CN114653741A - Composition with function of repairing organic matter polluted soil and/or underground water and application thereof - Google Patents
Composition with function of repairing organic matter polluted soil and/or underground water and application thereof Download PDFInfo
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- CN114653741A CN114653741A CN202011530321.4A CN202011530321A CN114653741A CN 114653741 A CN114653741 A CN 114653741A CN 202011530321 A CN202011530321 A CN 202011530321A CN 114653741 A CN114653741 A CN 114653741A
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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
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
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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
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
Abstract
The invention relates to the field of soil and/or underground water pollution remediation, and discloses a composition with a function of remedying organic matter-polluted soil and/or underground water and application thereof in remediation of polluted soil and/or underground water. The composition comprises sulfate, nutrient and optional solubilizer, wherein the weight ratio of the sulfate to the nutrient is (1-99): 1, preferably (1.1-30): 1. the composition provided by the invention can solve the problems of secondary pollution caused by a repairing agent, poor repairing effect and the like in the prior art, and has a wide application prospect.
Description
Technical Field
The invention relates to the field of soil and underground water pollution remediation, in particular to a composition with a function of remedying organic matter polluted soil and/or underground water and application thereof.
Background
China induces a large amount of polluted fields in the long-term economic development process, the environmental problems of soil and underground water are increasingly highlighted, and the environmental problems are aggravated to different degrees. The organic pollutants are pollutants which are serious in soil and underground water pollution and widely distributed, and the traditional industries such as petroleum exploitation, chemical engineering and the like occupy a large proportion in the pollution site investigation. Since the 80 s of the last century, a great deal of research and practice has been carried out in different countries to carry out soil and groundwater pollution remediation so far, and a technical system for managing and repairing the pollution risks of soil and groundwater is formed, wherein the technical system comprises an in-situ chemical oxidation technology, an in-situ permeable reaction barrier technology, an extraction treatment technology, an in-situ air disturbance technology and the like, but the methods either need to inject a large amount of oxidation agents or need to carry out on-site large-scale engineering construction, or need to treat secondary pollution such as waste water and waste gas generation and the like. Therefore, people have been concerned about how to effectively repair organic substance contaminated soil and groundwater.
CN104628120A discloses a novel groundwater remediation slow-release material and a preparation method thereof, wherein the slow-release material is mainly prepared from persulfate, cement, sand and distilled water, the preparation method comprises the steps of uniformly stirring and mixing the persulfate, the cement, the sand and the distilled water according to a certain mass ratio to prepare a slow-release material, and then injecting the slow-release material into a mold to prepare a hollow cubic structure; secondly, maintaining for 5 days at room temperature, and taking out from the die after shaping; and finally, adding solid powdery sodium persulfate into the hollow cube, and sealing the hollow cube by using the slow release material to prepare the slow release type sodium persulfate oxidant. The persulfate used in the method is easy to cause secondary pollution in the repair process.
CN103635265A discloses a method of bioremediating petroleum hydrocarbon contaminated groundwater by applying at least one electron acceptor salt to a ground surface overlying the contaminated groundwater. The method includes identifying characteristics of an aquifer in which the contaminated groundwater is found to enable treatment of aquifers within a range of depths below the surface of the earth. The method mainly sprays electron receptor solution on the ground surface, the electron receptor solution is only nitrate or sulfate ions, the condition that the proportion of carbon, nitrogen and phosphorus in underground environment is disordered due to the existence of organic matters is not considered, and nutrient substances for microbial growth are not added. And pouring a sufficient amount of water under gravity to allow the electron acceptor to reach the aquifer where the contaminant is located.
In summary, the above repairing agents and methods have the disadvantages that the repairing agents may cause secondary pollution and have poor repairing effects, and therefore, there is a need for an environmentally friendly composition and a repairing method capable of effectively repairing organic contaminated soil and groundwater.
Disclosure of Invention
The invention aims to overcome the technical problems that a repairing agent in the prior art causes secondary pollution and has poor repairing effect and the like, and provides a composition with the function of repairing organically-polluted soil and/or underground water and application thereof in repairing polluted soil and/or underground water.
In order to achieve the above objects, the present invention provides in a first aspect a composition having a function of remediating organic-contaminated soil and/or groundwater, the composition comprising sulfate, nutrients and optionally a solubilizing agent; wherein the weight ratio of the sulfate to the nutrient is (1-99): 1, preferably (1.1-30): 1.
in a second aspect, the present invention provides a method for remediating organic-contaminated soil and/or groundwater, the method comprising: contacting the soil and/or groundwater to be remediated with a composition as described in the preceding first aspect.
In a third aspect, the present invention provides a method for remediating organic-contaminated soil and/or groundwater using an electrochemical device, the method comprising: disposing an electrode or set of electrodes, a monitoring well in the soil and/or groundwater zone to be treated and introducing into said monitoring well a composition according to the preceding first aspect such that said composition is contacted with said organic matter under the control of said electrochemical device.
In a fourth aspect, the present invention provides the use of a composition according to the first aspect as hereinbefore described for the remediation of contaminated and/or groundwater.
