CN114085674A - VOC (volatile organic compound) pollution repairing agent and application thereof and method for repairing VOC polluted environment - Google Patents

VOC (volatile organic compound) pollution repairing agent and application thereof and method for repairing VOC polluted environment Download PDF

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Publication number
CN114085674A
CN114085674A CN202010857942.7A CN202010857942A CN114085674A CN 114085674 A CN114085674 A CN 114085674A CN 202010857942 A CN202010857942 A CN 202010857942A CN 114085674 A CN114085674 A CN 114085674A
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China
Prior art keywords
voc
cyclodextrin
agent
pollution
soil
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CN202010857942.7A
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Inventor
武陈
王岽
王彬
薛琳
赵桂瑜
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN202010857942.7A priority Critical patent/CN114085674A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • 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

Abstract

The invention relates to the technical field of environmental protection, in particular to a VOC (volatile organic compound) pollution repairing agent and application thereof and a method for repairing VOC polluted environment. The VOC pollution repairing agent comprises a cyclodextrin compound, a surfactant, an oxidant and water; wherein, in the VOC pollution repairing agent, the content of cyclodextrin compounds is 5-20 wt%, the content of surface active agent is 0.1-5 wt%, the content of oxidizing agent is 0.1-5 wt%, and the balance is water. The VOC pollution repair agent can collect gaseous VOC above polluted soil, inhibit the escape of the VOC in the soil to the air, decompose and remove the VOC in the soil, and has the advantages of cheap and easily-obtained components, high treatment speed and obvious effect. The method provided by the invention is suitable for various organic pollution, has wide application range, and can be used for inhibiting and removing VOC in different environments. Moreover, the operation is simple, and large-scale equipment is not needed.

