CN108690625A - It is a kind of to be used to handle sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil and preparation method thereof - Google Patents

It is a kind of to be used to handle sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil and preparation method thereof Download PDF

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CN108690625A
CN108690625A CN201810399648.9A CN201810399648A CN108690625A CN 108690625 A CN108690625 A CN 108690625A CN 201810399648 A CN201810399648 A CN 201810399648A CN 108690625 A CN108690625 A CN 108690625A
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bacterium
sustained release
soil
halogenated hydrocarbons
solution
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CN108690625B (en
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孟梁
汪华林
吉昌铃
杨洁
张施阳
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East China University of Science and Technology
Shanghai Normal University
Shanghai Academy of Environmental Sciences
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Shanghai Academy of Environmental Sciences
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ

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Abstract

The invention discloses a kind of sustained release complex repairation medicaments and preparation method thereof for handling Persistent halogenated hydrocarbons in soil.Preparation method includes 1) preparing bacterium solution to be saturated black wood charcoal;2) the colloidal solution A containing locust bean gum and organic carbon source is prepared;3) the gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is prepared;4) cross-linking reaction 2-6h;5) be delayed cross-linking reaction 2-6h, obtains a kind of sustained release complex repairation medicament for handling Persistent halogenated hydrocarbons in soil.Sustained release complex repairation medicament prepared by the present invention can utilize the dissimilatory iron reduction dehalogenation ability of the good absorption property of black wood charcoal, the efficient electronation of nanoscale zero-valent metal and functional microorganism, reach and repairing effect strengthened to the physics, chemistry and biological synergetic of Persistent halogenated hydrocarbons contaminated soil, and with action period length, stable structure, the of low cost and advantages such as environmental-friendly.

Description

It is a kind of for handle Persistent halogenated hydrocarbons in soil sustained release complex repairation medicament and its Preparation method
Technical field
The invention belongs to contaminated soil remediation technical field, it is related to a kind of contaminated soil remediation medicament and preparation method thereof, More particularly to a kind of to be used to handle sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil and preparation method thereof.
Background technology
Persistent halogenated hydrocarbons (PHHs, such as organo-chlorine pesticide, Polychlorinated biphenyls, polybrominated diphenyl ethers) are widely used in machinery During manufacture, electronic component cleaning, chemical and agricultural planting etc., there is " three cause " (carcinogenic, teratogenesis, mutagenesis) effect It answers, refractory organics, property easy to migrate and bioconcentration can make the ecosystem and human health once entering soil environment At serious harm.In view of the popularity and strong harmfulness, the control of the pollutant and treatment technology of Persistent halogenated hydrocarbons pollution Have become the research hotspot of field of environmental improvement.
Currently, the technology for being usually used in Persistent halogenated hydrocarbons contaminated soil remediation has concrete dynamic modulus Jie added with adsorption capacity Matter, the zero-valent metal with chemical reducing capability, physics, chemistry, the life such as organic carbon source for promoting indigenous microorganism reducing power Object space formula, but these methods have its corresponding limitation.As pollutant is only simply enriched with and is moved by porous medium It moves, can not thoroughly remove;The action effective of zero-valent metal is short, is also easy to produce secondary pollution and the oxidation that can reunite, leads to reactivity Decline;The period for adding organic carbon source processing mode is long, and carbon source burst size is not easy to control, and treatment effect is unstable.
In recent years, some scholars began to focus on the technology of the many-sided Combined Treatment pollutant of physics, chemistry, biology, ground The preparation for studying carefully various ingredients complex repairation medicament the problem of to make up monotechnics means, reaches synergistic effect, carries The treatment effect of high pollution object.Generally there is the preparation method of composite drug in these researchs:By zero-valent metal, organic carbon source, more The active principles such as pore media, dehalogenation bacterium are simply mixed, but the combination between active principle is weaker, cooperative reinforcing effect Not significantly;Active principle physically trapping is fixed with embedding mediums such as polyvinyl alcohol, but there are bad mechanical strengths, slow for common embedding medium Release that control ability is weak, easily causes the shortcomings of secondary pollution, to reduce the stability, validity and practical application of composite material Property.
Black wood charcoal is one kind of biomass carbon, with abundant pore structure, has very strong surface to inhale organic pollution Attached effect can be used as a kind of environmental-friendly natural sorbing material, and be the effective carrier for loading bacterial strain.Locust bean gum is thorn The sub- glue of plant that Chinese scholartree seed is process, internal carboxyl structure can pass through bivalent cation (such as Ca2+,Mg2+) electrostatic Effect crosslinking aggregation forms gel micro-ball, and strong, environmental-friendly, the antiacid alkali of its high mechanical strength, mass-transfer performance and enzyme decompose, valence Lattice are cheap, are a kind of ideal newtype drug sustained release embedding mediums.Shewanella bacterium (Shewanella) are a kind of wide in nature General existing dissimilatory iron reduction bacterium, can be with Fe (III) for terminal electron acceptor, by enzymatic reaction extracellularly by Fe (III) It is reduced to Fe (II), microorganism obtains energy promotion cell growth in the process.Meanwhile it is nearest researches show that Shewanella bacterium can also further halogenated hydrocarbons such as dealuminated USY cataluyst carbon tetrachloride during reduced iron.But currently with black wood charcoal As adsorbent and carrier, the microorganism with dissimilatory iron reduction dehalogenation ability is loaded, and using locust bean gum as embedding medium, system The standby long-acting complex repairation medicament suitable for Persistent halogenated hydrocarbons contaminated soil has not been reported.
