CN110420993A - A kind of restorative procedure of diesel fuel contaminated soil - Google Patents
A kind of restorative procedure of diesel fuel contaminated soil Download PDFInfo
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- CN110420993A CN110420993A CN201910796687.7A CN201910796687A CN110420993A CN 110420993 A CN110420993 A CN 110420993A CN 201910796687 A CN201910796687 A CN 201910796687A CN 110420993 A CN110420993 A CN 110420993A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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Abstract
The invention proposes a kind of restorative procedures of diesel fuel contaminated soil, the following steps are included: the modification of S1. algin: instilling a small amount of HCl solution into ethanol solution and adjust pH, algin and coupling agent are separately added into solution, heating stirring reaction, cyclodextrin is added, quickly stirring constant temperature, constant temperature drying, grinding obtain cyclo-dextrin-modified algin later in an oven after filtering；S2. soil collection；S3. soil remediation: by cyclo-dextrin-modified algin wiring solution-forming, being uniformly added into the contaminated soil of acquisition, stir soil and reacted, then wash away cyclo-dextrin-modified algin with clear water, dry, the soil after being repaired.The hydroxyl on cyclodextrin surface and algin are coupled by the present invention, improve the suction-operated to oily pollutant, algin has the function of oil of preferably degrading simultaneously, and the oily pollutant of absorption is degraded, is adsorbed, to realize removal oily in diesel fuel contaminated soil.
Description
Technical field
The present invention relates to technical field of soil remediation, and in particular to a kind of restorative procedure of diesel fuel contaminated soil.
Background technique
With the rapid development of society, people are gradually increased the exploitation dynamics of petroleum, in oil exploitation, handling, transport
In process, due to leaking and discharging etc. caused by Soil Environmental Pollution have become one get worse and by
The problem of concern.
Diesel oil is oils, is the fuels and energy of heavy-duty car, steamer etc., the polycyclic aromatic hydrocarbon contained in component
(Polycyclic aromatic hydrocarbons, PAHs) is a kind of persistence organic pollutant, has high biological concentration
Property, high toxicity and it is difficult to the features such as degrading, the long-term pollution sources of underground water are usually become after contaminated soil.After diesel fuel contaminated soil
It is not easy to remove in a short time, and the wettability of soil can be made to change to a certain degree, lead to the reduction of medium moisture holding capacity, therefore
It is most important to the monitoring of contaminated by diesel oil soil, and coastal area is important, the base that oil product is refined and stored, therefore coastal soil
Oil pollution should more draw attention.
Summary of the invention
The present invention provides a kind of restorative procedure of diesel fuel contaminated soil, by the way that the hydroxyl on cyclodextrin surface and algin is even
Connection improves the suction-operated to oily pollutant, while algin has the function of oil of preferably degrading, by the oil of absorption
Matter pollutant is degraded, is adsorbed, to realize removal oily in diesel fuel contaminated soil.
The present invention provides a kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S1. the modification of algin: a small amount of HCl solution is instilled into ethanol solution and adjusts pH=3-4, by algin and coupling agent
It is separately added into the solution of preparation, is reacted in 70 DEG C or so heating stirrings, cyclodextrin is added, is quickly heated with stirring to 75 DEG C of constant temperature
30min, 50 DEG C of constant temperature drying in an oven, obtain cyclo-dextrin-modified algin after filtering after grinding；
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: cyclo-dextrin-modified algin wiring solution-forming prepared by step S1 is uniformly added into the Polluted Soil of acquisition
Earth stirs after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue and piles stack, reacted, and then washes away ring paste with clear water
The modified algin of essence, dry, the soil after being repaired.
As further improvement of the invention, the cyclodextrin is selected from beta-cyclodextrin, hydroxypropyl-β-cyclodextrin, methyl-β-
One of cyclodextrin.
As further improvement of the invention, the content of ethyl alcohol is 70-80wt%, the HCl solution in the ethanol solution
For content 30-35wt% concentrated hydrochloric acid.
As further improvement of the invention, the coupling agent is silane coupling agent.
As further improvement of the invention, the content of the cyclo-dextrin-modified alginate solution is 30-55wt%, is launched
Amount is every 1m3Soil launch 1L cyclo-dextrin-modified alginate solution.
As further improvement of the invention, the cyclo-dextrin-modified algin wiring solution-forming also added surface-active
Agent.
As further improvement of the invention, the surfactant is zwitterionic surfactant；The both sexes from
Sub- surfactant is selected from one or more of lecithin, amino acid pattern or betaine type.
As further improvement of the invention, the additive amount of the cyclo-dextrin-modified alginate solution is every 1m3Soil adds
Add 1-2L.
