CN115246677A - Preparation method of novel zeolite-based iron-carbon filler for constructed wetlands - Google Patents
Preparation method of novel zeolite-based iron-carbon filler for constructed wetlands Download PDFInfo
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- CN115246677A CN115246677A CN202111219420.5A CN202111219420A CN115246677A CN 115246677 A CN115246677 A CN 115246677A CN 202111219420 A CN202111219420 A CN 202111219420A CN 115246677 A CN115246677 A CN 115246677A
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- carbon
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000010457 zeolite Substances 0.000 title claims abstract description 46
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000945 filler Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 3
- 239000010902 straw Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 239000003987 organophosphate pesticide Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 238000002161 passivation Methods 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract 2
- 238000011001 backwashing Methods 0.000 abstract 1
- 239000005944 Chlorpyrifos Substances 0.000 description 6
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000010865 sewage Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 gravel Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a preparation method of a novel zeolite-based iron-carbon filler for constructed wetlands, which is characterized in that iron-carbon powder is mixed according to a certain proportion and is sintered into iron-carbon ceramsite. The prepared zeolite-based iron-carbon artificial wetland novel filler has the function of removing organophosphorus pesticides and heavy metals by utilizing the potential difference between zero-valent iron and carbon to spontaneously generate electrochemical reaction in a solution. The novel zeolite-based iron-carbon human wetland filler solves the problems that iron chips are easy to harden and run off when iron-carbon powder is directly used for traditional iron-carbon micro-electrolysis, frequent backwashing and package replacement are needed, and the efficiency of micro-electrolysis reaction is improved.
Description
Technical Field
The invention relates to the field of constructed wetland fillers, in particular to a method for preparing a zeolite-based iron-carbon constructed wetland novel filler. The zeolite-based iron-carbon filler for artificial wetlands prepared by the method can remove organophosphorus pesticides and heavy metals by utilizing the spontaneous electrochemical reaction of the potential difference between zero-valent iron and carbon in a solution, and has high redox capability and adsorption flocculation function.
Background
In the research of removing organophosphorus pesticide and heavy metal in the artificial wetland, the absorption and accumulation of plants are limited, and the regional and seasonal growth characteristics of the plants limit the application and popularization of the plants. Compared with other traditional processes, the artificial wetland system starts later, people pay more attention to the action of plants in the artificial wetland in the early stage, and the research on the fillers is limited to traditional natural fillers such as soil, gravel, limestone and the like, industrial wastes and the like, but the fillers generally have some problems and limit the application of the artificial wetland in the treatment of organic phosphorus pesticides and heavy metal sewage. For example, the invention patent with the application number of CN209352644U discloses an artificial wetland filler, but the filler cannot be replaced and adjusted in time according to the requirements of treatment at different periods, and has a deficiency in environmental adaptability; the invention patent with the application number of 202110313186.6 discloses an artificial wetland filler for removing heavy metals, but the filler is not easy to replace, the later maintenance cost is low, the filler cannot be quickly adjusted according to the sewage conditions in different periods, and a water treatment and purification system is not sufficient. With the rapid development of modern industry, the components in sewage are increasingly complex, the land resources are increasingly in short supply, the adsorption efficiency is high, the pollutant load is high, and the performance is long-lasting, so that the research and development of the novel artificial wetland filler become an important way for solving the problem of treating the pesticide and heavy metal-containing wastewater by the current artificial wetland.
The research mixes the agricultural straw biochar and the reduced iron powder in proportion to prepare the zeolite-based iron carbon matrix so as to reduce the passivation degree of the matrix, prolong the service life of the matrix and provide a new choice for treating pesticides and heavy metals by the artificial wetland.
Disclosure of Invention
In order to overcome the defects of the traditional filler of the constructed wetland in the aspect of processing organophosphorus pesticide and heavy metal, the invention provides a method for preparing a novel zeolite-based iron-carbon filler of the constructed wetland.
The preparation method of the novel zeolite-based iron-carbon filler for the constructed wetland adopts the following technical scheme:
mixing reduced iron powder, straw biochar, zeolite powder, soluble starch and ammonium bicarbonate in proportion, taking the mixture as a precursor, and curing at high temperature for a short time to obtain the novel zeolite-based iron-carbon filler for the artificial wetland.
A preparation method of a novel zeolite-based iron-carbon filler for constructed wetlands comprises the following steps:
(1) Mixing 27%, 13%, 50%, 5% and 5% of reduced iron powder, straw biochar, zeolite powder, soluble starch and ammonium bicarbonate by volume ratio;
(2) Filling the mixed sample obtained in the step (1) into a spherical mold, transferring the spherical mold into an oven, heating for curing, naturally cooling to room temperature, and taking out the spherical mold to obtain a spherical sample with a certain size;
(3) And (3) putting the molded spherical sample into a muffle furnace, firing for 2h at 900 ℃, and curing and molding to obtain the novel zeolite-based iron-carbon filler for the constructed wetland.
