CN105964673B - A kind of Modified Iron cerium hydroxide and preparation method for stabilizing rehabilitating soil arsenic pollution and its application - Google Patents
A kind of Modified Iron cerium hydroxide and preparation method for stabilizing rehabilitating soil arsenic pollution and its application Download PDFInfo
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- CN105964673B CN105964673B CN201610191678.1A CN201610191678A CN105964673B CN 105964673 B CN105964673 B CN 105964673B CN 201610191678 A CN201610191678 A CN 201610191678A CN 105964673 B CN105964673 B CN 105964673B
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- cerium hydroxide
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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
A kind of Modified Iron cerium hydroxide and preparation method for stabilizing rehabilitating soil arsenic pollution and its application, Modified Iron cerium hydroxide is by Fe (OH)3With Ce (OH)3Two phase compositions, form that surface is smooth, uniform compound double-metal hydroxide by 0.25-1.60 μm of average grain diameter；Preparation method is: in 0.8-1.0% surfactant solution, iron chloride, ferrous sulfate, cerous sulfate are added respectively according to Fe (III): Fe (II): Ce (IV)=2~1.5:1~0.8:1~0.8 molar ratio, by 1~4mol/L sodium hydroxide regulation system pH to 7-7.5, obtained suspended matter is target product；Application method.Modified Iron cerium hydroxide prepared by the present invention is to the adsorption capacity of As (V) up to 200mgg‑1More than, the TCLP concentration of arsenic in soil can be made to decline about 92% or more, to significantly reduce its environmental risk.
Description
Technical field
The Modified Iron cerium hydroxide and preparation method that the present invention relates to a kind of for stabilizing rehabilitating soil arsenic pollution and
It is applied.
Background technique
Arsenic is to be distributed widely in one of soil microelement, be at present it is most common, most serious is endangered to public health
One of pollutant.It is announced according to the World Health Organization, global ten thousand populations at least more than 5000 are faced with endemic arsenic poisoning
It threatens, and China is exactly endangered one of country the most serious by arsenic poisoning.Cut-off 2013, China has become maximum arsenic system
Product producing country accounts for about 56% or more of world market share.Due to soil background is high, the random mining of the mineral resources containing arsenic,
The excessive use of the agricultural formulations containing arsenic, causes the large area regions such as Hunan China, Guangxi, Jiangxi arsenic in soil pollution problem occur,
And resident's health and economic society fast development are seriously threatened.
Stabilization technology has many advantages, such as that at low cost, environmental disruption is small, the production of the side Bian Xiufu, is to solve China's arsenic pollution to ask
The preferable selection of topic.It the use of more arsenic pollution stabilization material is mainly at present iron-bearing materials, including iron (hydrogen) oxide,
FeSO4/Fe2(SO4)3, Zero-valent Iron, iron-contained industrial byproduct etc..Zhang Qiaoli in 2006 etc., which is disclosed, a kind of goes arsenic in water removal to answer
It closes adsorbent material and preparation method thereof (CN 100386141C), the invention is by Fe3O4And Fe2O3Activity is carried on by co-precipitation
On charcoal, arsenic adsorption capacity maximum is up to 66.3mg/g.Painting book in 2009 is new etc. to disclose a kind of chemistry suitable for arsenic in soil
Fixed material and purposes (CN101695711A), the invention are prepared into using Zero-valent Iron, titanium dioxide, trees sawdust, straw powder
A kind of fixation material can be effectively reduced arsenic in soil biological effectiveness.Qu Jiuhui in 2009 etc. discloses a kind of Fe-Mn oxidation
The preparation of object/diatomite adsorbant, use and regeneration method (CN 100509137C), the invention is by ferrimanganic bimetallic oxide
It is carried on granular diatomaceous earth, being prepared into one kind can be effectively reduced the composite material of waste water A s (III).2010 sunlights etc. are delivered
One paper about iron cerium bimetallic oxide arsenic-adsorbing, the paper show iron cerium bimetallic oxide to As in solution
(V) adsorption capacity maximum is up to 138.75mg/kg, much higher than other iron-based materials being currently known.By the effort of many years,
It has been made great progress using stabilization technology in-situ immobilization As polluted soil.However it is practical when iron-based material to be applied to
When recovery project, engineers and technicians' discovery, since iron-based material has certain magnetic aggregation characteristic, in soil aperture easily
Assemble it is agglomerating, to significantly limit its migration circle and remediation efficiency.
