CN113637482B - Petroleum hydrocarbon organic contaminated soil remediation agent, preparation method thereof and contaminated soil remediation method - Google Patents
Petroleum hydrocarbon organic contaminated soil remediation agent, preparation method thereof and contaminated soil remediation method Download PDFInfo
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- CN113637482B CN113637482B CN202110724257.1A CN202110724257A CN113637482B CN 113637482 B CN113637482 B CN 113637482B CN 202110724257 A CN202110724257 A CN 202110724257A CN 113637482 B CN113637482 B CN 113637482B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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Abstract
The invention discloses a preparation method of a petroleum hydrocarbon organic contaminated soil remediation agent, which comprises the following components in parts by mass: 10 to 15 portions of gold mine tailings, 15 to 20 portions of sodium persulfate, 15 to 20 portions of sodium dimethyldithiocarbamate, 25 to 30 portions of quicklime, 15 to 20 portions of phosphogypsum and 5 to 10 portions of peroxy acid. The advantages are that: the method fully utilizes the existing large amount of industrial solid wastes while repairing the polluted soil, solves the problem of removal of the industrial solid wastes to a certain extent, realizes a novel treatment route of treating wastes with wastes, and has the advantages of simple construction, low cost, good short-term treatment effect and the like.
Description
Technical Field
The invention relates to an environment treatment technology, in particular to a polluted soil remediation technology.
Background
Petroleum hydrocarbons are one of the organic pollutants widely existing in the environment, including gasoline, kerosene, diesel oil, lubricating oil, paraffin, asphalt and the like, and are a mixture of various hydrocarbons (normal paraffin, branched paraffin, cycloparaffin and aromatic hydrocarbon) and small amount of other organic matters, such as sulfide, nitride, naphthenic acid and the like. With the development of economy, the demand of human beings for energy is continuously expanding, and petroleum becomes one of the most important energy sources of human beings. During the process of oil extraction, processing and utilization, more and more oil may enter soil environment and sea to cause pollution and destruction of the soil environment and sea water quality. Once in the soil, the excessive total petroleum hydrocarbon is difficult to remove, and causes serious harm to the society, the economy and the human beings. Therefore, the remediation of the petroleum hydrocarbon polluted soil is well done, and the method has positive practical significance for the green water and clean soil protection warfare in winning the blue sky. At present, in the relocation engineering of urban petrochemical plants, petroleum hydrocarbon pollution in original production sites is increasingly prominent, and the conventional restoration method has the defects of complicated process, high treatment cost, long restoration period and poor short-term effect, and becomes a 'hard bone' in the soil restoration industry.
Disclosure of Invention
In order to solve the problem of difficulty in repairing the petroleum hydrocarbon organic polluted soil in the prior art, the invention provides a petroleum hydrocarbon organic polluted soil repairing medicament and a preparation method thereof.
The technical scheme adopted by the invention is as follows: the preparation method of the petroleum hydrocarbon organic contaminated soil remediation agent is characterized in that a production raw material formula comprises the following components in parts by mass: 10 to 15 portions of gold mine tailings, 15 to 20 portions of sodium persulfate, 15 to 20 portions of sodium dimethyldithiocarbamate, 25 to 30 portions of quicklime, 15 to 20 portions of phosphogypsum and 5 to 10 portions of peroxy acid.
The gold mine tailings refer to wastes discharged after the mining and beneficiation of a gold mine.
As a further development of the invention, the peroxy acid is peroxyacetic acid or peroxyformic acid.
As a further improvement of the invention, the method also comprises the step of pretreating the phosphogypsum, and specifically comprises the following steps:
s1, washing with water to remove phosphate on the surface of phosphogypsum;
s2, drying the washed phosphogypsum at 65-70 ℃ for 24-72 h;
and S3, grinding the dried phosphogypsum to enable the mass ratio of particles with the particle size smaller than 1mm to be more than 80%, and obtaining the pretreated phosphogypsum.