The zeolite-based iron carbon used in the invention can be synthesized in a large amount and the synthesis method is simple. The novel zeolite-based iron-carbon filler for the constructed wetland has certain hardness and porosity, has higher adsorption capacity and good stability, and can be used for removing organophosphorus pesticide and heavy metal in wastewater. The preparation process is simple, expensive equipment is not needed, and the artificial wetland filler has bright prospect in large-scale application in the future.
Drawings
FIG. 1 is a diagram of a mechanism for removing cadmium and chlorpyrifos from a novel zeolite-based iron-carbon constructed wetland filler.
Fig. 2 is a process diagram of the preparation of the novel zeolite-based iron-carbon filler for constructed wetlands.
Fig. 3 is a schematic diagram of a laboratory scale constructed wetland (constructed wetland 1: zeolite-based iron-carbon base layer, no planting, constructed wetland 2: zeolite base layer, constructed wetland 3: zeolite-based iron-carbon base layer, toxic chlorpyrifos and cadmium inflow, constructed wetland 4: zeolite-based iron-carbon base layer, toxic chlorpyrifos inflow, constructed wetland 5: zeolite-based iron-carbon base layer, cadmium inflow).
Fig. 4 is SEM, XRD and XPS patterns of the novel zeolite-based iron-carbon constructed wetland filler.
Fig. 5-6 are graphs of the adsorption performance of the novel zeolite-based iron-carbon constructed wetland filler for adsorbing organophosphorus pesticides, heavy metals and water quality indexes.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The preparation method of the novel zeolite-based iron-carbon filler for the artificial wetland comprises the steps of firstly, uniformly mixing reduced iron powder, straw biochar, zeolite powder, soluble starch and ammonium bicarbonate in proportion, filling the mixture into a mold, and then curing the mixture at high temperature in a short time to obtain the novel zeolite-based iron-carbon filler for the artificial wetland.
The invention provides a preparation method of a novel zeolite-based iron-carbon filler for constructed wetlands, which comprises the following steps:
(1) Mixing 27%, 13%, 50%, 5% and 5% of reduced iron powder, straw biochar, zeolite powder, soluble starch and ammonium bicarbonate by volume ratio;
(2) Filling the mixed sample obtained in the step (1) into a spherical mold, transferring the spherical mold into an oven, heating for curing, naturally cooling to room temperature, and taking out the spherical mold to obtain a spherical sample with a certain size;
(3) And (3) putting the molded spherical sample into a muffle furnace, firing for 2h at 900 ℃, and curing and molding to obtain the novel zeolite-based iron-carbon filler for the constructed wetland. The present invention will be described in detail with reference to specific examples.
The first embodiment is as follows: activated sludge of a sewage treatment plant is used for film forming of the artificial wetland substrate, regular oxygenation is carried out, and nutrient solution is artificially added to promote microorganisms to secrete extracellular polymeric substances. And after 45 days, filling the gravels successfully filmed into the artificial wetland reactor layer by layer, and continuously feeding water from the surface of the wetland by using a peristaltic pump, wherein the hydraulic retention time is one day. The reactor is a cylindrical organic glass column (diameter 16cm, height 36 cm)) And the periphery of the wetland is wrapped by aluminum foil paper to simulate the wetland environment without illumination and avoid the influence of illumination on the growth of microorganisms and the degradation of chlorpyrifos. The height of the wetland filler part is 30cm, and gravels with the diameter of about 3.0-5.0 cm (the layer height is about 10 cm), a zeolite-based iron-carbon artificial wetland novel filler with the diameter of about 1.0cm (the layer height is about 10 cm) and coarse sand with the diameter of about 0.3-0.5 cm (the layer height is about 10 cm) are respectively filled from bottom to top. Water is injected from the bottom by a peristaltic pump, and a water sample is collected from an outlet for measurement. Washing gravels with tap water, drying, inoculating sludge, and continuously adding artificially prepared simulated farmland drainage (COD =60mg/L, NO) during the period 3 - -N＝10.5mg/L，NH 4 + N =1.5mg/L and TP =1.5 mg/L), and after the artificial wetland is operated, the relevant indexes are periodically measured.
Example two: the specific operation steps and operation conditions of the second example are the same as those of the first example, except that the zeolite (layer height is about 10 cm) is replaced by the novel filler (layer height is about 10 cm) of the middle-layer zeolite-based iron-carbon constructed wetland in the second example.
