CN110201994A - A kind of restorative procedure of the polycyclic aromatic hydrocarbon pollution based on vinegar grain and titanium powder plant waste sulfate ferrous iron - Google Patents
A kind of restorative procedure of the polycyclic aromatic hydrocarbon pollution based on vinegar grain and titanium powder plant waste sulfate ferrous iron Download PDFInfo
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- CN110201994A CN110201994A CN201910506805.6A CN201910506805A CN110201994A CN 110201994 A CN110201994 A CN 110201994A CN 201910506805 A CN201910506805 A CN 201910506805A CN 110201994 A CN110201994 A CN 110201994A
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- polycyclic aromatic
- aromatic hydrocarbon
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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
Abstract
The invention belongs to field of environmental technology, provide a kind of based on vinegar grain and titanium powder plant waste FeSO4·7H2The restorative procedure of the polycyclic aromatic hydrocarbon pollution of O.With vinegar grain and titanium powder plant waste FeSO4·7H2O is that raw material prepares soil remediation material I and material II.Material I is vinegar grain and titanium powder plant waste FeSO4·7H2Mixture after O co-grinding.Material II is the product obtained after roasting soil remediation material I at low temperature.When the total content of polycyclic aromatic hydrocarbon is lower than 1000mg polycyclic aromatic hydrocarbon/kg soil, the selection of material I.When the total content of polycyclic aromatic hydrocarbon is higher than 1000mg polycyclic aromatic hydrocarbon/kg soil, the selection of material II.Selected soil remediation material is stirred and shakeout with polycyclic aromatic hydrocarbon pollution, without adjusting the pH value of soil, is not necessarily to hydrogen peroxide, it is seen that, can polycyclic aromatic hydrocarbon in deep oxidation degradation soil under light irradiation.The present invention can greatly reduce the toxicity of pollutant in soil, and the coefficient of growth on soil after repair with the plant in unpolluted grown on soil does not have apparent difference.
Description
Technical field
The invention belongs to field of environmental technology, are related to the resource utilization of waste and the reparation of polycyclic aromatic hydrocarbon pollution
Method.
Background technique
China is vinegar production and consumption big country, and 1 ton of vinegar of every production will generate 0.8 ton of vinegar grain according to statistics, 2015
The vinegar grain of generation is as high as 3,200,000 tons.Vinegar grain water content more a height of 65%~75%, in acidity, the pH of filter liquor is acidity
(3~3.5).If the problems such as annual a large amount of acid vinegar grain cannot be effectively treated, will cause environmental pollution, soil acidification.Mesh
The resource utilization method of preceding vinegar grain mainly has fodder, Fertilizer Transformed, matrixing and energy etc., each method all exists
Obvious disadvantage, it is difficult to promote.Urgent need finds one kind and vinegar grain is effectively treated, the method for promoting vinegar grain added value.
The production method of titanium dioxide has sulfuric acid process and two kinds of chloridising, since the production cost of chloridising is higher than sulfuric acid
Method.So domestic titanium powder plant mainly uses Titanium White Production By Sulfuric Acid Process at present, can be produced in the process of production titanium dioxide
Raw a large amount of ferrous sulfate, the titanium dioxide of every 1 ton of production will generate 4 tons or so of FeSO according to statistics4.7H2O, and 2017
The titanium white powder yield of China has just reached 3,550,000 tons.The byproduct FeSO generated during producing titanium dioxide4.7H2O, no
Only it is in highly acid, also will cause environmental pollution if cannot be effectively treated containing a large amount of impurity.
Polycyclic aromatic hydrocarbon (Polycyclic aromatic hydrocarbons, PAHs) refers to by two or more
The hydrocarbon that phenyl ring is composed by linear, horn shape or tufted, is the persistence with carcinogenic, teratogenesis, mutagenicity
Organic pollutant (Persistent organic pollutants, POPs).Polycyclic aromatic hydrocarbon, which is mainly derived from petroleum, coal etc., to be had
The imperfect combustion of machine pollutant is a kind of POPs being widely present in environment.Since polycyclic aromatic hydrocarbon has stronger dredge more
Aqueous and stability, so that the polycyclic aromatic hydrocarbon in air and water environment finally accumulates in soil, soil is the weight of polycyclic aromatic hydrocarbon
Want home to return to.