The preparation method of the petroleum hydrocarbon organic contaminated soil remediation agent can specifically adopt the following steps:
A. weighing the raw materials according to the formula of the production raw materials;
B. uniformly mixing the gold mine tailings and the pretreated phosphogypsum to obtain a mixture A;
C. uniformly mixing the sodium persulfate, the sodium dimethyldithiocarbamate and the quick lime to obtain a mixture B;
D. mixing and stirring the mixture A and the mixture B for 3-10 min to obtain a mixture C;
E. adding the peroxy acid into the mixture C, mixing and stirring for 20-40 min to obtain a mixture D;
F. putting the mixture D into drying equipment, drying for 6-8 hours at 60-70 ℃, and naturally cooling to room temperature;
G. and crushing the dried mixture D into powder.
The invention also discloses a petroleum hydrocarbon organic contaminated soil remediation agent, which is prepared by the preparation method of the petroleum hydrocarbon organic contaminated soil remediation agent.
The invention also discloses a method for restoring the polluted soil, which is characterized in that the polluted soil is restored by using the petroleum hydrocarbon organic polluted soil restoration agent.
The polluted soil remediation method can be implemented according to the following steps:
(1) According to the scale of restoring the soil polluted by the petroleum hydrocarbon in the field, the soil polluted by the petroleum hydrocarbon is dug in layers and batches, the restoring depth is 2-3 m, pollution treatment is synchronously promoted, and the large soil generated in the digging process is crushed until the particle size is less than or equal to 50mm, and is independently stacked; carrying out closed transportation on the transport vehicle in the transportation process;
(2) Mixing and stirring the petroleum hydrocarbon organic contaminated soil remediation agent and petroleum hydrocarbon contaminated soil, flatly paving the contaminated soil into a rectangular soil body with the thickness of 0.8-1.2 m, and screening, crushing and mixing the soil by using screening and mixing equipment; the dosage of the petroleum hydrocarbon organic polluted soil remediation agent is 15-20% of the mass of the petroleum hydrocarbon polluted soil;
(3) Transferring the pretreated soil to a maintenance area, wherein the water content of the soil is required to be more than 30%, and the soil maintenance days are 3-7 d;
(4) Detecting and accepting the soil remediation and maintenance sample polluted by the petroleum hydrocarbon in batches, and repeating the steps (2) and (3) until the soil remediation and maintenance sample does not reach the standard;
(5) And backfilling the repaired up-to-standard soil after acceptance is qualified.
The invention has the beneficial effects that: the method fully utilizes the existing large amount of industrial solid wastes while repairing the polluted soil, solves the problem of removal of the industrial solid wastes to a certain extent, realizes a novel treatment route of treating wastes with wastes, and has the advantages of simple construction, low cost, good short-term treatment effect and the like.
Drawings
FIG. 1 is a characteristic parameter diagram of the granularity of tailings of gold ores of the examples.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
soil sample 1 was treated as follows (see table 1 for petroleum hydrocarbon concentrations in soil sample 1):
(1) The production raw materials are measured according to the following mass part ratio: 15 parts of gold ore tailings, 20 parts of sodium persulfate, 15 parts of sodium dimethyldithiocarbamate, 25 parts of quick lime, 15 parts of phosphogypsum and 10 parts of peroxyformic acid. Wherein the composition and particle size characteristics of the gold tailings are shown in table 2 and fig. 1.
(2) And (4) removing phosphate on the surface of the phosphogypsum through water washing, and performing water washing for multiple times until the phosphogypsum is white.
(3) And mechanically drying the washed phosphogypsum at the drying temperature of 70 ℃ for 48 hours.
(4) And putting the dried phosphogypsum into a ball mill to be ground until the mass ratio of particles with the particle size of less than 1mm is 89%, thus obtaining the pretreated phosphogypsum.
(5) And uniformly mixing the gold mine tailings and the pretreated phosphogypsum to obtain a mixture A.
(6) And uniformly mixing the sodium persulfate, the sodium dimethyldithiocarbamate and the quick lime to obtain a mixture B.
(7) And mixing and stirring the mixture A and the mixture B for 5min to obtain a mixture C.
(8) Adding the peroxyformic acid into the mixture C, and mixing and stirring for 30min to obtain a mixture D;
(9) Putting the mixture D into drying equipment, drying for 6 hours at 65 ℃, and naturally cooling to room temperature (17 ℃);
(10) And crushing the dried mixture D into powder to obtain the petroleum hydrocarbon organic contaminated soil remediation agent.