Example three: the specific operation steps and operation conditions of the third embodiment are the same as those of the third embodiment, except that chlorpyrifos and cadmium are flowed in the third embodiment.
Example four: the specific operation steps and operation conditions of the third embodiment are the same as those of the third embodiment, except that chlorpyrifos is flowed in the third embodiment.
Example five: the specific operation steps and operation conditions of the third embodiment are the same as those of the first embodiment, except that cadmium flows into the third embodiment.
It should be understood that while the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein, and any combination of the various embodiments may be made without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (5)
1. A preparation method of a novel zeolite-based iron-carbon filler for constructed wetlands is characterized by comprising the following steps: the iron-carbon powder is mixed according to a certain proportion and is sintered into iron-carbon ceramsite filler, and the potential difference between zero-valent iron and carbon is utilized to spontaneously generate electrochemical reaction in the solution to remove organophosphorus pesticide and heavy metal, so that the iron-carbon ceramsite filler has high redox capability and adsorption flocculation function.
2. The preparation method of the zeolite-based iron-carbon filler for constructed wetlands according to claim 1, which is characterized by comprising the following steps: the zeolite-based iron-carbon matrix prepared by mixing the agricultural straw biochar and the reduced iron powder in proportion can reduce the passivation degree of the matrix and prolong the service life of the matrix.
3. The zeolite-based iron-carbon filler for artificial wetlands as claimed in claim 1, wherein: the zeolite-based iron carbon substrate mainly comprises reduced iron powder, straw biochar, zeolite powder, soluble starch and ammonium bicarbonate, and the volume ratios of the zeolite-based iron carbon substrate to the straw biochar are respectively 27%, 13%, 50%, 5% and 5%.
4. The zeolite-based iron-carbon filler for artificial wetlands as claimed in claim 1, wherein: a spherical sample with the diameter of about 1cm is proved to have larger porosity by surface electron microscope analysis.
5. The method for preparing a novel zeolite-based iron-carbon filler for artificial wetlands according to any one of claims 1 to 4, wherein the method comprises the following steps: the preparation method comprises the following steps:
(1) Mixing 27%, 13%, 50%, 5% and 5% of reduced iron powder, straw biochar, zeolite powder, soluble starch and ammonium bicarbonate by volume ratio;
(2) Filling the mixed sample obtained in the step (1) into a spherical mold, transferring the spherical mold into an oven, heating for curing, naturally cooling to room temperature, and taking out the spherical mold to obtain a spherical sample with a certain size;
(3) And (3) putting the molded spherical sample into a muffle furnace, firing for 2h at 900 ℃, and curing and molding to obtain the novel zeolite-based iron-carbon filler for the constructed wetland.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111219420.5A CN115246677A (en) | 2021-10-13 | 2021-10-13 | Preparation method of novel zeolite-based iron-carbon filler for constructed wetlands |
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| CN202111219420.5A CN115246677A (en) | 2021-10-13 | 2021-10-13 | Preparation method of novel zeolite-based iron-carbon filler for constructed wetlands |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393112A (en) * | 2023-03-10 | 2023-07-07 | 山东科技大学 | Preparation method of iron-carbon particles and reinforced constructed wetland dephosphorization method based on iron-carbon particles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112266140A (en) * | 2020-11-24 | 2021-01-26 | 河南永泽环境科技有限公司 | Constructed wetland biomembrane coupling iron-carbon micro-electrolysis filler |
| CN113307371A (en) * | 2020-11-18 | 2021-08-27 | 西南大学 | Construction method of constructed wetland system |
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2021
- 2021-10-13 CN CN202111219420.5A patent/CN115246677A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307371A (en) * | 2020-11-18 | 2021-08-27 | 西南大学 | Construction method of constructed wetland system |
| CN112266140A (en) * | 2020-11-24 | 2021-01-26 | 河南永泽环境科技有限公司 | Constructed wetland biomembrane coupling iron-carbon micro-electrolysis filler |
Non-Patent Citations (1)
| Title |
|---|
| YU ZHANG ET AL.: "Interactions of chlorpyrifos degradation and Cd removal in iron-carbon-based constructed wetlands for treating synthetic farmland wastewater", JOURNAL OF ENVIRONMENTAL MANAGEMENT, pages 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116393112A (en) * | 2023-03-10 | 2023-07-07 | 山东科技大学 | Preparation method of iron-carbon particles and reinforced constructed wetland dephosphorization method based on iron-carbon particles |
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Application publication date: 20221028 |