CN109940032A - A kind of restorative procedure of organic pollutant-heavy-metal composite pollution soil - Google Patents
A kind of restorative procedure of organic pollutant-heavy-metal composite pollution soil Download PDFInfo
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Abstract
The present invention relates to technical field of soil remediation, more particularly to a kind of organic pollutant-heavy-metal composite pollution soil restorative procedure, include the following steps: that modification of chitosan is added in organic pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over, it is uniformly mixed modification of chitosan with soil, add water, irrigate soil, then Active gangue powder is applied again, Active gangue powder is uniformly mixed with soil, realizes the effective reparation of organic pollutant-heavy-metal composite pollution soil.The present invention can heavy metal in the organic pollutant and passivation soil effectively in pollution degradation soil, to achieve the purpose that rehabilitating soil, and repairing efficiency is short.
Description
Technical field
The present invention relates to technical field of soil remediation more particularly to a kind of organic pollutant-heavy-metal composite pollution soil
Restorative procedure.
Background technique
Soil refers to the loose surface layer that land surface has fertility, is capable of growing plant, and thickness is generally in 2m or so, soil
Earth not only provides mechanical support ability for plant growth, and required water, fertilizer, air and heat etc. can be provided for plant growth and development
The basis of fertility element and mankind's activity.But with the fast development of social economy and industry, solid waste is constantly to soil
Earth surface is stacked and is toppled over, and harmful waste water is constantly permeated into soil, and the pernicious gas and floating dust object in atmosphere are also constantly with rain
Water lands in the soil, results in soil pollution, and soil pollution is also increasingly severe.
Existing soil pollution is broadly divided into inorganic pollution and organic pollutant two major classes.Inorganic pollution includes
The pollution of the substances such as acid, alkali, heavy metal；Organic pollutant mainly includes the dirt of the substances such as organic agricultural chemicals, phenols, multiring aromatic hydrocarbon
Dye.And in soil pollutant, heavy metal pollution and it is polycyclic aromatic hydrocarbons contaminated be more typical two pollutant, especially with a huge sum of money
Belong to chromium and organic pollutant benzo pyrene it is most commonly seen, therefore, how degradable organic pollutant and it is heavy metal-passivated become Polluted Soil
The major subjects of earth reparation.
In view of the above-mentioned problems, the present inventor retrieves the prior art, in China Patent Publication No.
A kind of method for repairing heavy metal and organic pollutant in agricultural soil is disclosed in CN108672485A, is by biological carbon feedstock
The natural air drying after washing removes surface adhesion substance；After biomass after air-drying is crushed, it is pyrolyzed in pyrolysis oven；It will
Charcoal after pyrolysis wraps up molding with the plasticity net woven fabric with aperture, charcoal active filler is made, fills to be repaired
In soil；Percarbonate is soluble in water, it is configured to percarbonate leachate, periodically soil to be repaired is eluted.It should
Scheme is the heavy metal adsorbed in soil by charcoal, by the organic pollutant in carbonate degradation soil, is finally reached
Remove the purpose of heavy metal in soil and organic pollutant.But the charcoal is inhaled by pyrogenous origin charcoal active filler
Attached ability is limited, and can only adsorb to the heavy metal of soil, cannot achieve to Adsorption of Organic processing, and carbonate
It is that ground is imposed on by spray pattern, will appear a large amount of recoveries during to soil permeability in carbonate, influence carbonate and repair
The ability of earth backing earth, meanwhile, which is the organic pollutant handled in soil soil by mode of oxidizing, and needs chalybeate
The activation processing of matter could have the oxidability added, and there are organic pollutant process ability finiteness problems.
And a kind of soil-repairing agent is disclosed in China Patent Publication No. CN107641513A, component and component quality
Portion rate are as follows: Bronyl acetate 5-7；Diazolones 12-14；1,4- lupetazin 7-9；Asiaticosid 10-15；2- pyridinemethanol
4-6；Ammonium citrate 6-8；Fatty alcohol polyoxyethylene ether 10-16；Polyoxypropylene diol 10-15；4- aminoisoquinoline 0.5-
2；Polycarboxylate 1-2.5；Sodium Polyacrylate 4-12；Sodium chlorite 6-10；Sodium Trideceth 15-22；Deionization
Water 80-100.Soil-repairing agent in the program can renovation of organic pollution can will remove the heavy metal ion in soil simultaneously, but
It is that the soil-repairing agent contains excessive organic matter, there are problems that contaminated soil.
