CN106399697B - A kind of soil Compound Heavy Metals are administered and method of resource - Google Patents
A kind of soil Compound Heavy Metals are administered and method of resource Download PDFInfo
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- CN106399697B CN106399697B CN201610973346.9A CN201610973346A CN106399697B CN 106399697 B CN106399697 B CN 106399697B CN 201610973346 A CN201610973346 A CN 201610973346A CN 106399697 B CN106399697 B CN 106399697B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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- Soil Sciences (AREA)
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Abstract
The present invention relates to a kind of improvement of soil Compound Heavy Metals and method of resource, include the following steps：1) adsorbent material is added；2) magnetic separation；3) desorbed of adsorbed materials；4) stripping liquid Primary regulation；5) plate-frame filtering and stripping liquid Secondary Control；6) hypergravity Centrifugical extraction heavy metal；7) free stream cataphoresis；It is high, without secondary pollution that the present invention has the advantages that processing heavy metal wide variety, removal efficiency, and can Compound Heavy Metals is precisely separated and be recycled, and can be applied to the in-situ immobilization or showering by heavy-metal contaminated soil.
Description
Technical field
It administers and provides the present invention relates to technical field of environment pollution control more particularly to a kind of soil Compound Heavy Metals
Source method.
Background technique
Heavy metal is a kind of typical pollutant, and main source has 1) industrial production, especially mining and metallurgy industry
To a large amount of heavy metal contaminants of Environment release；2) biochemical rubbish, the garbage energy containing heavy metal penetrate into soil and water body；3) agriculture
Industry produces, and harmful substance discharges heavy metal in chemical fertilizer and pesticide.Heavy metal-polluted water, soil have animal and plant serious
Harmfulness.The heavy metal-polluted soil being especially contaminated is not easy to remove, and causes heavy metal in crops to severely exceed, passes through food
Chain is enriched with and shifts into the human body, endangers human health.
Due to the seriousness of heavy-metal contaminated soil harm, domestic and foreign scholars have carried out greatly heavy metal pollution soil remediation
Quantifier elimination simultaneously achieves more achievement.Mainly there are 1) physical measure, including engineering technology, electric power chemistry and vitrifying skill
Art, but generally existing project amount is big, the high disadvantage of energy consumption；2) chemical measure, including immobilization technology and elution method, but it is fixed
Change technology cannot be thoroughly by heavy metals removal, and heavy metal is still in soil；The woods method of washing can generate a large amount of leacheate, processing
Difficulty is big, is also easy to produce secondary pollution；3) biological control measure, including plant, animal and microorganism remediation, but there are the cycles of operation
It is long, the disadvantages such as governance efficiency is low.
High magnetic adsorbent material as novel environmental improvement functional material, have absorption property it is strong, it is applied widely,
The advantages such as at low cost show very big application potential in terms of administering polluted soil.
In addition, it is more to the research of heavy metal-polluted soil improvement at present, but returned for administering heavy metal in soil and resource
The research in debit face is rarely reported, and is returned especially for improvement heavy metal in soil efficient, inexpensive, without secondary pollution and resource
The research of receipts is not yet carried out.
Summary of the invention
The present invention provides a kind of improvement of soil Compound Heavy Metals and method of resource, have processing heavy metal type
Diversification, removal efficiency height, advantage without secondary pollution, and Compound Heavy Metals can be precisely separated and be recycled, it can answer
For the in-situ immobilization or showering by heavy-metal contaminated soil.
