabilization efficiency η (%).
C in formula0And CsRespectively plus before and after stabilizer, for the concentration of Pb and Cd in examination soil extract.
Stabilization efficiency of the different stabilizers to Pb in soil and Cd after 30d and 180dWithIt is shown in Table 1.
In table 1 statistics indicate that, chitosan, humic acid and the crosslinked soil weight being prepared into based on natural polymer of lignin
After metallic stabilizer, the stabilization efficiency of Pb and Cd in soil are remarkably reinforced, and under field conditions (factors), stability keeps good
It is good.
Table 1
Wherein growth cycle of the 180d substantially near a crop.
It should be noted that the present invention is instead of by the permanent stabilization of heavy metal in soil, in crop growth period
It is stable to the heavy metal on crop root periphery, be not absorbed by crops.In the crop maturity later period, stabilizer of the invention will gradually by
It is degraded into fertilizer and promotes plant growth.Heavy metal in crop body is limited in root system or stalk in this way, prevents heavy metal from entering
The seed of crop, to avoid the harm to eater.
From above-described embodiment as can be seen that heavy metal-polluted soil stabilizer provided by the invention based on natural polymer and its
Preparation method can pass through the effects of complexing, hydrogen bond for the heavy metal P in soil under field conditions (factors)bAnd CdStablize 3~5 months,
To limit crop in growth period to PbAnd CdAbsorption.Degradation with natural environment to heavy metal stabilizer later, in composition
Chitosan, humic acid, lignin or lignosulfonates or its residuum be dispersed in soil, can give full play to its promote plant
Object growth, improvement soil function.
Claims (4)
1. a kind of preparation method of the heavy metal-polluted soil stabilizer based on natural polymer, it is characterised in that：Include the following steps：
(1) chitosan that deacetylation is 70%~90% is placed in 1vt%~3vt% acetum, chitosan is in acetic acid
Mass concentration in solution is 1wt%~3wt%, under stirring at room temperature 0.5~1.5h, mixing speed 80-100rpm, keeps shell poly-
Sugared sufficiently swelling；
(2) humic acid and lignin or lignosulfonates are dissolved in water of the pH more than or equal to 10, are filtered to remove not molten object,
Wherein humic acid mass concentration be 0.5wt%~1.5wt%, lignin or lignosulfonates mass concentration be 0wt%~
3wt%；
(3) by the chitosan solution through being sufficiently swollen in step (1), in the case where revolving speed is 80-100rpm stirring, water-bath is heated to 65 DEG C
~85 DEG C, 20~30min of glutaraldehyde solution that mass concentration is 10vt% is added dropwise, then the humic acid of a dropping step (2) preparation
With lignin or lignin sulfonic acid 5~10min of saline solution, then be added dropwise mass concentration be 10vt% glutaraldehyde solution, front and back two
The 10vt% glutaraldehyde solution volume of secondary dropwise addition is equal, is stirred to react 4~8h under the conditions of being kept for 65 DEG C~85 DEG C after being added dropwise
Go out slurry afterwards；
(4) 1~2h of alcohol solution dipping that slurry prepared by step (3) is added to same volume 1vt%~3vt% acetic acid, is filtered, weight
It operates 3~4 times, is then washed with deionized to neutrality again, filtering, then to add standby slurry same volume saturated sodium bicarbonate molten
Liquid soaked overnight, filtering are washed with deionized to neutrality, dry to constant weight at 70-90 DEG C after filtering.
2. the preparation method of heavy metal-polluted soil stabilizer as described in claim 1, which is characterized in that chitosan, humic acid, wood
The mass ratio of quality or lignosulfonates, glutaraldehyde is：Chitosan：Humic acid：Lignin or lignosulfonates：Glutaraldehyde
=1~6：1~3：0~6：0.5~1.0.
3. the preparation method of heavy metal-polluted soil stabilizer as claimed in claim 1 or 2, which is characterized in that the sulfomethylated lignin
Hydrochlorate is sodium lignin sulfonate.
4. a kind of heavy metal-polluted soil stabilizer prepared using method as described in any one of claims 1 to 3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662727A (en) * | 2020-07-17 | 2020-09-15 | 北京市环境保护科学研究院 | Improver for soil polluted by primary explosive |
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| CN105315084A (en) * | 2015-11-27 | 2016-02-10 | 安徽帝元生物科技有限公司 | Synergistic environment-friendly fertilizer aid and fertilizer |
| CN105733596A (en) * | 2016-03-21 | 2016-07-06 | 中国科学院烟台海岸带研究所 | Soil conditioner for passivation of heavy metals and preparation method of soil conditioner |
-
2018
- 2018-05-04 CN CN201810420023.6A patent/CN108865149B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315084A (en) * | 2015-11-27 | 2016-02-10 | 安徽帝元生物科技有限公司 | Synergistic environment-friendly fertilizer aid and fertilizer |
| CN105733596A (en) * | 2016-03-21 | 2016-07-06 | 中国科学院烟台海岸带研究所 | Soil conditioner for passivation of heavy metals and preparation method of soil conditioner |
Non-Patent Citations (1)
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| 魏云霞等: "壳聚糖交联不溶性腐殖酸吸附剂的制备及其吸附性能", 《离子交换与吸附》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662727A (en) * | 2020-07-17 | 2020-09-15 | 北京市环境保护科学研究院 | Improver for soil polluted by primary explosive |
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