阅读说明：本技术 石油烃类有机污染土壤修复药剂及其制备方法，污染土壤修复方法 (Petroleum hydrocarbon organic contaminated soil remediation agent, preparation method thereof and contaminated soil remediation method ) 是由 邓奇军 王攀 尹玲 王佳 杨海 陈东 于 2021-06-29 设计创作，主要内容包括：本发公开了一种石油烃类有机污染土壤修复药剂的制备方法,生产原料配方包括如下质量份数比例的各组分：金矿尾砂10～15份,过硫酸钠15～20份,二甲基二硫代氨基甲酸钠15～20份,生石灰25～30份,磷石膏15～20份,过氧酸5～10份。其优点是：在修复污染土壤的同时,充分利用现大宗工业固废,从一定程度上解决了工业固废的去处问题,实现了“以废治废”的新型治理路线,同时该修复药剂具有施工简便,成本低廉,短期治理效果好等优点。(The invention discloses a preparation method of a petroleum hydrocarbon organic contaminated soil remediation agent, which comprises the following components in parts by mass: 10-15 parts of gold ore tailings, 15-20 parts of sodium persulfate, 15-20 parts of sodium dimethyldithiocarbamate, 25-30 parts of quick lime, 15-20 parts of phosphogypsum and 5-10 parts 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.)

1. The preparation method of the petroleum hydrocarbon organic contaminated soil remediation agent is characterized in that the 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 quick lime, 15-20 parts of phosphogypsum and 5-10 parts of peroxy acid.

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 the phosphogypsum;

s2, drying the washed phosphogypsum at 65-70 ℃ for 24-72 h;

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 method for preparing the agent for remediating petroleum hydrocarbon organic-contaminated soil as claimed in claim 3, comprising the steps of:

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.

5. The agent for remediating organic petroleum-contaminated soil prepared by the method for remediating organic petroleum-contaminated soil as set forth in any one of claims 1 to 4.

6. 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 5.

7. The contaminated soil remediation method of claim 6, 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 a layered and batched mode, the restoring depth is 2-3 m, pollution treatment is synchronously promoted, and large soil generated in the digging process is crushed until the particle size is smaller than or equal to 50mm, and the large soil 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.

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 the soil environment and the ocean to cause pollution and damage to the water quality of the soil environment and the ocean. 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 winning the blue sky, clear water and clean soil protection war. 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 the 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 quick lime, 15-20 parts of phosphogypsum and 5-10 parts 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 the phosphogypsum;

s2, drying the washed phosphogypsum at 65-70 ℃ for 24-72 h;

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 the temperature of 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 a layered and batched mode, the restoring depth is 2-3 m, pollution treatment is synchronously promoted, and large soil generated in the digging process is crushed until the particle size is smaller than or equal to 50mm, and the large soil 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, 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;

(13) and (5) transferring the pretreated soil to a maintenance area by using an excavator, wherein the maintenance days are 7 d.

(14) The restored soil sample was taken for petroleum hydrocarbon content, and the test results are shown in table 4.

Example two:

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 4.

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 4.

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) the production raw materials are measured according to the following mass part ratio: 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, 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;

(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 7 d.

(13) The restored soil sample was taken for petroleum hydrocarbon content, and the test results are shown in table 4.

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 7 d.

(10) The restored soil sample was taken for petroleum hydrocarbon content, and the test results are shown in table 4.

TABLE 1 initial concentration of petroleum hydrocarbons in the original contaminated soil

TABLE 2 composition table of gold mine tailings

SiO2	TiO2	AL2O3	Fe2O3	FeO2	MnO2	CaO2	MgO	Na2O	K2O	CO2	Loss on ignition
												73.86	0.44	6.10	7.90	1.14	0.12	2.16	0.80	0.41	2.71	3.84	99.49

TABLE 4 Petroleum Hydrocarbon concentration test result table of soil sample for remediation

As can be seen from the first, second and third examples in Table 4, 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, the first and the second examples in Table 4, 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.