Description

VOC (volatile organic compound) pollution repairing agent and application thereof and method for repairing VOC polluted environment
Technical Field
The invention relates to the technical field of environmental protection, in particular to a VOC (volatile organic compound) pollution repairing agent and application thereof and a method for repairing VOC polluted environment.
Background
Soil is the most basic environmental element for human survival and development, and is closely related to human production and life. When pollutants enter the soil through various ways, and the quantity and the speed of the pollutants exceed the self-cleaning capacity of the soil, the soil pollution can be caused.
Volatile Organic Compounds (VOCs) are the most common pollutants in the petrochemical industry, are complex and diverse in components, have strong volatility, are harmful to the environment, are severely toxic to human bodies, are difficult to treat and can be accumulated in soil for a long time. Many developed countries have clear regulations that soil contaminated with volatile organic compounds must be properly disposed of to ensure the safety of living beings and their environment.
Remediation of soil pollution refers to the physical, chemical and biological methods used to transfer, absorb, degrade and transform pollutants in soil to reduce their concentration to acceptable levels, or to transform toxic and harmful pollutants into harmless substances. A series of remediation technologies for VOC contaminated soil are developed aiming at different pollution conditions. From the restoration principle, the method can be divided into physical/chemical restoration and biological restoration, wherein the physical/chemical restoration mainly comprises a thermal desorption technology, a soil vapor extraction technology, a soil leaching technology and the like, and the biological restoration method comprises a microbial restoration method, a plant restoration method, an animal restoration method and the like.
The research of China on the remediation of volatile organic contaminated soil is still in a simulation test stage, mainly focuses on the treatment of heavy metals, and does not find a set of technology and process which can be used on site, and has low remediation cost, high efficiency and strong operability for the treatment of organic matters, particularly VOC.
Disclosure of Invention
The invention aims to provide a VOC (volatile organic compound) pollution repairing agent, application thereof and a method for repairing VOC polluted environment. The gaseous VOC above the polluted soil can be collected by spraying the VOC pollution repair agent, the dissipation of the VOC in the soil to the air is inhibited, and the VOC in the soil is decomposed and removed.
In order to achieve the above object, the present invention provides in a first aspect a VOC pollution remediation agent comprising a cyclodextrin-based compound, a surfactant, an oxidizing agent and water;
wherein, in the VOC pollution repairing agent, the content of cyclodextrin compounds is 5-20 wt%, the content of surface active agent is 1-5 wt%, the content of oxidizing agent is 1-5 wt%, and the balance is water.
The second aspect of the present invention provides the use of the VOC pollution remediation agent as described above for the remediation of VOC polluted environments.
In a third aspect, the present invention provides a method for remediating a VOC contaminated environment, comprising: the VOC pollution remediation agent as described above is contacted with a VOC polluted environment.
The VOC pollution remediation agent can capture gaseous VOC above polluted soil, inhibit the escape of the VOC in the soil into the air, and decompose and remove the VOC in the soil.
The VOC pollution repairing agent has the advantages of cheap and easily obtained components, high treatment speed and obvious effect.
The VOC pollution repairing agent has no pollution to the environment, all components can be naturally degraded, secondary pollution is avoided, no waste gas, waste liquid or waste residue is generated in the treatment process, and no obvious influence is caused on the biochemical state of soil.
The method provided by the invention is suitable for various organic pollution, has wide application range, and can be used for inhibiting and removing VOC in different environments. Moreover, the operation is simple, and large-scale equipment is not needed.
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.
In order to achieve the above object, the present invention provides in a first aspect a VOC pollution remediation agent comprising a cyclodextrin-based compound, a surfactant, an oxidizing agent and water;
wherein, in the VOC pollution repairing agent, the content of cyclodextrin compounds is 5-20 wt%, the content of surface active agent is 1-5 wt%, the content of oxidizing agent is 1-5 wt%, and the balance is water.
In the VOC pollution remediation agent according to the present invention, the content of the cyclodextrin compound is 5 to 20 wt%, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20 wt%, or any range between any two values, and preferably, the content of the cyclodextrin compound in the VOC pollution remediation agent is 8 to 15 wt%.
In the VOC pollution remediation agent according to the present invention, the surfactant is present in an amount of 1-5 wt%, for example, 1, 2, 3, 4, 5 wt% and any range between any two values, preferably 2-4 wt%.
In the VOC pollution remediation agent according to the present invention, the amount of the oxidizing agent is 1 to 5 wt%, for example, 1, 2, 3, 4, 5 wt% and any range between any two values, preferably 2 to 4 wt%.
In the present invention, the cyclodextrin compound may be any one of existing cyclodextrin compounds, and preferably, the cyclodextrin compound is selected from cyclodextrin and/or cyclodextrin ether derivatives.
The cyclodextrin includes, but is not limited to, alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin. Preferably, the cyclodextrin is selected from at least one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
Among them, the substituent in the cyclodextrin ether derivative includes, but is not limited to, an alkyl group, a hydroxyalkyl group, or a sulfoalkyl group. Cyclodextrin ether derivatives include, but are not limited to, hydroxypropyl- β -cyclodextrin, randomly methylated- β -cyclodextrin, and sulfobutyl- β -cyclodextrin. Preferably, the cyclodextrin ether derivative is selected from at least one of hydroxypropyl- β -cyclodextrin, randomly methylated- β -cyclodextrin, and sulfobutyl- β -cyclodextrin.
Among them, Randomly methylated- β -Cyclodextrin (random methylated- β -Cyclodextrin, RM- β -CD) is commercially available.
In a preferred embodiment of the invention, the cyclodextrin is selected from at least one of randomly methylated- β -cyclodextrin, sulfobutyl- β -cyclodextrin and hydroxypropyl- β -cyclodextrin. Under the preferable conditions, the adsorption efficiency and the removal efficiency of the VOC by the repairing agent can be improved.
In the present invention, the surfactant may be a surfactant that is conventional in the art, and preferably, the surfactant has a structure represented by formula (I),
Figure BDA0002647028360000041
wherein R is C10-C18 linear alkyl, and n is an integer of 5-10.
Preferably, R is a C12-C14 linear alkyl group and n is 6 or 7. Under the preferable conditions, the adsorption efficiency and the removal efficiency of the VOC by the repairing agent can be improved.
In the present invention, the oxidizing agent may be a conventionally used oxidizing agent, preferably, the oxidizing agent is selected from at least one of peroxides, persulfates and permanganates, more preferably persulfates and/or permanganates. In the preferred case, the escape of volatile organic compounds in the soil can be suppressed for a long time.
Among them, the peroxide is preferably hydrogen peroxide.
