CN104607452A - Method for ultrasonically repairing heavy metal contaminated soil - Google Patents
Method for ultrasonically repairing heavy metal contaminated soil Download PDFInfo
- Publication number
- CN104607452A CN104607452A CN201510028474.1A CN201510028474A CN104607452A CN 104607452 A CN104607452 A CN 104607452A CN 201510028474 A CN201510028474 A CN 201510028474A CN 104607452 A CN104607452 A CN 104607452A
- Authority
- CN
- China
- Prior art keywords
- soil
- heavy metal
- ultrasonic wave
- extracting agent
- citric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002689 soil Substances 0.000 title claims abstract description 59
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000011133 lead Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000010358 mechanical oscillation Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 230000029087 digestion Effects 0.000 claims description 15
- 238000011109 contamination Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract 1
- 238000002137 ultrasound extraction Methods 0.000 abstract 1
- 230000008439 repair process Effects 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 231100000749 chronicity Toxicity 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for ultrasonically repairing heavy metal contaminated soil. The method comprises at least following steps: preparation of an extracting agent- citric acid solution; mixing of an extracting agent and polluted soil; mechanical oscillation extraction or ultrasonic-assisted extraction for soil; centrifugal separation and filtration of soil after extraction. According to the method, citric acid is selected as the extracting agent, so that the cost is relatively lower, influence on basic physicochemical property of soil is smaller, secondary pollution cannot be caused, the citric acid is an environment-friendly extracting agent, and four heavy metals including cadmium, copper, lead and zinc in the soil can be effectively removed when the extracting agent and ultrasonic waves are jointly applied to repairing of the heavy metal contaminated soil. The method has the characteristics of good removal effect, small extracting agent dosage and short repairing time.
Description
Technical field
The present invention relates to recovery technique field, the particularly method of ultrasonic wave remediating heavy metal combined contamination soil that heavy metal in soil pollutes.
Background technology
In recent years, heavy metal pollution of soil constitutes a serious threat to food security, ecological environment and agricultural sustainable development.Heavy metal be mainly derived from dirty to fill with, a large amount of uses of fertilizer and pesticide, " three wastes " in plating and dyestuff factory, municipal refuse and atmospheric fallout etc.Heavy metal pollution has the feature of disguise, chronicity and irreversibility, and it can not be degraded by microorganisms, and can affect crop and biological growth, and is detrimental to health and life by food chain.
At present, heavy-metal contaminated soil restorative procedure mainly contains engineering (comprise soil moved in improve the original method, soil replacement method and deep ploughing dig method), physical-chemical process (comprising electric driving method, electrothermal way and elution method), stable curing method and biological restoration (comprising phytoremediation and microorganism remediation) etc.Soil leaching recovery technique technique is simple, and repairing effect is stable, thorough, has become the study hotspot that soil environment repairs field.
Soil leaching technology is transferred in digestion agent by heavy metal in soil by oscillation method, thus reach the object of restoration of soil polluted by heavy metal.Conventional eluent inorganic solution, chelating agent and surfactant.Inorganic solution can cause the change of soil pH and the decline of soil fertility, and not easily regeneration; Artificial chelating agent and artificially synthesised surfactant expensive, biological degradability is poor, easily causes secondary pollution; Biosurfactant yields poorly.If find a kind of environmentally friendly digestion agent, cost is low, and biological degradability is good, little on soil physico-chemical property impact, and efficiently can remove the leach extraction method of heavy metal in soil at short notice, will be very meaningful for restoration of soil polluted by heavy metal.
Summary of the invention
The object of the invention is to solve heavy-metal contaminated soil long for repair time, high in cost of production problem, provides a kind of digestion agent consumption few, affects little, non-secondary pollution on soil physico-chemical property, repair time the short and leach extraction method that efficiency is high.
Object of the present invention is achieved through the following technical solutions:
The method of ultrasonic wave remediating heavy metal combined contamination soil of the present invention, comprises at least following steps:
(1) preparation of digestion agent citric acid solution;
(2) digestion agent of step (1) and mixing of contaminated soil;
(3) the soil mechanical oscillation lixiviate of step (2), or Ultrasonic Wave-Assisted Extraction;
(4) centrifugation of soil and filtration after step (3) lixiviate;
In step (1), digestion agent citric acid concentration is 0.6-1.0 molL
-1.
The solid-to-liquid ratio that in step (2), contaminated soil mixes with digestion agent is 1:20-30.
