CN115532806A - Method for repairing site chlorinated hydrocarbon polluted source area by heat treatment-microbial technology - Google Patents
Method for repairing site chlorinated hydrocarbon polluted source area by heat treatment-microbial technology Download PDFInfo
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- CN115532806A CN115532806A CN202211233335.9A CN202211233335A CN115532806A CN 115532806 A CN115532806 A CN 115532806A CN 202211233335 A CN202211233335 A CN 202211233335A CN 115532806 A CN115532806 A CN 115532806A
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- 150000008280 chlorinated hydrocarbons Chemical class 0.000 title claims abstract description 58
- 238000005516 engineering process Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 109
- 239000002689 soil Substances 0.000 claims abstract description 68
- 230000000813 microbial effect Effects 0.000 claims abstract description 52
- 241000894006 Bacteria Species 0.000 claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 claims abstract description 30
- 230000015556 catabolic process Effects 0.000 claims abstract description 29
- 230000008439 repair process Effects 0.000 claims abstract description 18
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 13
- 231100000719 pollutant Toxicity 0.000 claims abstract description 13
- 230000000593 degrading effect Effects 0.000 claims abstract description 11
- 230000008859 change Effects 0.000 claims abstract description 9
- 238000012544 monitoring process Methods 0.000 claims abstract description 5
- 210000002966 serum Anatomy 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000012360 testing method Methods 0.000 claims description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005067 remediation Methods 0.000 claims description 16
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 15
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006298 dechlorination reaction Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical class CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000012863 analytical testing Methods 0.000 claims description 4
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000004255 ion exchange chromatography Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 11
- 238000006042 reductive dechlorination reaction Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical compound Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 241000205145 Desulfobacterium Species 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- B09C1/06—Reclamation of contaminated soil thermally
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mycology (AREA)
- Soil Sciences (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
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Abstract
The invention discloses a method for repairing a site chlorinated hydrocarbon polluted source area by combining heat treatment and microbial technology, which comprises the following steps: carrying out heat treatment on a site polluted by the chlorohydrocarbon; after the heat treatment, injecting chlorohydrocarbon degradation engineering bacteria into the chlorohydrocarbon polluted site, and carrying out reductive dechlorination on chlorohydrocarbon by using the electron donor released in the heat treatment stage; and monitoring the concentration change of the chlorohydrocarbon in the chlorohydrocarbon polluted site, and when the concentration of the chlorohydrocarbon is less than a repair target preset value, indicating that the repair is finished. According to the method, a heat treatment technology is adopted to remove high-concentration pollutants and promote the decomposition of soil organic matters to release electron donors; after the heat treatment is finished, the field is deeply repaired by combining the microbial technology, and the degrading bacteria in situ utilize the electron donor generated in the heat treatment stage. The technology can carry out deep restoration on the polluted site of the high-concentration source region, avoids adding an electron donor to the underground additionally, and realizes high-efficiency and low-consumption restoration of the polluted site.
Description
Technical Field
The application relates to the technical field of soil and underground water pollution remediation, in particular to a method for remedying a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology.
Background
Chlorinated hydrocarbons and the like are widely used in cleaning, extraction, dry cleaning, and spray and solvent manufacturing industries, and common chlorinated hydrocarbons include Trichloroethylene (TCE), tetrachloroethylene, 1, 2-dichloroethane, chlorobenzene, and the like. The chlorinated hydrocarbon has special smell, density higher than that of water, low solubility, low boiling point and stable chemical structure, and may exist continuously in natural environment. After the chlorinated hydrocarbons are leaked into the environment, vertical migration occurs, and the chlorinated hydrocarbons exist in the forms of gas phase, free phase heavy non-aqueous phase liquid (DNAPL), adsorption state and dissolution state. When the chlorohydrocarbons form discontinuous phase residual DNAPL in the aquifer or gather above the water-resisting layer to form DNAPL 'pool', the chlorohydrocarbons are continuously dissolved and release pollutants to the aquifer through the back diffusion effect, and become a continuous pollution source. Without artificial repair, dissolution and release may last for hundreds of years.
