CN115432781A - Suspended iron-carbon micro-electrolysis filler and preparation method and application thereof - Google Patents
Suspended iron-carbon micro-electrolysis filler and preparation method and application thereof Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 89
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 50
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 27
- 230000005484 gravity Effects 0.000 claims description 21
- 239000002351 wastewater Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000009827 uniform distribution Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 2
- 238000005339 levitation Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 description 7
- 239000010865 sewage Substances 0.000 description 6
- 238000002161 passivation Methods 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 230000032770 biofilm formation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010914 pesticide waste Substances 0.000 description 1
- 239000010826 pharmaceutical waste Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000011020 pilot scale process Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 description 1
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Molecular Biology (AREA)
- Microbiology (AREA)
- Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
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- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a suspended iron-carbon micro-electrolysis filler and a preparation method and application thereof, wherein the filler comprises a suspended carrier and an iron-carbon micro-electrolysis layer loaded on the surface of the suspended carrier; the iron-carbon micro-electrolysis layer is loaded on the suspension carrier in an electrostatic spraying way. The suspension carrier comprises: the upper half part is a cone consisting of a plurality of sheet structures which are distributed at intervals along the circumferential direction; the lower half part comprises a rotator and a plurality of blades distributed on the surface of the rotator; a connecting portion connecting the upper half portion and the lower half portion; the top cover is of an umbrella-shaped structure and is positioned at the top of the upper half part, and the top cover is connected with the connecting part through a reinforcing rib. The filler combines a biofilm method with an iron-carbon micro-electrolysis technology, so that the problems that the traditional suspended biological filler is low in film hanging efficiency, the iron-carbon micro-electrolysis filler is easy to harden and passivate, the treatment effect is poor when the filler is used alone and the like are solved.
Description
Technical Field
The invention belongs to the technical field of environmental engineering materials, and particularly relates to a preparation method and application of a suspension type iron-carbon micro-electrolysis filler.
Background
The iron-carbon micro-electrolysis (IC-ME) technology is an environment-friendly and low-resource-consumption wastewater pretreatment process, mainly uses cheap scrap iron or processed zero-valent iron and carbon particles as raw materials, and generates Fe through the electrochemical reaction of Fe/C materials in a reaction solution to form a microscopic primary battery and generate Fe 2+ And Fe 3+ The pollutants are removed through oxidation-reduction reaction, flocculation, adsorption and coprecipitation, so that the wastewater is purified, and the purpose of treating the waste with the waste is realized"is considered a green, environmentally friendly pretreatment technique. The technology is discovered by British scientists studying zero-valent iron theory in groundwater, and is applied to water resource utilization and sewage purification.
At present, the iron-carbon micro-electrolysis technology is widely applied to treatment of various waste water such as pharmaceutical waste water, dye waste water, pesticide waste water, heavy metal waste water, coking waste water and the like, and particularly, the IC-ME and the bioreactor show better performance and treatment effect when combined. Zhu et al, in IC-ME pilot scale system pretreatment of ultra-high concentration organic wastewater, failed to achieve ideal COD removal. However, the IC-ME used by Wang et al performed well in UASB bioreactors for treating coal gasification wastewater. The main difference between these two systems is whether the IC-ME is directly bound to the biological process, compared to the performance of the IC-ME when bound to the biological process. The IC-ME is also used for treating phenolic compounds in coal gasification, and under the synergistic action of the IC-ME, the biological treatment of phenols is enhanced, and some functional microorganisms are enriched. Traditional little electrolysis of iron carbon filler has a lot of defects in practical application, for example specific surface is little, the porosity is low, the little electrolysis reaction efficiency of material is low, and throw the mode and mostly be the filler and sink the end, can appear hardening passivation phenomenon after operation a period of time, reduces the treatment effect of little electrolysis filler to waste water.