Compared with the prior art, the composition provided by the invention has simple components and low price, is easy for large-scale production, can enhance the speed of degrading organic matters by indigenous microorganisms in the underground environment by using sulfate in the composition provided by the invention when being used for repairing soil and/or underground water, does not cause secondary pollution, is environment-friendly, and has high solubility of the sulfate in the underground environment and various injection modes, thereby achieving the aim of economically and efficiently repairing underground organic pollution.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composition with the function of repairing soil and/or underground water polluted by organic matters, which comprises sulfate, nutrient substances and optional solubilizer; wherein the weight ratio of the sulfate to the nutrient is (1-99): 1, preferably (1.1-30): 1.
in the present invention, the sulfate may be preferably contained in an amount of 40 to 99% by weight, preferably 85 to 99% by weight, based on the total weight of the composition (based on the components excluding the solvent).
According to some embodiments of the present invention, preferably, the nutrient may be present in an amount of 0.1 to 50% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the composition (based on the ingredients excluding the solvent).
According to some embodiments of the present invention, the composition may contain an amount of solubilizing agent to facilitate desorption of the organic material from the soil aquifer medium environment and thereby into the groundwater and increase solubility of the organic contaminant, preferably the solubilizing agent may be present in an amount of 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the composition (based on the components excluding the solvent).
According to some embodiments of the present invention, the sulfate may be selected from water-soluble sulfates, preferably from at least one of sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, iron sulfate and ferrous sulfate, more preferably from at least one of sodium sulfate, calcium sulfate and magnesium sulfate, and further preferably from sodium sulfate and/or magnesium sulfate.
In the present invention, the nutrients in the composition provide a more favorable environment for the indigenous microorganisms in the soil and/or groundwater to live.
In the present invention, the indigenous microorganisms are not particularly limited, and may generally include sulfate-reducing bacteria such as genus Desulfurvibrio, genus Desulfuromonas, genus Desulfofola, genus Desulfoenterococcus, genus Desulfococcus, genus Desulfosarcina and genus Desulfozona.
It should be noted that the carbon source required by the microorganism of the present invention can be provided by organic substances in the soil and/or groundwater, and no additional carbon source is required, and therefore, the nutrient substance preferably includes a nitrogen source and a phosphorus source.
In the present invention, in order to make the ratio of carbon, nitrogen and phosphorus in the soil and/or groundwater better meet the requirement of the microorganism, there is a certain requirement on the weight content of the nitrogen source and phosphorus source in the nutrient, preferably, the weight content of the nitrogen source may be 20-99%, more preferably 25-50%, based on the total weight of the nutrient; the phosphorus source may be present in an amount of 1 to 80% by weight, more preferably 50 to 75% by weight.
In the present invention, the nitrogen source may be selected from organic nitrogen or inorganic nitrogen, preferably at least one selected from sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, ammonium sulfate, ammonium nitrate, ammonium carbonate and urea, and more preferably at least one selected from sodium nitrate, ammonium nitrate and ammonium sulfate.
In the present invention, the phosphorus source may be at least one selected from the group consisting of sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, ammonium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, and ammonium dihydrogen phosphate, and preferably at least one selected from the group consisting of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, and calcium hydrogen phosphate.
It is noted that the phosphorus source may also serve as a pH buffer, for example, when the phosphorus source is a mixture of disodium hydrogen phosphate and sodium dihydrogen phosphate, providing a more excellent living environment for the microorganism.
According to some embodiments of the present invention, preferably, the solubilizer may be selected from at least one of rhamnolipid, polyethylene glycol octylphenyl ether (Triton X-100), cyclodextrin, ethanol, polysorbate (Tween), sodium dodecyl sulfate, preferably rhamnolipid or cyclodextrin.
In a second aspect, the present invention provides a method for remediating organic-contaminated soil and/or groundwater, the method comprising: contacting the soil and/or groundwater to be remediated with a composition as described in the preceding first aspect.
In the present invention, in order to obtain a better restoration effect when restoring the soil and/or groundwater, there is a certain requirement for the amount of the composition, and preferably, the amount of the composition may be 0.001 to 2g, more preferably 0.01 to 1g, based on 100g of the soil. And/or, preferably, the composition may be used in an amount of 0.01 to 20g, more preferably 0.1 to 10g, based on 1L of the groundwater.
According to a preferred embodiment of the invention, the composition is added in such an amount that the initial concentration of sulfate is between 10 and 200000ppm, preferably 100 and 100000 ppm.
According to a preferred embodiment of the present invention, the contacting conditions may include: the temperature is 15-35 deg.C, preferably 18-25 deg.C, and pH is controlled to 6-8, preferably 6.5-7.5.
In the present invention, when the composition is in contact with the soil and/or groundwater, there is no particular requirement on the form of the composition as long as the composition can be brought into sufficient contact with the soil and/or groundwater; for example, the composition is dissolved in water in the form of a solid in contact with the soil and/or groundwater and the composition is in aqueous solution in contact with the soil and/or groundwater.