In step (3), mechanical oscillation speed is 160-200 rmin
-1, duration of oscillation is 3-5 h; Ultrasonic frequency is 30-50 kHz, and ultrasonic power is 400-600 W, and ultrasonic time is 20-40 min.
In step (4), centrifugation rotating speed is 3500-4500 rmin
-1, centrifugation time is 8-12 min, and filter sizes is 0.45 μm.
Heavy metal in described heavy-metal composite pollution soil is cadmium, copper, lead and zinc.
Compared with prior art, advantage of the present invention is:
(1) digestion agent selected by the present invention is citric acid, for digestion agent EDTA (the patent Shen in existing patent
Please numbers 201310437954.4), price is relatively low, and biological degradability is also fine, and less on physiochemical properties of soil impact, can not cause secondary pollution, be a kind of environmentally friendly digestion agent with applications well prospect.
Compared with EDTA, citric acid degradable 70% in average degradable 20%, 20 days in 1-4 days; EDTA degradability is poor, only degradable 14% after 20 days.Citric acid reaches the effect of restoration of soil polluted by heavy metal by acid-soluble effect and chelation.
(2) ultrasonic wave and citric acid are together acted on heavy-metal composite pollution soil, required digestion agent by the present invention
Consumption is few, and repair time is short, can effectively remove Cadmium in Soil, copper, lead and zinc, and can not produce secondary pollution to environment.This is because ultrasonic wave energy directly acts on sample interior, and the cavitation produced can be resolved the set state heavy metal in soil and form free state, thus increases the clearance of heavy metal.
Detailed description of the invention
Below in conjunction with case study on implementation, the present invention is described in detail.
Embodiment 1: the method for ultrasonic wave remediating heavy metal combined contamination soil
Contaminated soil picks up from Cd, Cu, Pb and Zn combined contamination soil near copper works of Fuyang City of Zhejiang Province.Air-dry soil sample rejects milled 2 mm stainless steel sifts, wherein part soil sample ground 0.15 mm nylon mesh further after stone and undesirable root.The content of Cadmium in Soil, copper, lead and zinc is respectively 13.3 mgkg after measured
-1, 740 mgkg
-1, 426 mgkg
-1with 2133 mgkg
-1.After pretreatment, take 1.0000 g soil samples, add in 100 mL centrifuge tubes.
Vibration lixiviate subsequent step is as follows:
(1) concentration preparing citric acid solution is 1.0 molL
-1;
(2) by solid-to-liquid ratio 1:25 mixing, above-mentioned soil sample is 1.0000 g, and described citric acid solution volume is 25
mL；
(3) mechanical oscillation lixiviate, oscillation rate is 180 rmin
-1, duration of oscillation is 4 h;
(4) centrifugal after lixiviate and filtration, centrifugal rotational speed is 4000 rmin
-1, centrifugation time is 10 min, 0.45
μm membrane filtration, to be measured.
After measured, the clearance of Cadmium in Soil, copper, lead and zinc is respectively 53.0%, 69.6%, 74.5% and 98.6%.
Mechanical oscillation lixiviate of the present invention also can replace with Ultrasonic Wave-Assisted Extraction, and concrete steps are as follows:
(1) concentration preparing citric acid solution is 0.6 molL
-1;
(2) by solid-to-liquid ratio 1:25 mixing, above-mentioned soil sample is 1.0000 g, and described citric acid solution volume is 25
mL；
(3) Ultrasonic Wave-Assisted Extraction, ultrasonic frequency is 40 kHz, and ultrasonic power is 500 W, ultrasonic time
Be 30 min;
(4) centrifugal after lixiviate and filtration, centrifugal rotational speed is 4000 rmin
-1, centrifugation time is 10 min, 0.45
μm membrane filtration, to be measured.
After measured, the clearance of Cadmium in Soil, copper, lead and zinc is respectively 52.9%, 64.2%, 59.8% and 97.4%.
Claims (6)
1. the method for ultrasonic wave remediating heavy metal combined contamination soil, is characterized in that the method comprises at least following steps:
(1) preparation of digestion agent citric acid solution;
(2) digestion agent of step (1) and mixing of contaminated soil;
(3) the soil mechanical oscillation lixiviate of step (2), or Ultrasonic Wave-Assisted Extraction;
(4) centrifugation of soil and filtration after step (3) lixiviate.