Based on this, a kind of organic pollutant-heavy-metal composite pollution soil is made by a large number of experiments and research in the present inventor
The restorative procedure of earth, to solve problems of the prior art.
Summary of the invention
In view of the above-mentioned analysis to the prior art, the present invention provides a kind of organic pollutant-heavy-metal composite pollution soil
Restorative procedure, can heavy metal in the organic pollutant and passivation soil effectively in pollution degradation soil, to reach reparation
The purpose of soil, and repairing efficiency is short.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of restorative procedure of organic pollutant-heavy-metal composite pollution soil, includes the following steps: in organic contamination
Modification of chitosan is added in object-heavy-metal composite pollution soil, and contaminated soil is turned over, makes modification of chitosan and soil
It is uniformly mixed, adds water, irrigate soil, then apply Active gangue powder again, Active gangue powder is mixed with soil
It is even, realize the effective reparation of organic pollutant-heavy-metal composite pollution soil.
It is more preferred, specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, is turned over daily once,
Controlling the soil moisture is 15-25 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils mixes Active gangue powder with soil
It is even, and add water to and flood soil；
(4) watering daily, is turned over once, and control 10-15 DEG C of the soil moisture daily during.
More preferred, the additional amount of the modification of chitosan is the 1.5%-4.5% of contaminated soil dry weight.
More preferred, the additional amount of the Active gangue powder is the 1%-4% of contaminated soil dry weight.
More preferred, the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is complete to chitosan again
Fully dissolved obtains chitosan solution；
(2) chitosan solution is placed in deaeration 0.5-1h under the conditions of vacuum degree 0.07-0.09MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and at 40-50 DEG C
Lower evaporation 1-2h, takes off naturally to film and falls, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases,
The distance between chitosan film and electrode be 5-10mm, processing power 50-70W, discharge frequency 10kHz, processing the time be
8-12min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor taken out true
After the logical nitrogen of sky, 5-8h, hunting speed 90-110rpm, by reactor in temperature are vibrated in 35-40 DEG C of air surge bath
It is ultrasound 30-40min at 5-10 DEG C, when solution is clarified in reactor, stops ultrasound, adjusts solution with sodium hydroxide solution
PH is 4.0-5.0, and alcohol reflux 1-2h is added and obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate simultaneously
Solvent, drying are removed, modification of chitosan is obtained.
More preferred, the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and the bonding with 0.5 times of its quality is added
Agent is simultaneously sufficiently mixed, and is then added and is mixed, mediates with 2.5 times of its quality of deionized water, then obtains through cuber compound stalk forming
Briquetting material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify
After 1.5h, 550 DEG C of charing 2h are directly warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K2CO3 solution that concentration is 5mol/L is added,
It is warming up to 350-450 DEG C, is stirred to react 5h, is then obtained by obtaining activated material crystallization after filtering and washing after layering kettle layering
To activated material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80
DEG C activation 5h, be finally warming up to 90 DEG C of activations processing 10h, being washed out dry, pulverize, mistake 200 meshes to get modified gangue
Powder.
More preferred, the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is one of Cu, Pb and Cd
Or at least two.
More preferred, the polycyclic aromatic hydrocarbon is benzo (a) pyrene.