In the present invention, when the composition is dissolved in water and brought into contact with the soil and/or groundwater in the form of the aqueous composition solution, the weight content ratio of the composition to water in the aqueous composition solution may be (0.05 to 0.3) to 1, preferably (0.1 to 0.2): 1.
according to some embodiments of the invention, preferably, the manner of contacting may be selected from at least one of the following manners: adding the composition to the soil and/or groundwater monitoring well to form an in situ reaction zone (i.e., direct mixing), mixing the composition with the soil and/or groundwater under agitation, infiltrating the composition into the soil and/or groundwater under the influence of gravity in a spray irrigation manner, and injecting the composition into the soil and/or groundwater in a liquid jet spray manner.
More preferably, the contacting is by injecting the composition into the soil and/or groundwater in a liquid jet or adding the composition to the soil and/or groundwater monitoring well to form an in situ reaction zone.
According to some embodiments of the invention, when the composition is mixed with the soil and/or groundwater under agitation, the rotation speed of the agitation may be 20 to 200 revolutions per minute.
According to some embodiments of the invention, preferably, when the composition is allowed to penetrate into the soil and/or groundwater under the action of gravity in the form of a spray irrigation, the spray irrigation refers to: the aqueous solution containing the composition is uniformly sprayed directly onto the surface and allowed to reach the soil and/or underground aquifer containing the contaminants.
According to some embodiments of the present invention, preferably, when the composition is injected into the soil and/or groundwater in the form of liquid jet, the conditions of the jet may include: the pressure is 5-30MPa, and the influence radius is 0.3-1.5 m; wherein, the rotary spraying can be high-pressure rotary spraying.
In a third aspect, the present invention provides a method for remediating organic-contaminated soil and/or groundwater using an electrochemical device, the method comprising: disposing an electrode or set of electrodes, a monitoring well in the soil and/or groundwater zone to be treated and introducing into said monitoring well a composition according to the preceding first aspect such that said composition is contacted with said organic matter under the control of said electrochemical device.
In the present invention, the electrochemical device may include: a power supply, electrodes and/or electrode groups, a transformer, a rectifier and/or frequency converter, conductors and switches;
wherein the switch is used for controlling the on-off of the circuit in the electrochemical device and changing the current direction of the circuit in the electrochemical device; the transformer is used for the electric field strength in and around the electrochemical device; the rectifier is used for converting alternating current output by the power supply into direct current.
According to some embodiments of the invention, preferably the electrodes or groups of electrodes of the electrochemical device are arranged to enable electrode polarity switching.
In the present invention, preferably, the electrode or the electrode group may comprise a plurality of cathodes and a plurality of anodes, and the distribution form of the cathodes and the anodes may be selected according to the actual situation of horizontal and vertical distribution of the organic matter pollution area in the soil and/or groundwater, and preferably, the anodes and the cathodes may be distributed in a lattice manner, for example, the anodes and the cathodes are embedded in the monitoring well according to a straight line, a curved line or an irregular line.
According to some embodiments of the present invention, preferably, the anode may be one of a graphite electrode, a metal oxide inert electrode, and a metal electrode; the cathode may be one of a graphite electrode, a metal oxide inert electrode, and a metal electrode.
In the present invention, preferably, the metal oxide inert electrode may be TiO2And an electrode.
In the present invention, preferably, the metal electrode may be a stainless steel electrode.
In the present invention, preferably, the graphite electrode may be selected from one of a graphite rod electrode, a carbon brush electrode, and a carbon felt electrode; the metal oxide inert electrode may be selected from a rod electrode or a porous electrode.
In the present invention, the diameter of the electrode is not particularly limited as long as the requirements of the present invention can be satisfied, and for example, may be 10 to 100mm, and preferably 10 to 50 mm.
In the present invention, preferably, the horizontal distance between the anode and the cathode may be 0.1 to 5m, preferably 0.5 to 3 m. Wherein, the horizontal distance refers to a distance without height difference in the horizontal direction.
In the present invention, the electrolyte of the electrochemical device may adsorb water and/or groundwater to the surface of the soil particles, and the monitoring well may be used as an electrolytic cell for the cathode and anode of the electrochemical device.
According to some embodiments of the invention, the electric field strength between the anode and the cathode of the electrode and/or the set of electrodes is preferably between 0.1 and 100V/m, preferably between 5 and 30V/m.
According to some embodiments of the present invention, preferably, the composition is added in an amount such that the initial weight concentration of sulfate is 10-200000ppm, preferably 100-100000 ppm.
In the present invention, preferably, the method may further comprise introducing a pH buffer into the monitoring well such that the pH of the soil and/or groundwater is in the range of 6.5 to 8, more preferably 6.5 to 7.5.
In the present invention, preferably, the pH buffering agent may be selected from at least one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium acetate, and potassium acetate, more preferably from at least one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate; further preferably at least two selected from the group consisting of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate, and still further preferably selected from the group consisting of potassium dihydrogen phosphate and disodium hydrogen phosphate, sodium dihydrogen phosphate and dipotassium hydrogen phosphate.
In the present invention, preferably, the method may further include: and monitoring the pH value change of the anode and the cathode in real time, and switching the polarity of the electrodes according to the monitoring result.