The present invention further protects cyclo-dextrin-modified obtained in a kind of a kind of above-mentioned restorative procedure of diesel fuel contaminated soil
Algin.
The present invention further protects a kind of application of above-mentioned cyclo-dextrin-modified algin in absorption degradation oily pollutant.
The invention has the following beneficial effects: cyclodextrin to have hollow cylinder three-dimensional ring structure, and a kind of with parent
The amphoteric compound of water, oleophylic performance.It is hydrophilic radical outside its ring, internal cavities are hydrophobic region.Due to its unique structure,
It can be acted on the petroleum pollution in soil, inclusion compound be formed, so that pollutant be eluted from soil.By cyclodextrin
The hydroxyl and algin on surface are coupled, and improve the suction-operated to oily pollutant, while algin has preferable degradation
The effect of oil, the oily pollutant of absorption is degraded, is adsorbed, to realize removal oily in diesel fuel contaminated soil；
Zwitterionic surfactant, mostly environment-friendly type surfactant are separately added in the solution, avoids residue to soil
Pollution, while surface tension is reduced, promote the removal of oily pollutant when clear water washs soil, most of oil can
It degrades, adsorb with cyclo-dextrin-modified algin, a part is embedded by surfactant, is removed, is improved the effect of soil remediation
Rate, in 1-2L/m3Additive amount under conditions of, the absorption degradation of half a day can realize the removal of 90% or more soil oil.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is the modified brown alga glue yield comparison diagram of embodiment 1-4 cyclodextrin in test case 1 of the present invention
Fig. 2 is the comparison diagram of each group crude oil removal in test case 2 of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation of cyclo-dextrin-modified algin:
A small amount of 30wt% HCl solution is instilled into 70wt% ethanol solution adjusts pH=3,10g algin and 0.1g is silane coupled
Agent KH550 is separately added into the solution of preparation, is reacted in 70 DEG C or so heating stirrings, 20g beta-cyclodextrin is added, quickly stirring adds
Heat is to 75 DEG C of constant temperature 30min, and 50 DEG C of constant temperature drying in an oven, obtain cyclo-dextrin-modified algin after grinding, obtain after filtering
Rate is 95%.
Embodiment 2
A kind of preparation of cyclo-dextrin-modified algin:
A small amount of 35wt% HCl solution is instilled into 80wt% ethanol solution adjusts pH=4,8g algin and 0.1g is silane coupled
Agent KH550 is separately added into the solution of preparation, is reacted in 70 DEG C or so heating stirrings, 20g hydroxypropyl-β-cyclodextrin is added, fastly
Speed is heated with stirring to 75 DEG C of constant temperature 30min, and it is brown to obtain cyclo-dextrin-modified after grinding for 50 DEG C of constant temperature drying in an oven after filtering
Phycocolloid, yield 97%.
Embodiment 3
A kind of preparation of cyclo-dextrin-modified algin:
A small amount of 32wt% HCl solution is instilled into 75wt% ethanol solution adjusts pH=3.5,12g algin and 0.1g silane is even
Connection agent KH550 is separately added into the solution of preparation, is reacted in 70 DEG C or so heating stirrings, 20g methyl-B-cyclodextrin is added, fastly
Speed is heated with stirring to 75 DEG C of constant temperature 30min, and it is brown to obtain cyclo-dextrin-modified after grinding for 50 DEG C of constant temperature drying in an oven after filtering
Phycocolloid, yield 99%.
Embodiment 4
A kind of preparation of cyclo-dextrin-modified algin:
A small amount of 39wt% HCl solution is instilled into 40wt% ethanol solution adjusts pH=2,12g algin and 0.1g is silane coupled
Agent KH550 is separately added into the solution of preparation, is reacted in 70 DEG C or so heating stirrings, 20g methyl-B-cyclodextrin is added, quickly
75 DEG C of constant temperature 30min are heated with stirring to, 50 DEG C of constant temperature drying in an oven, obtain cyclo-dextrin-modified brown alga after filtering after grinding
Glue, yield 53%.
