CN115382900A - Method for leaching and repairing heavy metal contaminated soil by using thiomalic acid - Google Patents
Method for leaching and repairing heavy metal contaminated soil by using thiomalic acid Download PDFInfo
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- CN115382900A CN115382900A CN202211251549.9A CN202211251549A CN115382900A CN 115382900 A CN115382900 A CN 115382900A CN 202211251549 A CN202211251549 A CN 202211251549A CN 115382900 A CN115382900 A CN 115382900A
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- 239000002689 soil Substances 0.000 title claims abstract description 117
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002386 leaching Methods 0.000 title claims abstract description 52
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 77
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003480 eluent Substances 0.000 claims abstract description 19
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims description 41
- -1 mercury ions Chemical class 0.000 abstract description 51
- 230000000694 effects Effects 0.000 abstract description 31
- 239000000126 substance Substances 0.000 abstract description 7
- 238000011109 contamination Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 description 36
- 239000000706 filtrate Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 26
- 238000005303 weighing Methods 0.000 description 18
- 239000012982 microporous membrane Substances 0.000 description 17
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 14
- 238000007789 sealing Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005067 remediation Methods 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KBKPZJIPQDPSHG-UHFFFAOYSA-N 2-hydroxy-2-sulfobutanedioic acid Chemical compound OC(=O)CC(O)(C(O)=O)S(O)(=O)=O KBKPZJIPQDPSHG-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 208000008763 Mercury poisoning Diseases 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for eluting heavy metal contaminated soil by using thiomalic acid as an eluent, in particular for eluting soluble mercury ions in the mercury contaminated soil, which is used for solving the increasingly severe problem of heavy metal contamination of the soil at present. The chemical leaching method is simple to operate, has a good leaching and repairing effect, and has leaching removal rates of 82.5% and 78.9% for mercury and cadmium heavy metal contaminated soil.
Description
Technical Field
The invention belongs to the technical field of heavy metal soil remediation and chemical leaching, and relates to leaching of heavy metal (including mercury, copper, lead and cadmium) polluted soil by thiomalic acid.
Background
With the rapid development of the world industrial technology and the excessive exploitation of mineral resources, the problem of heavy metal pollution of soil is increasingly severe. The heavy metals not only can affect the fertility of soil, but also can enter human bodies through food chains to cause various diseases and endanger the health of people. How to fundamentally solve the heavy metal pollution of soil has become a difficult problem which people have to face and need to solve urgently.
Heavy metals mercury, copper, lead and cadmium have adverse effects on human bodies. For example, mercury is a toxic heavy metal, primarily Hg, in soil 0 、Hg 2 2+ 、Hg 2+ And mercury alkyls, e.g. HgS, hgCl 2 HgO and methyl mercury. Inorganic mercury can be converted into alkyl mercury through sulfate reducing bacteria, so that the metabolism of cells is damaged, and the function of a body is influenced. Mercury poisoning can not only damage the liver and kidney functions of a person, but also can have serious effects on the central nervous system.
The heavy metal soil remediation technology is a key point of domestic and foreign research in recent years, and can be mainly divided into physical adsorption, chemical leaching and biodegradation, wherein the chemical leaching is one of the most widely applied methods due to the characteristics of simple operation and high heavy metal removal efficiency. The method is mainly characterized in that heavy metal eluting agent is used for acting molecules of the eluting agent with heavy metal in soil in a vibration washing mode, so that exchangeable heavy metal in the soil is washed away. The selection of the eluting agent directly influences the eluting efficiency of the heavy metal polluted soil. Inorganic acids represented by hydrochloric acid can act on soil contaminated with heavy metals to elute the heavy metals from the soil, but also can damage the surface layer structure of the soil to some extent. Moreover, in previous researches, small-molecule organic acids, such as tartaric acid, malic acid, citric acid and the like, are found to play a significant role in removing some heavy metal ions, but related reports on the aspect of mercury ion elution are extremely rare.
The theory of soft and hard acids and bases is the theory of dividing the acids and bases with different properties into two types of soft and hard, which was proposed by r.g. pierce in 1963. In the field of chemical research, it is often used to judge the stability of compounds and to make reasonable explanations for some reaction mechanisms. The theory of the soft acid and the hard acid is that the hard acid has the characteristics of small volume, high charge number and low polarizability, while the soft acid has low charge number and high polarizability. According to the theory, heavy metal ions such as mercury, copper, lead, cadmium and the like are soft acids and have strong affinity with sulfides of soft alkali. According to the characteristics, sulfur-containing small molecular organic acid interacts with heavy metal ions such as mercury, copper, lead, cadmium and the like in soil to form a stable soft and hard acid-base complex, so that the aims of removing harmful heavy metals in the soil and repairing the soil are fulfilled.