(11) The method comprises the following steps of 1, clearing and digging soil samples in layers and batches, wherein the restoration depth is 2.6m, synchronously propelling pollution treatment, crushing large soil blocks generated in the clearing and digging process until the particle size is less than or equal to 50mm, and independently stacking; carrying out closed transportation on the transport vehicle in the transportation process;
(12) Mixing and stirring the petroleum hydrocarbon organic contaminated soil remediation agent and the soil sample 1 to pollute the soil
The soil is flatly paved into a rectangular soil body with the thickness of 1m, and screening, crushing and mixing of the soil are realized by using screening and mixing equipment; said oil
The dosage of the hydrocarbon organic contaminated soil remediation agent is 15% of the mass of the soil sample 1;
(13) And (5) transferring the pretreated soil to a maintenance area by using an excavator, wherein the maintenance days are 7d.
(14) The restored soil sample is taken for petroleum hydrocarbon content, and the detection result is shown in table 3.
The second embodiment:
the soil sample 2 is treated by the same method and steps as in the first embodiment (the concentration of the petroleum hydrocarbon in the soil sample 2 is shown in table 1), the adopted technological parameters are unchanged, the petroleum hydrocarbon content of the repaired soil sample is carried out after the treatment is finished, and the detection result is shown in table 3.
Example three:
the soil sample 3 is treated by the same method and steps as in the first embodiment (the concentration of the petroleum hydrocarbon in the soil sample 3 is shown in table 1), the adopted technological parameters are unchanged, the petroleum hydrocarbon content of the repaired soil sample is carried out after the treatment is finished, and the detection result is shown in table 3.
Comparative example one:
this comparative example is a control experiment of example one, carried out according to the same procedures and conditions as example one, keeping the process parameters unchanged, with the only difference that: the production raw material formula does not contain gold mine tailings, and the dosage of the phosphogypsum is the sum of the dosage of the gold mine tailings and the dosage of the phosphogypsum in the first embodiment. The method comprises the following specific steps:
soil sample 1 was treated as follows (see table 1 for petroleum hydrocarbon concentrations in soil sample 1):
(1) Weighing the raw materials according to the following production raw material formula in parts by mass: 20 parts of sodium persulfate, 15 parts of sodium dimethyldithiocarbamate, 25 parts of quick lime, 30 parts of phosphogypsum and 10 parts of peroxyformic acid.
(2) And (4) removing phosphate on the surface of the phosphogypsum through water washing, and performing water washing for multiple times until the phosphogypsum is white.
(3) And mechanically drying the washed phosphogypsum at the drying temperature of 70 ℃ for 48 hours.
(4) And putting the dried phosphogypsum into a ball mill to be ground until the mass ratio of particles with the particle size of less than 1mm is 89%, thus obtaining the pretreated phosphogypsum.
(5) And uniformly mixing the sodium persulfate, the sodium dimethyldithiocarbamate and the quick lime to obtain a mixture B.
(6) And mixing and stirring the pretreated phosphogypsum and the mixture B for 5min to obtain a mixture C.
(7) Adding the peroxyformic acid into the mixture C, and mixing and stirring for 30min to obtain a mixture D;
(8) Putting the mixture D into drying equipment, drying for 6 hours at 65 ℃, and naturally cooling to room temperature (17 ℃);
(9) And crushing the dried mixture D into powder to obtain the petroleum hydrocarbon organic contaminated soil remediation agent.
(10) The method comprises the following steps of (1) carrying out layered and batch clearing and digging on a soil sample 1, wherein the restoration depth is 2.6m, synchronously carrying out pollution treatment, crushing large soil blocks generated in the clearing and digging process until the particle size is less than or equal to 50mm, and independently stacking; carrying out closed transportation on the transport vehicle in the transportation process;
(11) Mixing and stirring the petroleum hydrocarbon organic contaminated soil remediation agent and the soil sample 1, flatly paving the contaminated soil into a rectangular soil body with the thickness of 1m, and screening, crushing and mixing the soil by using screening and mixing equipment; the dosage of the petroleum hydrocarbon organic contaminated soil remediation agent is 15% of the mass of the soil sample 1;
(12) And (5) transferring the pretreated soil to a maintenance area by using an excavator, wherein the maintenance days are 7d.
(13) The restored soil sample is taken for petroleum hydrocarbon content, and the detection result is shown in table 3.