The in-situ remediation means of the chlorinated hydrocarbon polluted site comprises in-situ chemical oxidation/reduction, in-situ washing technology, in-situ thermal remediation technology, in-situ microbial remediation and the like. The in-situ chemical oxidation/reduction and in-situ washing technologies have poor treatment effects and long treatment period. The heat treatment technology has short repair period and high efficiency, but the cost is high, the energy consumption is high, and the heat treatment technology is not suitable for long-term operation. The microbial remediation technology is widely applied due to the advantages of environmental friendliness, environmental friendliness and the like, however, the microbial remediation of the chlorinated hydrocarbon polluted site still has the problems of long remediation period, limited site pollutant concentration, lack of electron donors and the like. As can be seen, conventional repair techniques tend to have their limitations and difficulty in achieving the repair goals.
Disclosure of Invention
On the basis, aiming at the problems of long restoration period, low efficiency, high cost, high energy consumption, unsuitability for long-term operation, limited site pollutant concentration, lack of electron donors and the like existing in the traditional technology, a method for restoring a site chlorinated hydrocarbon polluted source region by combining a heat treatment technology and a microbial technology is needed. The method for repairing the site chlorinated hydrocarbon polluted source area by combining the heat treatment and the microbial technology can carry out deep repair on the site by combining the microbial technology after removing pollutants in the high-concentration source area by heat treatment, and in the heat treatment process, organic matters in the soil are decomposed to generate an electron donor for in-situ utilization by subsequent degrading bacteria, so that the microbial repair effect is improved.
An embodiment of the application provides a method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology.
A method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology comprises the following steps:
(1) Carrying out heat treatment on a chlorohydrocarbon polluted site;
(2) After the heat treatment, injecting chlorohydrocarbon degradation engineering bacteria into the chlorohydrocarbon polluted site, wherein the chlorohydrocarbon degradation engineering bacteria carry out chlorohydrocarbon reduction dechlorination by utilizing the electron donor released in the heat treatment stage;
(3) And monitoring the concentration change of the chlorohydrocarbon in the chlorohydrocarbon polluted site, and when the concentration of the chlorohydrocarbon is less than a repair target preset value, indicating that the repair is finished.
In some of the embodiments, the heat treatment in step (1) includes the following steps:
and heating the chlorinated hydrocarbon polluted site at 60-100 ℃ for not less than 7-20 days.
In some of these embodiments, prior to the thermal treatment of the chlorinated hydrocarbon contaminated site in step (1), the chlorinated hydrocarbon contaminated site is subjected to a bench test comprising the steps of:
collecting a soil sample of the chlorohydrocarbon contaminated site, introducing nitrogen into the soil sample to treat the soil sample to form an anaerobic environment, and performing heat treatment on the soil sample by using a constant-temperature water bath to simulate the environmental temperature of a thermal remediation area of the chlorohydrocarbon contaminated site;
introducing chlorohydrocarbon into the soil sample after the heat treatment to simulate that the soil sample after the heat treatment still has residual pollutants, and introducing dechlorination bacteria into the soil sample to carry out microbial remediation on the chlorohydrocarbon.