2. the method for ultrasonic wave remediating heavy metal combined contamination soil according to claim 1, is characterized in that: in step (1), digestion agent citric acid concentration is 0.6-1.0 molL
-1.
3. the method for ultrasonic wave remediating heavy metal combined contamination soil according to claim 1, is characterized in that: the solid-to-liquid ratio that in step (2), contaminated soil mixes with digestion agent is 1:20-30.
4. the method for ultrasonic wave remediating heavy metal combined contamination soil according to claim 1, is characterized in that: in step (3), mechanical oscillation speed is 160-200 rmin
-1, duration of oscillation is 3-5 h; Ultrasonic frequency is 30-50 kHz, and ultrasonic power is 400-600 W, and ultrasonic time is 20-40 min.
5. the method for ultrasonic wave remediating heavy metal combined contamination soil according to claim 1, is characterized in that: in step (4), centrifugation rotating speed is 3500-4500 rmin
-1, centrifugation time is 8-12 min, and filter sizes is 0.45 μm.
6. the method for ultrasonic wave remediating heavy metal combined contamination soil according to claim 1, is characterized in that described heavy metal is cadmium, copper, lead and zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510028474.1A CN104607452A (en) | 2015-01-21 | 2015-01-21 | Method for ultrasonically repairing heavy metal contaminated soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510028474.1A CN104607452A (en) | 2015-01-21 | 2015-01-21 | Method for ultrasonically repairing heavy metal contaminated soil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104607452A true CN104607452A (en) | 2015-05-13 |
Family
ID=53142247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510028474.1A Pending CN104607452A (en) | 2015-01-21 | 2015-01-21 | Method for ultrasonically repairing heavy metal contaminated soil |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105728450A (en) * | 2016-05-05 | 2016-07-06 | 四川农业大学 | Method for removing lead, zinc and cadmium in soil by increasing low-molecular organic acids by virtue of nano materials |
| CN106167706A (en) * | 2016-06-30 | 2016-11-30 | 长江大学 | A kind of external source easily extracts preparation method and the using method thereof of glomalin soil conditioner |
| CN106396314A (en) * | 2016-11-30 | 2017-02-15 | 河海大学 | Method using ultrasonic to assist nanoscale zero-valence iron to remedy soil or sludge polluted by heavy metals |
| CN106493164A (en) * | 2016-08-24 | 2017-03-15 | 天津市北方创业园林股份有限公司 | A kind of method that utilization citric acid extracts drip washing restoration of soil polluted by heavy metal |
| CN106563692A (en) * | 2015-10-08 | 2017-04-19 | 韩国地质资源研究院 | Method of restoring heavy-metal-contaminated soil |
| CN106746395A (en) * | 2016-11-30 | 2017-05-31 | 河海大学 | The method and its special purpose device of nano zero valence iron removal Heavy Metals in Sludge |
| CN106746399A (en) * | 2016-12-14 | 2017-05-31 | 广东工业大学 | A kind of purification method of Heavy Metals in Sludge and its application |
| CN108196033A (en) * | 2017-12-22 | 2018-06-22 | 镇江市宇驰检测技术有限公司 | A kind of detection method of heavy metal in soil |
| CN108971215A (en) * | 2018-06-11 | 2018-12-11 | 华东理工大学 | The heavy-metal contaminated soil restorative procedure filtered based on ultrasound |
| GB2572522A (en) * | 2019-05-08 | 2019-10-02 | Yiwu Wanju Electronics Co Ltd | An Agricultural heavy metal in soil removal device |
| CN111085537A (en) * | 2019-12-07 | 2020-05-01 | 重庆市固体废物管理服务中心有限公司 | Method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials |
| CN112157120A (en) * | 2020-08-25 | 2021-01-01 | 中国科学院烟台海岸带研究所 | Method and device for repairing soil by solubilizing and increasing drainage mode |
| CN113109108A (en) * | 2021-03-26 | 2021-07-13 | 中国科学院合肥物质科学研究院 | Sampling method for obtaining soil solution by efficient online leaching |
| CN113182338A (en) * | 2021-04-25 | 2021-07-30 | 三明学院 | Method for restoring molybdenum-polluted soil by ultrasonic/oscillation-assisted chemical leaching |