Comparative example two:
this comparative example is a control experiment of example one, carried out according to the same procedures and conditions as example one, keeping the process parameters unchanged, with the only difference that: the production raw material formula does not contain phosphogypsum, and the dosage of the gold mine tailings is the sum of the dosage of the gold mine tailings and the dosage of the phosphogypsum in the first embodiment. The method comprises the following specific steps:
soil sample 1 was treated as follows (see table 1 for petroleum hydrocarbon concentrations in soil sample 1):
(1) The production raw materials are measured according to the following mass part ratio: 30 parts of gold ore tailings, 20 parts of sodium persulfate, 15 parts of sodium dimethyldithiocarbamate, 25 parts of quicklime and 10 parts of peroxyformic acid. Wherein the composition and particle size characteristics of the gold tailings are shown in table 2 and fig. 1.
(2) And uniformly mixing the sodium persulfate, the sodium dimethyldithiocarbamate and the quick lime to obtain a mixture B.
(3) And mixing and stirring the gold mine tailings and the mixture B for 5min to obtain a mixture C.
(4) Adding the peroxyformic acid into the mixture C, and mixing and stirring for 30min to obtain a mixture D;
(5) Putting the mixture D into drying equipment, drying for 6 hours at 65 ℃, and naturally cooling to room temperature (17 ℃);
(6) And crushing the dried mixture D into powder to obtain the petroleum hydrocarbon organic contaminated soil remediation agent.
(7) The method comprises the following steps of 1, clearing and digging soil samples in layers and batches, wherein the restoration depth is 2.6m, synchronously propelling pollution treatment, crushing large soil blocks generated in the clearing and digging process until the particle size is less than or equal to 50mm, and independently stacking; carrying out closed transportation on the transport vehicle in the transportation process;
(8) Mixing and stirring the petroleum hydrocarbon organic contaminated soil remediation agent and the soil sample 1, flatly paving the contaminated soil into a rectangular soil body with the thickness of 1m, and screening, crushing and mixing the soil by using screening and mixing equipment; the dosage of the petroleum hydrocarbon organic contaminated soil remediation agent is 15% of the mass of the soil sample 1;
(9) And (5) transferring the pretreated soil to a maintenance area by using an excavator, wherein the maintenance days are 7d.
(10) The restored soil sample is taken for petroleum hydrocarbon content, and the detection result is shown in table 3.
TABLE 1 initial concentration of petroleum hydrocarbons in the original contaminated soil
TABLE 2 composition table of gold mine tailings
TABLE 3 Petroleum Hydrocarbon concentration test result table of soil remediation samples
As can be seen from the first, second and third examples in Table 3, the soil remediation agent provided by the present invention can significantly reduce the content of petroleum hydrocarbons in contaminated soil.
As can be seen from the first embodiment, the first comparative embodiment and the second comparative embodiment in the table 3, the gold tailings and the phosphogypsum both have a certain effect of reducing the content of petroleum hydrocarbon in the soil, but the effect of the combination of the gold tailings and the phosphogypsum is obviously better than that of any one of the gold tailings and the phosphogypsum when the gold tailings and the phosphogypsum are used alone under the premise of equal dosage.
Claims (6)
1. The preparation method of the petroleum hydrocarbon organic contaminated soil remediation agent is characterized in that a production raw material formula comprises the following components in parts by mass: 10-15 parts of gold ore tailings, 15-20 parts of sodium persulfate, 15-20 parts of sodium dimethyldithiocarbamate, 25-30 parts of quicklime, 15-20 parts of phosphogypsum and 5-10 parts of peroxy acid; the method comprises the following steps:
A. weighing the raw materials according to the formula of the production raw materials;
B. uniformly mixing the gold mine tailings and the pretreated phosphogypsum to obtain a mixture A;
C. uniformly mixing the sodium persulfate, the sodium dimethyldithiocarbamate and the quick lime to obtain a mixture B;
D. mixing and stirring the mixture A and the mixture B for 3-10 min to obtain a mixture C;
E. adding the peroxy acid into the mixture C, mixing and stirring for 20-40 min to obtain a mixture D;
F. putting the mixture D into drying equipment, drying for 6-8 hours at the temperature of 60-70 ℃, and naturally cooling to room temperature;
G. and crushing the dried mixture D into powder.
2. The method for producing a remedy for soil contaminated with petroleum hydrocarbon according to claim 1, which comprises: the peroxy acid is peroxyacetic acid or peroxyformic acid.