Currently, the recovery technique of polycyclic aromatic hydrocarbon pollution mainly has bioremediation technology, peripheral doses technology and chemistry
Aoxidize recovery technique.Peripheral doses technology is mainly using the polycyclic aromatic hydrocarbon removal in soil between a variety of different physical processes
Technology, mainly have steam extraction process, solidification stabilization method, thermal desorption method etc..The generally existing energy consumption of peripheral doses technology it is high and at
This high disadvantage.It is biological prosthetic mainly to utilize plant, animal or microorganism biological species the characteristics of interior, specific
Under the conditions of to polycyclic aromatic hydrocarbon carry out biodegrade.Bioremediation technology is at low cost, secondary pollution is few, but repairing effect is by periphery
Environmental factor is affected, and repairing efficiency is longer.Chemical oxidation recovery technique is mainly aoxidized by adding into soil
Agent realizes the reparation to organic polluted soil by the organic pollutant in oxidizing degradation soil.Common oxidation
Agent mainly has ozone, hydrogen peroxide, potassium permanganate, persulfate and Fenton reagent etc..It is repaired using chemical oxidizing agent polycyclic
Aromatic hydrocarbons contaminated soil, since oxidant is the medicament with strong oxidizing property, while oxidative degradation polycyclic aromatic hydrocarbon, oxidation
Agent can also destroy the structure and composition of soil, result even in the secondary pollution of soil, be unfavorable for the growth of plant after repairing.
There are various disadvantages in the recovery technique of above-mentioned polycyclic aromatic hydrocarbon pollution, therefore, it is necessary to grope a kind of pair of ring
Border is friendly, while removing pollutant in soil, does not destroy the soil remediation material and method of soil constitution and structure also.
Summary of the invention
Deficiency existing for recovery technique for current polycyclic aromatic hydrocarbon pollution, the present invention provides one kind to be based on vinegar
Industry waste vinegar grain and titanium dioxide industry waste FeSO4.7H2The restorative procedure of the polycyclic aromatic hydrocarbon pollution of O.
What the invention is realized by the following technical scheme:
Step 1: polycyclic aromatic hydrocarbon pollution being pre-processed: including air-drying, rolling crushing, sieving processing, obtaining institute
The soil particle needed；
Step 2: the total content of polycyclic aromatic hydrocarbon in measurement polycyclic aromatic hydrocarbon pollution；
Step 3: to vinegar grain and titanium powder plant waste FeSO4.7H2O carries out different pretreatments method, and processing method is as follows:
(1) by vinegar grain and titanium powder plant waste FeSO4.7H2O is put into pulverizer according to certain mass ratio and is pulverized and mixed
It is even to get arrive soil remediation material I；
(2) by the vinegar grain after being pulverized and mixed in step 1 and titanium powder plant waste FeSO4.7H2O is placed in Muffle furnace and roasts
It burns, soil remediation material II is obtained after roasting；
Step 4: according to the content for the PAHs in soil that step 2 is measured, selecting soil remediation material made from step 3
Expect I or soil remediation material II:
When the total content of PAHs in soil is lower than 1000mg polycyclic aromatic hydrocarbon/kg soil, soil remediation material is used
I；
When the total content of PAHs in soil is more than 1000mg polycyclic aromatic hydrocarbon/kg soil, soil remediation material is used
II；
The soil remediation material of selection is stirred evenly in proportion with polycyclic aromatic hydrocarbon pollution, then shakeouts to form thickness
Soil layer no more than 1cm；
Step 5: the soil layer shakeout being placed under visible light and is irradiated, spray water is needed during irradiation, the water content of soil is allowed to protect
It holds 50%~90%；Illumination after a certain period of time, can remove the polycyclic aromatic hydrocarbon in soil.
Described to air-dry as natural drying in step 1, the time is one week；Sieving processing uses 60 mesh soil sieves.
In step 3, vinegar grain and titanium powder plant waste FeSO4.7H2The mass ratio of O is 1:1~4:1.
In step 3, the maturing temperature is 300~400 DEG C, calcining time 3h.