In order to achieve the above object, the present invention is implemented with the following technical solutions：
A kind of soil Compound Heavy Metals are administered and method of resource, include the following steps：
1) adsorbent material is added；Add magnetic adsorptive material in the soil by heavy metal pollution, and by magnetic absorption material
Material mixes well withs the soil, and makes the heavy metal transformation in soil into magnetic adsorptive material, realizes the separation of heavy metal and soil；
2) magnetic separation；The magnetic adsorptive material of adsorption saturation is separated from soil using multi-stage magnetic separation method, is collected,
Reach the repairing and treating by heavy-metal contaminated soil；
3) desorbed of adsorbed materials；The magnetic adsorptive material of adsorption saturation is thrown in desorption mixing plant, by magnetic absorption
Mixing is sufficiently stirred in material and stripping liquid, separates heavy metal from magnetic adsorptive material, enters in stripping liquid；
4) stripping liquid Primary regulation；It is carried out in stripping liquid regulating tank, stripping liquid adjustment parameter is concentration, the temperature of stripping liquid
Degree and pH value；
5) plate-frame filtering and stripping liquid Secondary Control；Stripping liquid containing heavy metal retains magnetic absorption material by plate-frame filtering
Material, and Secondary Control is carried out in conditioning tank, adjustment parameter is temperature and pH value；
6) hypergravity Centrifugical extraction heavy metal；The stripping liquid containing heavy metal in conditioning tank enters hypergravity Centrifugical extraction
Machine by addition Extraction of Heavy Metals agent separation and is enriched with different types of heavy metal；
7) free stream cataphoresis；Separating liquid freedom of entry flow electrophoresis equipment containing high concentration heavy metal or Compound Heavy Metals
In, it is precisely separated, recycles heavy metal.
The magnetic adsorptive material is one of magnetic zeolite, magnetic charcoal, magnetic porous ceramics or more than one are any
Combination, adsorbed heavy metal includes mercury, thallium, arsenic, lead, calcium halophosphate activated by antimony andmanganese, chromium, cadmium, copper, zinc, cobalt, nickel, magnetic adsorptive material dosage
For 5~100kg/m3。
The liquid-solid ratio of stripping liquid and magnetic adsorptive material is 4~10 in the desorption mixing plant:1；Speed of agitator is 50
~200r/min, mixing time are 10~60min.
For heavy metal after separating in magnetic adsorptive material, magnetic adsorptive material carries out regeneration treatment in step 3).
The hypergravity centrifugal extractor uses 1~10 grade of serial or parallel connection, and revolving speed is in 1000~5000r/min；Containing weight
Metal stripping liquid and the ratio of Extraction of Heavy Metals agent are 2~10:1.
In step 6), the stripping liquid containing heavy metal after hypergravity Centrifugical extraction, the removal rate of heavy metal is 95~
100%, the stripping liquid after removing removing heavy metals is recycled and is recycled.
The free stream cataphoresis device both end voltage is 1~1000V, and the extractant flow velocity containing heavy metal is 1~100mL/
min；Extractant after separating beavy metal is recycled and is recycled.
Using hydrochloric acid, sulfuric acid or sodium hydroxide solution as regulator when adjusting pH value in step 4), step 5).
Compared with prior art, the beneficial effects of the invention are as follows：
1) various heavy in soil is efficiently removed using magnetic adsorptive material, easy to operate, magnetic adsorptive material and soil
Earth is easily isolated, and heavy metal removing rate is high, without secondary pollution；
2) the heavy metal desorption efficiency in magnetic adsorptive material is high, and stripping liquid and magnetic adsorptive material can be recycled and repeat
It uses, treatment cost can be reduced；
3) heavy metal after desorbing can efficiently, quickly be enriched with concentration, and be precisely separated, extract, recycling heavy metal, realize
Heavy metal-polluted soil is administered and recycling.
