CN117772778A - Method for restoring hexachlorobenzene-polluted soil by ferric salt-reinforced indigenous bacteria - Google Patents
Method for restoring hexachlorobenzene-polluted soil by ferric salt-reinforced indigenous bacteria Download PDFInfo
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- CN117772778A CN117772778A CN202410100887.5A CN202410100887A CN117772778A CN 117772778 A CN117772778 A CN 117772778A CN 202410100887 A CN202410100887 A CN 202410100887A CN 117772778 A CN117772778 A CN 117772778A
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- hexachlorobenzene
- polluted soil
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- 239000002689 soil Substances 0.000 title claims abstract description 47
- 241000894006 Bacteria Species 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims abstract description 38
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 24
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 23
- 239000012153 distilled water Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000007605 air drying Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 29
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000010170 biological method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 ferric sulfate Chemical class 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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Abstract
The invention discloses a method for restoring hexachlorobenzene-polluted soil by ferric salt reinforced indigenous bacteria, which comprises the following steps: air-drying, grinding and screening hexachlorobenzene polluted soil; adding hexachlorobenzene polluted soil and deoxidized distilled water into a reaction container, wherein the solid-liquid ratio is 1:1-1:1.5; the oxidation-reduction potential of the mixture in the reaction vessel is within the range of-100 mV to-50 mV, so that a reaction system with a flooded anaerobic environment is formed; adding ferric chloride powder, wherein the concentration of ferric chloride in the reaction system is 5-10 g/L; the initial pH value of the reaction is controlled to be 3-7; vacuumizing the reactor, sealing, and standing in a biological incubator for 15-24 days; and naturally air-drying the soil. The invention can solve the problems of long repair period, lower repair efficiency and the like existing in the process of repairing hexachlorobenzene-polluted soil by singly utilizing the biological repair mode of indigenous bacteria.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a method for repairing hexachlorobenzene-polluted soil by ferric salt reinforced indigenous bacteria.
Background
Hexachlorobenzene is one of the first-controlled 12 Persistent Organic Pollutants (POPs) in the international convention of the united nations environmental planning agency, the stockholm convention on persistent organic pollutants, 2001, and is also one of the new pollutants in the key management and new pollutant list (2023 edition) issued by the united five major committee of the 2022 ecological environment department. At present, the restoration methods of hexachlorobenzene-polluted soil at home and abroad mainly comprise a physical method, a chemical method and a biological method. The biological method has gradually replaced physical and chemical methods because of the advantages of small investment, no need of special equipment, small occupied area, simple operation, small influence on the surrounding environment, no secondary pollution and the like, and becomes a hot spot and leading edge for research and development of the technology for restoring the hexachlorobenzene contaminated soil at home and abroad. Studies have shown that the soil polluted by hexachlorobenzene can be directly repaired by indigenous bacteria. However, the bioremediation mode of solely utilizing indigenous bacteria has the problems of low activity of indigenous microorganisms, long repair period, low repair efficiency and the like, and further restricts the development of the type of bioremediation technology.
Disclosure of Invention
The invention aims to provide a method for repairing hexachlorobenzene-polluted soil by ferric salt reinforced indigenous bacteria, which aims to solve the problems of long repairing period, lower repairing efficiency and the like existing in a biological repairing mode by independently utilizing indigenous bacteria. The invention aims at realizing the following technical scheme:
a method for restoring hexachlorobenzene-polluted soil by ferric salt reinforced indigenous bacteria comprises the following steps:
step one: after the hexachlorobenzene polluted soil is air-dried, grinding and screening to be less than 5 mm;
step two: adding hexachlorobenzene polluted soil and deoxidized distilled water into a reaction container, wherein the solid-liquid ratio of the hexachlorobenzene polluted soil to the deoxidized distilled water is 1:1-1:1.5 (g/ml); the oxidation-reduction potential of the mixture in the reaction vessel is within the range of-100 mV to-50 mV, so that a reaction system with a flooded anaerobic environment is formed; adding ferric chloride powder, wherein the concentration of ferric chloride in the reaction system is 5-10 g/L;
step three: regulating the pH value of the reaction system to control the initial pH value of the reaction to 3-7;
step four: vacuumizing the reaction vessel, sealing, and standing in a biological incubator at 40-50 ℃ for 15-24 days;
step five: and (3) naturally air-drying the soil treated in the step four.