In step 4, the mass percent of soil remediation material and polycyclic aromatic hydrocarbon pollution is controlled 5%~10%.
Phytotoxicity evaluating method after polycyclic aromatic hydrocarbon pollution is repaired is as follows:
Phytotoxicity evaluating is by carrying out planting experiment of the lettuce in different soils.Lactuca sativa seeds are planted respectively
In uncontaminated soil, in the polycyclic aromatic hydrocarbon pollution and polycyclic aromatic hydrocarbon pollution repaired, every kind of soil carry out four groups it is flat
Row planting experiment.The coefficient of growth (germination percentage, root long, leaf length and fresh weight) for the lettuce planted in every kind of soil is investigated,
To assess the phytotoxicity of soil.
By 5 lettuce plantings in a flowerpot equipped with soil, every kind of soil plants four flowerpots altogether namely every kind of soil is total
20 lactuca sativa seeds are planted.Flowerpot equipped with lactuca sativa seeds is put into plant incubator, in incubator when the illumination of fluorescent lamp
Between and interlunation be respectively 16 hours and 8 hours, corresponding temperature is 22 degrees Celsius and 16 degrees Celsius.In incubation, soil
The water content of earth is controlled 60%, therefore needs regular replenishment moisture.After lactuca sativa seeds cultivate 5 days in the soil, count at three kinds
The germination percentage of seed in soil.After having counted germination percentage, two plants of lettuce rice shoots are left in each flowerpot and carry out growth experiment.After
After continuous culture two weeks, lettuce is harvested, counts root long, leaf length and fresh weight in three kinds of geophilous lettuces.It will be in three kinds of soil
The coefficient of growth (germination percentage, root long, leaf length and fresh weight) of the lettuce of acquisition, is arranged by software (SPSS software)
Analysis, to compare the phytotoxicity after polycyclic aromatic hydrocarbon pollution is repaired.
The invention has the advantages that
(1) with Vinegar Industry waste vinegar grain and titanium dioxide industry waste FeSO4.7H2O is raw material to polycyclic aromatic hydrocarbon dirt
Dye soil is repaired, and the resource utilization of solid waste is realized；
(2) vinegar grain and titanium dioxide industry waste FeSO are based on4.7H2The soil remediation material of O under visible light illumination, i.e.,
It can be activated to generate the superoxide radical of strong oxidizing property, thus the polycyclic aromatic hydrocarbon in deep oxidation degradation soil；
(3) vinegar grain and titanium dioxide industry waste FeSO are based on4.7H2The soil remediation material of O is in oxidative degradation soil
Polycyclic aromatic hydrocarbon during the entire process of, without adjusting the pH value of soil；
(4) vinegar grain and titanium dioxide industry waste FeSO are based on4.7H2The soil remediation method of O can remove soil with depth
In polycyclic aromatic hydrocarbon, the toxicity of polycyclic aromatic hydrocarbon pollution is greatly lowered.Soil after reparation, will not be to the growth of plant
It has adverse effect on, the life of the plant of grown on soil after repair and the plant in unpolluted grown on soil
Long coefficient (germination percentage, root long, leaf length, fresh weight) is without apparent difference.
Detailed description of the invention
Fig. 1 is the raw material for preparing soil remediation material I, and a is vinegar factory waste vinegar grain and b is titanium powder plant waste
FeSO4.7H2O；
Fig. 2 is under visible light and under no light, and soil remediation material I is bent to the degradation rate of low concentration phenanthrene in contaminated soil
Line；
Fig. 3 is degradation rate curve of the soil remediation material II to contaminated soil middle and high concentration phenanthrene under visible light；
Fig. 4 is under visible light that soil remediation material II is to naphthalene, anthracene, phenanthrene, the pyrene in compound polycyclic aromatic hydrocarbon pollution
Degradation rate histogram；
Fig. 5 is the ESR spectrogram of soil remediation material II under visible light.
Specific embodiment
With reference to the accompanying drawings of the specification and specific embodiment the present invention is further illustrated, but protection of the invention
Range is not limited to this.
