CN109626481A - A kind of method of iron modification biological charcoal remediation of high As groundwater - Google Patents
A kind of method of iron modification biological charcoal remediation of high As groundwater Download PDFInfo
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- CN109626481A CN109626481A CN201811521095.6A CN201811521095A CN109626481A CN 109626481 A CN109626481 A CN 109626481A CN 201811521095 A CN201811521095 A CN 201811521095A CN 109626481 A CN109626481 A CN 109626481A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of methods of iron modification biological charcoal remediation of high As groundwater, belong to groundwater remediation technical field.The method of the present invention is the following steps are included: S1, prepare iron modified biomass；S2, iron modified biomass progress high temperature pyrolysis is obtained into iron modification biological Carbon Materials；S3, the iron modification biological Carbon Materials that step S2 is obtained are added to the arsenic removed in underground water in high-arsenic underground water；S4, the iron modification biological Carbon Materials for being fixed with arsenic are separated from the water out.Trivalent arsenic in high-arsenic underground water is first oxidized to that toxicity is lower, the worse pentavalent arsenic of migration by the collective effect of iron and charcoal by the method for the present invention, then the arsenic in underground water is removed in a manner of absorption, complexing and co-precipitation etc., removal efficiency is high, program is simple, and project amount is few, facilitates easy to operate.
Description
Technical field
The present invention relates to groundwater remediation technical field more particularly to a kind of iron modification biological charcoal remediation of high As groundwater
Method.
Background technique
In the natural environment, arsenic is mainly with the presence of the form of inorganic trivalent arsenic As (III) and pentavalent arsenic As (V)；Wherein, three
The toxicity and migration of valence arsenic As (III) is much larger than pentavalent arsenic As (V).For many years, the underground water of High Concentration of Arsenic seriously threatens people
The health of class；Chronic intake will cause endemic arsenic poisoning containing As groundwater, cause skin, bladder, the canceration of kidney and blood vessel
Disease.As the drinking water source of the most of populations in China, the quality of quality of groundwater situation is related to the resident using it as water source
Life and health, therefore it is extremely urgent to find a kind of efficient, cheap high-arsenic underground water restorative procedure.
The purification method of high-arsenic underground water common at present has: oxidation-reduction method, precipitating-flocculence, bioanalysis, ion are handed over
Change method, lime softening method, membrane separation process, absorption method etc.；However all there is respective drawback: (1) oxidation-reduction method in above method
Toxic and carcinogenic by-product can be generated, (2) precipitating-flocculence can generate unstable sludge, when required for (3) bioanalysis
Between it is long, (4) ion-exchange can generate new waste liquid, long processing period, the presence of organic matter can contaminated ion resin, (5) stone
Grey tenderizer needs to carry out secondary treatment adjustment pH, and (6) membrane separation process is also easy to produce embolism, needs periodic maintenance, later period operating cost
Very high, (7) absorption method is regenerated and is regularly replaced, and operation cost is high.
Summary of the invention
In view of this, the present invention provides a kind of biological raws material of wood-charcoal modified containing the iron of charcoal and ferriferous oxide simultaneously
Highly toxic trivalent arsenic is oxidized to pentavalent arsenic by the modified biological carbon materials of iron by material, then with absorption, complexing and co-precipitation etc.
Mode removes the arsenic in high-arsenic underground water, realizes the efficient reparation of high-arsenic underground water.
The present invention provides a kind of methods of iron modification biological charcoal remediation of high As groundwater, comprising the following steps:
S1, iron modified biomass is prepared；
S2, the iron modified biomass for obtaining step S1 carry out high temperature pyrolysis, obtain iron modification biological Carbon Materials；
S3, the iron modification biological Carbon Materials that step S2 is obtained are added in high-arsenic underground water, pass through iron modification biological charcoal
Oxidation, absorption, complexing and the co-precipitation of material remove the arsenic in underground water, reach remediation of high As groundwater purpose；
S4, the iron modification biological Carbon Materials for being fixed with arsenic are separated from the water out.