Invention content:
It is an object of the invention to:It is seriously polluted for Persistent halogenated hydrocarbons in current soil, existing reparation medicament and Restorative procedure removal effect is bad, action effective is short, stability is poor, easily causes secondary pollution problems to environment, provides one kind With long-acting sustained release complex repairation medicament and its preparation side for handling Persistent halogenated hydrocarbons in soil for strengthening repairing effect Method.
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil of the present invention, step It is as follows:
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor:The dosage for adding 0.1-1.0g microorganism freeze-dried powders by every liter of physiological saline, by microorganism Freeze-dried powder, which is added in the physiological saline that mass concentration is 0.8-1.0%, to be dissolved, and it is 0.1- that bacterial concentration, which is made, The bacterium seed liquor of 1.0mg/mL;The microorganism freeze-dried powder is the freeze-dried powder of dissimilatory iron reduction bacterium.
Black wood charcoal pre-processes:The HCl solution that black wood charcoal is first 1.0-5.0% with mass concentration impregnates 12-24h, deionization washing Only;12-24h is impregnated with the NaOH of a concentration of 10-20g/L again, deionized water is cleaned;It is finally 0.8-1.0% with mass concentration Physiological saline impregnate 12-24h after, be placed in 120-125 DEG C of moist heat sterilization pot the 15-30 min that sterilize, be dried for standby.
Nanoscale zero-valent metal pre-processes:It is 0.1-2.0% that the zero-valent metal powder of 10-100nm, which is placed in mass concentration, HCl solution in, be acidified 5-15min, it is 7-8 to be rinsed to pH value with deionized water after taking-up, be placed in anaerobic box air-dry it is standby With.
(2) it is sustained the preparation of complex repairation medicament:
1) it prepares bacterium solution and is saturated black wood charcoal:The dosage for adding 10.0-1000.0g black wood charcoals by every liter of bacterium seed liquor, will pre-process Good black wood charcoal is added in the bacterium seed liquor that the bacterial concentration prepared is 0.1-1.0mg/mL, by above-mentioned mixing suspension It is placed in 100-200r/min in shaken cultivation case and vibrates 6-12h, air-dry 25-35 DEG C of anaerobic of solid matter after filtering off solution, most Required bacterium solution is made eventually and is saturated black wood charcoal;
2) the colloidal solution A containing locust bean gum and organic carbon source is prepared:By every 100mL water add 0.5-4.5g locust bean gums and Locust bean gum and organic carbon source are added in deoxygenation deionized water, are placed on heater by the dosage of 1.5-3.5g organic carbon sources It is heated to 60-80 DEG C, machine mixer 100-250r/min is used in combination persistently to stir, until locust bean gum is completely dissolved and mixing, It is cooled to 25-50 DEG C, obtains the colloidal solution A containing locust bean gum and organic carbon source;
3) the gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is prepared: Add 0.5-2.0g nanoscale zero-valent metals and 2.0-8.0g bacterium solutions to be saturated the dosage of black wood charcoal by every 100mL water, is obtained to step 2) Colloidal solution A in bacterium solution made from the nanoscale zero-valent metal powder that pre-process and step 1) be added be saturated black wood charcoal, be used in combination Machine mixer 100-250r/min is persistently stirred, until nanoscale zero-valent metal powder is saturated the complete mixing of black wood charcoal with bacterium solution, The gluey suspension B for obtaining being saturated black wood charcoal containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is for use;
4) cross-linking reaction:Using peristaltic pump, pump discharge hose connects 2-8 Medical injection needles, will be obtained in step 3 To gluey suspension B be added dropwise to the speed of 3-7mL/min the CaCl of the mass content containing 1.5-4.5%2Saturation boric acid it is molten In liquid, it is placed in mechanical agitator room temperature 150-250r/min stirring crosslinkings reaction 2-6h, crosslinked fluid is then positioned over 2-6 DEG C 6-24h is reinforced in refrigerator;
5) be delayed cross-linking reaction:Crosslinked fluid filtering after being reinforced in step 4), obtained gel micro-ball are transferred to quality The Na of a concentration of 0.5-1.0%2SO4Be delayed cross-linking reaction 2-6h in solution, filters off Na2SO4Solution, thus obtained microsphere quality are dense The physiological saline that degree is 0.8-1.0% cleans 2-3 times, room temperature natural air drying, obtains a kind of for handling persistence halogen in soil For the sustained release complex repairation medicament of hydrocarbon, it is placed in anaerobic environment and saves backup.