Further optimizing, in the second step: pouring deoxidized distilled water into a reaction container, adding weighed hexachlorobenzene polluted soil in batches, adding ferric chloride powder, and standing for 24 hours.
Further, in the second step: the solid-to-liquid ratio of the polluted soil to the deoxidized distilled water is 1:1 (g/ml), and the adding concentration of the ferric chloride powder is 5g/L.
Further, in step three: sodium hydroxide and sulfuric acid were used to adjust the pH of the reaction system to 5.
Further, in the fourth step: the temperature in the biological incubator was 45℃and the reaction time was 18 days.
Further, in the fifth step: naturally air-drying for 2-3 days.
The invention has the advantages and beneficial effects that:
the invention solves the problems of long repair time and low repair efficiency existing in the soil polluted by hexachlorobenzene by indigenous bacteria biotechnology, and obtains good strengthening effect.
The removal rate of hexachlorobenzene in the polluted soil can reach more than 30%, and compared with the removal rate of hexachlorobenzene without adding ferric chloride under the same experimental condition, the removal rate of hexachlorobenzene can be improved by more than 20%; can provide theoretical guidance and technical support for the research and development of biological repair technology of the soil polluted by the persistent chlorinated organic compound.
Detailed Description
Example 1
A method for restoring hexachlorobenzene-polluted soil by ferric salt reinforced indigenous bacteria comprises the following steps:
step one: after the hexachlorobenzene polluted soil is air-dried, grinding and screening to be less than 5 mm;
step two: adding hexachlorobenzene polluted soil and deoxidized distilled water into a reaction container, wherein the solid-to-liquid ratio of the hexachlorobenzene polluted soil to the deoxidized distilled water is 1:1 (g/ml); the oxidation-reduction potential of the mixture in the reaction vessel is set at-100 mV to form a reaction system with a flooded anaerobic environment; adding ferric chloride powder, wherein the concentration of ferric chloride in a reaction system is 5g/L; pouring deoxidized distilled water into a reaction container, adding weighed hexachlorobenzene polluted soil in batches, adding ferric chloride powder, and standing;
step three: regulating the pH value of the reaction system to control the initial pH value of the reaction to be 5;
step four: vacuumizing the reactor, sealing, and standing in a biological incubator at 45 ℃ for 18 days;
step five: and (3) naturally air-drying the soil treated in the fourth step for 3 days.
In this example, a reaction time of 18 days is a comprehensive preference. The reaction time is within 15-24, and the result is acceptable. The effect is basically not good below 15 days, and the degradation effect is not changed obviously above 24 days.
Example 2
In this example, the concentration of ferric chloride in the reaction system in the second removal step was 10g/L, and the other operations and parameters were the same as in example 1.
Comparative example 1
In this comparative example, the concentration of ferric chloride in the reaction system in the second removal step was 0g/L, and the other operations and parameters were the same as in example 1.
Comparative example 2
In this example, the concentration of ferric chloride in the reaction system in the second removal step was 1g/L, and the other operations and parameters were the same as in example 1.
Comparative example 3
In this example, the concentration of ferric chloride in the reaction system in the second removal step was 50g/L, and the other operations and parameters were the same as in example 1. Hexachlorobenzene degradation rate= (initial amount of hexachlorobenzene in soil-residual amount of hexachlorobenzene in soil)/initial amount of hexachlorobenzene in soil ×100%.
The results of examples 1, 2 and comparative examples 1, 2, 3 are shown in table 1.
TABLE 1
Note that: the values in the table are the average of 3 determinations.
As can be seen from table 1, under the conditions of example 1 and example 2, the degradation rate of hexachlorobenzene in the soil to be measured can reach more than 30%, which is improved by more than 30% compared with the blank control group of comparative example 1. Whereas the degradation rate of both comparative example 2 and comparative example 3 was not 30%. It can be seen that too high or too low an addition of ferric chloride has an effect on the degradation rate of hexachlorobenzene.
Example 3
In this example, the solid-to-liquid ratio of hexachlorobenzene contaminated soil to deoxygenated distilled water in step two was 1:1.5, and the other operations and parameters were the same as in example 1.
Comparative example 4
In this comparative example, the solid-to-liquid ratio of hexachlorobenzene contaminated soil and deoxygenated distilled water in step two was 1:0.5, and the other operations and parameters were the same as in example 1.