Compared with prior art, the present invention have it is following the utility model has the advantages that
The present invention first carries out scarifying to soil before to soil remediation, can make modification of chitosan and Active gangue powder with
Soil mixes more uniform, and chitosan is added can form tridimensional network after modification, has stronger absorption
Ability can adsorb organic contaminants in soil and heavy metal, and by organic matter heavy metal adsorption in tridimensional network
In, soil remediation is acted on to realize, meanwhile, modified chitosan chemical activity enhancing, degrading organic pollutant, separately
Outside, modification of chitosan internal defect, is manured into soil, and can improve loosing soil state, enhances soil permeability permeability, improves
Soil remediation effect, and modification of chitosan is environment friendly and pollution-free；
And the Active gangue powder being added passes through charing and activation process step, so that jet mountain flour has preferable ion
Exchange capacity and organic-philic ability can effectively adsorb the heavy metal ion in soil, and since its parent having has
Machine performance can be adsorbed again in soil in remaining organic contamination, to reduce organic contaminants in soil and heavy metal contains
Amount, and then realize the purpose of rehabilitating soil；
The present invention passes through the mutual cooperation of modification of chitosan and Active gangue powder, first passes through modification of chitosan and realizes tentatively
Repairing effect, and the special tridimensional network of modification of chitosan can create preferable absorption ring for Active gangue powder
Border, improves the adsorption capacity of Active gangue powder, to reach preferable soil remediation effect；
In addition, the present invention can make modification of chitosan and active coal by the moisture content of control soil and the temperature of soil
Spoil powder has preferable activity, to improve the effect for improving soil remediation.
Specific embodiment
Form by the following examples is described in further detail above content of the invention again, but should not be by this
The range for being interpreted as the above-mentioned theme of the present invention is only limitted to following embodiment, all technologies based on realization belonging to above content of the present invention
It all belongs to the scope of the present invention.
Embodiment 1
The organic pollutant of the present embodiment-heavy-metal composite pollution soil restorative procedure, includes the following steps: organic
The modification of chitosan for accounting for soil dry weight 1.5% is added in pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil, adds water, irrigate soil, the active coal for the dry weight 1% that is then manured into soil again
Active gangue powder is uniformly mixed by spoil powder with soil, realizes that organic pollutant-heavy-metal composite pollution soil is effectively repaired
It is multiple.
Wherein, specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, is turned over daily once,
Controlling the soil moisture is 15 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils mixes Active gangue powder with soil
It is even, and add water to and flood soil；
(4) watering daily, is turned over once, and control 10 DEG C of the soil moisture daily during.
Wherein, the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is complete to chitosan again
Fully dissolved obtains chitosan solution；
(2) chitosan solution is placed in deaeration 0.5h under the conditions of vacuum degree 0.07MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and steamed at 40 DEG C
1h is sent out, takes off and falls naturally to film, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases,
The distance between chitosan film and electrode are 5mm, processing power 50W, discharge frequency 10kHz, and the processing time is 8min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor taken out true
After the logical nitrogen of sky, 5h, hunting speed 90rpm are vibrated in 35 DEG C of air surges bath, in temperature is 5-10 DEG C by reactor
Lower ultrasound 30-40min stops ultrasound when solution is clarified in reactor, is 4.0 with the pH that sodium hydroxide solution adjusts solution,
Alcohol reflux 1h is added and obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate simultaneously
Solvent, drying are removed, modification of chitosan is obtained.
Wherein, the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and the bonding with 0.5 times of its quality is added
Agent is simultaneously sufficiently mixed, and is then added and is mixed, mediates with 2.5 times of its quality of deionized water, then obtains through cuber compound stalk forming
Briquetting material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify
After 1.5h, 550 DEG C of charing 2h are directly warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K that concentration is 5mol/L is added2CO3Solution,
350 DEG C are warming up to, 5h is stirred to react, is then lived by obtaining activated material crystallization after filtering and washing after layering kettle layering
Material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80
DEG C activation 5h, be finally warming up to 90 DEG C of activations processing 10h, being washed out dry, pulverize, mistake 200 meshes to get modified gangue
Powder.
Wherein, the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is for one of Cu, Pb and Cd or at least
Two kinds.
Wherein, the polycyclic aromatic hydrocarbon is benzo (a) pyrene.
Embodiment 2
The organic pollutant of the present embodiment-heavy-metal composite pollution soil restorative procedure, includes the following steps: organic
The modification of chitosan for accounting for soil dry weight 4.5% is added in pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil, adds water, irrigate soil, the active coal for the dry weight 4% that is then manured into soil again
Active gangue powder is uniformly mixed by spoil powder with soil, realizes that organic pollutant-heavy-metal composite pollution soil is effectively repaired
It is multiple.