The dissimilatory iron reduction bacterium is a kind of bacterium with dissimilatory iron reduction dehalogenation ability;It is described that there is dissimilatory iron reduction The bacterium of dehalogenation ability, that is, dissimilatory iron reduction bacterium is Shewanella putrefaciens CN32, Shewanella Piezotolerans WP3, Shewanella oneidensis MR-1 etc. belong to Shewanella (Shewanella) Pseudomonas Bacterium.
The organic carbon source is that the low molecular organic acids and xylose, fructose, maltose etc. such as acetic acid, oxalic acid, malic acid are single Sugar or biglycan.
The nanoscale zero-valent metal is that nano zero valence iron, nano zero-valence zinc, nano zero-valence aluminium etc. are de- with electronation The nanoscale zero-valent metal of halogen ability.
In the step 1), black wood charcoal is 2.0 × 10 to the saturated extent of adsorption of bacterium solution6-4.0×109cfu/g。
In gluey suspension B made from the step 3), the mass percentage that bacterium solution is saturated black wood charcoal is preferably 2.0- 8.0%, the mass percentage of locust bean gum is preferably 0.5-4.5%, and the mass percentage of nanoscale zero-valent metal is preferred Mass percentage for 0.5-2.0%, organic carbon source is preferably 1.5-3.5%.
The grain size of the complex repairation medicament is preferably 0.5-2.0mm.
The present invention be prepared as described above method be prepared it is a kind of for handle Persistent halogenated hydrocarbons in soil sustained release it is compound Repair medicament.
Method with Persistent halogenated hydrocarbons in sustained release complex repairation chemicals treatment soil of the present invention is as follows:
Topsoil turns over broadcast application in situ:Contaminated soil is turned in advance, by a certain amount of sustained release complex repairation medicine Agent is directly spread fertilizer over the fields in the soil after turning over, mixing of raking the soil level, and is watered and kept certain water content, is finally covered and is protected in soil surface After sheath, anaerobic reduction dehalogenation reaction is carried out, achievees the purpose that long-acting removal topsoil Persistent halogenated hydrocarbons in situ.
In the topsoil turns over broadcast application in situ, the sustained release complex repairation medicament amount of spreading fertilizer over the fields is contaminated soil dry weight 0.05-1.5%, the ploughed depth of soil is generally 25-40cm, and sustained release complex repairation medicament spreads fertilizer over the fields rear soil moisture content and adjusts To the 50-80% of maximum field capacity, soil surface protective layer is PVC film or HDPE film, is repaiied with sustained release complex repairation medicament The time handled again is preferably 30-350d.
The Persistent halogenated hydrocarbons are in organo-chlorine pesticide, Polychlorinated biphenyls, polybrominated diphenyl ethers etc. and their degradation Between product.
Beneficial effects of the present invention:
Mass transfer is used in combination using strong microorganism of the black wood charcoal load with dissimilatory iron reduction dehalogenation ability of adsorption capacity in the present invention Performance is high, had good sustained release effect locust bean gum is by the black wood charcoal of loading microorganisms and chemical reducing agent nanoscale zero-valent metal and micro- life Object electron donor organic carbon source is coated, and is cross-linked to form that mechanical strength is big, microsphere particle of stable structure.The reparation medicament energy Utilize the good absorption property of black wood charcoal, the dissimilatory iron reduction of nanoscale zero-valent metal efficient electronation and functional microorganism Dehalogenation ability reaches and strengthens repairing effect to the physics, chemistry and biological synergetic of Persistent halogenated hydrocarbons contaminated soil, and with work With period length, stable structure, the of low cost and advantages such as environmental-friendly.
Compared with prior art, the present invention has the following advantages:
(1) the dissimilatory iron reduction bacterium in complex repairation medicament has the ability of reductive dehalogenation degradation Persistent halogenated hydrocarbons, and And the bacterium is easy to survive to the adaptable of environment, helps to improve biology of the complex repairation medicament to Persistent halogenated hydrocarbons Degradation efficiency, meanwhile, which is facultative anaerobic bacteria, to the of less demanding of medicament preparation condition;The ratio table of nanoscale zero-valent metal Area and reactivity are much larger than micron order zero-valent metal, more efficient to the electronation dealuminated USY cataluyst of Persistent halogenated hydrocarbons; Organic carbon source as microorganism electron donor, can promotion functions bacterium (dissimilatory iron reduction bacterium) reductive dehalogenation activity.Have above-mentioned After component is imitated by embedding medium (locust bean gum) combination, the physics, chemistry and biology of Persistent halogenated hydrocarbons contaminated soil can be realized Cooperative reinforcing reparation makes the removal effect of target contaminant more preferably.
(2) compared with traditional microorganism immobilization method, the suction-operated of black wood charcoal, organic carbon source supplied for electronic act on And the coating function of locust bean gum, suitable growing environment is provided for functional microorganism (dissimilatory iron reduction bacterium), enhances it Activity and external interference resistance help to improve the ability of its Persistent halogenated hydrocarbons of degrading.