Thiomalic acid is thiolated malic acid, and the thiol group of the thiomalic acid is used as a characteristic functional group with chelation, and is often used for modification of various compounds and determination of some metal elements. For example, beta-cyclodextrin with a special cavity structure is grafted with baker's yeast by modifying the beta-cyclodextrin as a cross-linking agent, so that Pb (II) and Cd (II) in wastewater can be well chelated, and the adsorption capacity can reach 150.08mg/g and 102.8mg/g respectively. And secondly, the silica gel modified by the thiomalic acid can be used as an adsorbent to measure trace lead and cadmium in a water sample, and can also be used as a complexing titration masking agent to measure lead in the copper alloy.
The invention uses thiomalic acid as a chemical eluent of organic acids to carry out leaching remediation on the soil polluted by heavy metals such as mercury, cadmium, lead, copper and the like so as to achieve the purpose of removing soluble heavy metal ions such as mercury, cadmium, lead, copper and the like in the soil.
Disclosure of Invention
The invention discloses a method for restoring mercury-polluted heavy metal by using a chemical leaching technology, which comprises the following steps: (1) Mixing the soil sample with a certain amount of Hg (NO) 3 ) 2 Uniformly mixing the solution, and air-drying to prepare mercury-polluted heavy metal soil; (2) And mixing the prepared sulfo-malic acid solution with the prepared mercury-polluted soil, and shaking at room temperature to wash out mercury ions in the soil.
The formula of thiomalic acid is as follows:
in the step (1), the original pH of the soil is 6.53, the content of organic matters is 32.41g/kg, the cation exchange capacity is 39.80mmol/kg, the total amount of nitrogen, phosphorus and potassium is 1520mg/kg, 700mg/kg and 12980mg/kg respectively, the content of total mercury is increased from 0.6364mg/kg to 120mg/kg, and the percentage content of the particle size is respectively as follows: <0.002mm (49.70%), 0.002-0.02mm (36.46%), >0.02mm (13.84%).
In the step (2), the adsorption of the thiomalic acid leaching solution and the mercury ions quickly reach equilibrium, and when the oscillation time is increased from 5 minutes to 60 minutes, hg in the leaching solution is increased 2+ The content of (A) is increased from 5.0092mg/kg to 6.3898mg/kg, and Hg in the eluent solution is increased along with the increase of time 2+ The content value of (A) keeps a relatively smooth level.
In the step (2), the ratio of the soil mass of the soil and the eluting agent to the volume of the thiomalic acid aqueous solution is set to be 1:10 to 1: a gradient of 60, wherein the volume ratio of soil mass to thiomalic acid aqueous solution is 1: and 20, the action of mercury ions and thiomalic acid in the soil is balanced, and the leaching rate reaches a higher level. According to the measurement result, the content of mercury ions in the filtrate is regularly changed along with the change of the volume ratio of the soil mass to the thiomalic acid aqueous solution, and when the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. When the ratio of the mass of the soil to the volume of the aqueous thiomalic acid solution is 1 to 10, the leaching rate is 70.4% by calculation, and when the ratio of the mass of the soil to the volume of the aqueous thiomalic acid solution is increased to 1 to 20, the leaching rate is 77.1%, and as the volume of the leaching solution is added, the removal efficiency for mercury ions is maintained at a relatively stable level, for example, 1.
In the step (2), acidity also has a certain influence on the soil washing efficiency. By changing the concentration of the thiomalic acid to prepare eluent solutions with different acidity, when the concentration of the thiomalic acid is 0.005mol/L, the measured concentration of mercury ions is 6.9392mg/kg, and when the concentration is increased to 0.05mol/L, the measured concentration of mercury ions is increased to 12.1961mg/kg, and the maximum value is reached. As the concentration continues to rise, the concentration of mercury ions in the solution is maintained in a relatively steady state.
The method for leaching heavy metal soil can remove Hg in soil 2+ Outside of the ions, for Cd 2+ 、Pb 2+ And Cu 2+ The removal effect of (2) is also significant.