The raw material for preparing soil remediation material I and soil remediation material II is that the vinegar grain of vinegar factory generation and titanium powder plant produce
Raw FeSO4.7H2O, Fig. 1 are the vinegar grain that vinegar factory generates and the FeSO that titanium powder plant generates4.7H2O photo.Table 1 is
FeSO4.7H2Constituent content in O, it is seen that main metallic element be Fe, Mg, Mn and Ti, wherein the content of Mg, Mn and Ti compared with
It is low.
The FeSO that 1. titanium powder plant of table generates4.7H2Constituent content in O
Embodiment 1: under visible light, soil remediation material I is used for the reparation of low concentration phenanthrene-polluted soil
1. the contaminated soil sampled from pollution plot, pre-processes polycyclic aromatic hydrocarbon pollution: firstly, will fit
Polycyclic aromatic hydrocarbon pollution natural air drying one week or so of amount.Then, pair soil carries out rolling crushing.Finally, 60 mesh soil
Sieve carries out sieving processing to soil, obtains required soil particle；
It is phenanthrene through the major pollutants in detection soil, content is 2. a pair pretreated soil particle detects
180mg phenanthrene/kg soil；
3. by vinegar grain and titanium powder plant waste FeSO4.7H2O is put into pulverizer according to mass ratio 4:1 and is pulverized and mixed uniformly,
Obtain soil remediation material I；
4. soil remediation material I is stirred evenly with polycyclic aromatic hydrocarbon pollution, wherein soil remediation material I and polycyclic virtue
The mass percent of soil contaminated with hydrocarbons is 5%, then shakeouts the soil layer to form 1cm thickness；
5. the soil layer shakeout is placed in (wavelength is greater than 420nm, and average intensity is about 8100Lux) irradiation 10 hours, illumination
Period water content is controlled 50%, and the degradation rate of soil China and Philippines is about 98.6% (as shown in Figure 2).
6. the plant evaluation after phenanthrene-polluted soil reparation:
Lettuce is planted in uncontaminated soil respectively, in the phenanthrene-polluted soil and phenanthrene-polluted soil repaired.By 19 days
Culture, phenanthrene-polluted soil has biggish toxicity to lettuce, and the growth of lettuce is totally constrained.Phenanthrene-polluted soil is by soil
After earth repair materials I is repaired, toxicity is greatly diminished, the lettuce planted above it and unpolluted grown on soil
Lettuce there is no apparent difference.
Table 2 is germination percentage, root long, leaf length and fresh weight number of the lettuce in the native and luxuriant and rich with fragrance Polluted Soil after uncontaiminated soil, reparation
According to.It can be seen that the phenanthrene in soil does not influence the germination percentage of lactuca sativa seeds significantly, but for root long, leaf length and fresh weight
There is apparent inhibiting effect.For phenanthrene-polluted soil after soil remediation material I reparation, the lettuce of growth is long and fresh in root long, leaf
Weight is not distinguished significantly with the lettuce grown in unpolluted soil, it was demonstrated that the soil based on soil remediation material I is repaired
Compound method is a kind of environment friendly material and its method.
Germination percentage, root long, leaf length and fresh weight of 2. lettuce of table in different soils
Embodiment 2: under visible light, the reparation of high concentration phenanthrene-polluted soil is repaired
1. the contaminated soil sampled from pollution plot, pre-processes polycyclic aromatic hydrocarbon pollution: firstly, will fit
Polycyclic aromatic hydrocarbon pollution natural air drying one week or so of amount.Then, pair soil carries out rolling crushing.Finally, 60 mesh soil
Sieve carries out sieving processing to soil, obtains required soil particle；
It is phenanthrene through the major pollutants in detection soil, content contains 2. a pair pretreated soil particle detects
Amount is up to 2150mg phenanthrene/kg soil；
3. by vinegar grain and titanium powder plant waste FeSO4.7H2O is put into pulverizer according to mass ratio 2:1 and is pulverized and mixed uniformly,
Then smashed mixture is placed in Muffle furnace, temperature is 300 DEG C, obtains soil remediation material II after roasting 3h.