(3) compared with common biomass carbon, black wood charcoal have higher mechanical strength and smaller grain size, using black wood charcoal as Basis material can mitigate gel-type and repair the swelling level of breakage of medicament in water, enhance its structural stability, help to carry Height repairs the long-term effect of medicament.
(4) compared with traditional embedding medium, the mass-transfer performance of locust bean gum is strong, high mechanical strength, antiacid alkali and enzyme decompose, Active principle slow release in medicament can be controlled, and it is made to be come into full contact with pollutant, while can further improve reparation medicine The structural stability of agent.In addition, the coating function of locust bean gum, solves the agglomeration of nanoscale zero-valent metal, and slow down Its oxidation rate is degraded the efficiency of Persistent halogenated hydrocarbons to improve zero-valent metal electronation.
(6) present invention in repair medicament preparation method it is easy to operate, raw material economics is easy to get, can mass production, without secondary Pollution has huge application potential, the Persistent halogenated hydrocarbons poor especially suitable for high concentration or dehalogenation functional microorganism dirty Contaminate soil remediation.
Description of the drawings
Fig. 1 is the influence relational graph for repairing medicament applied amount to DDT treatment effects in soil;
Fig. 2 is the influence relational graph for loading different function strain to repairing heptachlor effect in chemicals treatment topsoil;
Fig. 3 is influence relational graph of the different DDT concentration to DDT effects in reparation chemicals treatment topsoil.
Specific implementation mode
Present disclosure is described further with reference to specific embodiment, makes the objects and effects of the present invention more Obviously, and is not intended to limit the present invention.The scope of the present invention should be defined by the claims.
It is mass percentage or mass concentration in following embodiment.
Embodiment 1:
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, steps are as follows:
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor:The physiological saline solution 0.5g Shewanella for being 0.9% with 5L mass concentrations The Shewanella that bacterial concentration is 0.1mg/mL is made in putrefaciens CN32 Shewanella freeze-dried powders Putrefaciens CN32 bacterium seed liquors.
Black wood charcoal pre-processes:Black wood charcoal first uses the HCl solution that mass concentration is 1.0% to impregnate 12h, and deionized water is cleaned;It uses again The NaOH of a concentration of 10g/L impregnates 12h, and deionized water is cleaned;The physiological saline that mass concentration is 0.9% is finally used to impregnate 12h Afterwards, it is placed in 121 DEG C of moist heat sterilization pots the 15-30min that sterilizes, is dried for standby.
Nano zero valence iron pre-processes:The zeroth order iron powder of 10nm is placed in the HCl solution that mass concentration is 0.1%, acid Change 5min, it is 7 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare.
(2) it is sustained the preparation of complex repairation medicament:
1) prepared by bacterium solution saturation black wood charcoal:The 1L made from step (1) is added in the black wood charcoal that 10g step (1) has been pre-processed In bacterium seed liquor (bacterial concentration 0.1mg/mL), above-mentioned mixing suspension is placed in 100r/min in shaken cultivation case and is vibrated 6h air-dries 25 DEG C of anaerobics of solid matter after filtering off solution, and finally obtained saturated extent of adsorption is 2.0 × 106The bacterium solution of cfu/g is full And black wood charcoal;
2) it weighs the locust bean gum of 0.5g and 1.5g malic acid is added in 100mL deoxygenation deionized waters, be placed in heater On be heated to 60 DEG C, be used in combination machine mixer 100r/min persistently to stir, until locust bean gum is completely dissolved and mixing, be cooled to 25 DEG C of colloidal solution A obtained containing locust bean gum and malic acid;
3) nano zero valence iron and 2.0g steps 1) that addition 0.5g step (1) has pre-processed into colloidal solution A are made Bacterium solution be saturated black wood charcoal, be used in combination machine mixer 100r/min persistently to stir, until nano zero valence iron and bacterium solution saturation black wood charcoal it is complete Full mixing is obtained containing 0.5% locust bean gum, 1.5% malic acid, 0.5% nano zero valence iron and 2.0% bacterium solution saturation black wood charcoal ( For mass percentage) gluey suspension B it is for use;
4) utilize peristaltic pump (pump discharge hose connects No. 2 Medical injection needles) by gluey suspension B with 3 mL/min Speed be added dropwise to the CaCl containing 1.5% mass content2Saturation boric acid solution in, be placed in mechanical agitator room temperature 150r/ Then crosslinked fluid is positioned in 2 DEG C of refrigerators and reinforces 6h by min stirring crosslinking 2h;
5) crosslinked fluid after reinforcing is filtered, obtained gel micro-ball is transferred to the Na that mass concentration is 0.5%2SO4Solution Middle delay is crosslinked 2h, filters off Na2SO4Solution, thus obtained microsphere are cleaned 3 times with the physiological saline that mass concentration is 0.9%, and room temperature is certainly It so air-dries, obtains the sustained release complex repairation medicament OZBB-1 of grain size 0.5mm.