The biofilm method is a common technology for treating wastewater by microorganisms, and mainly removes pollutants by using a microbial film attached to the surface of a filler carrier. Compared with the traditional activated sludge method, the method has better organic matter removal efficiency and nitrogen and phosphorus removal capability, simple operation and management, low sludge yield and no sludge bulking, so the method is more and more widely applied to treatment of domestic sewage and industrial wastewater in recent years. The filler is used as a microbial carrier, the performance of the filler is an important factor influencing the treatment effect of a biofilm method, but most of the suspended biological fillers used at present are regular-shaped ceramsite fillers or polyethylene fillers, on one hand, the specific surface area of the filler is small, so that the film hanging efficiency is low, on the other hand, materials such as polyethylene and the like are difficult to degrade, and the generation of 'white garbage' can be caused.
Disclosure of Invention
The invention provides a novel suspension type iron-carbon micro-electrolysis filler, and a preparation method and application thereof. The filler combines a biofilm method with an iron-carbon micro-electrolysis technology, the problems that the traditional suspended biological filler is low in film hanging efficiency, the iron-carbon micro-electrolysis filler is easy to harden and passivate, the treatment effect is not good when the filler is used alone are solved, the prepared iron-carbon micro-electrolysis filler is large in specific surface area and high in strength, larger current density is provided for wastewater treatment, the micro-electrolysis effect is good, the long-term operation is stable, passivation and hardening are not easy to occur, and meanwhile, the filler has higher micro-organism film hanging efficiency, so that the effluent quality is excellent, and the filler has the characteristics of environmental friendliness and can not cause environmental pollution.
A suspension carrier for supporting iron-carbon micro-electrolysis fillers, comprising:
the upper half part is a cone consisting of a plurality of sheet structures which are distributed at intervals along the circumferential direction;
the lower half part comprises a rotating body and a plurality of blades distributed on the surface of the rotating body;
a connecting portion connecting the upper half portion and the lower half portion;
the top cover is of an umbrella-shaped structure and is positioned at the top of the upper half part, and the top cover is connected with the connecting part through a reinforcing rib.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Optionally, the center of gravity and the center of buoyancy of the suspension carrier are located on the same vertical line; the center of gravity of the floating carrier is located at the lower half.
The lower half part of the suspension carrier has higher specific gravity, the gravity center of the whole structure is lower, and the gravity center and the floating center are on the same vertical line, so that the filler can be suspended in water and keep stable balance, as shown in figure 6. When the filler is put into water, the height of the stable center is gradually reduced in the process of submerging from the water surface to the water, the floating center is superposed with the stable center after the filler is completely submerged in the water, and the initial stability height is the distance between the floating center and the center of gravity. Because the whole gravity center of the filler is arranged below and the floating center is arranged above, when the filler is inclined in water, the buoyancy and the gravity can form a new restoring moment, so that the filler is righted and cannot be laterally turned, as shown in fig. 7.
Optionally, the whole suspension carrier is of a hollow structure.
Optionally, the rotating body is a hollow cylinder; the blades extend along the axial direction on the surface of the hollow cylinder and are distributed at intervals along the circumferential direction; the vertical distance between the axial outer edge and the outer surface of the rotating body is gradually increased from the bottom of the rotating body to the connecting part; all the blades are spirally deflected in the same direction at the same angle.
Optionally, the pitch angle of all the blades is 15-30 °
Optionally, water holes are formed in the positions, close to the bottom of the rotating body, of all the blades; is favorable for water flow to enter.
As a more specific shape option for the lower half, the lower half is in the form of a spiral bevel gear.
Optionally, the connecting portion is a connecting plate in a shape of a reuleaux triangle; the sheet structure is fixed on the top surface of the connecting plate; a through hole is formed in the geometric center of the connecting plate; the top cover is connected with the triangular part of the connecting part through the reinforcing ribs.
The upper half part of the suspension carrier is a cone consisting of a sheet structure and an umbrella structure connected with the connector through a reinforcing rib, so that the structural strength is enhanced, and the buffering effect is also realized when the filler is added into the wastewater, so that the filler slowly enters the water and is kept stable; the middle part is a Lailou triangle-shaped connector; the lower half part is a structure which is formed by blades and is approximately in the shape of a spiral bevel gear, and can be in a rotation state under the impact of wastewater flowing in the horizontal direction, so that all surfaces can uniformly contact sewage, and the hardening and passivation phenomena among the fillers can be avoided.