Summary of the invention
It is an object of the present invention to: it provides a kind of for stabilizing the Modified Iron cerium hydroxide of rehabilitating soil arsenic pollution
Object and preparation method；Another object of the present invention is to provide the economy and efficient application of a kind of above-mentioned Modified Iron cerium hydroxide
Method.
One of the technology of the present invention solution, it is a kind of for stabilizing the Modified Iron cerium hydroxide of rehabilitating soil arsenic pollution
Object, the Modified Iron cerium hydroxide is by Fe (OH)3With Ce (OH)3Two phase compositions, molar ratio are 3~2.5:1~0.8, are formed equal
Even compound double-metal hydroxide.The average grain diameter of the Modified Iron cerium hydroxide is 0.25-1.60 μm, and surface is smooth.
The two of the technology of the present invention solution: a method of the Modified Iron cerium hydroxide is prepared, realizes step
Are as follows:
(1) surfactant is added in deionized water, is heated under the conditions of magnetic agitation, obtains clear surfactant
Solution；
(2) by iron chloride, ferrous sulfate, cerous sulfate according to Fe (III): Fe (II): Ce (IV)=2~1.5:1~0.8:1
~0.8 molar ratio is added separately in surfactant solution, and by sodium hydroxide regulation system pH to 7-7.5, what is obtained is outstanding
Floating object is Modified Iron cerium hydroxide.
The surfactant is starch.
The ratio that surfactant is added in deionized water in the step (1) is 0.8~1.0%.
The revolving speed of magnetic agitation is 500~1000rpm in the step (1).
Step (1) heating temperature is 80-95 DEG C, heating time 30-60min.
Concentration of sodium hydroxide solution is 1~4mol/L in the step (2).
The three of the technology of the present invention solution: a kind of method of Modified Iron cerium hydroxide described in application realizes step
Are as follows:
Modified Iron cerium hydroxide and pH adjusting agent are passed through into injection pump respectively, turbine flowmeter, flow control valve, shut off
Valve is introduced to injection well head, injects arsenic pollution stabilization formulations to different depth soil in-situ by scalable injection pipe.
The charge velocity is 8-15L/min in depth 0-3m, is 35-42L/min in depth > 3m.
The injection well head spacing is 2-4m for sand-shale sand from being 5-12m for gravel-sand, for
Heavy mud-clay is 1-3m.
The invention has the following advantages that
(1) Modified Iron cerium hydroxide prepared by the present invention is to the adsorption capacity of As (V) up to 200.32mgg-1, and energy
Making the TCLP concentration of arsenic in soil reduces by 92% or more.
(2) Modified Iron cerium hydroxide source of the present invention is abundant, and preparation method is simple, it is easy to accomplish large-scale production.
Detailed description of the invention
Fig. 1 is X difraction spectrum (XRD) figure of product in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of product in embodiment 1；
Fig. 3 is the TCLP data of soil after repairing in embodiment 3；
Fig. 4 is the schematic diagram of the method for implanting in situ of embodiment 4.
Specific embodiment
With reference to the accompanying drawing and the present invention is discussed in detail in specific embodiment.But embodiment below is only limitted to explain this hair
Bright, protection scope of the present invention should include the full content of claim, be not limited only to the present embodiment.
Embodiment 1
20g starch is added in 2L deionized water, 500~1000rpm magnetic agitation heats 30- under the conditions of 80-95 DEG C
60min obtains 1.0% clarification starch solution；By iron chloride, ferrous sulfate, cerous sulfate according to Fe (III): Fe (II): Ce
(IV)=2:1:0.8 molar ratio is added separately in above-mentioned starch solution, passes through 2mol/L sodium hydroxide regulation system pH to 7-
7.5, obtained suspended matter is target product, and lattice structure characteristic and scanning electron microscope (SEM) photograph difference are as depicted in figs. 1 and 2.By
For Fig. 1 and Fig. 2 it is found that the iron cerium hydroxide surfaces after starch conversion are very smooth, intergranular aggregation extent is relatively small,
It and is a kind of stabilization material of amorphous structure.