In some embodiments, the pilot test comprises the steps of:
a. collecting and treating a soil sample: collecting a soil sample, sieving the soil sample through a 2-3mm mesh sieve, fully mixing to obtain a sieved soil sample, and storing for later use;
b. bottling soil and anaerobic treatment: transferring 20-30g of the sieved soil sample into a serum bottle, adding 50-100mL of ultrapure water, inserting a nitrogen pipeline with an injector into the bottom of the serum bottle, introducing nitrogen into the serum bottle to ensure that the serum bottle is in an anaerobic environment, and sealing the serum bottle;
c. and (3) soil constant-temperature heating treatment: placing the serum bottle in a water bath kettle to maintain a preset temperature, and heating for 7-20 days in a dark place;
d. introducing chlorinated hydrocarbon and degrading bacteria: introducing 2-5mL of saturated hydrochloric ether solution into the serum bottle, introducing 2-5mL of dechlorination bacteria, and placing the serum bottle in a constant-temperature incubator at 25 ℃ for microbial degradation;
e. analytical testing of the samples: sampling at different time points, extracting 500 mu L of headspace gas in the serum bottle, injecting the headspace gas into a gas chromatography sample inlet for analyzing the concentration change of the hydrochloric ether, extracting 500 mu L of water sample in the serum bottle, and testing the electron donor content of formic acid, acetic acid and propionic acid by using ion chromatography after the water sample passes through a 0.45 mu m water system filter membrane;
f. and determining the heating temperature and the heating time of the heat treatment according to the degradation effect of the pilot test.
In some of these embodiments, in step a, the soil sample is taken at a depth <20cm.
In some of these embodiments, in step b, the serum bottle is capped and sealed with a butyl rubber stopper and an aluminum sealing cap.
In some of these embodiments, in step c, the predetermined temperatures include 25 ℃, 45 ℃, 60 ℃,75 ℃ and 90 ℃.
In some of these embodiments, the dechlorinated bacteria is inoculated in an amount of 4% to 5%.
In some of these embodiments, the chlorinated hydrocarbon introduced in the pilot test is trichloroethylene.
In some embodiments, in the step (2), the chlorohydrocarbon degradation engineering bacteria are injected into the chlorohydrocarbon contaminated site in an injection well mode.
The method for repairing the site chlorinated hydrocarbon polluted source area by combining the heat treatment and the microbial technology removes high-concentration pollutants by adopting the heat treatment technology, promotes the decomposition of soil organic matters to release an electron donor; after the heat treatment is finished, the field is deeply repaired by combining the microbial technology, and the degrading bacteria in situ utilize the electron donor generated in the heat treatment stage. The technology can deeply repair the high-concentration source area polluted site, avoids adding an electron donor to the underground additionally, and realizes high-efficiency and low-consumption repair of the polluted site.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings used in the description of the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the application, and that other drawings can be derived from these drawings by a person skilled in the art without inventive effort.
For a more complete understanding of the present application and its advantages, reference is now made to the following descriptions taken in conjunction with the accompanying drawings. Wherein like reference numerals refer to like parts in the following description.
FIG. 1 is a graph showing the organic acid concentrations of formic acid, acetic acid and propionic acid at different temperatures during heating for 14d and degradation for 7d in example 1;
FIG. 2 is a graph showing the relationship between Trichloroethylene (TCE) concentration and degradation time in example 1;
FIG. 3 is a graph showing the degradation products cis-1,2-DCE in example 1 as a function of degradation time.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, as those skilled in the art will recognize without departing from the spirit and scope of the present invention.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present numbers, and the above, below, within, etc. are understood as including the present numbers. If there is a description of first and second for the purpose of distinguishing technical features only, this is not to be understood as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of technical features indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the application provides a method for repairing a site chlorinated hydrocarbon polluted source region by combining a heat treatment technology and a microbial technology, and aims to solve the problems of long repair period, low efficiency, high cost, high energy consumption, unsuitability for long-term operation, site pollutant concentration limitation, lack of an electron donor and the like in the traditional technology. The method for repairing the site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology is described in the following by combining the attached drawings.
The method for repairing the site chlorinated hydrocarbon polluted source region by combining heat treatment with microbial technology provided by the embodiment of the application can be used for deep repair of the high-concentration chlorinated hydrocarbon polluted source region.
In order to more clearly illustrate the structure of the method for repairing the site chlorinated hydrocarbon polluted source region by combining the heat treatment and the microbial technology, the method for repairing the site chlorinated hydrocarbon polluted source region by combining the heat treatment and the microbial technology is described in the following by combining the attached drawings.
An embodiment of the application provides a method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology.