The lower half part of the whole filler has higher specific gravity, the gravity center of the whole structure is lower, and the gravity center and the floating center are on the same vertical line, so that the filler can be suspended in water and keep stable balance; when the filler is inclined in water, the buoyancy and the gravity can form a new restoring moment to right the filler and prevent the filler from turning over laterally.
The invention also provides a suspended iron-carbon micro-electrolysis filler which comprises the suspended carrier and an iron-carbon micro-electrolysis layer loaded on the surface of the suspended carrier.
The invention also provides a preparation method of the suspension type iron-carbon micro-electrolysis filler, which comprises the following steps:
(1) Mixing raw materials: respectively sieving sponge iron powder, graphene powder, a catalyst and a pore-forming agent, taking the materials according to a preset proportion, adding water, uniformly mixing, and performing ultrasonic enhancement in the mixing process to promote uniform distribution of each component to obtain an initial raw material a;
(2) Ball milling of raw materials: performing ball milling on the initial raw material a to obtain an initial raw material b with the particle size of less than or equal to 100 mu m;
(3) Electrostatic spraying: pretreating the suspension carrier to enable the suspension carrier to have conductive performance, coating the whole suspension carrier framework with the obtained initial raw material b in an electrostatic spraying mode, and forming an iron-carbon micro-electrolysis coating with the thickness of 3-5 mm on the surface of the suspension carrier;
(4) And (3) filler sintering: and (3) placing the formed filler into a tubular furnace, sintering at high temperature in an oxygen-free atmosphere, naturally cooling to room temperature, and soaking and cleaning for later use.
The invention couples the iron-carbon micro-electrolysis technology with the biofilm method, the iron-carbon micro-electrolysis layer coated on the surface is rough enough, the porosity is large, the specific surface area is large, and the invention has better hydrophilicity and biological affinity, so that the microorganism biofilm formation efficiency is high.
In the step (1):
optionally, in the process of preparing the initial raw material a, the ratio of each component is as follows: 50-60 parts of sponge iron powder, 25-30 parts of graphene powder, 6-8 parts of a catalyst and 9-12 parts of a pore-forming agent.
Optionally, the catalyst comprises the following components in percentage by mass:
perovskite manganese oxide LaCeMnO 3 10% of powder, 8% of aluminum powder, 8% of copper powder, 8% of nickel powder, 8% of manganese powder, 8% of cobalt powder, and 8% of copper powder8% of lanthanum powder, 6% of lead oxide and 6% of antimony-doped tin oxide.
Optionally, the pore-forming agent is one or more of ammonium carbonate, ammonium bicarbonate and ammonium chloride.
Optionally, the raw materials are respectively sieved by a sieve of 100-110 meshes, so that the granularity of the raw materials is small, the raw materials are in full contact, and the micro-electrolysis efficiency is improved.
Optionally, the intensified ultrasonic frequency is 70-90 kHz.
In the step (2):
optionally, a roller ball mill is used in the ball milling process, the ball milling frequency is 100-400 Hz, the ball milling time is set to 30-150 min, and the ball-material ratio (mass ratio of the medium balls to the materials) is 1-7: 1, the rotating speed is 300-500 r/min.
In the step (3):
optionally, the pretreatment is: firstly, spraying a layer of UV primer on the surface of the central carrier, drying, and then plating a metal layer on the surface in a vacuum sputtering mode.
Optionally, the metal layer is a metal aluminum layer.
Optionally, a nozzle with a diameter of 14-18mm is used in the electrostatic spraying process, the electrostatic pressure is set to be 30-70KV, the flow rate pressure is set to be 0.3-0.5Mpa, the powder flow rate is controlled to be 150-300g/min, and the distance between the nozzle and the central carrier is kept to be 200-300mm.
In the step (4):
optionally, the temperature of the tube furnace is gradually increased during high-temperature sintering at a rate of 15 ℃/min, and the tube furnace is sintered for 4-5 hours at a temperature of 700-950 ℃.