According to a preferred embodiment of the present invention, the condition for performing the electrode polarity switching operation satisfies: the pH value of the anode is reduced to 2.5-6, and the pH value of the cathode is increased to 8.5-12.5; more preferably, the pH of the anode is lowered to 4-6 and the pH of the cathode is raised to 8.5-10.
In the invention, during the process of repairing the soil and/or underground water polluted by organic matters, the pH value of the soil and/or underground water is maintained between 6.5 and 8, preferably between 6.5 and 7.5 through the addition of a pH regulator and/or the switching of electrodes.
In the invention, preferably, sulfate is introduced into an initial cathode monitoring well, and nutrient substances are introduced into the initial cathode and/or anode monitoring well, wherein the initial cathode monitoring well is a monitoring well added with a cathode electrode before electrode switching, and the anode monitoring well is a monitoring well added with an anode electrode before electrode switching.
According to a particularly preferred embodiment, the remediation of organic-contaminated soil and/or groundwater is carried out by means of an electrochemical device: disposing an electrode or set of electrodes, a monitoring well in a region of soil and/or groundwater to be treated and introducing into said monitoring well a composition according to the first aspect as hereinbefore described such that said composition is contacted with said organic matter under the control of said electrochemical device;
and arranging the electrodes according to regular hexagon distribution, and arranging and forming anode monitoring wells inserted into the anode electrodes and cathode monitoring wells inserted into the cathode electrodes according to the electrode distribution. The horizontal distance between the cathode electrode and the anode electrode is 0.5-2m, the cathode electrode is a metal electrode with the diameter of 10-20mm, and the anode electrode is a metal oxide inert electrode with the diameter of 10-20 mm;
adding the composition of the first aspect to the cathode and anode monitoring wells such that the initial weight concentration of sulfate is 500-;
the circuit of the electrochemical device is communicated, voltage is applied, the electric field intensity between the anode and the cathode is 10-20V/m, when the pH value of the underground water of the anode monitoring well is reduced to 4.5-6, the pH value of the underground water of the cathode monitoring well is increased to 8.5-9.5, the current direction of the circuit in the electrochemical device is changed, the initial anode is changed into the cathode, the initial cathode is changed into the anode, and the pH value of the underground water in the anode and cathode monitoring wells is maintained between 6.5-7.5; and in the repairing process, the pH value of underground water in the cathode and anode monitoring wells is circularly regulated and controlled through electrode switching.
In the present invention, the organic material is selected from biodegradable organic materials, and may be at least one of volatile organic materials, semi-volatile organic materials, and polycyclic aromatic hydrocarbons, and specifically, the organic material may be preferably selected from at least one of petroleum hydrocarbons, halogenated hydrocarbons, alcohols, and ethers, and more preferably selected from at least one of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, methyl t-butyl ether, t-butyl alcohol, dichloroethane, dichloroethylene, vinyl chloride, benzo a pyrene, anthracene, and naphthalene.
According to some embodiments of the present invention, the soil and/or groundwater preferably has a maximum concentration of the organic matter that should not contain mobile phase water insoluble phase contaminants and may contain residual water insoluble phase contaminants. For example, preferably, the initial weight concentration of the organic matter in the soil is 10-10000mg/kg, preferably 100-5000 mg/kg; the initial weight concentration of the organic matter in the groundwater is 10-200000. mu.g/L, preferably 100-100000. mu.g/L.
In a fourth aspect, the present invention provides the use of a composition according to the first aspect as hereinbefore described for the remediation of contaminated and/or groundwater.
As used herein, "ppm" refers to the concentration in parts per million of the mass of solute in the total solution, also referred to as parts per million concentration.
In the present invention, the petroleum hydrocarbon means C6-C40All hydrocarbons in between.
In the present invention, the lithology of the aquifer medium of the groundwater is selected from at least one of sandy soil, silt and clay, preferably at least one of viscous silt, silty clay and clay.
The present invention will be described in detail below by way of examples.
In the following examples, the concentrations of sulfate and nutrients were measured by ion chromatography, and the types and contents of organic contaminants in samples were measured by HJ639-2012 "mass spectrometry for measuring volatile organic compounds in water", HJ605-2011 "mass spectrometry for measuring volatile organic compounds in soil and sediments, HJ 834-2017" mass spectrometry for measuring semi-volatile organic compounds in soil and sediments ", USEPA 8270E-2018" measurement for measuring semi-volatile organic compounds in soil ", and HJ 894-2017" gas chromatography for measuring extractable petroleum hydrocarbons in water ". The first order reaction rate constant is calculated as: k-ln (C)0/Ct) T, where k is the first order reaction rate constant, C0As initial concentration, CtFor the final concentration, t is the reaction time, and a smaller value of the first order reaction rate constant indicates a lower degradation rate.
Example 1
By weight, 85 parts of sodium sulfate, 5 parts of ammonium nitrate, 5 parts of disodium hydrogen phosphate and 5 parts of potassium dihydrogen phosphate are accurately weighed and fully mixed to obtain the composition for later use.