Embodiment 5
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: being made into the solution that content is 30wt% for cyclo-dextrin-modified algin prepared by embodiment 1, uniformly plus
Enter the contaminated soil of acquisition, every 1m3Soil launch 2L, stir after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue and pile
Stack is reacted, and then washes away cyclo-dextrin-modified algin with clear water, dry, the soil after being repaired, and goes the oil cut rate to be
90%。
Embodiment 6
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: being made into the solution that content is 55wt% for cyclo-dextrin-modified algin prepared by embodiment 2, uniformly plus
Enter the contaminated soil of acquisition, every 1m3Soil launch 3L, stir after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue and pile
Stack is reacted, and then washes away cyclo-dextrin-modified algin with clear water, dry, the soil after being repaired, and goes the oil cut rate to be
92%。
Embodiment 7
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: being made into the solution that content is 40wt% for cyclo-dextrin-modified algin prepared by embodiment 3, uniformly plus
Enter the contaminated soil of acquisition, every 1m3Soil launch 2.5L, stir heap after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue
It at stack, is reacted, then washes away cyclo-dextrin-modified algin with clear water, dry, the soil after being repaired goes the oil cut rate to be
95%。
Embodiment 8
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: being made into the solution that content is 40wt% for cyclo-dextrin-modified algin prepared by embodiment 4, uniformly plus
Enter the contaminated soil of acquisition, every 1m3Soil launch 2.5L, stir heap after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue
It at stack, is reacted, then washes away cyclo-dextrin-modified algin with clear water, dry, the soil after being repaired goes the oil cut rate to be
57%。
Embodiment 9
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: being made into the solution that content is 30wt% for cyclo-dextrin-modified algin prepared by embodiment 3, according to
Lecithin is added in 0.1g/mL, is uniformly added into the contaminated soil of acquisition, every 1m3Soil launch 1L, stir soil to cyclodextrin and change
Property alginic glue be uniformly dispersed after pile stack, reacted, then wash away cyclo-dextrin-modified algin with clear water, it is dry, obtain
Soil after to reparation, going oil cut rate is 96%.
Embodiment 10
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: being made into the solution that content is 30wt% for cyclo-dextrin-modified algin prepared by embodiment 3, according to
0.1g/mL amino acid type amphoteric ionic surface active agent is uniformly added into the contaminated soil of acquisition, every 1m3Soil launch 2L, turn over
It breaks ground after earth is uniformly dispersed to cyclo-dextrin-modified alginic glue and piles stack, reacted, then wash away cyclodextrin with clear water and change
Property algin, dry, the soil after being repaired, going oil cut rate is 99%.
Comparative example 1
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: cyclodextrin is made into the solution that content is 55wt%, is uniformly added into the contaminated soil of acquisition, every 1m3's
Soil launches 3L, stirs after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue and piles stack, is reacted, then use clear water
Cyclodextrin is washed away, dry, the soil after being repaired, going oil cut rate is 55%.
Comparative example 2
A kind of restorative procedure of diesel fuel contaminated soil, comprising the following steps:
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: algin is made into the solution that content is 55wt%, is uniformly added into the contaminated soil of acquisition, every 1m3's
Soil launches 3L, stirs after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue and piles stack, is reacted, then use clear water
Algin is washed away, dry, the soil after being repaired, going oil cut rate is 60%.
Test case 1
The synthesis yield of cyclo-dextrin-modified algin prepared by 1-4 of the embodiment of the present invention is calculated, the result is shown in Figure 1 is obtained.
Annotation: * is P < 0.05 compared with Example 4.
As shown in Figure 1, the yield of the cyclo-dextrin-modified algin of embodiment 1-3 preparation is real in 95% or more (P < 0.05)
It applies and uses concentrated hydrochloric acid condition pH in example 4 concentration of alcohol is lower, is not suitable for the synthesis of cyclo-dextrin-modified algin, yield for 2
It is lower, only 53%.
Test case 2
Soil after repairing by 5-10 of the embodiment of the present invention and comparative example 1-2 and using the prior art carries out oil content measurement,
As a result see Fig. 2.Annotation: * indicates P < 0.05 compared with art methods.
As shown in Figure 2, cyclo-dextrin-modified algin is prepared for oil-contaminated soil using the method for the present invention known to embodiment 5-7
It is repaired, crude oil removal reaches 90-95%, hence it is evident that be better than the prior art 47%.The cyclo-dextrin-modified added in embodiment 8 is brown
Phycocolloid, different from the parameter of the method for the present invention preparation, cyclo-dextrin-modified brown alga performance obtained is poor, cannot play good soil
The effect of earth reparation, crude oil removal are only 57%.Embodiment 9-10 is to be added to two on the basis of cyclo-dextrin-modified algin
Property ionic surface active agent, achieve better removal effect, it may be possible to which crude oil is first wrapped up and being emulsified by surfactant, then by ring
Dextrin modified algin adsorbs it, and better effect, crude oil removal reaches 96-99%.Comparative example 1 and comparative example 2 directly adopt
Cyclodextrin or algin carry out Adsorption to crude oil, and effect is obviously not so good as cyclo-dextrin-modified algin, and crude oil removal is only
For 55-60%.