Optionally, the suspension carrier is made of cellulose nanofiber sheets; the whole density of the suspension carrier loaded with the iron-carbon micro-electrolysis layer is 0.96-0.98 g/cm 3 . The density of the biofilm is equivalent to that of water.
The invention also provides application of the suspension type iron-carbon micro-electrolysis filler in wastewater purification.
As an implementation mode of application, the suspended iron-carbon micro-electrolysis filler is added into a wastewater body to be treated, wherein the adding filling rate of the filler is 30-35% of the volume of the reaction tank.
Compared with the prior art, the suspension type iron-carbon micro-electrolysis filler prepared by the invention has at least one of the following beneficial effects:
(1) The special structure of the suspension carrier designed by the invention has the following advantages: the specific surface area is large, the contact with the wastewater is sufficient, and the microbial film forming efficiency is high; the lower half part is in a helical gear shape, and can be driven to be in a self-rotating state under the impact of wastewater flowing horizontally, so that all surfaces can uniformly contact sewage, and the hardening and passivation phenomena among the fillers can be avoided; the trompil of every sector of the latter half is favorable to inside the waste water extrusion gets into the filler, has effectively increased the area of contact of filler.
(2) The invention adopts the ultrasonic strengthening means in the preparation process of the raw materials, can promote the uniform distribution of all components and also improves the porosity of the material to a certain extent.
(3) The suspension carrier designed by the invention is prepared by taking the cellulose nano-fiber board as a raw material, the production cost of the cellulose nano-fiber board is lower than that of most plastics, and the cellulose nano-fiber board has low density, excellent strength, toughness and thermal dimensional stability, all the characteristics exceed those of the traditional metal, ceramic and polymer, so the cellulose nano-fiber board can be used as a high-performance and environment-friendly substitute product, firstly, the low density of the whole filler is ensured based on the low density characteristic, secondly, the high strength of the material improves the performance of the filler, and finally, the filler can also become an environment-friendly material.
(4) According to the invention, the graphene powder is used as one of the raw materials, and based on the advantages of high electron mobility and strong chemical stability, compared with the traditional iron-carbon micro-electrolysis filler prepared from materials such as activated carbon, the iron-carbon micro-electrolysis filler has better reaction efficiency and pollutant removal rate.
(5) The iron-carbon micro-electrolysis layer coated on the outer layer of the suspension type iron-carbon micro-electrolysis filler prepared by the invention has high porosity and rough surface under the reinforcing action of ultrasound and the existence of pore-forming agent, and has higher microorganism biofilm formation efficiency compared with the traditional regular biological filler with smooth surface.
(6) The suspended iron-carbon micro-electrolysis filler prepared by the invention has the overall density of0.96～0.98g/cm 3 The filler can be in a suspension state instead of being sunk in the wastewater, so that the utilization efficiency of the filler is improved, and the hardening probability of the filler is reduced.
Drawings
FIGS. 1 to 3 are schematic views of different angles of the suspension carrier of the present invention;
FIG. 4 is a top view of a suspension carrier of the present invention;
FIG. 5 is a bottom view of the suspension carrier of the present invention;
FIG. 6 is a schematic diagram of the force analysis of a suspended carrier in water;
FIG. 7 is a schematic representation of the stability of a suspended carrier in water.
The reference numerals shown in the figures are as follows:
10. the upper half part, 11, a sheet structure;
20. a connecting portion;
30. the lower half part 31, the rotating body 32, the blades 33, the central hole 34 and the water through hole;
40. a top cover;
50. and (5) reinforcing ribs.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Fig. 1 to 3 are schematic diagrams showing a three-dimensional structure of a suspension carrier according to the present invention at different angles, and fig. 4 and 5 are a top view and a bottom view of the suspension carrier according to the present invention, respectively.