Embodiment 2:
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, steps are as follows:
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor:With the Shewanella for the physiological saline solution 2.5g that 5L mass concentrations are 0.8% The Shewanella that bacterial concentration is 0.5mg/mL is made in piezotolerans WP3 Shewanella freeze-dried powders Piezotolerans WP3 bacterium seed liquors.
Black wood charcoal pre-processes:Black wood charcoal first uses the HCl solution that mass concentration is 3.0% to impregnate 16h, and deionized water is cleaned;It uses again The NaOH of a concentration of 15g/L impregnates 16h, and deionized water is cleaned;The physiological saline that mass concentration is 0.8% is finally used to impregnate 16h Afterwards, it is placed in 125 DEG C of moist heat sterilization pots the 20min that sterilizes, is dried for standby.
Nano zero-valence aluminium pre-processes:The nano zero-valence aluminium powder of 50nm is placed in the HCl solution that mass concentration is 1.0% In, it is acidified 10min, it is 7.5 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare.
(2) prepared by complex repairation medicament:
1) prepared by bacterium solution saturation black wood charcoal:The black wood charcoal that 100.0g step (1) has pre-processed is added and is made by step (1) 1L bacterium seed liquors in (bacterial concentration 0.5mg/mL), above-mentioned mixing suspension is placed in 150r/min in shaken cultivation case 8h is vibrated, air-dries 30 DEG C of anaerobics of solid matter after filtering off solution, finally obtained saturated extent of adsorption is 5.0 × 108The bacterium of cfu/g Liquid is saturated black wood charcoal;
2) 3.0g locust bean gums are weighed and 2.5g acetic acid is added in 100mL deoxygenation deionized waters, is placed on heater and adds Heat is used in combination machine mixer 150r/min persistently to stir to 70 DEG C, until locust bean gum is completely dissolved and mixing, is cooled to 35 DEG C Obtain the colloidal solution A containing locust bean gum and acetic acid;
3) the nano zero-valence aluminium and 4.0g steps 1) that addition 1.0g step (1) has pre-processed into colloidal solution A are made Bacterium solution be saturated black wood charcoal, be used in combination machine mixer 150r/min persistently to stir, until nano zero-valence aluminium and bacterium solution saturation black wood charcoal it is complete Full mixing, obtain containing 3.0% locust bean gum, 2.5% acetic acid, 1.0% nano zero-valence aluminium and 4.0% bacterium solution saturation black wood charcoal (be Mass percentage) gluey suspension B it is for use;
4) utilize peristaltic pump (pump discharge hose connects No. 4 Medical injection needles) by gluey suspension B with 5 mL/min Speed be added dropwise to the CaCl containing 2.5% mass content2Saturation boric acid solution in, be placed in mechanical agitator room temperature 200r/ Then crosslinked fluid is positioned in 4 DEG C of refrigerators and reinforces 12h by min stirring crosslinking 4h;
5) crosslinked fluid after reinforcing is filtered, obtained gel micro-ball is transferred to the Na that mass concentration is 0.7%2SO4Solution Middle delay is crosslinked 4h, filters off Na2SO4Solution, thus obtained microsphere are cleaned 2 times with the physiological saline that mass concentration is 0.8%, and room temperature is certainly It so air-dries, obtains the sustained release complex repairation medicament OZBB-2 of grain size 1.0mm.
Embodiment 3:
A kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, steps are as follows:
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor:With the Shewanella for the physiological saline solution 5.0g that 5L mass concentrations are 1.0% The Shewanella oneidensis that bacterial concentration is 1.0mg/mL are made in oneidensis MR-1 Shewanella freeze-dried powders MR-1 bacterium seed liquors.
Black wood charcoal pre-processes:Black wood charcoal first uses the HCl solution that mass concentration is 5.0% to impregnate for 24 hours, and deionized water is cleaned;It uses again The NaOH of a concentration of 20g/L impregnates for 24 hours, and deionized water is cleaned;The physiological saline that mass concentration is 1.0% is finally used to impregnate for 24 hours Afterwards, it is placed in 120 DEG C of moist heat sterilization pots the 30min that sterilizes, is dried for standby.
Nano zero-valence zinc pre-processes:The nano zero-valence zinc powder of 100nm is placed in the HCl solution that mass concentration is 2.0% In, it is acidified 15min, it is 8 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare.