The method is characterized in that groundwater polluted by petroleum hydrocarbon is pumped from a sulfate reduction zone polluted area of a certain petrochemical site by using groundwater sampling, air disturbance is avoided as much as possible in the process, and the initial weight concentration of the petroleum hydrocarbon is 1600 mug/L through detection.
1L of the above petroleum hydrocarbon-contaminated groundwater was taken and placed in a 5L beaker, and as a sample to be restored, 174mg of the above composition was directly mixed in the above groundwater sample, wherein the initial weight concentration of sulfate group was measured as 100ppm and the pH was measured as 6.9.
The underground water sample is placed at room temperature (18 ℃), after reaction for one week, the weight concentration of petroleum hydrocarbon is reduced to 800 mu g/L, and the first-order reaction rate constant is 0.099d-1(ii) a After two weeks of reaction, the weight concentration of petroleum hydrocarbon was reduced to 600. mu.g/L, and the first order reaction rate constant was 0.07d-1。
Example 2
According to the weight, 95 parts of potassium sulfate, 2.5 parts of diammonium hydrogen phosphate and 2.5 parts of ammonium dihydrogen phosphate are accurately weighed and fully mixed to obtain the composition for later use.
The polluted underground water of petroleum hydrocarbon is pumped by utilizing underground water sampling from a certain petrochemical site, air disturbance is avoided as much as possible in the process, and the initial weight concentration of the petroleum hydrocarbon is 1600 mug/L through detection.
1L of the petroleum hydrocarbon-contaminated underground water was placed in a 5L beaker and used as a sample to be restored, 9430mg of the above composition was directly mixed with the above underground water sample, and the initial weight concentration of sulfate was measured to be 5000ppm, and the pH was measured to be 7.1.
The underground water sample is placed at room temperature (18 ℃), after reaction for one week, the weight concentration of the petroleum hydrocarbon is reduced to 1050 mu g/L, and the first-order reaction rate constant is 0.06d-1(ii) a After two weeks of reaction, the weight concentration of the petroleum hydrocarbon was reduced to 736. mu.g/L, and the first-order reaction rate constant was 0.055d-1。
Example 3
Weighing 90 parts of magnesium sulfate, 2 parts of sodium nitrate, 3 parts of disodium hydrogen phosphate, 3 parts of monopotassium phosphate and 2 parts of rhamnolipid accurately by weight, dissolving in deionized water after weighing accurately, and obtaining a composition solution with 204000ppm of sulfate radical by weight for later use.
Air-entrained organic contaminated soil samples are taken from a certain gas station site, wherein the initial weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene are respectively 150mg/kg, 231mg/kg, 29mg/kg and 19mg/kg, and the soil medium is silty clay.
24.5 parts of the organic contaminated soil and 1 part of the composition solution were mixed by stirring sufficiently so that the initial weight concentration of sulfate groups in the soil sample was 10000ppm, and the pH was 7.2. And (4) placing the wide-mouth bottle in a closed wide-mouth bottle, and introducing nitrogen into the wide-mouth bottle to completely exhaust air on the upper part of the wide-mouth bottle.
After one week of reaction at room temperature (18 ℃), the weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene are respectively reduced to 65mg/kg, 124mg/kg, 21mg/kg and 12mg/kg, and the first-order reaction rate constants are respectively 0.112d-1、0.082d-1、0.039d-1、0.059d-1(ii) a After two weeks of reaction, the weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene were reduced to 45mg/kg, 96mg/kg, 15mg/kg and 8mg/kg, respectively, and the first-order reaction rate constant was 0.082d-1、0.059d-1、0.043d-1、0.058d-1。
Example 4
Accurately weighing 25 parts by weight of sodium sulfate, 25 parts by weight of potassium sulfate, 10 parts by weight of calcium nitrate, 10 parts by weight of ammonium phosphate, 15 parts by weight of sodium dihydrogen phosphate, 10 parts by weight of calcium hydrophosphate and 5 parts by weight of cyclodextrin, dissolving the mixture in deionized water after accurately weighing to obtain a composition solution with the sulfate radical weight concentration of 150000ppm for later use.
The method comprises the steps of taking a sample of organic contaminated soil of an aquifer from a certain refinery enterprise site, wherein the initial weight concentrations of petroleum hydrocarbon and benzo a pyrene are 6550mg/kg and 69mg/kg respectively, the soil medium is mucky soil, and the petroleum hydrocarbon exists in a residual non-water-soluble phase form.
And (3) taking 6.5 parts of the organic contaminated soil and 1 part of the composition solution, fully stirring and mixing to obtain a mixture with initial weight concentration of sulfate radical of 20000ppm and pH of 6.8, placing the mixture in a closed wide-mouth bottle, and introducing nitrogen into the wide-mouth bottle to completely exhaust air at the upper part of the wide-mouth bottle.