As shown in fig. 1, the suspension carrier includes an upper half 10, a connecting portion 20, a lower half 30, and a top cover 40, wherein the upper half 10 and the lower half 30 are connected by the connecting portion 20, the top cover 40 is located on top of the upper half 10, and the top cover 40 and the connecting portion 20 are connected by a reinforcing rib 50. The lower half part of the suspension carrier has higher specific gravity, namely the gravity center of the suspension carrier is positioned at the lower half part of the suspension carrier, the gravity center of the whole structure is deviated downwards, the gravity center and the floating center are positioned on the same vertical line, and the floating center is positioned above the gravity center, so that the filler can be suspended in water and keep stable balance, as shown in fig. 6. When the filler is put into water, the height of the stable center is gradually reduced in the process of submerging from the water surface to the water, the floating center is superposed with the stable center after the filler is completely submerged in the water, and the initial stability height is the distance between the floating center and the center. Because the whole gravity center of the filler is arranged below and the floating center is arranged above, when the filler is inclined in water, the buoyancy and the gravity can form a new restoring moment, so that the filler is righted and cannot be laterally turned, as shown in fig. 7.
Referring to fig. 1 and 4, the upper half 10 is substantially conical and is formed by a plurality of sheet structures 11 arranged at intervals along the circumferential direction. In one embodiment of the upper half 10, the single sheet structure 11 is substantially in the shape of a right triangle, and is vertically disposed on the top surface of the connecting portion at a right angle close to the geometric center of the connecting portion 20, the triangular sheet structure includes a bevel edge and two right-angle edges, one of the right-angle edges is fixed to the top surface of the connecting portion, and the included angle between the bevel edge and the top surface of the connecting portion may be 20 to 40 degrees, and more preferably 30 degrees; the height of the vertebral body can be set to 25-35 mm, preferably 30mm.
Referring to fig. 1, 2 and 5, the lower half 30 includes a rotator 31 and a plurality of blades 32 distributed on the surface of the rotator 31. As a specific option of the rotating body and the blades, the rotating body 31 is a hollow cylinder with a central hole 33 along the axial direction and coaxial, and the height of the hollow cylinder can be set to 40-50 mm, preferably 45mm; the blades 32 extend along the axial direction on the surface of the hollow cylinder and are distributed at intervals along the circumferential direction; the vertical distance between the axial outer edge of all the blades 32 and the outer surface of the rotating body 31 increases gradually from the bottom of the rotating body 31 to the connecting part 20, the width of the bottom of the blade (the vertical distance from the outer edge to the outer surface of the cylinder) may be set to 10-20 mm, the width of the top of the blade may be set to 35-45 mm, and preferably, the width of the bottom of the blade is 15mm, and the width of the top of the blade is 40mm. All the blades 32 deflect at a certain angle in the same direction at the same angle, and the helical angle is 15-30 degrees, so that the blades can be in a self-rotating state under the impact of wastewater flowing in the horizontal direction, all the surfaces can uniformly contact with the sewage, and the hardening and passivation phenomena among the fillers can be avoided. All the blades 32 are provided with water through holes 34 near the bottom of the rotating body 31 to facilitate the water flow. As a more specific shape option for the lower half, the lower half is in the shape of a spiral bevel gear.
The connecting portion 20 is used for connecting the upper half portion 10 and the lower half portion 20, and the thickness of the connecting portion can be set to be about 15mm, and as a specific scheme of the connecting portion, the connecting portion 20 is a connecting plate in a shape of a leilo triangle as shown in fig. 1, 4 and 5; the sheet structure 11 of the upper half part is fixed on the top surface of the connecting plate, and the top of the cylinder of the lower half part and the tops of all the blades are fixed on the bottom surface of the connecting plate; the web has a through hole at its geometric center which is aligned with the central hole 33 of the hollow cylinder forming the lower half.
As shown in fig. 1, the top cover 40 has an umbrella structure, and is connected to the connecting portion 20 by the reinforcing ribs 50, and when the connecting portion 20 has a shape of a leilo triangle, the top cover is connected to three corners of the connecting portion by the reinforcing ribs 50. Preferably, the coverage area of the umbrella-shaped structure is preferably 50% of the area of the top of the connecting part, wherein the projection area of the umbrella-shaped structure on the connecting part accounts for 50%.