Comparative example 5
In this comparative example, the solid-to-liquid ratio of hexachlorobenzene contaminated soil and deoxygenated distilled water in step two was removed at 1:2, and the other operations and parameters were the same as in example 1.
The results of example 3 and comparative examples 4 and 5 are shown in table 2.
TABLE 2
Note that: the values in the table are the average of 3 determinations.
As can be seen from table 2, the hexachlorobenzene degradation rate of example 3 was 25% or more, lower than that of example 1 but significantly higher than that of comparative examples 4 and 5. A solid to liquid ratio higher than 1:1 or lower than 1:1.5 will affect the degradation rate of hexachlorobenzene in the soil.
Example 4
In this example, the oxidation-reduction potential in the second removal step was-50 mV, and the other operations and parameters were the same as in example 1.
Comparative example 6
In this example, the oxidation-reduction potential in the second removal step was-150 mV, and the other operations and parameters were the same as in example 1.
The results of example 4 and comparative example 6 are shown in table 3.
TABLE 3 Table 3
As can be seen from Table 3, the oxidation-reduction potential was in the range of-50 mV to-100 mV, the hexachlorobenzene degradation rate was 30% or more, and the hexachlorobenzene degradation rate was reduced to 10% or less when it became-150 mV, and it was found that the oxidation-reduction potential was a key parameter. If the oxidation-reduction potential is too high than-50 mV, the reaction system tends to oxidize the environment with the increase of the oxidation-reduction potential, which is unfavorable for the anaerobic degradation of hexachlorobenzene.
Example 5
In this example, the initial pH in the third step was controlled to 3, and the other operations and parameters were the same as in example 1.
Example 6
In this example, the initial pH in the third step was controlled at 7, and the other operations and parameters were the same as in example 1.
The results of example 5 and example 6 are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, the initial pH value is in the range of 3 to 7, and the hexachlorobenzene degradation rate is above 30%, with the best pH5 effect.
Comparative example 7
In this comparative example, the reaction temperature in the removal step four was controlled at 25℃and the other operations and parameters were the same as in example 1.
Comparative example 8
In this comparative example, the reaction temperature in the removal step four was controlled at 35℃and the other operations and parameters were the same as in example 1.
The results of comparative example 7 and comparative example 8 are shown in Table 5.
TABLE 5
As can be seen from Table 5, the degradation rate of hexachlorobenzene was significantly reduced when the reaction temperature was lowered below 40 ℃. If the reaction temperature is higher than 50 ℃, the degradation activity of indigenous bacteria is affected, which is unfavorable for the degradation of hexachlorobenzene.
Comparative example 9
In this comparative example, iron chloride in the second removal step was replaced with a different amount of ferrous sulfate, and the other operations were the same as in example 1.
Comparative example 10
In this comparative example, iron chloride was replaced with ferrous chloride in the removal step two, and the other operations were the same as in example 1.
Comparative example 11
In this comparative example, ferric chloride was replaced with ferric sulfate in the second removal step, and the other operations were the same as in example 1.
The results of the experiments of comparative examples 9, 10 and 11 are shown in Table 6.
TABLE 6
It can be seen from table 6 that the substitution of ferric chloride for other ferric salts, such as ferric sulfate, was similar in effect to ferric chloride under optimal conditions, but the effect was significantly reduced with slight changes in conditions, and the overall effect stability was inferior to that of the ferric chloride group. And the substitution of ferric chloride for ferrous salts is less effective.
Finally, it should be noted that the above only illustrates the technical solution of the present invention and is not limiting, and although the present invention has been described in detail with reference to the preferred arrangement, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. A method for restoring hexachlorobenzene-polluted soil by ferric salt reinforced indigenous bacteria is characterized by comprising the following steps: the method comprises the following steps:
step one: after the hexachlorobenzene polluted soil is air-dried, grinding and screening to be less than 5 mm;
step two: adding hexachlorobenzene polluted soil and deoxidized distilled water into a reaction container, wherein the solid-liquid ratio of the hexachlorobenzene polluted soil to the deoxidized distilled water is 1:1-1:1.5; the oxidation-reduction potential of the mixture in the reaction vessel is within the range of-100 mV to-50 mV, so that a reaction system with a flooded anaerobic environment is formed; adding ferric chloride powder, wherein the concentration of ferric chloride in the reaction system is 5-10 g/L;
step three: regulating the pH value of the reaction system to control the initial pH value of the reaction to 3-7;
step four: vacuumizing the reaction vessel, sealing, and standing in a biological incubator at 40-50 ℃ for 15-24 days;
step five: and (3) naturally air-drying the soil treated in the step four.