Among them, the persulfate is preferably at least one selected from the group consisting of sodium persulfate, potassium persulfate, and ammonium persulfate.
Among them, the permanganate is preferably at least one selected from the group consisting of potassium permanganate, lithium permanganate, sodium permanganate, ammonium permanganate, calcium permanganate, zinc permanganate, and magnesium permanganate.
In the present invention, the water may be water commonly used in the art, and may be, for example, deionized water, ultrapure water, and tap water.
In a preferred embodiment of the present invention, the VOC pollution remediation agent comprises a cyclodextrin-based compound, a surfactant, an oxidizing agent, and water. Wherein, in the VOC pollution repairing agent, the content of cyclodextrin compounds is 8-15 wt%, the content of surface active agent is 2-4 wt%, the content of oxidizing agent is 2-4 wt%, and the balance is water. Wherein the cyclodextrin compound is at least one selected from random methylated-beta-cyclodextrin, sulfobutyl-beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin and beta-cyclodextrin, the surfactant has a structure shown in a formula (I),
Figure BDA0002647028360000042
wherein R is C12-C14 linear alkyl, n is 6 or 7, and the oxidant is persulfate and/or permanganate. Under the preferable conditions, the adsorption efficiency and the removal efficiency of the VOC by the repairing agent can be further improved.
In the present invention, reagents and materials used are commercially available unless otherwise specified.
The second aspect of the present invention provides the use of the VOC pollution remediation agent as described above for the remediation of VOC polluted environments.
In a third aspect, the present invention provides a method for remediating a VOC contaminated environment, comprising: the VOC pollution remediation agent as described above is contacted with a VOC polluted environment.
Preferably, the VOC contaminated environment is selected from at least one of VOC contaminated air, soil and water.
In the present invention, the concentration of VOC in the VOC polluted environment may not be limited.
In the present invention, preferably, the contacting is performed at room temperature. No special treatment is needed for the environment and VOC pollution repairing agent.
In the present invention, the method of using the VOC pollution remediation agent may not be particularly limited, and for example, the VOC pollution remediation agent may be sprayed into a VOC polluted environment.
In a preferred embodiment of the present invention, the VOC pollution remediation agent is sprayed over the VOC polluted soil. In this case, the VOC pollution remediation agent is dispersed into fine droplets by spraying, and then the fine droplets are sprayed on the contaminated soil, and then slowly fall on the surface of the soil due to gravity. In the process, the cyclodextrin compound and the surfactant increase the solubility of VOC in the VOC pollution remediation agent, and the liquid drops can effectively absorb and capture gaseous organic matters in the air and carry the gaseous organic matters into soil. Meanwhile, as the cyclodextrin compound in the VOC pollution repairing agent has a unique cavity structure with hydrophilic outside and hydrophobic inside, particularly random methylated-beta-cyclodextrin, sulfobutyl-beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin, on one hand, the cyclodextrin compound can be well dissolved in water, and on the other hand, the cyclodextrin compound can absorb and capture small organic molecules and keep the small organic molecules in the molecular structure of the cyclodextrin compound. The VOC pollution repairing agent can form a layer of loose water film after falling on the surface layer of the soil, and can play a role in inhibiting and blocking the dissipation of VOC in the soil to the air. After the VOC pollution remediation agent reaches the soil, the VOC pollution remediation agent continues to slowly permeate into the soil along with the prolonging of time. The oxidant can oxidize and decompose the VOC in the soil, thereby achieving the purpose of removing the VOC.
In the present invention, the spraying mode may be a continuous mode or a batch mode.
The present invention will be described in detail below by way of examples.
In the following examples, reagents and materials used were all commercially available unless otherwise specified.
The preparation method of the VOC contaminated soil comprises the following steps: weighing 100g of clean soil (soil not polluted by organic pollutants) and placing the clean soil into a 5L beaker, adding 10mL of deionized water and 20 mu L of toluene, stirring and shaking uniformly, placing the mixture into a simple glove box and standing for one hour to obtain the VOC polluted soil. Then, the prepared VOC-contaminated soil was used in the following examples and comparative examples.
VOC concentrations were determined using a Mini RAE model 3000 VOC detector.
In the following examples, the surfactants were:
Figure BDA0002647028360000061
in the following examples, SDBS refers to sodium dodecylbenzenesulfonate.
Example 1
This example illustrates the VOC contamination remediation agent of the present invention and methods of use
The repairing agent is prepared according to the formula shown in table 1, and the concrete steps comprise: dissolving a cyclodextrin compound, a surfactant and an oxidant in deionized water, quantifying to 100g by using the deionized water, and uniformly mixing to obtain the repairing agent.
The prepared repairing agent is sprayed in a glove box (with VOC concentration of 2781ppm in the glove box) filled with VOC contaminated soil, wherein the VOC concentration of the glove box is described in the preparation example, the difference between the quality of the spraying pot before and after spraying is recorded as the using amount of the repairing agent, when the using amount of the repairing agent is 31g, the spraying is stopped, and the VOC concentration in the glove box is measured and recorded as the VOC concentration of the glove box of 0 h. The VOC concentration in the glove box was again checked 24 hours after the spraying was finished, and the VOC concentration in the treated soil was analyzed by gas chromatography-mass spectrometry, and the specific results are shown in table 3 (in ppm).
The VOC content of the glove box during spraying is shown in Table 4 for a conditioner formulated according to formulation S1 in Table 1.
TABLE 1
Figure BDA0002647028360000071
Comparative example 1
VOC pollution remediation agent for reference and use method thereof
The repairing agent is prepared according to the formula shown in table 2, and the concrete steps comprise: and (3) dissolving the component A, the component B and the component C in deionized water, quantifying to 100g by using the deionized water, and uniformly mixing to obtain the repairing agent.
The remediation agent was used as described in example 1 and the VOC concentration was measured at 0h glove box. The VOC concentration in the glove box was again checked 24 hours after the spraying was finished, and the VOC concentration in the treated soil was analyzed by gas chromatography-mass spectrometry, and the specific results are shown in table 3 (in ppm).
TABLE 2
Figure BDA0002647028360000072
TABLE 3
Numbering 0h glove box 24h glove box 24h soil
S1 21 40 19
S2 35 45 31
S3 31 36 21
S4 81 89 65
S5 34 79 90
S6 74 81 75
S7 57 65 35
D1 65 49 188
D2 86 96 91
TABLE 4
Amount of repairing agent used (g) VOC content (ppm) in glove box
6.2 1435
12.4 1064
18.6 325
24.8 89
31.0 21
The results show that the remediation agent provided by the invention can be used for treating VOC polluted environment, so that the VOC in the air above the soil can be effectively absorbed, and the VOC in the soil can be removed.
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 combinations of various technical features 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 (10)