Wherein, specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, is turned over daily once,
Controlling the soil moisture is 25 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils mixes Active gangue powder with soil
It is even, and add water to and flood soil；
(4) watering daily, is turned over once, and control 15 DEG C of the soil moisture daily during.
Wherein, the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is complete to chitosan again
Fully dissolved obtains chitosan solution；
(2) chitosan solution is placed in deaeration 1h under the conditions of vacuum degree 0.09MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and steamed at 50 DEG C
2h is sent out, takes off and falls naturally to film, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases,
The distance between chitosan film and electrode are 10mm, processing power 70W, discharge frequency 10kHz, and the processing time is 12min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor taken out true
After the logical nitrogen of sky, 8h, hunting speed 110rpm are vibrated in 40 DEG C of air surge bath, by reactor in the case where temperature is 10 DEG C
Ultrasonic 40min stops ultrasound when solution is clarified in reactor, is 5.0 with the pH that sodium hydroxide solution adjusts solution, is added
Alcohol reflux 2h obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate simultaneously
Solvent, drying are removed, modification of chitosan is obtained.
Wherein, the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and the bonding with 0.5 times of its quality is added
Agent is simultaneously sufficiently mixed, and is then added and is mixed, mediates with 2.5 times of its quality of deionized water, then obtains through cuber compound stalk forming
Briquetting material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify
After 1.5h, 550 DEG C of charing 2h are directly warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K2CO3 solution that concentration is 5mol/L is added,
450 DEG C are warming up to, 5h is stirred to react, is then lived by obtaining activated material crystallization after filtering and washing after layering kettle layering
Material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80
DEG C activation 5h, be finally warming up to 90 DEG C of activations processing 10h, being washed out dry, pulverize, mistake 200 meshes to get modified gangue
Powder.
Wherein, the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is for one of Cu, Pb and Cd or at least
Two kinds.
Wherein, the polycyclic aromatic hydrocarbon is benzo (a) pyrene.
Embodiment 3
The organic pollutant of the present embodiment-heavy-metal composite pollution soil restorative procedure, includes the following steps: organic
The modification of chitosan for accounting for soil dry weight 3.0% is added in pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil, adds water, irrigate soil, the activity for the dry weight 2.5% that is then manured into soil again
Active gangue powder is uniformly mixed by coal gangue powder with soil, realizes that organic pollutant-heavy-metal composite pollution soil is effective
It repairs.
Wherein, specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, is turned over daily once,
Controlling the soil moisture is 20 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils mixes Active gangue powder with soil
It is even, and add water to and flood soil；
(4) watering daily, is turned over once, and control 13 DEG C of the soil moisture daily during.
Wherein, the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is complete to chitosan again
Fully dissolved obtains chitosan solution；
(2) chitosan solution is placed in deaeration 0.7h under the conditions of vacuum degree 0.08MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and steamed at 45 DEG C
1.5h is sent out, takes off and falls naturally to film, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases,
The distance between chitosan film and electrode are 7mm, processing power 60W, discharge frequency 10kHz, and the processing time is 10min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor taken out true
After the logical nitrogen of sky, 6.5h, hunting speed 100rpm are vibrated in 38 DEG C of air surges bath, in temperature is 7.5 by reactor
Ultrasound 35min at DEG C stops ultrasound when solution is clarified in reactor, is 4.5 with the pH that sodium hydroxide solution adjusts solution,
Alcohol reflux 1.5h is added and obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate simultaneously
Solvent, drying are removed, modification of chitosan is obtained.
Wherein, the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and the bonding with 0.5 times of its quality is added
Agent is simultaneously sufficiently mixed, and is then added and is mixed, mediates with 2.5 times of its quality of deionized water, then obtains through cuber compound stalk forming
Briquetting material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify
After 1.5h, 550 DEG C of charing 2h are directly warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K2CO3 solution that concentration is 5mol/L is added,
400 DEG C are warming up to, 5h is stirred to react, is then lived by obtaining activated material crystallization after filtering and washing after layering kettle layering
Material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80
DEG C activation 5h, be finally warming up to 90 DEG C of activations processing 10h, being washed out dry, pulverize, mistake 200 meshes to get modified gangue
Powder.
Wherein, the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is for one of Cu, Pb and Cd or at least
Two kinds.