2. The method for restoring hexachlorobenzene-contaminated soil by using ferric salt-reinforced indigenous bacteria according to claim 1, which is characterized in that: in the second step: pouring deoxidized distilled water into a reaction container, adding weighed hexachlorobenzene polluted soil in batches, adding ferric chloride powder, and standing for 24 hours.
3. The method for restoring hexachlorobenzene-contaminated soil by using ferric salt-reinforced indigenous bacteria according to claim 1, which is characterized in that: in the second step: the solid-liquid ratio of the polluted soil to the deoxidized distilled water is 1:1, and the adding concentration of the ferric chloride powder is 5g/L.
4. The method for restoring hexachlorobenzene-contaminated soil by using ferric salt-reinforced indigenous bacteria according to claim 1, which is characterized in that: in the third step: sodium hydroxide and sulfuric acid were used to adjust the pH of the reaction system to 5.
5. The method for restoring hexachlorobenzene-contaminated soil by using ferric salt-reinforced indigenous bacteria according to claim 1, which is characterized in that: in the fourth step: the temperature in the biological incubator was 45℃and the reaction time was 18 days.
6. The method for restoring hexachlorobenzene-contaminated soil by using ferric salt-reinforced indigenous bacteria according to claim 1, which is characterized in that: step five,: naturally air-drying for 2-3 days.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999059743A1 (en) * | 1998-05-18 | 1999-11-25 | Stauffer Management Company | Decontamination of soil contaminated with hcb |
| US5994121A (en) * | 1998-04-27 | 1999-11-30 | Rmt, Inc. | Method for degrading recalcitrant organic contaminants |
| US20030068202A1 (en) * | 2001-10-03 | 2003-04-10 | Lin Hsing Kuang | Heap and in-situ remediation of contaminated soil using metallic iron and hydrogen peroxide |
| CN103521516A (en) * | 2013-10-21 | 2014-01-22 | 北京市环境保护科学研究院 | Bio-remediation method of hexachlorobenzene-contaminated soil |
| CN109759433A (en) * | 2019-01-25 | 2019-05-17 | 湖南新九方科技有限公司 | Contaminated site restorative procedure |
| CN110280582A (en) * | 2019-07-09 | 2019-09-27 | 浙江大学 | The method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride |
| CN110303039A (en) * | 2019-07-25 | 2019-10-08 | 北京高能时代环境技术股份有限公司 | The method of Zero-valent Iron joint indigenous microorganism in-situ immobilization soil polluted by organic chloride |
| WO2023144190A1 (en) * | 2022-01-26 | 2023-08-03 | Livskvalitet Aps | A method of accelerated biodegradation of toxic, organic chemicals |
-
2024
- 2024-01-25 CN CN202410100887.5A patent/CN117772778A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5994121A (en) * | 1998-04-27 | 1999-11-30 | Rmt, Inc. | Method for degrading recalcitrant organic contaminants |
| WO1999059743A1 (en) * | 1998-05-18 | 1999-11-25 | Stauffer Management Company | Decontamination of soil contaminated with hcb |
| US20030068202A1 (en) * | 2001-10-03 | 2003-04-10 | Lin Hsing Kuang | Heap and in-situ remediation of contaminated soil using metallic iron and hydrogen peroxide |
| CN103521516A (en) * | 2013-10-21 | 2014-01-22 | 北京市环境保护科学研究院 | Bio-remediation method of hexachlorobenzene-contaminated soil |
| CN109759433A (en) * | 2019-01-25 | 2019-05-17 | 湖南新九方科技有限公司 | Contaminated site restorative procedure |
| CN110280582A (en) * | 2019-07-09 | 2019-09-27 | 浙江大学 | The method of Zero-valent Iron reduction joint indigenous microorganism remedying soil polluted by organic chloride |
| CN110303039A (en) * | 2019-07-25 | 2019-10-08 | 北京高能时代环境技术股份有限公司 | The method of Zero-valent Iron joint indigenous microorganism in-situ immobilization soil polluted by organic chloride |
| WO2023144190A1 (en) * | 2022-01-26 | 2023-08-03 | Livskvalitet Aps | A method of accelerated biodegradation of toxic, organic chemicals |
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