Further, in the step S1, iron modified biomass is prepared method particularly includes:
S1.1, Fe (NO is weighed3)3·9H2O solid, is dissolved in deionized water, and stirring is made into Fe until sufficiently dissolution
(NO3)3Solution；
Poplar biomass is cut into cube block of the same size by S1.2, the poplar biomass for weighing drying；
S1.3, Fe (NO made from the poplar biomass and step S1.1 that step S1.2 is handled will be passed through3)3Solution is mixed
It closes, then impregnates 48h, irregularly stirred in soaking process, obtain fully absorbing Fe (NO3)3The poplar biomass of solution；
S1.4, Fe (NO will be fully absorbed3)3The poplar biomass of solution filters out, obtained by drying to arrive Fe (NO3)3Modification biological
Matter.
Further, in the step S1.1, the Fe (NO that is made into3)3Solution concentration is 0.5mol/L.
Further, in the step S1.2, side length < 2mm of cube block.
Further, in the step S1.3, poplar biomass and Fe (NO3)3Solution is according to poplar biomass and element of Fe
Mass ratio be 5:1 mixed.
Further, in the step S1.4, drying temperature is 105 DEG C.
Further, in the step S2, to the Fe (NO of acquisition3)3Modified biomass carries out high temperature pyrolysis, Gao Wenre
The temperature of cracking is 300 DEG C -900 DEG C, and time of high temperature pyrolysis is 2h, entire high temperature pyrolysis process under anaerobic into
Row.
Further, in the step S4, the Fe (NO of arsenic will be fixed with using externally-applied magnetic field3)3Modification biological Carbon Materials from
It is separated in water.
Compared with prior art, the invention has the following advantages:
(1) iron modification biological Carbon Materials are able to achieve the collective effect of charcoal and ferriferous oxide in the present invention, pass through this material
Oxidation, absorption, complexing and the co-precipitation of material remove the arsenic in high-arsenic underground water；Biological carbon materials after iron is modified are aobvious
Work improves its ability to cure and repairing effect to arsenic, especially in the lower situation of thermal cracking temperature, iron modification biological
Carbon Materials have increased significantly to the removal efficiency less modification biological Carbon Materials of arsenic in high-arsenic underground water；
(2) iron modification biological Carbon Materials have certain magnetism in the present invention, and it is magnetic will not fail in a short time, can be with
Iron modification biological Carbon Materials are separated from underground water by externally-applied magnetic field, good separating effect, operating procedure is simple；
(3) iron modification biological Carbon Materials convert trivalent arsenic to after pentavalent arsenic and are fixed again in the present invention, while pentavalent
The transfer ability of arsenic is weaker compared to trivalent arsenic, and toxicity is smaller；Arsenic after fixation is not easy secondary release, small toxicity；
(4) method and step of remediation of high As groundwater of the present invention is simple, and project amount is few, facilitates easy to operate.
Detailed description of the invention
Attached drawing is only used for showing the purpose of specific embodiment, and is not to be construed as limiting the invention.
Fig. 1 is a kind of preparation flow figure of the iron modification biological Carbon Materials of remediation of high As groundwater in the embodiment of the present invention；
Fig. 2 is a kind of method flow using iron modification biological Carbon Materials remediation of high As groundwater in the embodiment of the present invention
Figure；
Fig. 3 is a kind of schematic diagram using iron modification biological Carbon Materials remediation of high As groundwater in the embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
In embodiments of the present invention, if without specified otherwise, raw materials used and instrument is commercially available.
The embodiment of the invention provides a kind of iron modification biological charcoals of remediation of high As groundwater, as shown in Figure 1, preparation process
The following steps are included:
S1, preparation Fe (NO3)3Modified biomass；
The step specifically:
S1.1, Fe (NO is weighed3)3·9H2O powder, is dissolved in deionized water, and stirring is made into Fe until sufficiently dissolution
(NO3)3Solution；Preferably, it is made into Fe (NO3)3The concentration of solution is 0.5mol/L.