In the specific implementation process, after the shaking and leaching process is finished, the suspension is transferred into a centrifugal tube, is centrifuged for 20 minutes at the rotating speed of 3000 r/min, is filtered by a 0.45-micron microporous filter membrane, and the total amount of heavy metals such as mercury, cadmium, lead, copper and the like in the filtrate is measured by ICP-OES. And (4) dividing the obtained contents of the mercury, cadmium, lead, copper and other heavy metals by the total amount of the mercury, cadmium, lead, copper and other heavy metals in the original soil, and calculating the leaching efficiency of the leaching agent. The calculation formula is as follows:
the invention has the beneficial effects that: the invention applies a new micromolecular organic acid, namely thiomalic acid, to generate remarkable effect on removing heavy metals in soil. The remediation of heavy metal polluted soil such as mercury, cadmium, lead, copper and the like by thiomalic acid is greatly superior to that of other common small molecular organic acids (malic acid, tartaric acid, citric acid, acetic acid, oxalic acid and maleic acid). In addition, the removal process can reach equilibrium within a short time, generally 1 hour, and a higher leaching rate is achieved. The process is carried out at room temperature, and the leaching rate of mercury ions can reach more than 80% particularly under the condition of lower leaching agent concentration. The results of the tests on the concentration of mercury ions in the filtrates of some soil samples as a function of the thiomalic acid concentration are shown in Table 1. The discovery provides a new method for restoring the soil polluted by the heavy metals such as mercury, cadmium, lead, copper and the like.
TABLE 1 concentration of mercury ions in the filtrate as a function of thiomalic acid concentration
The embodiments of the present invention clearly and completely describe the technical solutions of the present invention, and do not limit the present invention.
Detailed Description
Example 1
Preparation of mercury contaminated soil
Soil samples dug in the open country of the city of Sichuan province were ground and naturally air-dried at room temperature for 30 days. And continuously grinding the air-dried sample, and sieving the ground sample by using a 200-mesh sieve for later use. Taking out appropriate Hg (NO) 3 ) 2 And adding deionized water into the solid to prepare heavy metal ion solution, mixing the heavy metal ion solution with the prepared soil sample in a culture dish, and fully stirring to uniformly mix the heavy metal ion solution and the prepared soil sample. And finally, placing the mixed sample in a ventilated place, naturally drying the mixed sample for 7 days at room temperature, mashing and grinding the mixed sample again after the water in the sample is completely evaporated, sieving the ground soil by a 50-target standard sample sieve, and collecting the ground soil for later use.
Example 2
Test of leaching effect of thiomalic acid on lead-polluted soil
Weighing Pb-containing materials 2+ 0.50 of the soil sampleAnd g, adding 10mL of 0.05mol/L thiomalic acid solution into a 100mL conical flask, and placing the sealed conical flask into a constant-temperature water bath shaking pot to shake for 24 hours at room temperature. The suspension after shaking was taken out, placed in a 10mL centrifuge tube, centrifuged at 3000 rpm for 20 minutes and then taken out, followed by filtration through a 0.45 μm microporous membrane filter, and finally the total amount of lead in the filtrate was detected by ICP-OES. The leaching rate of the solution to the lead ions of the soil is 45.0 percent through calculation.
Example 3
Test of leaching effect of thiomalic acid on cadmium-polluted soil
Weighing Cd in 2+ 0.50g of the soil sample is added with 10mL of thiomalic acid solution of 0.05mol/L into a 100mL conical flask, and the sealed conical flask is placed into a constant-temperature water bath shaking pot to be shaken for 24 hours at room temperature. And taking out the suspension after shaking, putting the suspension into a 10mL centrifuge tube, centrifuging the suspension for 20 minutes at the rotating speed of 3000 rpm, then taking out the suspension, filtering the suspension by using a 0.45-micron microporous filter membrane, and finally detecting the total amount of cadmium in the filtrate by ICP-OES. The leaching rate of the solution to the cadmium ions in the soil is 78.9 percent according to calculation.
Example 4
Test of leaching effect of thiomalic acid on copper-polluted soil
Weighing Cu-containing 2+ Adding 10mL of thiomalic acid solution of 0.05mol/L into a 100mL conical flask, and placing the sealed conical flask into a constant-temperature water bath shaking pot to shake for 24 hours at room temperature. The suspension after shaking was taken out, placed in a 10mL centrifuge tube, centrifuged at 3000 rpm for 20 minutes and then taken out, followed by filtration through a 0.45 μm microporous membrane and finally the total amount of copper in the filtrate was measured by ICP-OES. The leaching rate of the solution to the soil copper ions is 60.6 percent according to calculation.