Compared with prior art, cyclodextrin has hollow cylinder three-dimensional ring structure, and a kind of with hydrophilic, lipophilic
The amphoteric compound of energy.It is hydrophilic radical outside its ring, internal cavities are hydrophobic region.It, can be with soil due to its unique structure
Petroleum pollution effect in earth, forms inclusion compound, so that pollutant be eluted from soil.By the hydroxyl on cyclodextrin surface
Base and algin are coupled, and improve the suction-operated to oily pollutant, while algin has the work of preferable degradation oil
With the oily pollutant of absorption is degraded, is adsorbed, to realize removal oily in diesel fuel contaminated soil；
Zwitterionic surfactant, mostly environment-friendly type surfactant are separately added in the solution, avoids residue to soil
Pollution, while surface tension is reduced, promote the removal of oily pollutant when clear water washs soil, most of oil can
It degrades, adsorb with cyclo-dextrin-modified algin, a part is embedded by surfactant, is removed, is improved the effect of soil remediation
Rate, in 1-2L/m3Additive amount under conditions of, the absorption degradation of half a day can realize the removal of 90% or more soil oil.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of restorative procedure of diesel fuel contaminated soil, which comprises the following steps:
S1. the modification of algin: a small amount of HCl solution is instilled into ethanol solution and adjusts pH=3-4, by algin and coupling agent
It is separately added into the solution of preparation, is reacted in 70 DEG C or so heating stirrings, cyclodextrin is added, is quickly heated with stirring to 75 DEG C of constant temperature
30min, 50 DEG C of constant temperature drying in an oven, obtain cyclo-dextrin-modified algin after filtering after grinding；
S2. soil collection: contaminated soil of the acquisition gas station nearby at different depth mixes, after it is air-dried crushing, impurity elimination,
It is mixed after crossing 20 meshes, obtains soil powder；
S3. soil remediation: cyclo-dextrin-modified algin wiring solution-forming prepared by step S1 is uniformly added into the Polluted Soil of acquisition
Earth stirs after soil is uniformly dispersed to cyclo-dextrin-modified alginic glue and piles stack, reacted, and then washes away ring paste with clear water
The modified algin of essence, dry, the soil after being repaired.
2. a kind of restorative procedure of diesel fuel contaminated soil according to claim 1, which is characterized in that the cyclodextrin is selected from β-
One of cyclodextrin, hydroxypropyl-β-cyclodextrin, methyl-B-cyclodextrin.
3. a kind of restorative procedure of diesel fuel contaminated soil according to claim 1, which is characterized in that in the ethanol solution
The content of ethyl alcohol is 70-80wt%, and the HCl solution is concentrated hydrochloric acid of the content in 30-35wt%.
4. a kind of restorative procedure of diesel fuel contaminated soil according to claim 1, which is characterized in that the coupling agent is silane
Coupling agent.
5. a kind of restorative procedure of diesel fuel contaminated soil according to claim 1, which is characterized in that the cyclo-dextrin-modified is brown
The content of phycocolloid solution is 30-55wt%, and injected volume is every 1m3Soil launch 2-3L cyclo-dextrin-modified alginate solution.
6. a kind of restorative procedure of diesel fuel contaminated soil according to claim 1, which is characterized in that the cyclo-dextrin-modified is brown
Phycocolloid wiring solution-forming also added surfactant.
7. a kind of restorative procedure of diesel fuel contaminated soil according to claim 6, which is characterized in that the surfactant is
Zwitterionic surfactant；The zwitterionic surfactant in lecithin, amino acid pattern or betaine type one
Kind is several.
8. a kind of restorative procedure of diesel fuel contaminated soil described according to claim 6 or 7, which is characterized in that the cyclodextrin changes
Property alginate solution additive amount be every 1m3Soil adds 1-2L.
9. ring obtained in a kind of restorative procedure of diesel fuel contaminated soil a kind of as described in any one of claim 1-8 claim
Dextrin modified algin.
10. a kind of application of cyclo-dextrin-modified algin as claimed in claim 9 in absorption degradation oily pollutant.
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| DE19628454A1 (en) * | 1996-07-15 | 1998-01-29 | Mfh Marienfelde Gmbh Unternehm | New rhamno-lipid-alginate polymer complexes |
| CN102603918A (en) * | 2012-03-16 | 2012-07-25 | 扬州大学 | Preparation method of beta-cyclodextrin-grafted alginic acid derivative |
| CN104128363B (en) * | 2014-06-20 | 2016-02-03 | 浙江工商大学 | A kind of method utilizing crosslinking agent structural modification marine alga cadmium pollution soil repair |
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| CN110420993B (en) | 2021-08-10 |
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