A method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology comprises the following steps:
(1) Carrying out heat treatment on a site polluted by the chlorohydrocarbon;
(2) After heat treatment, injecting the chlorohydrocarbon degradation engineering bacteria into a chlorohydrocarbon polluted site, and carrying out reductive dechlorination on chlorohydrocarbon by using electron donors released in the heat treatment stage;
(3) And monitoring the concentration change of the chlorinated hydrocarbons in the chlorinated hydrocarbon polluted site, and when the concentration of the chlorinated hydrocarbons is smaller than the target preset value of the restoration, indicating that the restoration is finished.
In the method for repairing the site chlorohydrocarbon polluted source region by combining the heat treatment and the microbial technology, the temperature of the polluted site soil and underground water is increased by adopting the heat treatment technology, the pollutants are promoted to be separated from the surface of soil particles and enter a gas phase or a liquid phase, and the treatment is carried out by combining an extraction process. Furthermore, the invention adopts the microbial remediation technology to promote the degradation of pollutants by utilizing the metabolic activity of microorganisms, has the advantages of environmental friendliness, economy and environmental friendliness, in the underground anaerobic environment, the most common microbial degradation way of chlorohydrocarbons is reductive dechlorination, the microbial remediation technology can utilize the electron donor released in the heat treatment technology stage to carry out reductive dechlorination of chlorohydrocarbons, and the electron donor can ensure the continuous performance of microbial remediation.
In some embodiments, the heat treatment in step (1) comprises the following steps:
heating the site polluted by the chlorohydrocarbon at the temperature of 60-100 ℃ for not less than 7 days. For example, the heating time is 7-20d.
In some of these embodiments, the chlorohydrocarbon contaminated site is subjected to a pilot test prior to the heat treatment of the chlorohydrocarbon contaminated site in step (1), the pilot test comprising the steps of:
collecting a soil sample of a chlorohydrocarbon contaminated site, introducing nitrogen into the soil sample to treat the soil sample to form an anaerobic environment, and performing heat treatment on the soil sample by using a constant-temperature water bath to simulate the environmental temperature of a thermal remediation area of the chlorohydrocarbon contaminated site;
introducing chlorohydrocarbons into the soil sample after the heat treatment to simulate the residual pollutants in the soil sample after the heat treatment, and introducing dechlorination bacteria into the soil sample to carry out microbial remediation on the chlorohydrocarbons, such as microbial liquid containing desulfurous (desulfulobacterium).
In some of these embodiments, the pilot test comprises the steps of:
a. collecting and treating a soil sample: collecting a soil sample, sieving the soil sample through a 2-3mm mesh sieve, fully mixing to obtain a sieved soil sample, and storing for later use; soil samples employed may include, but are not limited to, black soil, grey soil, loess, and the like.
b. Bottling soil and anaerobic treatment: transferring 20-30g of the sieved soil sample into a serum bottle, adding 50-100mL of ultrapure water, inserting a nitrogen pipeline with an injector into the bottom of the serum bottle, introducing nitrogen into the serum bottle to ensure that the serum bottle is in an anaerobic environment, and sealing the serum bottle;
c. and (3) soil constant-temperature heating treatment: placing the serum bottle in a water bath kettle, maintaining the preset temperature, and heating in a dark place for 7-20 days;
d. introducing chlorinated hydrocarbon and degrading bacteria: introducing 2-5mL of saturated hydrochloric ether solution into a serum bottle, and introducing 2-5mL of dechlorination bacteria; placing the serum bottle in a constant-temperature incubator at 25 ℃ for microbial degradation; the dechlorination bacteria may be a microbial liquid containing a genus of desulfulfite (desulfobacterium).
e. Analytical testing of the samples: samples are taken at different time points, 500 mu L of headspace gas is extracted from a serum bottle and injected into a gas chromatography sample inlet to analyze the concentration change of the hydrochloric ether, and after 500 mu L of water sample is extracted from the serum bottle and passes through a 0.45 mu m water system filter membrane, the electron donor content of formic acid, acetic acid and propionic acid is tested by using ion chromatography;
f. and determining the heating temperature and the heating time of the heat treatment according to the degradation effect of the small test.