3. The preparation method of the petroleum hydrocarbon organic contaminated soil remediation agent according to claim 1, further comprising the step of pretreating the phosphogypsum, specifically:
s1, washing with water to remove phosphate on the surface of phosphogypsum;
s2, drying the washed phosphogypsum at 65-70 ℃ for 24-72 h;
and S3, grinding the dried phosphogypsum to enable the mass ratio of particles with the particle size smaller than 1mm to be more than 80%, and obtaining the pretreated phosphogypsum.
4. The agent for remediating organic-contaminated petroleum hydrocarbon soil, which is obtained by the method for remediating organic-contaminated petroleum hydrocarbon soil according to any one of claims 1 to 3.
5. A contaminated soil remediation method is characterized in that: comprising the step of remediating contaminated soil using the petroleum hydrocarbon organic contaminated soil remediation agent of claim 4.
6. The contaminated soil remediation method of claim 5, specifically comprising the steps of:
(1) According to the scale of restoring the soil polluted by the petroleum hydrocarbon in the field, the soil polluted by the petroleum hydrocarbon is dug in layers and batches, the restoring depth is 2-3 m, pollution treatment is synchronously promoted, and the large soil generated in the digging process is crushed until the particle size is less than or equal to 50mm, and is independently stacked; carrying out closed transportation on the transport vehicle in the transportation process;
(2) Mixing and stirring the petroleum hydrocarbon organic contaminated soil remediation agent and petroleum hydrocarbon contaminated soil, flatly paving the contaminated soil into a rectangular soil body with the thickness of 0.8-1.2 m, and screening, crushing and mixing the soil by using screening and mixing equipment; the dosage of the petroleum hydrocarbon organic polluted soil remediation agent is 15-20% of the mass of the petroleum hydrocarbon polluted soil;
(3) Transferring the pretreated soil to a maintenance area, wherein the water content of the soil is required to be more than 30%, and the soil maintenance days are 3-7 d;
(4) Detecting and accepting the soil remediation and maintenance sample polluted by the petroleum hydrocarbon in batches, and repeating the steps (2) and (3) until the soil remediation and maintenance sample does not reach the standard;
(5) And backfilling the repaired up-to-standard soil after acceptance is qualified.
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| US4124405A (en) * | 1975-08-06 | 1978-11-07 | Pec-Engineering Societe Anonyme | Process for solidifying aqueous wastes and products thereof |
| US5347077A (en) * | 1991-10-01 | 1994-09-13 | Pelt & Hooykaas B.V. | Toxic waste fixant and method for using same |
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| CN112680231A (en) * | 2020-12-08 | 2021-04-20 | 广西博世科环保科技股份有限公司 | Repairing agent and repairing method for repairing aged petroleum polluted soil |
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| US7351191B2 (en) * | 2004-09-02 | 2008-04-01 | Rmt, Inc | Method for stabilizing contaminated waste |
| CA2960104C (en) * | 2014-09-04 | 2023-05-02 | Clean Chemistry, Inc. | Method of water treatment utilizing a peracetate oxidant solution |
| US11697043B2 (en) * | 2019-04-29 | 2023-07-11 | HMR Solutions, Inc. | Method and reagents for treating materials contaminated with mercury, PFAS, or other contaminants |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4124405A (en) * | 1975-08-06 | 1978-11-07 | Pec-Engineering Societe Anonyme | Process for solidifying aqueous wastes and products thereof |
| US5347077A (en) * | 1991-10-01 | 1994-09-13 | Pelt & Hooykaas B.V. | Toxic waste fixant and method for using same |
| US5494649A (en) * | 1991-10-03 | 1996-02-27 | Cognis, Inc. | Process for removing heavy metals from paint chips |
| WO2014009613A1 (en) * | 2012-07-10 | 2014-01-16 | Greenmade Development Limited | Method for stabilizing and solidifying urban and/or industrial and/or marine waste |
| CN109429610A (en) * | 2019-01-04 | 2019-03-08 | 杰瑞(莱州)矿山治理有限公司 | It is a kind of to carry out the artificial soil and its reclamation method that land reclamation uses using gold mine tailings slag backfill mining area |
| CN112680231A (en) * | 2020-12-08 | 2021-04-20 | 广西博世科环保科技股份有限公司 | Repairing agent and repairing method for repairing aged petroleum polluted soil |
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