The suspension type iron-carbon micro-electrolysis filler comprises the suspension carrier and the iron-carbon micro-electrolysis layer loaded on the surface of the suspension carrier, wherein the iron-carbon micro-electrolysis layer is loaded on the suspension carrier in an electrostatic spraying mode. The iron-carbon micro-electrolysis filler can be used as a suspended biological filler, can be suspended in wastewater and can keep rotating under the impact of water flow due to the special structure, is prevented from hardening and passivating, has large specific surface area, rough surface and high porosity, is beneficial to improving the biofilm formation efficiency of microorganisms and improving the quality of effluent water, is made of environment-friendly materials, and belongs to an environment-friendly filler.
The following description is given by way of specific examples:
example 1:
the preparation method of the suspension type iron-carbon micro-electrolysis filler comprises the following steps:
(1) Preparing a suspension carrier: preparing a cellulose nano-fiber plate into a structure as shown in figures 1-5 by mechanical cutting, wherein the structure is used as a central carrier of suspension type iron-carbon micro-electrolysis;
(2) Mixing raw materials: respectively sieving 55 parts of sponge iron powder, 30 parts of graphene powder, 7 parts of catalyst and 8 parts of pore-forming agent by a 100-mesh sieve, adding water, uniformly mixing, and performing ultrasonic enhancement by using ultrasonic waves with the frequency of 80kHz in the mixing process to promote uniform distribution of each component to obtain an initial raw material a;
wherein the catalyst component comprises perovskite manganese oxide LaCeMnO 3 26% of powder, 10% of aluminum powder, 10% of copper powder, 10% of nickel powder, 10% of manganese powder, 10% of cobalt powder, 10% of lanthanum powder, 7% of lead oxide and 7% of antimony-doped tin oxide; the pore-forming agent is ammonium bicarbonate.
(3) Ball milling of raw materials: using a roller ball mill, setting the ball milling frequency to be 270Hz, setting the ball milling time to be 90min, and setting the ball-material ratio (the mass ratio of the medium balls to the materials) to be 6: 1. under the condition that the rotating speed is 450r/min, carrying out ball milling on the initial raw material a to obtain an initial raw material b with the particle size of 100 mu m;
(4) Electrostatic spraying: spraying a layer of UV primer on the surface of the central carrier, drying, plating a layer of metal Al on the surface in a vacuum sputtering mode to enable the central carrier to have conductivity, coating the whole carrier framework with the obtained initial raw material b in an electrostatic spraying mode, and forming an iron-carbon micro-electrolysis layer with the thickness of 5mm on the surface of the carrier. Wherein the electrostatic spraying uses a nozzle with the diameter of 15mm, the electrostatic pressure is set to be 70KV, the flow velocity pressure is 0.5Mpa, the powder flow is 160g/min, and the distance between the nozzle and the central carrier is controlled to be 250mm;
(5) And (3) filler sintering: and placing the formed filler into a tubular furnace to perform gradual temperature rise sintering in an oxygen-free atmosphere, wherein the temperature rise rate is 15 ℃/min, sintering for 5 hours at the temperature of 850 ℃, naturally cooling to room temperature, and then soaking and cleaning for later use.
The filler prepared by the embodiment has high structural strength and the overall density of 0.96-0.98 g/cm 3 Can be stably suspended in the wastewater. The filler is added into a bioreactor to treat domestic sewage, the COD of inlet water is 200mg/L, the ammonia nitrogen is 30mg/L, the removal rate of the filler and the bioreactor to the COD and the ammonia nitrogen within 90min is more than 90%, the outlet water can reach the first-level A standard of discharge Standard of pollutants for municipal wastewater treatment plants, the efficiency of the microorganisms on the surface of the filler is high, the inoculated sludge can be intercepted efficiently, and the amount of the outlet sludge is reduced.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. A suspension carrier for supporting iron-carbon micro-electrolysis fillers, comprising:
the upper half part is a cone consisting of a plurality of sheet structures which are distributed at intervals along the circumferential direction;
the lower half part comprises a rotating body and a plurality of blades distributed on the surface of the rotating body;
a connecting portion connecting the upper half portion and the lower half portion;
the top cover is of an umbrella-shaped structure and is positioned at the top of the upper half part, and the top cover is connected with the connecting part through a reinforcing rib.