In some of these embodiments, in step a, the soil sample is collected to a depth <20cm.
In some of these examples, in step b, the serum bottle was capped and sealed with a butyl rubber stopper and an aluminum sealing cap.
In some of these embodiments, the predetermined temperatures in step c include 25 ℃, 45 ℃, 60 ℃,75 ℃ and 90 ℃.
In some embodiments, the inoculum size of the microbial inoculum is 4% to 5%.
In some of these examples, the chlorinated hydrocarbon introduced in the pilot plant was trichloroethylene.
In some embodiments, in the step (2), the chlorohydrocarbon degradation engineering bacteria are injected into a chlorohydrocarbon polluted site in an injection well mode.
Example 1
The embodiment provides a method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology.
A method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology comprises the following steps:
(1) Carrying out a small test on a chlorinated hydrocarbon polluted site, wherein the small test comprises the following steps:
a. collecting and treating a soil sample: a soil sample was collected, wherein the soil sample in the invention was collected in the southern school district of Jilin university (43 ° 49'9 "N, 125 ° 16' 27" E, jilin province, china) and a black soil sample was collected, wherein the soil sample collection depth was <20cm. And (4) sieving the soil sample through a 2-3mm mesh sieve, fully mixing to obtain a sieved soil sample, and storing for later use.
b. Bottling soil and anaerobic treatment: the 20g of the sieved soil sample was transferred to a serum bottle, 50mL of ultrapure water was added, a nitrogen line with a syringe was inserted into the bottom of the serum bottle to conduct nitrogen treatment so as to be in an anaerobic environment, and the serum bottle was capped and sealed with a butyl rubber stopper and an aluminum sealing cap.
c. And (3) soil constant-temperature heating treatment: placing the serum bottle in a water bath kettle, maintaining the predetermined temperature including 25 deg.C, 45 deg.C, 60 deg.C, 75 deg.C and 90 deg.C, and heating in dark for 7-20 days.
d. Introducing chlorinated hydrocarbon and degrading bacteria: to the serum bottle was introduced 2mL of a saturated solution of chlorinated hydrocarbon, trichloroethylene in a pilot experiment. Then 2mL of microbial inoculum containing the desulfidation bacterium is introduced, and the inoculation amount of the microbial inoculum is 4% -5%. And (3) placing the serum bottle in a constant-temperature incubator at 25 ℃ for microbial degradation.
e. Analytical testing of the samples: samples are taken at different time points, 500 mu L of headspace gas is extracted from a serum bottle and injected into a gas chromatography sample inlet to analyze the concentration change of the hydrochloric ether, and after 500 mu L of water sample is extracted from the serum bottle and passes through a 0.45 mu m water system filter membrane, the electron donor content of formic acid, acetic acid and propionic acid is tested by using ion chromatography;
f. and determining the heating temperature and the heating time of the heat treatment according to the degradation effect of the small test, wherein when the actual chlorohydrocarbon site is repaired, the heating time of the heat treatment is ensured to be longer than the heating time determined by the small test, so that sufficient electron donor release is ensured.
As shown in FIG. 1, the formation of organic acids was detected under heating conditions of not less than 75 ℃ for 14 days, the organic acid species released from the soil at 75 ℃ included formic acid, acetic acid and propionic acid, and only formic acid and acetic acid at 90 ℃. After 7 days of microbial degradation, the total amount of organic acid in the system in the serum bottle is further increased, which shows that the organic acid is continuously released to the water phase in the microbial degradation process of the trichloroethylene.
As shown in FIG. 2, the degrading effect of dechlorination bacteria on trichloroethylene is positively correlated to the heat treatment temperature in the previous stage. After 90 ℃ pretreatment, the trichloroethylene is almost completely degraded within 3 days, and through a 75 ℃ pretreatment system, the time for completely degrading the trichloroethylene is prolonged to 10 days. The degradation is not completed under the condition of the rest heat treatment temperature.