The mixture is placed at room temperature (20 ℃), after reaction for two weeks, the weight concentrations of the petroleum hydrocarbon and the benzo a pyrene are respectively reduced to 4500mg/kg and 52mg/kg, the first-order reaction rate constants are respectively 0.017d-1、0.0099d-1(ii) a After four weeks of reaction, the heavy ends of petroleum hydrocarbons and benzo a pyreneThe amount concentration is respectively reduced to 3760mg/kg and 46mg/kg, and the first-order reaction rate constant is 0.015d-1、0.0093d-1。
Example 5
By weight, accurately weighing 40 parts of magnesium sulfate, 55 parts of potassium sulfate, 2.5 parts of sodium dihydrogen phosphate and 2.5 parts of diammonium hydrogen phosphate, and dissolving in deionized water after accurately weighing to obtain a composition solution with the weight concentration of sulfate radicals of 150000ppm for later use.
The field test is carried out at a gas station site along the Yangtze river, the average weight concentrations of dichloroethane and petroleum hydrocarbon in soil polluted by organic matters in a water-bearing layer are respectively 450mg/kg and 2600mg/kg, and the soil medium is clay silt.
Injecting the composition solution by adopting a high-pressure rotary spraying process, calculating the injection amount of the composition according to the rotary spraying influence radius of 0.8m, wherein the injection depth of the composition is 4.5m, injecting 9 parts of organic contaminated soil and 1 part of the composition solution according to the proportion, obtaining the initial weight concentration of sulfate radicals in the mixed reaction of 15000ppm, and measuring the pH value to be 7.
After two weeks of reaction at room temperature (18 ℃), samples were taken at a distance of 0.5m from the composition solution injection hole and analyzed, and it was found that the weight concentrations of dichloroethane and petroleum hydrocarbon were respectively reduced to 385mg/kg and 2050mg/kg, and the first-order reaction rate constants were respectively 0.011d-1、0.017d-1(ii) a After four weeks of reaction, the weight concentrations of dichloroethane and petroleum hydrocarbon are respectively reduced to 342mg/kg and 1760mg/kg, and the first-order reaction rate constant is 0.0098d-1、0.014d-1。
Example 6
The procedure was followed as in example 1, except that 50 parts by weight of sodium sulfate, 40 parts by weight of ammonium nitrate, 5 parts by weight of disodium hydrogenphosphate and 5 parts by weight of potassium dihydrogenphosphate were accurately weighed and sufficiently mixed to obtain a composition for use.
After one week of reaction, the weight concentration of the petroleum hydrocarbon is reduced to 1048 mu g/L, and the first-order reaction rate constant is 0.060d-1(ii) a After two weeks of reaction, the weight concentration of petroleum hydrocarbon was reduced to 907. mu.g/L, and the first order reaction rate constant was 0.041d-1。
Example 7
The procedure is as in example 3, except that rhamnolipids are not added to the system.
After one week of reaction, the weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene are respectively reduced to 85mg/kg, 135mg/kg, 21mg/kg and 12mg/kg, and the first-order reaction rate constants are respectively 0.081d-1、0.077d-1、0.039d-1、0.059d-1(ii) a After two weeks of reaction, the weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene were reduced to 49mg/kg, 108mg/kg, 15mg/kg and 8mg/kg, respectively, and the first-order reaction rate constant was 0.080d-1、0.054d-1、0.043d-1、0.058d-1。
Example 8
The procedure is as in example 3, except that a composition solution having a sulfate radical concentration of 1020ppm by weight is prepared. The initial weight concentration of sulfate radical in the soil sample after the composition solution is fully stirred and mixed with the soil is 60 ppm.
After one week of reaction, the weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene are respectively reduced to 146mg/kg, 216mg/kg, 29mg/kg and 19 mg/kg; after two weeks of reaction, the weight concentrations of benzene, toluene, methyl tert-butyl ether and trimethylbenzene were reduced to 143mg/kg, 203mg/kg, 28mg/kg and 18mg/kg, respectively, which indicates that the concentrations of benzene, methyl tert-butyl ether and tert-butyl alcohol were not significantly changed, but only the concentration of toluene was significantly reduced, and the first-order reaction rate constant was 0.009d after two weeks-1。
Example 9
The procedure is as in example 5 except that the composition is allowed to penetrate into the contaminated underground aquifer by gravity in a spray irrigation manner.
Because the stratum is clay, the permeability is poor, the composition aqueous solution is difficult to permeate into the polluted underground aquifer, and because the composition aqueous solution stays near the groundwater level only under the action of gravity, the composition aqueous solution cannot contact pollutants below the water level in a short time, so that the contact effect of sulfate and the pollutants is poor.
After two weeks of reaction, the underground water multi-stage monitoring well samples and analyzes to find that the weight concentrations of dichloroethane and petroleum hydrocarbon in the soil near the underground water level are respectively reduced to 398mg/kg and 2150mg/kg, and the first-stage reaction rate constants are respectively 0.0088d-1、0.0136d-1At 1.5m below the groundwater level, the weight concentrations of dichloroethane and petroleum hydrocarbons in the soil were essentially unchanged.
Example 10
Area 30m of example 5 was selected2As an experimental area.