2. The levitation vehicle of claim 1, wherein the center of gravity and the center of buoyancy of the levitation vehicle are in a common vertical line; the center of gravity of the floating carrier is located at the lower half.
3. The suspension carrier of claim 1, wherein the rotating body is a hollow cylinder; the blades extend along the axial direction on the surface of the hollow cylinder and are distributed at intervals along the circumferential direction; the vertical distance between the outer edge of all the blades along the axial direction and the outer surface of the rotating body is gradually increased from the bottom of the rotating body to the connecting part; all the blades are helically deflected in the same direction at the same angle.
4. The suspension carrier of claim 1 wherein all of the blades are perforated with water holes near the bottom of the rotating body.
5. The levitation carrier of claim 1, wherein the connecting portion is a connecting plate in the shape of a Lelo triangle; the sheet structure is fixed on the top surface of the connecting plate; a through hole is formed in the geometric center of the connecting plate; the top cover is connected with the triangle of the connecting part through the reinforcing ribs.
6. A suspended iron-carbon micro-electrolysis filler, which comprises a suspended carrier and an iron-carbon micro-electrolysis layer loaded on the surface of the suspended carrier, wherein the suspended carrier is the suspended carrier according to any one of claims 1 to 5.
7. A preparation method of a suspension type iron-carbon micro-electrolysis filler is characterized by comprising the following steps:
(1) Mixing raw materials: respectively sieving sponge iron powder, graphene powder, a catalyst and a pore-forming agent, taking the sieved materials according to a preset proportion, adding water, uniformly mixing, and performing ultrasonic enhancement in the mixing process to promote uniform distribution of each component to obtain an initial raw material a;
(2) Ball milling of raw materials: performing ball milling on the initial raw material a to obtain an initial raw material b with the particle size of less than or equal to 100 mu m;
(3) Electrostatic spraying: pretreating the suspension carrier as claimed in any one of claims 1 to 5 to enable the suspension carrier to have conductivity, coating the whole suspension carrier framework with the obtained initial raw material b in an electrostatic spraying manner, and forming an iron-carbon micro-electrolysis coating with the thickness of 3-5 mm on the surface of the suspension carrier;
(4) And (3) filler sintering: and (3) placing the formed filler into a tubular furnace, sintering at high temperature in an oxygen-free atmosphere, naturally cooling to room temperature, and soaking and cleaning for later use.
8. The production method according to claim 7,
in the step (1): in the process of preparing the initial raw material a, the mixture ratio of each component is as follows: 50-60 parts of sponge iron powder, 25-30 parts of graphene powder, 6-8 parts of a catalyst and 9-12 parts of a pore-forming agent;
in the step (3): the pretreatment comprises the following steps: firstly, spraying a layer of UV primer on the surface of a suspension carrier, drying, and then plating a metal layer on the surface in a vacuum sputtering mode;
in the step (4): during high-temperature sintering, the temperature of the tube furnace is gradually increased at a rate of 15 ℃/min, and the tube furnace is sintered for 4 to 5 hours at a temperature of between 700 and 950 ℃.
9. The production method according to claim 7, wherein the carrier is made of a cellulose nanofiber sheet; the whole density of the suspension carrier loaded with the iron-carbon micro-electrolysis layer is 0.96-0.98 g/cm 3 。
10. Use of the suspended iron-carbon micro-electrolysis filler according to claim 6 or the suspended iron-carbon micro-electrolysis filler prepared by the preparation method according to any one of claims 7 to 9 in wastewater purification.
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| CN116119780A (en) * | 2023-03-30 | 2023-05-16 | 广东广深环保科技股份有限公司 | Novel suspension micro-electrolysis filler and preparation method thereof |
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| CN115432781B (en) | 2023-11-14 |
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