As shown in FIG. 3, when the temperature of the heat treatment was not lower than 60 ℃, the degradation product cis-1,2-DCE began to be produced, and the effect of the pretreatment before the heat treatment on the promotion of the degradation of the subsequent microorganisms was confirmed. In the system of 75 ℃ and 90 ℃, the product concentration is consistent when the product concentration is 10 days, which indicates that the product reaches distribution equilibrium in the soil-water-gas three-phase. At temperatures below 60 c, no formation of trichloroethylene degradation products was detected, indicating that the reduced trichloroethylene concentration was due to soil adsorption. By contrast, the electron donor released by the soil in the heating process can promote the reductive dechlorination effect of the subsequent microorganisms. After 90 ℃ thermal repair pretreatment, the trichloroethylene is completely degraded within 3 d. Within 10 days of degradation time, the trichloroethylene removal rate after 75 ℃ thermal restoration pretreatment is more than 98 percent and is far higher than the trichloroethylene removal rate under the conditions of 25 ℃, 45 ℃ and 60 ℃ pretreatment.
(2) According to the small test, the chlorinated hydrocarbon polluted site is subjected to heat treatment, and based on the small test, the heat treatment temperature of the chlorinated hydrocarbon polluted site is determined to be 75-90 ℃, and the treatment time is 14d.
(3) After the heat treatment, injecting the chlorohydrocarbon degradation engineering bacteria into a chlorohydrocarbon polluted site in an injection well mode, and carrying out reductive dechlorination on the chlorohydrocarbon by using the electron donor released in the heat treatment stage by using the chlorohydrocarbon degradation engineering bacteria.
(4) Monitoring the concentration change of the chlorohydrocarbon in the chlorohydrocarbon polluted site, wherein the soil in the chlorohydrocarbon polluted site can decompose and release organic acid after being subjected to heat treatment, and the type and the release amount of the organic acid are related to the temperature. After the heating treatment of 14d, the concentration of the total organic acid released at the temperature of 90 ℃ is 61.81mg/L and is far higher than that (9.65 mg/L) at the temperature of 75 ℃. Below 75 ℃, no organic acids were detected. And 7d, degrading, and continuously releasing the organic acid for the utilization of microorganisms. In the microbial degradation stage, the consumption of formic acid is obvious, the concentration of formic acid is reduced from 35.50mg/L to 0.97mg/L at 90 ℃, and the repair is completed.
The method for repairing the site chlorinated hydrocarbon polluted source area by combining the heat treatment and the microbial technology removes high-concentration pollutants by adopting the heat treatment technology, promotes the decomposition of soil organic matters to release an electron donor; after the heat treatment is finished, the field is deeply repaired by combining the microbial technology, and the degrading bacteria in situ utilize the electron donor generated in the heat treatment stage. The technology can carry out deep restoration on the polluted site of the high-concentration source region, avoids adding an electron donor to the underground additionally, and realizes high-efficiency and low-consumption restoration of the polluted site.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to the related descriptions of other embodiments.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for repairing a site chlorinated hydrocarbon polluted source region by combining heat treatment and microbial technology is characterized by comprising the following steps:
(1) Carrying out heat treatment on a chlorohydrocarbon polluted site;
(2) After the heat treatment, injecting chlorohydrocarbon degradation engineering bacteria into the chlorohydrocarbon polluted site, wherein the chlorohydrocarbon degradation engineering bacteria carry out chlorohydrocarbon reduction dechlorination by utilizing the electron donor released in the heat treatment stage;
(3) And monitoring the concentration change of the chlorohydrocarbon in the chlorohydrocarbon polluted site, and when the concentration of the chlorohydrocarbon is less than a repair target preset value, indicating that the repair is finished.
2. The method for repairing the site chlorinated hydrocarbon polluted source area by the combination of the heat treatment and the microbial technology according to claim 1, wherein the heat treatment in the step (1) comprises the following steps:
and heating the site polluted by the chlorohydrocarbon at the temperature of 60-100 ℃ for not less than 7 days.