4. soil remediation material II is stirred evenly with polycyclic aromatic hydrocarbon pollution, wherein soil remediation material II with it is polycyclic
The mass percent of aromatic hydrocarbons contaminated soil is 10%, then shakeouts the soil layer to form 0.5cm thickness；
5. the soil layer shakeout is placed in (wavelength is greater than 420nm, and average intensity is about 8100Lux) irradiation 10 hours, illumination
Period water content is controlled 70%, and luxuriant and rich with fragrance degradation rate is about 91% (as shown in Figure 3).
6. the plant evaluation after phenanthrene-polluted soil reparation:
Lettuce is planted in uncontaminated soil respectively, in the phenanthrene-polluted soil and phenanthrene-polluted soil repaired, by 19 days
Culture, coefficient of growth such as the following table 3.Different from low concentration phenanthrene-polluted soil, in the soil of high concentration phenanthrene, the hair of lactuca sativa seeds
Bud rate receives apparent inhibition, but soil is after soil remediation material II reparation, the germination of germination percentage and not comtaminated soil
Rate is not distinguished significantly.The lettuce grown in root long, leaf length and fresh weight and unpolluted soil is also without apparent area
Not.
Germination percentage, root long, leaf length and fresh weight of 3. lettuce of table in the soil repaired
| Germination percentage (%) | Root long (centimetre) | Leaf is long (centimetre) | Fresh weight (gram) | |
| Uncontaiminated soil | 90.1 | 3.05 | 2.6 | 0.042 |
| Soil after reparation | 89.8 | 3.01 | 2.58 | 0.040 |
| High concentration phenanthrene Polluted Soil | 63.1 | 0.51 | 0.61 | 0.031 |
Embodiment 3: under visible light, the compound polycyclic aromatic hydrocarbon pollution of high concentration is repaired
1. the contaminated soil sampled from pollution plot, pre-processes polycyclic aromatic hydrocarbon pollution: firstly, will fit
Polycyclic aromatic hydrocarbon pollution natural air drying one week or so of amount.Then, pair soil carries out rolling crushing.Finally, 60 mesh soil
Sieve carries out sieving processing to soil, obtains required soil particle；
It is naphthalene, anthracene, phenanthrene, pyrene through the major pollutants in detection soil 2. a pair pretreated soil particle detects,
Concentration is respectively 350mg naphthalene/kg soil, 1350mg anthracene/kg soil, 531mg phenanthrene/kg soil and 768mg pyrene/kg soil；
3. by vinegar grain and titanium powder plant waste FeSO4.7H2O is put into pulverizer according to mass ratio 1:1 and is pulverized and mixed uniformly,
Then smashed mixture is placed in Muffle furnace, temperature is 350 DEG C, obtains soil remediation material II after roasting 3h.
4. soil remediation material II is stirred evenly with polycyclic aromatic hydrocarbon pollution, wherein soil remediation material II with it is polycyclic
The mass percent of aromatic hydrocarbons contaminated soil is 10%, then shakeouts the soil layer to form 0.5cm thickness；
5. the soil layer shakeout is placed in (wavelength is greater than 420nm, and average intensity is about 8100Lux) irradiation 10 hours, illumination
The control of period water content in 90%, soil naphthalene, anthracene, phenanthrene, pyrene degradation rate be respectively 98%, 90%, 93% and 91% (such as
Shown in Fig. 4).
Fig. 5 is the DMPO-O under dark and radiation of visible light respectively of soil remediation material II2 ·-ESR spectrogram.Visible
Light irradiation is lower it can be observed that DMPO-O2 ·-Six characteristic peaks of spin adduct, but do not detect in the dark obvious
Signal.In addition, can not detect DMPO-OH spin adduct under visible light illumination.ESR spectral results show can
Under light-exposed irradiation condition, soil remediation material II can produce the O of a large amount of strong oxidizing properties2 ·-, thus having in oxidative degradation soil
Machine pollutant, here it is be based on vinegar grain and titanium powder plant waste FeSO4.7H2The soil remediation material of O can repair polycyclic virtue
The reason of soil contaminated with hydrocarbons.