1. A VOC pollution remediation agent, wherein the VOC pollution remediation agent comprises a cyclodextrin compound, a surfactant, an oxidant, and water;
wherein, in the VOC pollution repairing agent, the content of cyclodextrin compounds is 5-20 wt%, the content of surface active agent is 1-5 wt%, the content of oxidizing agent is 1-5 wt%, and the balance is water.
2. The VOC pollution remediation agent of claim 1, wherein the amount of cyclodextrin compounds is 8-15 wt%, the amount of surfactant is 2-4 wt%, the amount of oxidant is 2-4 wt%, and the balance is water.
3. A VOC pollution remediation agent according to claim 1 or 2, wherein the cyclodextrin compound is selected from cyclodextrin and/or cyclodextrin ether derivatives.
4. The VOC contamination remediation agent of claim 3, wherein the cyclodextrin is selected from at least one of a-cyclodextrin, β -cyclodextrin, and γ -cyclodextrin; and/or
The cyclodextrin ether derivative is selected from at least one of hydroxypropyl-beta-cyclodextrin, randomly methylated-beta-cyclodextrin and sulfobutyl-beta-cyclodextrin.
5. The VOC contamination remediation agent of any one of claims 1-4, wherein the cyclodextrin is selected from at least one of randomly methylated-beta-cyclodextrin, sulfobutyl-beta-cyclodextrin, and hydroxypropyl-beta-cyclodextrin.
6. The VOC contamination remediation agent of any of claims 1-5, wherein the surfactant has a structure according to formula (I),
Figure FDA0002647028350000011
wherein R is C10-C18 linear alkyl, and n is an integer of 5-10;
preferably, R is a C12-C14 linear alkyl group and n is 6 or 7.
7. The VOC contamination remediation agent of any of claims 1-6, wherein the oxidizing agent is selected from at least one of a peroxide, a persulfate, and a permanganate.
8. Use of the VOC pollution remediation agent of any one of claims 1 to 7 for the remediation of VOC polluted environments.
9. A method of remediating a VOC contaminated environment, comprising: contacting the VOC contaminated remediation agent of any of claims 1-7 with a VOC contaminated environment.
10. The method of claim 9, wherein said VOC contaminated environment is selected from at least one of VOC contaminated air, soil, and water.
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