| CN113732046A (en) * | 2021-08-26 | 2021-12-03 | 中国科学院烟台海岸带研究所 | Method for removing soil heavy metals by using agriculture and forestry waste leaching liquor |
| CN116855254A (en) * | 2023-07-03 | 2023-10-10 | 江苏莘野生物科技有限公司 | Long-acting controllable acid soil conditioner and preparation method thereof |
-
2015
- 2015-01-21 CN CN201510028474.1A patent/CN104607452A/en active Pending
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563692A (en) * | 2015-10-08 | 2017-04-19 | 韩国地质资源研究院 | Method of restoring heavy-metal-contaminated soil |
| CN106563692B (en) * | 2015-10-08 | 2020-02-14 | 韩国地质资源研究院 | Method for restoring heavy metal contaminated soil |
| CN105728450B (en) * | 2016-05-05 | 2019-01-29 | 四川农业大学 | The method that nano material promotes low molecular organic acids removal Pb in Soil, zinc and cadmium |
| CN105728450A (en) * | 2016-05-05 | 2016-07-06 | 四川农业大学 | Method for removing lead, zinc and cadmium in soil by increasing low-molecular organic acids by virtue of nano materials |
| CN106167706A (en) * | 2016-06-30 | 2016-11-30 | 长江大学 | A kind of external source easily extracts preparation method and the using method thereof of glomalin soil conditioner |
| CN106167706B (en) * | 2016-06-30 | 2019-10-15 | 长江大学 | A kind of external source easily extracts the preparation method and its application method of glomalin soil conditioner |
| CN106493164A (en) * | 2016-08-24 | 2017-03-15 | 天津市北方创业园林股份有限公司 | A kind of method that utilization citric acid extracts drip washing restoration of soil polluted by heavy metal |
| CN106396314A (en) * | 2016-11-30 | 2017-02-15 | 河海大学 | Method using ultrasonic to assist nanoscale zero-valence iron to remedy soil or sludge polluted by heavy metals |
| CN106746395A (en) * | 2016-11-30 | 2017-05-31 | 河海大学 | The method and its special purpose device of nano zero valence iron removal Heavy Metals in Sludge |
| CN106746399B (en) * | 2016-12-14 | 2020-09-11 | 广东工业大学 | Method for purifying heavy metal in sludge and application thereof |
| CN106746399A (en) * | 2016-12-14 | 2017-05-31 | 广东工业大学 | A kind of purification method of Heavy Metals in Sludge and its application |
| CN108196033A (en) * | 2017-12-22 | 2018-06-22 | 镇江市宇驰检测技术有限公司 | A kind of detection method of heavy metal in soil |
| CN108971215A (en) * | 2018-06-11 | 2018-12-11 | 华东理工大学 | The heavy-metal contaminated soil restorative procedure filtered based on ultrasound |
| CN108971215B (en) * | 2018-06-11 | 2020-07-24 | 华东理工大学 | Heavy metal contaminated soil remediation method based on ultrasonic suction filtration |
| GB2572522A (en) * | 2019-05-08 | 2019-10-02 | Yiwu Wanju Electronics Co Ltd | An Agricultural heavy metal in soil removal device |
| CN111085537A (en) * | 2019-12-07 | 2020-05-01 | 重庆市固体废物管理服务中心有限公司 | Method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials |
| CN112157120A (en) * | 2020-08-25 | 2021-01-01 | 中国科学院烟台海岸带研究所 | Method and device for repairing soil by solubilizing and increasing drainage mode |
| CN113109108A (en) * | 2021-03-26 | 2021-07-13 | 中国科学院合肥物质科学研究院 | Sampling method for obtaining soil solution by efficient online leaching |
| CN113109108B (en) * | 2021-03-26 | 2022-08-09 | 中国科学院合肥物质科学研究院 | Sampling method for obtaining soil solution by efficient online leaching |
| CN113182338A (en) * | 2021-04-25 | 2021-07-30 | 三明学院 | Method for restoring molybdenum-polluted soil by ultrasonic/oscillation-assisted chemical leaching |
| CN113732046A (en) * | 2021-08-26 | 2021-12-03 | 中国科学院烟台海岸带研究所 | Method for removing soil heavy metals by using agriculture and forestry waste leaching liquor |
| CN116855254A (en) * | 2023-07-03 | 2023-10-10 | 江苏莘野生物科技有限公司 | Long-acting controllable acid soil conditioner and preparation method thereof |
| CN116855254B (en) * | 2023-07-03 | 2024-06-07 | 江苏莘野生物科技有限公司 | Long-acting controllable acid soil conditioner and preparation method thereof |
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Application publication date: 20150513 |
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