Wherein, the polycyclic aromatic hydrocarbon is benzo (a) pyrene.
Embodiment 4
The organic pollutant of the present embodiment-heavy-metal composite pollution soil restorative procedure, includes the following steps: organic
The modification of chitosan for accounting for soil dry weight 2.0% is added in pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil, adds water, irrigate soil, the active coal for the dry weight 2% that is then manured into soil again
Active gangue powder is uniformly mixed by spoil powder with soil, realizes that organic pollutant-heavy-metal composite pollution soil is effectively repaired
It is multiple.
Wherein, specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, is turned over daily once,
Controlling the soil moisture is 18 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils mixes Active gangue powder with soil
It is even, and add water to and flood soil；
(4) watering daily, is turned over once, and control 12 DEG C of the soil moisture daily during.
Wherein, the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is complete to chitosan again
Fully dissolved obtains chitosan solution；
(2) chitosan solution is placed in deaeration 0.6h under the conditions of vacuum degree 0.07MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and steamed at 43 DEG C
1.3h is sent out, takes off and falls naturally to film, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases,
The distance between chitosan film and electrode are 6mm, processing power 55W, discharge frequency 10kHz, and the processing time is 9min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor taken out true
After the logical nitrogen of sky, 6h, hunting speed 95rpm are vibrated in 36 DEG C of air surge bath, is surpassed at being 6 DEG C in temperature by reactor
Sound 33min stops ultrasound when solution is clarified in reactor, is 4.3 with the pH that sodium hydroxide solution adjusts solution, second is added
Alcohol reflux 1.3h obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate simultaneously
Solvent, drying are removed, modification of chitosan is obtained.
Wherein, the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and the bonding with 0.5 times of its quality is added
Agent is simultaneously sufficiently mixed, and is then added and is mixed, mediates with 2.5 times of its quality of deionized water, then obtains through cuber compound stalk forming
Briquetting material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify
After 1.5h, 550 DEG C of charing 2h are directly warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K2CO3 solution that concentration is 5mol/L is added,
380 DEG C are warming up to, 5h is stirred to react, is then lived by obtaining activated material crystallization after filtering and washing after layering kettle layering
Material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80
DEG C activation 5h, be finally warming up to 90 DEG C of activations processing 10h, being washed out dry, pulverize, mistake 200 meshes to get modified gangue
Powder.
Wherein, the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is for one of Cu, Pb and Cd or at least
Two kinds.
Wherein, the polycyclic aromatic hydrocarbon is benzo (a) pyrene.
Embodiment 5
The organic pollutant of the present embodiment-heavy-metal composite pollution soil restorative procedure, includes the following steps: organic
The modification of chitosan for accounting for soil dry weight 4.0% is added in pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil, adds water, irrigate soil, the active coal for the dry weight 3% that is then manured into soil again
Active gangue powder is uniformly mixed by spoil powder with soil, realizes that organic pollutant-heavy-metal composite pollution soil is effectively repaired
It is multiple.
Wherein, specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over
It ploughs, is uniformly mixed modification of chitosan with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, is turned over daily once,
Controlling the soil moisture is 22 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils mixes Active gangue powder with soil
It is even, and add water to and flood soil；
(4) watering daily, is turned over once, and control 14 DEG C of the soil moisture daily during.
Wherein, the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is complete to chitosan again
Fully dissolved obtains chitosan solution；
(2) chitosan solution is placed in deaeration 0.9h under the conditions of vacuum degree 0.09MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and at 40-50 DEG C
Lower evaporation 1-2h, takes off naturally to film and falls, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases,
The distance between chitosan film and electrode are 9mm, processing power 65W, discharge frequency 10kHz, and the processing time is 11min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor taken out true
After the logical nitrogen of sky, 7h, hunting speed 105rpm are vibrated in 38 DEG C of air surge bath, by reactor in the case where temperature is 9 DEG C
Ultrasonic 38min stops ultrasound when solution is clarified in reactor, is 4.8 with the pH that sodium hydroxide solution adjusts solution, is added
Alcohol reflux 1.8h obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate simultaneously
Solvent, drying are removed, modification of chitosan is obtained.