The electrodes are distributed according to regular hexagon distribution, anode monitoring wells inserted into the anode electrodes and cathode monitoring wells inserted into the cathode electrodes are distributed according to specifications (trial) of local survey sample collection, storage and circulation technical specifications of key industry enterprises, and the anode monitoring wells and the cathode monitoring wells are distributed according to the electrode distribution. The horizontal distance between the cathode and anode was 1m, the cathode was a 10mm (diameter) stainless steel electrode, and the anode was 20mm (diameter) TiO2And an electrode.
By weight, 40 parts of magnesium sulfate, 55 parts of potassium sulfate and 2.5 parts of sodium dihydrogen phosphate are added into a cathode monitoring well, and 2.5 parts of diammonium hydrogen phosphate is added into an anode monitoring well, wherein the initial weight concentration of sulfate radicals is 15000 ppm.
The power supply of the electrochemical device is a 220V alternating current power supply, the alternating current power supply is converted into a direct current power supply through a rectifier, a circuit is communicated, 90V voltage is applied, the electric field intensity between an anode and a cathode is 15V/m, after 2 days of voltage application, the pH value of underground water of an anode monitoring well is reduced to 5.6, the pH value of underground water of a cathode monitoring well is increased to 8.8, the current direction of the circuit in the electrochemical device is changed, an initial anode is changed into a cathode, and an initial cathode is changed into an anode, so that the pH value of underground water in the anode and cathode monitoring wells is maintained between 6.5 and 7.5. And in the repairing process, the pH value of underground water in the cathode and anode monitoring wells is circularly regulated and controlled through electrode switching.
After the above process was carried out at room temperature (18 ℃ C.) for 2 weeks, the current direction was adjusted 4 times in the process, and the weight concentration of petroleum hydrocarbon was reduced to 1950mg/kg by monitoring the concentration of contaminants in a plurality of soil samples between the cathode and the anode, and the primary reaction was carried outRate constant of 0.021d-1(ii) a After four weeks of reaction, the weight concentration of the petroleum hydrocarbon was reduced to 1436mg/kg, and the first order reaction rate constant was 0.021d-1。
Comparative example 1
The procedure was as in example 1. Except that no composition was added.
After one week of reaction, the weight concentration of the petroleum hydrocarbon is reduced to 1560 mu g/L, and the first-order reaction rate constant is 0.0036d-1(ii) a After two weeks of reaction, the weight concentration of the petroleum hydrocarbon is reduced to 1553 mu g/L, and the first-order reaction rate constant is 0.0021d-1。
Comparative example 2
The procedure is as in example 1, except that 500mg CaO is added to the groundwater2And (3) powder.
After one week of reaction, the weight concentration of the petroleum hydrocarbon is reduced to 1470 mu g/L, and the first-order reaction rate constant is 0.012d-1(ii) a After two weeks of reaction, the weight concentration of petroleum hydrocarbon was reduced to 1423. mu.g/L, and the first order reaction rate constant was 0.0084d-1。
Comparative example 3
The procedure of example 1 was followed except that 45 parts by weight of sodium sulfate, 45 parts by weight of ammonium nitrate, 5 parts by weight of disodium hydrogen phosphate and 5 parts by weight of potassium dihydrogen phosphate were accurately weighed and mixed to obtain a composition for use.
After one week of reaction, the weight concentration of the petroleum hydrocarbon is reduced to 1284 mu g/L, and the first-order reaction rate constant is 0.031d-1(ii) a After two weeks of reaction, the weight concentration of the petroleum hydrocarbon was reduced to 1105. mu.g/L, and the first order reaction rate constant was 0.026d-1。
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A composition having the function of remediating organic-contaminated soil and/or groundwater, characterized in that it comprises sulphate, nutrients and optionally solubilisers; wherein the weight ratio of the sulfate to the nutrient is (1-99): 1, preferably (1.1-30): 1.
2. the composition of claim 1, wherein the sulfate is present in an amount of 40 to 99%, preferably 85 to 99%, by weight based on the total weight of the composition;
the weight content of the nutrient substances is 0.1-50 percent, preferably 0.5-5 percent, based on the total weight of the composition;
the solubilizer is present in an amount of 0.5 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of the composition.
3. The composition according to claim 1 or 2, wherein the sulfate is selected from water soluble sulfates, preferably from at least one of sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, ferric sulfate and ferrous sulfate, more preferably from at least one of sodium sulfate, calcium sulfate and magnesium sulfate.
4. The composition of any one of claims 1-3, wherein the nutrients comprise a nitrogen source and a phosphorous source,
preferably, the nitrogen source is present in an amount of 20 to 99% by weight, more preferably 25 to 50% by weight, based on the total weight of the nutrient;
preferably, the phosphorus source is present in an amount of 1 to 80% by weight, more preferably 50 to 75% by weight, based on the total weight of the nutrient.
5. The composition of claim 4, wherein the nitrogen source is selected from at least one of sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, ammonium sulfate, ammonium nitrate, ammonium carbonate and urea, preferably from at least one of sodium nitrate, ammonium nitrate and ammonium sulfate;
and/or the phosphorus source is selected from at least one of sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, ammonium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate and ammonium dihydrogen phosphate, preferably at least one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate and calcium hydrogen phosphate.