(2) it is sustained the preparation of complex repairation medicament:
1) prepared by bacterium solution saturation black wood charcoal:The black wood charcoal that 1000.0g step (1) has pre-processed is added and is made by step (1) 1L bacterium seed liquors in (bacterial concentration 1.0mg/mL), above-mentioned mixing suspension is placed in 200r/min in shaken cultivation case 12h is vibrated, air-dries 35 DEG C of anaerobics of solid matter after filtering off solution, finally obtained saturated extent of adsorption is 4.0 × 109Cfu/g's Bacterium solution is saturated black wood charcoal;
2) 4.5g locust bean gums are weighed and 3.5g fructose is added in 100mL deoxygenation deionized waters, is placed on heater and adds Heat is used in combination machine mixer 250r/min persistently to stir to 80 DEG C, until locust bean gum is completely dissolved and mixing, is cooled to 50 DEG C Obtain the colloidal solution A containing locust bean gum and fructose;
3) the nano zero-valence zinc and 8.0g steps 1) that addition 2.0g step (1) has pre-processed into colloidal solution A are made Bacterium solution be saturated black wood charcoal, be used in combination machine mixer 250r/min persistently to stir, until nano zero-valence zinc and bacterium solution saturation black wood charcoal it is complete Full mixing, obtain containing 4.5% locust bean gum, 3.5% fructose, 2.0% nano zero-valence zinc and 8.0% bacterium solution saturation black wood charcoal (be Mass percentage) gluey suspension B it is for use;
4) utilize peristaltic pump (pump discharge hose connects No. 8 Medical injection needles) by gluey suspension B with 7 mL/min Speed be added dropwise to the CaCl containing 4.5% mass content2Saturation boric acid solution in, be placed in mechanical agitator room temperature 250r/ Then crosslinked fluid is positioned in 6 DEG C of refrigerators and reinforces for 24 hours by min stirring crosslinking 6h;
5) crosslinked fluid after reinforcing is filtered, obtained gel micro-ball is transferred to the Na that mass concentration is 1.0%2SO4Solution Middle delay is crosslinked 6h, filters off Na2SO4Solution, thus obtained microsphere are cleaned 3 times with the physiological saline that mass concentration is 1.0%, and room temperature is certainly It so air-dries, obtains the sustained release complex repairation medicament OZBB-3 of grain size 2.0mm.
Embodiment 4:
Influence of the medicament applied amount to chemicals treatment topsoil Persistent halogenated hydrocarbons effect is repaired in research, and specific steps are such as Under:
Substantially sustained release complex repairation medicament OZBB-4 is prepared by the step of embodiment 1, the difference is that:Step (2) quality hundred of locust bean gum, malic acid, nano zero valence iron and bacterium solution saturation black wood charcoal in gluey suspension B obtained by step 3) Point content is respectively 4.0%, 3.0%, 2.0% and 6.0%.
DDT (DDT) contaminated soil 5g is weighed respectively to be placed in four 150mL tool plug glass culture bottles (in contaminated soil A concentration of 1.5mg/kg of DDT), it is added by the 0.05% of soil dry weight, 0.2%, 0.8%, 1.5% repair medicament OZBB- respectively 4.Medicament will be repaired to mix well with contaminated soil, mixed system cultivates 50d in 25 DEG C of growth cabinets, during which maintains soil Moisture content soil sampling after 70% maximum field capacity, culture measures the wherein residual concentration of DDT, and calculates removal Rate, the results are shown in Figure 1.As shown in Figure 1, with the increase for repairing medicament applied amount, the removal rate of DDT constantly increases in soil Add, removal rate reaches 81.7% when applied amount is 1.5%, but at the scene during use should in conjunction with prepare and use cost etc. because Element determines the best applied amount for repairing medicament.
Embodiment 5:
Study influence of the black wood charcoal load different function strain to Persistent halogenated hydrocarbons effect in chemicals treatment topsoil, tool Steps are as follows for body:
Substantially by preparation sustained release complex repairation medicament the step of embodiment 3, the difference is that:The function that black wood charcoal is loaded Strain be respectively Shewanella putrefaciens CN32, Shewanella piezotolerans WP3 and Shewanella oneidensis MR-1 respectively obtain sustained release complex repairation medicament OZBB-C, OZBB-W and OZBB-M.
Heptachlor contaminated soil 10g is weighed respectively is placed in four 250mL tool plug glass culture bottles that (heptachlor is dense in contaminated soil Degree is 5.0mg/kg), medicament OZBB-C, OZBB-W and OZBB-M will be repaired respectively by the 1.0% of soil dry weight, and Polluted Soil is added In earth.Medicament will be repaired to mix well with soil, mixed system cultivates 60d in 25 DEG C of growth cabinets, during which maintains soil Moisture content soil sampling after 80% maximum field capacity, culture measures the residual concentration of wherein heptachlor, and calculates removal Rate, the results are shown in Figure 2.As shown in Figure 2, the OZBB-C of load Shewanella putrefaciens CN32 bacterium is to heptachlor Removal effect it is best, removal rate reaches 89.6% when 60d, load Shewanella piezotolerans WP3 bacterium OZBB-W effects are taken second place (83.6%), and the OZBB-M effects for loading Shewanella oneidensis MR-1 bacterium are poor (76.1%).
Embodiment 6:
Study influence of the different concentrations of contaminants to Persistent halogenated hydrocarbons effect in chemicals treatment topsoil, specific steps It is as follows:
Sustained release complex repairation medicament OZBB-3 is made by the preparation method of embodiment 3.