Wherein, the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and the bonding with 0.5 times of its quality is added
Agent is simultaneously sufficiently mixed, and is then added and is mixed, mediates with 2.5 times of its quality of deionized water, then obtains through cuber compound stalk forming
Briquetting material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify
After 1.5h, 550 DEG C of charing 2h are directly warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K2CO3 solution that concentration is 5mol/L is added,
420 DEG C are warming up to, 5h is stirred to react, is then lived by obtaining activated material crystallization after filtering and washing after layering kettle layering
Material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80
DEG C activation 5h, be finally warming up to 90 DEG C of activations processing 10h, being washed out dry, pulverize, mistake 200 meshes to get modified gangue
Powder.
Wherein, the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is for one of Cu, Pb and Cd or at least
Two kinds.
Wherein, the polycyclic aromatic hydrocarbon is benzo (a) pyrene.
Comparative example 1
The reparation of soil is carried out using the method for China Patent Publication No. CN108672485A.
Comparative example 2
In addition to changing modification of chitosan into common chitosan, other steps and method and embodiment 1 are unanimously.
Comparative example 3
In addition to changing Active gangue powder into common coal gangue powder, other steps and method and embodiment 1 are unanimously.
Test example
Test soil preparation.
The aqueous solution of the water soluble compound of Cd metal and the aqueous solution of benzo (a) pyrene are added in common vegetable garden soil, are pressed
Heavy metal element Hg, As, Pb, Cd content in soil is " requirement of agricultural product quality and safety pollution-free vegetable home environment " (GB/
T18407.1-2001) 5 times or so of corresponding standard Limited Doses.With the aqueous solution of heavy metal compound and benzo (a) pyrene
After aqueous solution and vegetable garden soil mix well, the content and benzo (a) pyrene content for carrying out detection Cd after a week, specific detection knot are placed
Fruit such as table 1.
The concentration of soil available cadmium and benzo (a) pyrene before table 1 is handled
| Pollutant | Concentration (mg/kg) |
| Available state Cd | 18 |
| Benzo (a) pyrene | 3.2 |
The restorative procedure of embodiment 1-5 and comparative example 1-3 is respectively adopted to contaminated vegetable garden soil reparation, and after reparation
The content of available state Cd in soil and the content of benzo (a) pyrene are tested, and concrete outcome is shown in Table 2.
Table 2
From the data in above-mentioned table 2 can be seen that the Cd after being repaired using method of the invention to contaminated soil and
The repairing effect of benzo (a) pyrene is good, and the residual rate of Cd is lower in soil, obvious to the degradation effect of benzo (a) pyrene, illustrates to be modified
Chitosan, which combines repair to combined contamination soil with Active gangue powder, reaches preferable repairing effect, and embodiment 3
It is last to the repairing effect of contaminated soil.Compared with prior art, it improves to heavy metal and polycyclic aromatic hydrocarbon composite pollution soil
The repairing effect of earth is more advantageous to the reparation in practice to contaminated soil, together and by comparative example 2 and comparative example 3 it is found that passing through
Modification of chitosan is added and the repairing effect of soil can be improved in Active gangue powder.
To sum up, the present invention provides a kind of restorative procedure of organic pollutant-heavy-metal composite pollution soil, can effectively degrade
The heavy metal in organic pollutant and passivation soil in contaminated soil, to achieve the purpose that rehabilitating soil, and repairing efficiency
It is short.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of organic pollutant-heavy-metal composite pollution soil restorative procedure, which comprises the steps of:
Modification of chitosan is added in organic pollutant-heavy-metal composite pollution soil, and contaminated soil is turned over, keeps modified shell poly-
Sugar is uniformly mixed with soil, is added water, is irrigated soil, then apply Active gangue powder again, by Active gangue powder and soil
Earth is uniformly mixed, and realizes the effective reparation of organic pollutant-heavy-metal composite pollution soil.