6. The composition according to any one of claims 1-5, wherein the solubilizing agent is selected from at least one of rhamnolipids, polyethylene glycol octylphenyl ether, cyclodextrin, ethanol, polysorbate and sodium dodecyl sulfate, preferably rhamnolipids and/or cyclodextrin.
7. A method of remediating organic-contaminated soil and/or groundwater, comprising: contacting the soil and/or groundwater to be remediated with a composition according to any one of claims 1 to 6.
8. The method according to claim 7, wherein the composition is used in an amount of 0.001-2g, preferably 0.01-1g, based on 100g of the soil; and/or, the dosage of the composition is 0.01-20g, preferably 0.1-10g based on 1L of the groundwater;
and/or the composition is added in such an amount that the initial weight concentration of sulfate is 10-200000ppm, preferably 100-100000 ppm.
9. The method of claim 7 or 8, wherein the conditions of the contacting comprise: the temperature is 15-35 deg.C, preferably 18-25 deg.C, and pH is controlled between 6-8, preferably 6.5-7.5.
10. The method according to any one of claims 7 to 9, wherein the composition is contacted with the soil and/or groundwater in the form of a solid or dissolved in water in the form of an aqueous composition solution.
11. The method of any one of claims 7-10, wherein the contacting is by a means selected from at least one of: adding the composition to the soil and/or groundwater monitoring well to form an in situ reaction zone, mixing the composition with the soil and/or groundwater under agitation, infiltrating the composition into the soil and/or groundwater under the action of gravity in a spray irrigation manner, and injecting the composition into the soil and/or groundwater in a liquid jet manner;
preferably, the contacting is by injecting the composition into the soil and/or groundwater in a liquid jet or adding the composition to the soil and/or groundwater monitoring well to form an in situ reaction zone.
12. A method for remediating organic-contaminated soil and/or groundwater using an electrochemical device, the method comprising: -laying an electrode or set of electrodes, a monitoring well in the soil and/or groundwater zone to be treated, and introducing into said monitoring well a composition according to any of claims 1 to 6, such that said composition is in contact with said organic matter under the control of said electrochemical device.
13. The method of claim 12, wherein the electrodes or groups of electrodes of the electrochemical device are configured to enable electrode polarity switching;
and/or the electric field strength between the anode and the cathode of the electrode and/or the electrode group is 0.1-100V/m, preferably 5-30V/m;
and/or the composition is added in such an amount that the initial weight concentration of sulfate is 10-200000ppm, preferably 100-100000 ppm.
14. A method according to claim 12 or 13, wherein the method further comprises introducing a pH buffer into the monitoring well such that the soil and/or groundwater has a pH of 6.5-8, preferably 6.5-7.5;
preferably, the pH buffering agent is selected from at least one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium acetate, and potassium acetate, preferably at least one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate.
15. The method of any of claims 12-14, wherein the method further comprises: monitoring the pH value change of the anode and the cathode in real time, switching the polarity of the electrodes according to the monitoring result,
preferably, the condition for performing the electrode polarity switching operation satisfies: the pH value of the anode is reduced to 2.5-6, and the pH value of the cathode is increased to 8.5-12.5; more preferably, the pH of the anode is lowered to 4-6 and the pH of the cathode is raised to 8.5-10.
16. The method according to any one of claims 7 to 13, wherein the organic matter is selected from at least one of petroleum hydrocarbons, halogenated hydrocarbons, alcohols, and ethers, preferably from at least one of benzene, toluene, ethylbenzene, xylene, trimethylbenzene, methyl tert-butyl ether, tert-butanol, dichloroethane, dichloroethylene, vinyl chloride, benzo a pyrene, anthracene, and naphthalene;
and/or the initial weight concentration of the organic matters in the soil is 10-10000mg/kg, preferably 100-5000 mg/kg; the initial weight concentration of the organic matters in the underground water is 10-200000ug/L, and preferably 100-100000 ug/L.
17. Use of a composition according to any one of claims 1 to 6 for the remediation of contaminated and/or groundwater.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5833855A (en) * | 1996-01-05 | 1998-11-10 | Auburn University | Situ bioremediation of contaminated groundwater |
| CN108856275A (en) * | 2018-07-03 | 2018-11-23 | 南京万德斯环保科技股份有限公司 | A kind of method of repairing polluted soil and Organic Chemicals In Groundwater |
| CN109420677A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Soil remediation composition and application and geobiont repair method |
| CN109423294A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Soil remediation composition and application and geobiont repair method |
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| US5833855A (en) * | 1996-01-05 | 1998-11-10 | Auburn University | Situ bioremediation of contaminated groundwater |
| CN109420677A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Soil remediation composition and application and geobiont repair method |
| CN109423294A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Soil remediation composition and application and geobiont repair method |
| CN108856275A (en) * | 2018-07-03 | 2018-11-23 | 南京万德斯环保科技股份有限公司 | A kind of method of repairing polluted soil and Organic Chemicals In Groundwater |
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