Example 5
Test of leaching effect of thiomalic acid on mercury-contaminated soil
Weighing Hg-containing 2+ Adding 0.05 mol/L10 mL of thiomalic acid solution into a 100mL conical flask, placing the sealed conical flask into a constant-temperature water bath shaking pot, and shaking at room temperature for 2And 4h. The suspension after shaking was taken out, placed in a 10mL centrifuge tube, centrifuged at 3000 rpm for 20 minutes and then taken out, followed by filtration through a 0.45 μm microporous membrane, and finally the total amount of mercury in the filtrate was measured by ICP-OES. The leaching rate of the solution to the mercury ions in the soil is 80.0 percent through calculation.
Example 6
Influence of leaching time on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, transferring the suspension into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, taking out after 20 minutes, filtering with a 0.45 mu m microporous filter membrane, and measuring the content of each group of mercury ions in the obtained filtrate by ICP-OES. The measured concentration of mercury ions was 5.0092mg/L, and the calculated leaching rate was 62.8%.
Example 7
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of thiomalic acid aqueous solution of 0.05mol/L (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, the suspension is transferred into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, the suspension is taken out after 20 minutes and filtered by a 0.45 mu m microporous filter membrane, and the content of mercury ions in the obtained filtrate is determined by ICP-OES. The measured concentration of mercury ions is 5.1709mg/L, and the calculated leaching rate is 64.5%.
Example 8
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, the suspension is transferred into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, the suspension is taken out after 20 minutes and filtered by a 0.45 mu m microporous filter membrane, and the content of mercury ions in the obtained filtrate is determined by ICP-OES. The measured concentration of mercury ions is 5.1657mg/L, and the calculated leaching rate is 63.0%.
Example 9
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, the suspension is transferred into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, the suspension is taken out after 20 minutes and filtered by a 0.45 mu m microporous filter membrane, and the content of mercury ions in the obtained filtrate is determined by ICP-OES. The concentration of mercury ions was found to be 6.2059mg/L with a leaching rate of 70.8%.
Example 10
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, the suspension is transferred into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, the suspension is taken out after 20 minutes and filtered by a 0.45 mu m microporous filter membrane, and the content of mercury ions in the obtained filtrate is determined by ICP-OES. The measured concentration of mercury ions was 6.3898mg/L, and the calculated leaching rate was 80.4%.
Example 11
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, the suspension is transferred into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, the suspension is taken out after 20 minutes and filtered by a 0.45 mu m microporous filter membrane, and the content of mercury ions in the obtained filtrate is determined by ICP-OES. The measured concentration of mercury ions was 6.4206mg/L, and the calculated leaching rate was 79.6%.
Example 12
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1. And a blank control was set. After shaking, the suspension is transferred into a 10mL centrifuge tube for centrifugation at the speed of 3000 rpm, the suspension is taken out after 20 minutes and filtered by a 0.45 mu m microporous filter membrane, and the content of mercury ions in the obtained filtrate is determined by ICP-OES. The measured concentration of mercury ions was 6.4606mg/L, and the calculated leaching rate was 80.9%.
Example 13
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 5mL of 0.05mol/L thiomalic acid aqueous solution into a 100mL conical flask, sealing, and oscillating in a constant-temperature water bath oscillating pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 11.2414mg/L, and the leaching rate is calculated to be 70.4%.
Example 14
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 7.5mL of 0.05mol/L thiomalic acid aqueous solution into the soil sample, sealing the soil sample in a 100mL conical flask, and oscillating the soil sample in a constant-temperature water bath oscillation pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 11.2414mg/L, and the leaching rate is calculated to be 70.4%.
Example 15
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 10mL of 0.05mol/L thiomalic acid aqueous solution into a 100mL conical flask, sealing, and oscillating in a constant-temperature water bath oscillating pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 6.1546mg/L, and the calculated leaching rate is 77.1 percent.
Example 16
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 15mL of 0.05mol/L thiomalic acid aqueous solution into a 100mL conical flask, sealing, and shaking in a constant-temperature water bath shaking pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 4.1428mg/L, and the leaching rate is calculated to be 78.1%.
Example 17
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 20mL of 0.05mol/L thiomalic acid aqueous solution into a 100mL conical flask, sealing, and shaking in a constant-temperature water bath shaking pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 3.0699mg/L, and the leaching rate is calculated to be 75.9%.