3. The method for repairing the chlorinated hydrocarbon polluted source area of the site by combining heat treatment and microbial technology according to claim 1, wherein a small test is carried out on the chlorinated hydrocarbon polluted site before the chlorinated hydrocarbon polluted site is subjected to heat treatment in the step (1), and the small test comprises the following steps:
collecting a soil sample of the chlorohydrocarbon-polluted site, introducing nitrogen into the soil sample to form an anaerobic environment, and carrying out heat treatment on the soil sample to simulate the environment temperature of a thermal remediation area of the chlorohydrocarbon-polluted site;
introducing chlorohydrocarbon into the soil sample after the heat treatment to simulate that the soil sample after the heat treatment still has residual pollutants, and introducing dechlorination bacteria into the soil sample to carry out microbial remediation on the chlorohydrocarbon.
4. The method for repairing the site chlorinated hydrocarbon polluted source area by combining heat treatment and microbial technology as claimed in claim 3, wherein the small test comprises the following steps:
a. collecting and treating a soil sample: collecting a soil sample, sieving the soil sample through a 2-3mm mesh sieve, fully mixing to obtain a sieved soil sample, and storing for later use;
b. bottling soil and anaerobic treatment: transferring 20-30g of the sieved soil sample into a serum bottle, adding 50-100mL of ultrapure water, inserting a nitrogen pipeline with an injector into the bottom of the serum bottle, introducing nitrogen into the serum bottle to ensure that the serum bottle is in an anaerobic environment, and sealing the serum bottle;
c. and (3) soil constant-temperature heating treatment: maintaining the serum bottle at a preset temperature, and heating for 7-20 days in a dark place;
d. introducing chlorinated hydrocarbon and degrading bacteria: introducing 2-5mL of saturated hydrochloric ether solution into the serum bottle, introducing 2-5mL of dechlorination bacteria, and placing the serum bottle in a constant-temperature incubator at 25 ℃ for microbial degradation;
e. analytical testing of the samples: sampling at different time points, extracting 500 mu L of headspace gas in the serum bottle, injecting the headspace gas into a gas chromatography sample inlet for analyzing the concentration change of the hydrochloric ether, extracting 500 mu L of water sample in the serum bottle, and testing the electron donor content of formic acid, acetic acid and propionic acid by using ion chromatography after the water sample passes through a 0.45 mu m water system filter membrane;
f. and determining the heating temperature and the heating time of the heat treatment according to the degradation effect of the pilot test.
5. The method for repairing the site chlorinated hydrocarbon polluted source area by combining heat treatment and microbial technology according to claim 4, wherein in the step a, the soil sample collection depth is less than 20cm.
6. The method for repairing the site chlorinated hydrocarbon polluted source area through combined heat treatment and microbial technology as claimed in claim 4, wherein in the step b, the serum bottle is capped and sealed through a butyl rubber plug and an aluminum sealing cover.
7. The method for repairing a site chlorinated hydrocarbon polluted source area through combined heat treatment and microbial technology as claimed in claim 4, wherein in the step c, the preset temperatures comprise 25 ℃, 45 ℃, 60 ℃,75 ℃ and 90 ℃.
8. The method for remediating the chlorinated hydrocarbon polluted source area of the field through the combination of heat treatment and microbial technology as claimed in claim 4, wherein the inoculation amount of dechlorination bacteria is 4% -5%.
9. The method for repairing the contaminated source area of the site chlorinated hydrocarbon through combined heat treatment and microbial technology according to any one of claims 3 to 8, wherein the chlorinated hydrocarbon introduced in the pilot test is trichloroethylene.
10. The method for repairing the site chlorinated hydrocarbon polluted source area by the combination of the heat treatment and the microbial technology according to any one of claims 1 to 8, wherein in the step (2), the chlorinated hydrocarbon degradation engineering bacteria are injected into the site contaminated by the chlorinated hydrocarbon by adopting an injection well mode.
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