Detailed description of the invention
Fig. 1 is the flow chart of soil Compound Heavy Metals improvement of the present invention and method of resource.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing：
As shown in Figure 1, a kind of soil Compound Heavy Metals of the present invention are administered and method of resource, including walk as follows
Suddenly：
1) adsorbent material is added：Add magnetic adsorptive material in the soil by heavy metal pollution, and by magnetic absorption material
Material mixes well withs the soil, and makes the heavy metal transformation in soil into magnetic adsorptive material, realizes the separation of heavy metal and soil；
2) magnetic separation：The magnetic adsorptive material of adsorption saturation is separated from soil using multi-stage magnetic separation method, is collected,
Reach the repairing and treating by heavy-metal contaminated soil；
3) desorbed of adsorbed materials：The magnetic adsorptive material of adsorption saturation is thrown in desorption mixing plant, by magnetic absorption
Mixing is sufficiently stirred in material and stripping liquid, separates heavy metal from magnetic adsorptive material, enters in stripping liquid；
4) stripping liquid Primary regulation：It is carried out in stripping liquid regulating tank, stripping liquid adjustment parameter is concentration, the temperature of stripping liquid
Degree and pH value；
5) plate-frame filtering and stripping liquid Secondary Control：Stripping liquid containing heavy metal retains magnetic absorption material by plate-frame filtering
Material, and Secondary Control is carried out in conditioning tank, adjustment parameter is temperature and pH value；
6) hypergravity Centrifugical extraction heavy metal：The stripping liquid containing heavy metal in conditioning tank enters hypergravity Centrifugical extraction
Machine by addition Extraction of Heavy Metals agent separation and is enriched with different types of heavy metal；
7) free stream cataphoresis：Separating liquid freedom of entry flow electrophoresis equipment containing high concentration heavy metal or Compound Heavy Metals
In, it is precisely separated, recycles heavy metal.
The magnetic adsorptive material is one of magnetic zeolite, magnetic charcoal, magnetic porous ceramics or more than one are any
Combination, adsorbed heavy metal includes mercury, thallium, arsenic, lead, calcium halophosphate activated by antimony andmanganese, chromium, cadmium, copper, zinc, cobalt, nickel, magnetic adsorptive material dosage
For 5~100kg/m3。
The liquid-solid ratio of stripping liquid and magnetic adsorptive material is 4~10 in the desorption mixing plant:1；Speed of agitator is 50
~200r/min, mixing time are 10~60min.
For heavy metal after separating in magnetic adsorptive material, magnetic adsorptive material carries out regeneration treatment in step 3).
The hypergravity centrifugal extractor uses 1~10 grade of serial or parallel connection, and revolving speed is in 1000~5000r/min；Containing weight
Metal stripping liquid and the ratio of Extraction of Heavy Metals agent are 2~10:1.
In step 6), the stripping liquid containing heavy metal after hypergravity Centrifugical extraction, the removal rate of heavy metal is 95~
100%, the stripping liquid after removing removing heavy metals is recycled and is recycled.
The free stream cataphoresis device both end voltage is 1~1000V, and the extractant flow velocity containing heavy metal is 1~100mL/
min；Extractant after separating beavy metal is recycled and is recycled.
Using hydrochloric acid, sulfuric acid or sodium hydroxide solution as regulator when adjusting pH value in step 4), step 5).
Following embodiment is implemented under the premise of the technical scheme of the present invention, gives detailed embodiment and tool
The operating process of body, but protection scope of the present invention is not limited to following embodiments.Method therefor is such as without spy in following embodiments
Not mentionleting alone bright is conventional method.
【Embodiment】
In the present embodiment, the soil by heavy metal pollution is certain mining area periphery paddy soil, sampled chemical examination, in soil
Heavy metal component and content are：
Cr：67.36mg/kg；
Pb：414.44mg/kg；
Cd：21.14mg/kg；
Cu：44.15mg/kg；
Zn：6184.41mg/kg；
Ni：88.38mg/kg；
Hg：2.58mg/kg；
As：40.68mg/kg.