Biomass is cut into of the same size cube for convenience of pollution removal by S1.2, the poplar biomass for weighing drying
Body block；Preferably, side length < 2mm of cube block.
S1.3, Fe (NO made from the poplar biomass and step S1.1 that step S1.2 is handled will be passed through3)3Solution is mixed
It closes, impregnates 48h, irregularly stirred in soaking process to guarantee to impregnate sufficiently, obtain fully absorbing Fe (NO3)3The poplar of solution is raw
Substance；Preferably, poplar biomass and Fe (NO3)3Solution is that 5:1 is mixed according to the mass ratio of poplar biomass and element of Fe
It closes.
S1.4, Fe (NO will be fully absorbed3)3The poplar biomass of solution filters out drying, it is preferable that dries under anaerobic
Dry, drying temperature is 105 DEG C, and drying is completed to obtain Fe (NO3)3Modified Poplar biomass.
S2, the Fe (NO for obtaining step S13)3Modified Poplar biomass carries out high temperature pyrolysis, obtains Fe (NO3)3It is modified
Biological carbon materials.
The step specifically: to the Fe (NO of acquisition3)3Modified Poplar biomass carries out high temperature hot tearing in tube type resistance furnace
Solution, the temperature of high temperature pyrolysis are 300 DEG C -900 DEG C, and the time of high temperature pyrolysis is 2h, and entire high temperature pyrolysis process is being detested
It is carried out under the conditions of oxygen.
It should be noted that when the embodiment of the present invention is respectively 300,600 and 900 degrees Celsius to step S2 thermal cracking temperature
Fe (the NO of acquisition3)3Modification biological Carbon Materials have carried out XRD characterization, and synchrotron radiation analysis fitting is combined to obtain at above-mentioned temperature
All Fe (the NO obtained3)3There is γ-Fe in modification biological Carbon Materials2O3In the presence of the Fe (NO of acquisition3)3Modification biological Carbon Materials
With the presence of Zero-valent Iron.
The embodiment of the invention also provides a kind of methods of remediation of high As groundwater, as shown in Figure 2, comprising the following steps:
S3, the Fe (NO for obtaining step S23)3Modification biological Carbon Materials are added in high-arsenic underground water, pass through Fe (NO3)3
Oxidation, absorption, complexing and the co-precipitation of modification biological Carbon Materials remove the arsenic in underground water, reach remediation of high As groundwater
Purpose.
S4, the Fe (NO that arsenic will be fixed with3)3Modification biological Carbon Materials are separated from the water out.
The step specifically: Fe (NO3)3Modification biological Carbon Materials have certain magnetism, and magnetism will not be lost in a short time
Effect, the Fe (NO of arsenic will be fixed with using externally-applied magnetic field3)3Modification biological Carbon Materials are separated from the water, that is, realize high-arsenic underground water
Reparation efficiently without secondary pollution.
Below with reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of iron modification biological Carbon Materials of remediation of high As groundwater, preparation process are as follows:
S1, preparation Fe (NO3)3Modified biomass；
The step specifically:
S1.1,202g Fe (NO is weighed3)3·9H2O powder is dissolved in 1L deionized water, and stirring is matched until sufficiently dissolution
At the Fe (NO of 0.5mol/L concentration3)3Solution；
S1.2, the poplar biomass for weighing drying, are cut to cube block of the same size, the side length of cube block
<2mm；
S1.3, Fe (NO made from the poplar biomass and step S1.1 that step S1.2 is handled will be passed through3)3Solution is mixed
It closes, the poplar biomass and Fe (NO of addition3)3Solution is mixed according to the mass ratio 5:1 of poplar biomass and element of Fe；So
After impregnate 48h, irregularly stirred in soaking process with guarantee impregnate sufficiently, obtain fully absorbing Fe (NO3)3The poplar of solution is raw
Substance；
What S1.4, under anaerobic baking step S1.3 were obtained fully absorbs Fe (NO3)3The poplar biomass of solution is dried
Dry temperature is 105 DEG C, and drying is completed to obtain Fe (NO3)3Modified poplar biomass.