Embodiment 2
Suspension in embodiment 1 is measured into 45mL into 50mL centrifuge tube respectively, by the As (V) of 0-5mL 1000mg/L
(Na2HAsO4.12H2O it) is separately added into above-mentioned centrifuge tube, adjusting solution system pH with 0.1mol/L NaOH is respectively 4.0, back
Scape electrolyte is 0.01mol/L NaNO3Solution, with deionized water by solution polishing in centrifuge tube to 50mL.Under the conditions of 200rpm
It vibrates for 24 hours, reaction terminating.As (V) the adsorption isotherm data such as table 1 of Modified Iron cerium hydroxide.As shown in Table 1, Modified Iron
Maximum As (V) adsorption capacity of cerium hydroxide up to 200.32mg/g, much higher than other iron-based materials being currently known and
Conventional iron cerium bimetallic oxide.
As (V) adsorption isotherm data of 1 Modified Iron cerium hydroxide of table
Embodiment 3
By the suspension in embodiment 1 with 3000rpm centrifugation, 45 DEG C of drying are for 24 hours.Product is to 50g after taking 1g to dry
In As polluted soil, after being sufficiently mixed, dry, wet, three kinds of moisture conditions of waterflooding are adjusted, seal triangle with hydrophobic permeable membrane
Bottle, continuously cultivates 30d, until adsorption effect reaches stable, TCLP data such as Fig. 3 of soil after reparation.From the figure 3, it may be seen that Modified Iron
Cerium hydroxide shows stronger stabilisation repairing effect to the As polluted soil of different in moisture condition, can make soil
TCLP concentration declines about 92-96%, and the soil TCLP concentration after reparation is below " Groundwater Environmental Quality standard " (GB/
T14848-1993) 50 μ g/L of grade III Standard.
Embodiment 4
The soil grains of sand, powder, three germplasm of clay are characterized respectively with 20-40 mesh, 60-80 mesh and 6000 mesh quartz sands (powder)
Ground, be arranged 3 one-dimensional quartz sand columns (50cm, diameter 25cm), fill above-mentioned quartz sand (powder) respectively with simulate sand (sand: powder:
Viscous=100:0:0), loam (sand: powder: viscous=60:40:0), clay (sand: powder: viscous=0:80:20).First use > 10 pore volumes
Deionized water inject quartz sand column, then by the suspension in 0.04mol/L embodiment 1 with charge velocity 0.5L/min flow velocity
One-dimensional column is injected, respectively at 0,30min, 1h, 2h, 4h, 8h, 16h, acquires leachate for 24 hours, stops injection afterwards for 24 hours.ICP-MS is surveyed
The content for determining Fe in leachate, it is theoretical by single collector, sand, earth of the suspension in embodiment 1 in 3m thickness can be predicted
Maximum migration distance is followed successively by 3m, 1m and 0.5m in soil and clay, thus its inject well head spacing from can be respectively set to 6m,
2m、1m。
Embodiment 5
By taking Guangdong chemical plant original position injection project as an example, contaminated site underground water buried depth 0.1-8.4m, wherein 0-
2.0m soil layer is based on fine sand.3 points are selected to carry out injection testing in situ, injection well depth is 1m, scalable injection pipe
Position is set to 1m.By in 0.04mol/L embodiment 1 suspension and pH adjusting agent pass through injection pump, turbine flowmeter, stream respectively
Control valve, shutoff valve are introduced to injection well head, inject in situ along injection pipe, charge velocity is respectively 8,10,12L/min (such as
Fig. 4).It after the completion of injection, equidistantly samples, analyze using injection well as the center of circle, find Modified Iron cerium hydroxide in shallow-layer fine sand
Average influence radius be followed successively by 2.6,3.0,2.8m.Therefore above-mentioned injection well head spacing from can be respectively set to 5.2m, 6m,
5.6m。
Embodiment 6
By taking Guangdong chemical plant original position injection project as an example, which is lauched buried depth 0.1-8.4m, wherein 2.0-
3.5m and 3.5-7.0m soil layer is respectively based on muck soil and silty clay.Injection well depth is respectively 4m and 7m, scalable
Injection pipe position be set to 4m and 7m, by 0.04mol/L embodiment 1 suspension and pH adjusting agent pass through injection pump, whirlpool respectively
Flowmeters, flow control valve, shutoff valve are introduced to injection well head, inject in situ along injection pipe, charge velocity 12L/min
(such as Fig. 4).It after the completion of injection, equidistantly samples, analyze using injection well as the center of circle, find Modified Iron cerium hydroxide at above-mentioned two layers
In average influence radius it is very small, only 0-0.2m or so.By the charge velocity of suspension in 0.04mol/L embodiment 1
After being promoted to 40L/min, average influence radius of the Modified Iron cerium hydroxide in muck soil and silty clay is followed successively by
1.4,0.8m.Therefore above-mentioned injection well head spacing is from can be respectively set to 2.8m, 1.6m.