2. organic pollutant according to claim 1-heavy-metal composite pollution soil restorative procedure, which is characterized in that
Specifically comprise the following steps:
(1) by organic pollutant-heavy-metal composite pollution soil scarifying, modification of chitosan is applied, and soil is turned over, is made
Modification of chitosan is uniformly mixed with soil；
(2) water is added, the contaminated soil containing modification of chitosan is irrigated, is during which watered daily, turns over primary, control daily
The soil moisture is 15-25 DEG C；
(3) Active gangue powder is then applied into soil, plowed soils is uniformly mixed Active gangue powder with soil, and
It adds water to and floods soil；
(4) watering daily, is turned over once, and control 10-15 DEG C of the soil moisture daily during.
3. organic pollutant according to claim 1 or 2-heavy-metal composite pollution soil restorative procedure, feature exist
In the additional amount of the modification of chitosan is the 1.5%-4.5% of contaminated soil dry weight.
4. organic pollutant according to claim 1 or 2-heavy-metal composite pollution soil restorative procedure, feature exist
In the additional amount of the Active gangue powder is the 1%-4% of contaminated soil dry weight.
5. organic pollutant according to claim 1 or 2-heavy-metal composite pollution soil restorative procedure, feature exist
In the modification of chitosan is to obtain by the following method:
(1) it dissolves the chitosan in glacial acetic acid aqueous solution, is stirred by ultrasonic, then high-speed stirred is completely molten to chitosan again
Solution, obtains chitosan solution；
(2) chitosan solution is placed in deaeration 0.5-1h under the conditions of vacuum degree 0.07-0.09MPa
(3) chitosan solution after deaeration is coated on smooth glass plate, is placed in vacuum tank, and steamed at 40-50 DEG C
1-2h is sent out, takes off and falls naturally to film, obtain chitosan film；
(4) by chitosan film using plasma technical treatment made from step (3), when processing is atmosphere of inert gases, and shell is poly-
The distance between sugared film and electrode are 5-10mm, processing power 50-70W, discharge frequency 10kHz, and the processing time is 8-
12min；
(5) chitosan film after step (4) plasma treatment is added in reactor, chloroform is added, reactor is vacuumized logical
After nitrogen, 35-40 DEG C air surge bath in vibrate 5-8h, hunting speed 90-110rpm, by reactor temperature be 5-
Ultrasound 30-40min at 10 DEG C stops ultrasound when solution is clarified in reactor, is with the pH that sodium hydroxide solution adjusts solution
4.0-5.0 is added alcohol reflux 1-2h and obtains reaction solution；
(6) reaction solution of step (5) is filtered, then uses ethyl alcohol alcohol, water, acetone washing filter cake, collect filtrate and removed
Solvent, drying, obtain modification of chitosan.
6. organic pollutant according to claim 1 or 2-heavy-metal composite pollution soil restorative procedure, feature exist
In the Active gangue powder is to obtain by the following method:
(1) gangue is placed in micronizer and is crushed to 150 mesh hereinafter, and being added with the binder of 0.5 times of its quality simultaneously
It is sufficiently mixed, is then added and mixes, mediate with 2.5 times of its quality of deionized water, then obtain briquetting through cuber compound stalk forming
Material；
(2) briquetting material is put into retort, under inert gas protection heating charing, prior to 300 DEG C at solidify 1.5h after,
550 DEG C of charing 2h directly are warming up to, 800 DEG C of charing 1h is finally warming up to, obtains carbonized material；
(3) carbonized material is crushed, is sieved with 100 mesh sieve, put into activation furnace, the K2CO3 solution that concentration is 5mol/L, heating is added
To 350-450 DEG C, it is stirred to react 5h, is then lived by obtaining activated material crystallization after filtering and washing after layering kettle layering
Material；
(4) by activated material be placed in concentration be 3mol/L KOH solution in, prior to 60 DEG C at activate 2h, then heat to 80 DEG C of work
Change 5h, be finally warming up to 90 DEG C of activation processing 10h, being washed out dry, pulverize, and cross 200 meshes to get modified gangue powder.
7. organic pollutant according to claim 1 or 2-heavy-metal composite pollution soil restorative procedure, feature exist
In the organic pollutant is polycyclic aromatic hydrocarbon；The heavy metal is one of Cu, Pb and Cd or at least two.
8. organic pollutant according to claim 7-heavy-metal composite pollution soil restorative procedure, which is characterized in that
The polycyclic aromatic hydrocarbon is benzo (a) pyrene.
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