Weigh respectively containing 0.5,2.0,6.0, the contaminated soil 20g of 15.0mg/kg DDT be placed in four 100mL tool plug glass In glass culture bottle, applies respectively according to the 1.5% of contaminated soil dry weight and repair medicament OZBB-3.Medicament will be repaired and soil is abundant Mixing, mixed system cultivate 90d in 25 DEG C of growth cabinets, during which maintain soil moisture content in 70% maximum field water holding Amount, soil sampling measures the wherein residual concentration of DDT after culture, and calculates removal rate, and the results are shown in Figure 3.It can by Fig. 3 Know, reparation medicament has apparent removal effect (89.6-90.5%), and soil to the DDT of various concentration in soil after handling 90d The removal rate of various concentration DDT is not significantly different in earth, illustrates that the complex repairation medicament pollutes low, medium and high concentration DDT The applicability of soil remediation is ideal.
Embodiment 7:
The sustained release complex repairation medicament OZBB-4 prepared in embodiment 4 is applied to the original position that six six six pollutes topsoil It turns over and spreads fertilizer over the fields in reparation, be as follows:
Contaminated soil is turned in advance, ploughed depth 25cm, prepares to repair medicine by the 0.05% of contaminated soil dry weight The applied amount of agent OZBB-4 spreads fertilizer over the fields ready reparation medicament OZBB-4 in turning in rear soil, and mixing of raking the soil level, watering is kept Soil moisture content is the 50% of field capacity, and covers PVC film in soil surface, and different sampled point soil are measured after handling 30d Pollutant concentration and removal rate is calculated in earth, the results showed that the removal rate of six six six is all higher than 79% in all sampled point soil, And residual concentration be showed no it is exceeded, it is believed that will sustained release complex repairation medicament OZBB-4 be applied to six six six pollute topsoil Original position turn over that spread fertilizer over the fields reparation be successful.
Embodiment 8:
The sustained release complex repairation medicament OZBB-W prepared in embodiment 5 is applied to the original that tetrachloro biphenyl pollutes topsoil Position, which is turned over, spreads fertilizer over the fields in reparation, is as follows:
Contaminated soil is turned in advance, ploughed depth 30cm, prepares to repair medicament by the 0.7% of contaminated soil dry weight The applied amount of OZBB-W spreads fertilizer over the fields ready reparation medicament OZBB-W in turning in rear soil, and mixing of raking the soil level, watering keeps soil Earth moisture content is the 60% of field capacity, and covers HDPE film in soil surface, and different sampled point soil are measured after handling 180d Pollutant concentration and removal rate is calculated in earth, the results showed that the removal rate of tetrachloro biphenyl is all higher than in all sampled point soil 88%, and residual concentration be showed no it is exceeded, it is believed that will sustained release complex repairation medicament OZBB-W be applied to tetrachloro biphenyl pollution The original position of topsoil turns over that spread fertilizer over the fields reparation be successful.
Embodiment 9:
The sustained release complex repairation medicament OZBB-C prepared in embodiment 5 is applied to tetrabromo Biphenyl Ether and pollutes topsoil Original position, which is turned over, spreads fertilizer over the fields in reparation, is as follows:
Contaminated soil is turned in advance, ploughed depth 40cm, prepares to repair medicament by the 1.5% of contaminated soil dry weight The applied amount of OZBB-C spreads fertilizer over the fields ready reparation medicament OZBB-C in turning in rear soil, and mixing of raking the soil level, watering keeps soil Earth moisture content is the 80% of field capacity, and covers HDPE film in soil surface, and different sampled point soil are measured after handling 350d Pollutant concentration and removal rate is calculated in earth, the results showed that the removal rate of tetrachloro biphenyl is all higher than in all sampled point soil 95%, and residual concentration be showed no it is exceeded, it is believed that will sustained release complex repairation medicament OZBB-C to be applied to tetrabromo Biphenyl Ether dirty The original position of dye topsoil turns over that spread fertilizer over the fields reparation be successful.