It follows that: Modified Iron cerium hydroxide prepared by the present invention is reachable to the adsorption capacity of As (V)
200.32mg·g-1, and the TCLP concentration of arsenic in soil can be made to reduce 92-96%, to significantly reduce its migration.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
The above, part specific embodiment only of the present invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all cover by what those skilled in the art
Within protection scope of the present invention.
Claims (4)
1. a kind of for stabilizing the Modified Iron cerium hydroxide of rehabilitating soil arsenic pollution, it is characterised in that: the Modified Iron cerium
Hydroxide is by Fe (OH)3With Ce (OH)3Two phase compositions, molar ratio are 3~2.5:1~0.8, form uniformly compound bimetallic
Hydroxide；The average grain diameter of the Modified Iron cerium hydroxide is 0.25-1.60 μm, and surface is smooth；
The preparation method of the Modified Iron cerium hydroxide realizes step are as follows:
(1) surfactant is added in deionized water, is heated under the conditions of magnetic agitation, it is molten obtains clear surfactant
Liquid；
(2) by iron chloride, ferrous sulfate, cerous sulfate according to Fe (III): Fe (II): Ce (IV)=2~1.5:1~0.8:1~
0.8 molar ratio is added separately in surfactant solution, by sodium hydroxide regulation system pH to 7-7.5, obtained suspension
Object is Modified Iron cerium hydroxide；
The surfactant is starch；
The ratio that surfactant is added in deionized water in the step (1) is 0.8~1.0%；
The revolving speed of magnetic agitation is 500~1000rpm in the step (1)；
Step (1) heating temperature is 80-95 DEG C, heating time 30-60min；
Concentration of sodium hydroxide solution is 1~4mol/L in the step (2).
2. a kind of method using Modified Iron cerium hydroxide described in claim 1, it is characterised in that realize step are as follows: will change
Property iron cerium hydroxide and pH adjusting agent pass through injection pump, turbine flowmeter, flow control valve, shutoff valve respectively and are introduced to injection
Well head injects arsenic pollution stabilization formulations to different depth soil in-situ by scalable injection pipe.
3. according to the method described in claim 2, it is characterized by: the charge velocity in depth 0-3m be 8-15L/min,
It is 35-42L/min in depth > 3m.
4. according to the method described in claim 2, it is characterized by: the injection well head spacing is from for gravel-sand
5-12m is 2-4m for sand-shale sand, is 1-3m for heavy mud-clay.
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| CN107983294B (en) * | 2017-12-04 | 2020-09-15 | 中国科学院地理科学与资源研究所 | Polysaccharide modified ferro-manganese bimetallic material and preparation method and application thereof |
| CN110327874B (en) * | 2019-07-04 | 2022-06-10 | 江西理工大学 | Core-shell structure composite iron-cerium oxide dearsenic adsorbent and preparation method and application thereof |
| CN111871372B (en) * | 2020-07-16 | 2022-07-08 | 广东省测试分析研究所（中国广州分析测试中心） | Preparation method of iron-manganese oxide/starch/biochar composite material for simultaneously adsorbing inorganic arsenic and organic arsenic in water body |
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