S2, the Fe (NO for obtaining step S13)3Modified poplar biomass carries out high temperature pyrolysis in tube type resistance furnace,
The temperature of high temperature pyrolysis is 300 DEG C, and time of high temperature pyrolysis is 2h, entire high temperature pyrolysis process under anaerobic into
Row；Fe(NO3)3Fe (NO is made in poplar biomass after the immersion high temperature pyrolysis at 300 DEG C3)3Modification biological Carbon Materials, letter
Write as FNBC300S.
It should be pointed out that be respectively set in step s 2 thermal cracking temperature be 600 DEG C and 900 DEG C when, obtain difference
At a temperature of Fe (NO3)3Modification biological Carbon Materials, are abbreviated as FNBC600S and FNBC900S respectively.
Fe (the NO obtained is completed to thermal cracking3)3Modification biological Carbon Materials have carried out phenetic analysis, obtain at the temperature disclosed above
Fe (the NO obtained3)3There is γ-Fe in modification biological Carbon Materials2O3Exist with Zero-valent Iron.
A kind of method of remediation of high As groundwater
By the Fe (NO of above-mentioned acquisition3)3Modification biological Carbon Materials are added in the high-arsenic underground water that simulation is prepared, simulated solution
In the concentration of initial arsenic (III) be 5mg/L.
S3, the 0.2g Fe (NO for obtaining step S23)3Modification biological Carbon Materials are added to what the above-mentioned simulation of 0.04L was prepared
In high-arsenic underground water, pass through Fe (NO3)3Oxidation, absorption, complexing and the co-precipitation of modification biological Carbon Materials remove underground water
In arsenic；Go the reaction principle of arsenic removal as shown in Fig. 3 1. -6. formula under:
Fe0+O2+2H+→Fe2++H2O2 ①
Fe2++H2O2→Fe3++·OH+OH- ②
As(III)+·OH→As(V) ④
FeOOH+As(III)→FeO-As(III)+OH- ⑤
FeOOH+As(V)→FeO-As(V)+OH- ⑥
In trivalent arsenic removal experiment, through FNBC300S, FNBC600S and FNBC900S treated above-mentioned high arsenic of simulation
The concentration of remaining arsenic is 0.26mg/L, 4.49mg/L and 2.56mg/L respectively in the aqueous solution of underground, removal rate is 94.8% respectively,
10.2% and 48.8%.
S4, the Fe (NO that arsenic will be fixed with using externally-applied magnetic field3)3Modification biological Carbon Materials are separated from the water, isolated
It is fixed with the Fe (NO of arsenic3)3The quality of modification biological Carbon Materials is 0.19-0.2g；It can be seen that will almost be added to the water
Fe(NO3)3Modification biological Carbon Materials recycle successfully, it is therefore prevented that cause secondary pollution to environment.
The present invention provides a kind of method of iron modification biological charcoal remediation of high As groundwater, iron modification in the method for the present invention
Biological carbon materials afterwards significantly improve its ability to cure and repairing effect to arsenic, especially in the lower feelings of thermal cracking temperature
Under condition, iron modification biological Carbon Materials have significantly the removal efficiency less modification biological Carbon Materials of arsenic in high-arsenic underground water
It improves；Iron modification biological Carbon Materials have certain magnetism in the method for the present invention, and magnetism will not fail in a short time, Ke Yitong
It crosses externally-applied magnetic field to separate iron modification biological Carbon Materials from underground water, good separating effect, operating procedure is simple.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method of iron modification biological charcoal remediation of high As groundwater, which comprises the following steps:
S1, iron modified biomass is prepared；
S2, the iron modified biomass for obtaining step S1 carry out high temperature pyrolysis, obtain iron modification biological Carbon Materials；
S3, the iron modification biological Carbon Materials that step S2 is obtained are added in high-arsenic underground water, iron modification biological Carbon Materials pass through
Oxidation, absorption, complexing and co-precipitation remove the arsenic in underground water；
S4, the iron modification biological Carbon Materials for being fixed with arsenic are separated from the water out.
2. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 1, which is characterized in that described
In step S1, iron modified biomass is prepared method particularly includes:
S1.1, molysite is weighed, be dissolved in deionized water, stirring is made into ferric ion solutions until sufficiently dissolution；
Biomass, is cut into the shapes and sizes of setting by S1.2, the biomass for weighing drying；
S1.3, ferric ion solutions made from the biomass handled by step S1.2 and step S1.1 are subjected to mixing immersion, soaked
Irregularly stirring, obtains the biomass for fully absorbing iron ion during bubble；
S1.4, the biomass for fully absorbing iron ion is filtered out, it is obtained by drying to arrive iron modified biomass.
3. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 2, which is characterized in that described
In step S1.1, the ferric ion solutions concentration being made into is 0.5mol/L.
4. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 2, which is characterized in that described
In step S1.2, biomass is cut into cube block, cube block side length < 2mm.
5. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 2, which is characterized in that described
In step S1.3, biomass and ferric ion solutions are mixed according to biomass with the mass ratio of element of Fe for 5:1.
6. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 2, which is characterized in that described
In step S1.4, drying temperature is 105 DEG C.
7. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 1, which is characterized in that described
In step S2, high temperature pyrolysis carried out to the iron modified biomass of acquisition, entire high temperature pyrolysis process under anaerobic into
Row.
8. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 1, which is characterized in that described
The temperature of step S2 high temperature thermal cracking is 300 DEG C -900 DEG C.
9. a kind of method of iron modification biological charcoal remediation of high As groundwater according to claim 1, which is characterized in that described
In step S4, the iron modification biological Carbon Materials for being fixed with arsenic are separated from the water out using externally-applied magnetic field.
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| CN110143661A (en) * | 2019-05-23 | 2019-08-20 | 华中科技大学 | A method of arsenic in rich calcium high-arsenic underground water is removed with charcoal |
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| CN112239259A (en) * | 2020-08-24 | 2021-01-19 | 中南大学 | Chemical remover for heavy metal polluted wastewater treatment and preparation method and application thereof |
| CN113477217A (en) * | 2021-07-26 | 2021-10-08 | 济南大学 | Preparation and application of poplar sawdust biochar loaded nano zero-valent iron composite material |
| CN113880193A (en) * | 2021-09-16 | 2022-01-04 | 同济大学 | Ferrocene modified MIL-88B electrode and preparation method and application thereof |
| CN114849644A (en) * | 2022-03-31 | 2022-08-05 | 生态环境部华南环境科学研究所 | Nano ferrihydrite biochar and preparation method and application thereof |
| CN115532228A (en) * | 2022-10-18 | 2022-12-30 | 广州大学 | Method for regulating and controlling toxicity of chromium and arsenic based on biochar and evaluation method |
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| CN114849644A (en) * | 2022-03-31 | 2022-08-05 | 生态环境部华南环境科学研究所 | Nano ferrihydrite biochar and preparation method and application thereof |
| CN114849644B (en) * | 2022-03-31 | 2023-09-08 | 生态环境部华南环境科学研究所 | Nano ferrihydrite biochar and preparation method and application thereof |
| CN115532228A (en) * | 2022-10-18 | 2022-12-30 | 广州大学 | Method for regulating and controlling toxicity of chromium and arsenic based on biochar and evaluation method |
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