6. the plant evaluation after compound polycyclic aromatic hydrocarbon pollution reparation:
Lettuce is planted in uncontaminated soil respectively, the polycyclic aromatic hydrocarbon pollution repaired and compound polycyclic aromatic hydrocarbon are dirty
It contaminates in soil, was cultivated by 19 days, coefficient of growth such as the following table 4.The toxicity of compound polycyclic aromatic hydrocarbon pollution is apparently higher than list
The toxicity of one Phenanthrene, lettuce can not germinating growths in this compound polycyclic aromatic hydrocarbon pollution.But it is compound
Polycyclic aromatic hydrocarbon pollution after soil remediation material II reparation, the lettuce of growth is in root long, leaf is long and fresh weight with it is not dirty
The lettuce grown in the soil of dye do not distinguish significantly, it was demonstrated that the toxicity of polycyclic aromatic hydrocarbon pollution is reduced significantly
?.
Germination percentage, root long, leaf length and fresh weight of 4. lettuce of table in the soil repaired
| Germination percentage (%) | Root long (centimetre) | Leaf is long (centimetre) | Fresh weight (gram) | |
| Uncontaiminated soil | 90.1 | 3.05 | 2.6 | 0.042 |
| Soil after reparation | 89.3 | 3.03 | 2.61 | 0.043 |
Claims (5)
1. a kind of restorative procedure of the polycyclic aromatic hydrocarbon pollution based on vinegar grain and titanium powder plant waste sulfate ferrous iron, feature exist
In including the following steps:
Step 1: polycyclic aromatic hydrocarbon pollution being pre-processed: including air-drying, rolling crushing, sieving processing, being obtained required
Soil particle；
Step 2: the total content of polycyclic aromatic hydrocarbon in measurement polycyclic aromatic hydrocarbon pollution；
Step 3: to vinegar grain and titanium powder plant waste FeSO4.7H2O carries out different pretreatments method, and processing method is as follows:
(1) by vinegar grain and titanium powder plant waste FeSO4.7H2O is put into pulverizer according to certain mass ratio and is pulverized and mixed uniformly, i.e.,
Obtain soil remediation material I；
(2) by the vinegar grain after being pulverized and mixed in step 1 and titanium powder plant waste FeSO4.7H2O is placed in Muffle kiln roasting, roasting
Soil remediation material II is obtained after burning；
Step 4: according to the content for the PAHs in soil that step 2 is measured, selecting soil remediation material I made from step 3
Or soil remediation material II:
When the total content of PAHs in soil is lower than 1000mg polycyclic aromatic hydrocarbon/kg soil, soil remediation material I is used；
When the total content of PAHs in soil is more than 1000mg polycyclic aromatic hydrocarbon/kg soil, soil remediation material II is used；
The soil remediation material of selection is stirred evenly in proportion with polycyclic aromatic hydrocarbon pollution, then shakeouts to form thickness and do not surpass
Cross the soil layer of 1cm；
Step 5: the soil layer shakeout being placed under visible light and is irradiated, spray water is needed during irradiation, the water content of soil is allowed to be maintained at
50%~90%；Illumination after a certain period of time, can remove the polycyclic aromatic hydrocarbon in soil.
2. restorative procedure as described in claim 1, which is characterized in that described to air-dry as natural drying in step 1, the time is
One week；Sieving processing uses 60 mesh soil sieves.
3. restorative procedure as described in claim 1, which is characterized in that in step 3, vinegar grain and titanium powder plant waste
FeSO4.7H2The mass ratio of O is 1:1~4:1.
4. restorative procedure as described in claim 1, which is characterized in that in step 3, the maturing temperature is 300~400 DEG C,
Calcining time is 3h.
5. restorative procedure as described in claim 1, which is characterized in that in step 4, soil remediation material with it is polycyclic aromatic hydrocarbons contaminated
The mass percent of soil is controlled 5%~10%.
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| CN113702623A (en) * | 2021-08-27 | 2021-11-26 | 河北科技大学 | Microwave leaching type soil remediation evaluation device and evaluation method |
| CN114907855A (en) * | 2022-07-07 | 2022-08-16 | 华东理工大学 | Method for preparing soil conditioner by using by-product in titanium dioxide production |
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| CN114907855A (en) * | 2022-07-07 | 2022-08-16 | 华东理工大学 | Method for preparing soil conditioner by using by-product in titanium dioxide production |
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