The soil Compound Heavy Metals that the present embodiment uses are administered and method of resource specific operation process is as follows：
1) magnetic adsorptive material is added in the soil by heavy metal pollution, and magnetic adsorptive material is mixed well withed the soil,
The dosage of magnetic adsorptive material is 20kg/m3；Heavy metal transformation in soil into magnetic adsorptive material, realize heavy metal with
The separation of soil；
2) the magnetic separation separation equipment of hydraulic flap is added to realize point of magnetic adsorptive material and soil using electromagnetism transmitting mechanical
From collection；
3) magnetic separation magnetic adsorptive material obtained after separation is added in desorption mixing plant, stripping liquid and magnetic absorption material
The liquid-solid ratio of material is 5:1；Speed of agitator is 150r/min, and mixing time 30min makes heavy metal from magnetic adsorptive material transfer
It moves on in stripping liquid；
4) stripping liquid in stripping liquid regulating tank be 2mol/L hydrochloric acid with 1% chitosan mixed liquor, adjust solve
The pH value of imbibition is 2~3, and temperature is 75 DEG C；
5) magnetic adsorptive material after desorption heavy metal is retained by plate filter, magnetic adsorptive material is sent at regeneration
Reason is reused；Stripping liquid containing heavy metal enters conditioning tank, and adjusting temperature is 50 DEG C, and pH value 4 is spare；
6) stripping liquid containing heavy metal in conditioning tank enters in hypergravity centrifugal extractor, the ratio with metal extraction agent
It is 4:1, the revolving speed of centrifuge is 4000r/min, and after 2 grades of crosscurrent extractions, heavy metal is transferred in extract liquor, a removal huge sum of money
The stripping liquid of category is recycled and is recycled；
7) in the extract liquor freedom of entry flow electrophoresis device containing high concentration Compound Heavy Metals, flow velocity 30mL/min, two
Hold 50~100V of voltage；After the step, Compound Heavy Metals are precisely separated and are recycled.
The present embodiment administer to Compound Heavy Metals soil and the effect of recycling is as follows：
After being adsorbed by magnetic adsorptive material, the content of beary metal in soil is decreased obviously, Cr, Pb, Cd, Cu, Zn, Ni,
The removal rate of Hg, As is respectively 67.35%, 74.32%, 85.26%, 52.63%, 75.38%, 69.35%, 85.62%,
53.47%.
The desorption efficiency of heavy metal is greater than 96% in magnetic adsorptive material.
Heavy metal in stripping liquid is by the way that after hypergravity Centrifugical extraction, the extraction yield of heavy metal is 98%, and cycles of concentration reaches
To 6 times.
After free stream cataphoresis device, heavy metal separation and recovery rate is 87.5%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of soil Compound Heavy Metals are administered and method of resource, which is characterized in that include the following steps：
1) adsorbent material is added：Add magnetic adsorptive material in the soil by heavy metal pollution, and by magnetic adsorptive material with
Soil mixes, and makes the heavy metal transformation in soil into magnetic adsorptive material, realizes the separation of heavy metal and soil；The magnetism
Adsorbent material is one of magnetic zeolite, magnetic charcoal, magnetic porous ceramics or more than one any combination, an adsorbed huge sum of money
Belong to includes mercury, thallium, arsenic, lead, calcium halophosphate activated by antimony andmanganese, chromium, cadmium, copper, zinc, cobalt, nickel；
2) magnetic separation：The magnetic adsorptive material of adsorption saturation is separated from soil using multi-stage magnetic separation method, is collected, is reached
By the repairing and treating of heavy-metal contaminated soil；
3) desorbed of adsorbed materials：The magnetic adsorptive material of adsorption saturation is thrown in desorption mixing plant, by magnetic adsorptive material
Mixing is sufficiently stirred with stripping liquid, separates heavy metal from magnetic adsorptive material, enters in stripping liquid；
4) stripping liquid Primary regulation：Hydrochloric acid that stripping liquid in stripping liquid regulating tank is 2mol/L is mixed with 1% chitosan
Liquid is closed, the pH value for adjusting stripping liquid is 2~3, and temperature is 75 DEG C；
5) plate-frame filtering and stripping liquid Secondary Control：Stripping liquid containing heavy metal retains magnetic adsorptive material by plate-frame filtering,
And Secondary Control is carried out in conditioning tank, adjusting temperature is 50 DEG C, pH value 4；
6) hypergravity Centrifugical extraction heavy metal：The stripping liquid containing heavy metal in conditioning tank enters hypergravity centrifugal extractor, leads to
It crosses addition Extraction of Heavy Metals agent separation and is enriched with different types of heavy metal；
7) free stream cataphoresis：In separating liquid freedom of entry flow electrophoresis equipment containing high concentration heavy metal or Compound Heavy Metals, essence
Really separation, recycling heavy metal.
2. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that magnetic
Property adsorbent material dosage be 5~100kg/m3。
3. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that institute
Stating the liquid-solid ratio of stripping liquid and magnetic adsorptive material in desorption mixing plant is 4~10:1；Speed of agitator is 50~200r/min,
Mixing time is 10~60min.
4. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that step
It is rapid 3) in heavy metal from magnetic adsorptive material separate after, magnetic adsorptive material carry out regeneration treatment.
5. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that institute
Hypergravity centrifugal extractor is stated using 1~10 grade of serial or parallel connection, revolving speed is in 1000~5000r/min；Stripping liquid containing heavy metal
Ratio with Extraction of Heavy Metals agent is 2~10:1.
6. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that step
It is rapid 6) in, for the stripping liquid containing heavy metal after hypergravity Centrifugical extraction, the removal rate of heavy metal is 95~100%, removal weight
Stripping liquid after metal is recycled and is recycled.
7. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that institute
Stating free stream cataphoresis device both end voltage is 1~1000V, and the extractant flow velocity containing heavy metal is 1~100mL/min；Separation weight
Extractant after metal is recycled and is recycled.
8. a kind of soil Compound Heavy Metals according to claim 1 are administered and method of resource, which is characterized in that step
It is rapid 4), in step 5) to use hydrochloric acid, sulfuric acid or sodium hydroxide solution as regulator when adjusting pH value.
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| CN107020294A (en) * | 2017-06-10 | 2017-08-08 | 贵州理工学院 | The method that External Calcium aids in wild cabbage rehabilitating soil thallium pollution |
| CN107904400B (en) * | 2017-12-13 | 2019-09-03 | 清远先导材料有限公司 | The separation and recovery method of thallium in a kind of sulfuric acid nickel and cobalt solution |
| CN109433812A (en) * | 2018-11-30 | 2019-03-08 | 昆明理工大学 | A method of strengthening elution repairing polluted soil |
| CN109837391A (en) * | 2019-01-22 | 2019-06-04 | 浙江科技学院 | The method of extraction thallium and adsorbent used from lead-zinc ore tailings contaminated soil |
| CN110523766B (en) * | 2019-09-05 | 2021-03-19 | 中国科学院过程工程研究所 | Method for repairing composite heavy metal contaminated soil and recovering chromium resources |
| CN114699802B (en) * | 2022-04-27 | 2022-11-22 | 华中科技大学 | Method for desorbing, enriching and recovering Cd/Pb step by step |
| CN115990610A (en) * | 2023-01-30 | 2023-04-21 | 中科鼎实环境工程有限公司 | Farmland heavy metal pollution treatment and restoration equipment |
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| EP0302293A1 (en) * | 1987-07-29 | 1989-02-08 | Siemens Aktiengesellschaft | Process for purifying solids and liquids |
| JP2007000853A (en) * | 2005-06-23 | 2007-01-11 | Katsuhiro Ito | Method for cleaning and treating pcb-contaminated soil |
| US20110192800A1 (en) * | 2010-02-11 | 2011-08-11 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Magnetic-cored dendrimer, the method for preparing the same, and the contaminant treatment method using the same |
| CN102319725A (en) * | 2011-05-26 | 2012-01-18 | 中国矿业大学(北京) | Method for removing heavy metal in soil |
| CA2893793A1 (en) * | 2013-05-29 | 2014-12-04 | Innord Inc. | A system and method for separation and purification of dissolved rare earth/precious metals elements/compounds |
| CN103521179B (en) * | 2013-09-29 | 2015-08-19 | 福建工程学院 | One-step method prepares the method for sludge based forming magnetic active carbon |
| CN104263928B (en) * | 2014-09-05 | 2016-06-08 | 昆明理工大学 | A kind of method of solvent extraction and separation nickel cobalt under super gravity field |
| CN105817469A (en) * | 2015-01-09 | 2016-08-03 | 武汉中地金盾环境科技有限公司 | Magnetic separation purifying treatment technology for removing heavy metal pollution of soil |
| CN104741076A (en) * | 2015-04-03 | 2015-07-01 | 中国地质科学院水文地质环境地质研究所 | Magnetic zeolite, and preparation method and application thereof |
| CN105170620B (en) * | 2015-09-30 | 2018-07-03 | 江苏省中成建设工程总公司 | A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal |
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