Example 18
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 25mL of 0.05mol/L thiomalic acid aqueous solution into a 100mL conical flask, sealing, and shaking in a constant-temperature water bath shaking pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 2.4756mg/L, and the leaching rate is calculated to be 76.1%.
Example 19
Influence of volume ratio of soil quality to thiomalic acid aqueous solution on mercury ion removal effect in soil
Weighing 0.50g of mercury-contaminated soil sample, adding 30mL of 0.05mol/L thiomalic acid aqueous solution, sealing in a 100mL conical flask, and oscillating in a constant-temperature water bath oscillating pot at a proper speed for 1h. And a blank control was set. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The measured result is that the concentration of mercury ions is 2.0658mg/L, and the leaching rate is calculated to be 76.6%.
Example 20
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing the thiomalic acid into an aqueous solution with the concentration of 0.005 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant temperature water bath shaking pot, shaking at appropriate speed for 1h. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 6.9392mg/L, with a leaching rate of 46.0%.
Example 21
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing the thiomalic acid into an aqueous solution with the concentration of 0.01 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant-temperature water bath shaking pot, and shaking at a proper speed for 1h. After shaking, the suspension was removed, transferred to a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 8.1205mg/L, with a leaching rate of 53.9%.
Example 22
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing the thiomalic acid into an aqueous solution with the concentration of 0.02 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant temperature water bath shaking pot, shaking at appropriate speed for 1h. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 9.9844mg/L, with a leaching rate of 66.2%.
Example 23
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing thiomalic acid into an aqueous solution with the concentration of 0.05 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant temperature water bath shaking pot, shaking at appropriate speed for 1h. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 12.1961mg/L, with an elution rate of 81.0%.
Example 24
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing the thiomalic acid into an aqueous solution with the concentration of 0.1 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant temperature water bath shaking pot, shaking at appropriate speed for 1h. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 12.4545mg/L, with an elution rate of 82.5%.
Example 25
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing the thiomalic acid into an aqueous solution with the concentration of 0.2 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant-temperature water bath shaking pot, and shaking at a proper speed for 1h. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 11.5019mg/L, with a leaching rate of 75.7%.
Example 26
Effect of eluent concentration on Mercury ion removal Effect in soil
Firstly, preparing the thiomalic acid into an aqueous solution with the concentration of 0.5 mol/L. Then, 0.50g of mercury contaminated soil sample was weighed into a 100mL Erlenmeyer flask, and then 10mL of eluent solution was weighed into the Erlenmeyer flask, using deionized water as a blank control. Sealing, placing in a constant temperature water bath shaking pot, shaking at appropriate speed for 1h. After the shaking was completed, the suspension was taken out, transferred into a centrifuge tube and placed in a centrifuge, centrifuged at 3000 rpm for 20 minutes, and finally filtered through a 0.45 μm microporous membrane. The content of mercury ions in the filtrate was measured by ICP-OES. The result was 12.0693mg/L, and the elution rate was 79.4%.
The above description is intended to be illustrative of the present invention and should not be taken as limiting the invention, but rather the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (1)
1. A method for leaching and repairing heavy metal contaminated soil is characterized by comprising the following steps: taking thiomalic acid as an eluent, placing a thiomalic acid aqueous solution (0.01 mol/L-0.05 mol/L) and mercury and cadmium polluted soil (the volume ratio of the soil mass to the thiomalic acid aqueous solution is 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10156315A (en) * | 1996-10-04 | 1998-06-16 | Nippon Kayaku Co Ltd | Treating agent for heavy metal-containing waste and stabilizing treatment of heavy metal-containing waste |
| CN103528980A (en) * | 2013-09-23 | 2014-01-22 | 桂林理工大学 | Flame atomic absorption spectrum method for separating, enriching and determining trace lead and cadmium in water sample by using thiomalamic acid modified silica gel |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10156315A (en) * | 1996-10-04 | 1998-06-16 | Nippon Kayaku Co Ltd | Treating agent for heavy metal-containing waste and stabilizing treatment of heavy metal-containing waste |
| CN103528980A (en) * | 2013-09-23 | 2014-01-22 | 桂林理工大学 | Flame atomic absorption spectrum method for separating, enriching and determining trace lead and cadmium in water sample by using thiomalamic acid modified silica gel |
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| Title |
|---|
| 罗明生等, 四川科学技术出版社 * |
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