Claims (10)

1. a kind of preparation method for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil, which is characterized in that It carries out according to the following steps:
(1) preparation of bacterium seed liquor and pretreatment of raw material
It is prepared by bacterium seed liquor:The dosage for adding 0.1-1.0g microorganism freeze-dried powders by every liter of physiological saline, microorganism is lyophilized Powder, which is added in the physiological saline that mass concentration is 0.8-1.0%, to be dissolved, and it is 0.1-1.0mg/mL that bacterial concentration, which is made, Bacterium seed liquor;The microorganism freeze-dried powder is the freeze-dried powder of dissimilatory iron reduction bacterium;
Black wood charcoal pre-processes:The HCl solution that black wood charcoal is first 1.0-5.0% with mass concentration impregnates 12-24h, and deionized water is cleaned;Again 12-24h is impregnated with the NaOH of a concentration of 10-20g/L, deionized water is cleaned;The physiology for being finally 0.8-1.0% with mass concentration After saline sook 12-24h, it is placed in 120-125 DEG C of moist heat sterilization pot the 15-30min that sterilizes, is dried for standby;
Nanoscale zero-valent metal pre-processes:The zero-valent metal powder of 10-100nm is placed in the HCl that mass concentration is 0.1-2.0% In solution, it is acidified 5-15min, it is 7-8 to be rinsed to pH value with deionized water after taking-up, is placed in anaerobic box air-dried spare;
(2) it is sustained the preparation of complex repairation medicament:
1) it prepares bacterium solution and is saturated black wood charcoal:The dosage for adding 10.0-1000.0g black wood charcoals by every liter of bacterium seed liquor, by what is pre-processed Black wood charcoal is added in the bacterium seed liquor that the bacterial concentration prepared is 0.1-1.0mg/mL, and above-mentioned mixing suspension is placed in 100-200r/min vibrates 6-12h in shaken cultivation case, air-dries 25-35 DEG C of anaerobic of solid matter after filtering off solution, final to make It obtains required bacterium solution and is saturated black wood charcoal;
2) the colloidal solution A containing locust bean gum and organic carbon source is prepared:Add 0.5-4.5g locust bean gums and 1.5- by every 100mL water Locust bean gum and organic carbon source are added in deoxygenation deionized water by the dosage of 3.5g organic carbon sources, are placed on heater and are heated To 60-80 DEG C, machine mixer 100-250r/min is used in combination persistently to stir, until locust bean gum is completely dissolved and mixing, it is cooling To 25-50 DEG C, the colloidal solution A containing locust bean gum and organic carbon source is obtained;
3) the gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is prepared:By every 100mL water adds 0.5-2.0g nanoscale zero-valent metals and 2.0-8.0g bacterium solutions to be saturated the dosage of black wood charcoal, the glue obtained to step 2) Bacterium solution saturation black wood charcoal made from the nanoscale zero-valent metal powder pre-processed and step 1) is added in shape solution A, machinery is used in combination Blender 100-250r/min is persistently stirred, until nanoscale zero-valent metal powder is saturated the complete mixing of black wood charcoal with bacterium solution, is obtained The gluey suspension B that black wood charcoal is saturated containing locust bean gum, organic carbon source, nanoscale zero-valent metal and bacterium solution is for use;
4) cross-linking reaction:Using peristaltic pump, pump discharge hose connects 2-8 Medical injection needles, the glue that will be obtained in step 3 Shape suspension B is added dropwise to the CaCl of the mass content containing 1.5-4.5% with the speed of 3-7mL/min2Saturation boric acid solution in, and It is placed in mechanical agitator room temperature 150-250r/min stirring crosslinkings reaction 2-6h, then crosslinked fluid is positioned in 2-6 DEG C of refrigerator Reinforce 6-24h;
5) be delayed cross-linking reaction:Crosslinked fluid filtering after being reinforced in step 4), obtained gel micro-ball are transferred to mass concentration For the Na of 0.5-1.0%2SO4Be delayed cross-linking reaction 2-6h in solution, filters off Na2SO4Solution, thus obtained microsphere are with mass concentration The physiological saline of 0.8-1.0% cleans 2-3 times, room temperature natural air drying, obtains a kind of for handling Persistent halogenated hydrocarbons in soil Sustained release complex repairation medicament, be placed in anaerobic environment and save backup.
2. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that the dissimilatory iron reduction bacterium is a kind of bacterium with dissimilatory iron reduction dehalogenation ability;It is described that there is alienation The bacterium of iron reductive dehalogenation ability, that is, dissimilatory iron reduction bacterium is Shewanella.
3. the preparation side as claimed in claim 2 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that the Shewanella is Shewanella putrefaciens CN32, Shewanella Piezotolerans WP3 or Shewanella oneidensis MR-1.
4. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that physiological saline used in the step 1) and the step 5) is the physiology salt that mass concentration is 0.9% Water.
5. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that the organic carbon source is the low molecular organic acids including acetic acid, oxalic acid, malic acid, and including wood Monosaccharide including sugar, fructose, maltose or biglycan.
6. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that the nanoscale zero-valent metal is nano zero valence iron, nano zero-valence zinc or nano zero-valence aluminium.
7. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that black wood charcoal is 2.0 × 10 to the saturated extent of adsorption of bacterium solution in the step 1)6-4.0×109cfu/g。
8. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that in gluey suspension B made from the step 3), the mass percentage that bacterium solution is saturated black wood charcoal is 2.0- 8.0%, the mass percentage of locust bean gum is 0.5-4.5%, and the mass percentage of nanoscale zero-valent metal is 0.5- 2.0%, the mass percentage of organic carbon source is 1.5-3.5%.
9. the preparation side as described in claim 1 for handling the sustained release complex repairation medicament of Persistent halogenated hydrocarbons in soil Method, which is characterized in that the grain size of the sustained release complex repairation medicament is 0.5-2.0mm.
10. a kind of be used to handle Persistent halogenated hydrocarbons in soil according to what any methods of claim 1-9 were prepared Sustained release complex repairation medicament.
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