CN115432781B - Suspension type iron-carbon micro-electrolysis filler and preparation method and application thereof - Google Patents
Suspension type iron-carbon micro-electrolysis filler and preparation method and application thereof Download PDFInfo
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- CN115432781B CN115432781B CN202211034997.3A CN202211034997A CN115432781B CN 115432781 B CN115432781 B CN 115432781B CN 202211034997 A CN202211034997 A CN 202211034997A CN 115432781 B CN115432781 B CN 115432781B
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- 239000000945 filler Substances 0.000 title claims abstract description 78
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 49
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000725 suspension Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000002351 wastewater Substances 0.000 claims description 23
- 230000005484 gravity Effects 0.000 claims description 22
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000007590 electrostatic spraying Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- 238000005245 sintering Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 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
- 244000005700 microbiome Species 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 239000002699 waste material Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 238000007792 addition Methods 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
- 230000031018 biological processes and functions Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental 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
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004544 sputter deposition Methods 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
- 238000002604 ultrasonography Methods 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C02F3/005—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
Abstract
The invention discloses a suspension type iron-carbon micro-electrolysis filler, a preparation method and application thereof, wherein the filler comprises a suspension carrier and an iron-carbon micro-electrolysis layer loaded on the surface of the suspension carrier; the iron-carbon micro-electrolysis layer is loaded on the suspension carrier in an electrostatic spraying mode. The suspension vehicle comprises: the upper half part is a cone formed by a plurality of sheet structures 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 and the lower half; the top cover is umbrella-shaped and is positioned at the top of the upper half part, and the top cover is connected with the connecting part through the reinforcing ribs. The filler combines the biomembrane method and the iron-carbon micro-electrolysis technology, not only solves the problems that the traditional suspended biomembrane filler has low film hanging efficiency, but also solves the problems that the iron-carbon micro-electrolysis filler is easy to harden and passivate, and the treatment effect is poor when being singly used.
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-protecting waste water pretreatment process with less resource consumption, mainly uses cheap waste iron scraps or processed zero-valent iron and carbon particles as raw materials, and adopts Fe/C material to make electrochemical reaction in reaction solution to form microscopic primary cell and produce Fe 2+ And Fe (Fe) 3+ The method removes pollutants by means of oxidation-reduction reaction, flocculation, adsorption and coprecipitation of the pollutants, so as to purify the wastewater, realize the aim of treating waste with waste, and is considered as a green and environment-friendly pretreatment technology. The technology is initially discovered by British scientists researching zero-valent iron theory in groundwater, and application research is carried out in water resource utilization and sewage purification.
At present, the iron-carbon micro-electrolysis technology is widely applied to the 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, when IC-ME is combined with a bioreactor, better performance and treatment effect are shown. Zhu et al did not achieve the ideal COD removal effect by pretreatment of ultra-high concentration organic wastewater using an IC-ME pilot scale system. 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 biological processes, which is compared to the performance of the IC-ME after binding to biological processes. IC-ME is also used for treating phenolic compounds in coal gasification, and under the synergistic effect of IC-ME, biological treatment of phenols is enhanced, and some functional microorganisms are enriched. The traditional iron-carbon micro-electrolysis filler has many defects in practical application, such as small specific surface area, low porosity, low micro-electrolysis reaction efficiency of materials, and most of adding modes are filler sinking, hardening and passivation phenomena can occur after a period of operation, and the treatment effect of the micro-electrolysis filler on wastewater is reduced.
The biofilm method is a common technology for treating wastewater by microorganisms, and mainly uses microbial films attached to the surfaces of filler carriers to remove pollutants. Compared with the traditional activated sludge method, the method has better organic matter removal efficiency and denitrification and dephosphorization capability, simple operation and management, low sludge yield and no sludge expansion, and therefore, the method has been widely applied to the treatment of domestic sewage and industrial wastewater in recent years. The performance of the filler is an important factor influencing the treatment effect of the biomembrane method as a microbial carrier, but most of the currently used suspended biomembrane fillers are regular-shaped ceramsite fillers or polyethylene fillers, on one hand, the specific surface area of the filler is small, so that the film forming efficiency is low, and on the other hand, polyethylene and other materials are difficult to degrade, so that white garbage is generated.
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 the biomembrane method and the iron-carbon micro-electrolysis technology, not only solves the problems that the traditional suspended biomembrane filler has low film hanging efficiency, but also solves the problems that the iron-carbon micro-electrolysis filler is easy to harden and passivate, the independent use treatment effect is poor, and the like, and the prepared iron-carbon micro-electrolysis filler has large specific surface area and high strength, provides larger current density for wastewater treatment, has good micro-electrolysis effect, runs stably for a long time, is not easy to passivate and harden, has higher microorganism film hanging efficiency, ensures excellent water quality, has the characteristic of environmental friendliness and does not cause environmental pollution.
A suspension carrier for supporting an iron-carbon micro-electrolysis filler, comprising:
the upper half part is a cone formed by a plurality of sheet structures 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 and the lower half;
the top cover is umbrella-shaped and is positioned at the top of the upper half part, and the top cover is connected with the connecting part through the reinforcing ribs.
The following provides several alternatives, but not as additional limitations to the above-described overall scheme, and only further additions or preferences, each of which may be individually combined for the above-described overall scheme, or may be combined among multiple alternatives, without technical or logical contradictions.
Optionally, the gravity center and the floating center of the suspension carrier are positioned on the same vertical line; the center of gravity of the suspension carrier is located in the lower half.
The lower part of the suspension carrier has larger 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 fig. 6. When the filler is put into water, the height of the center of stability gradually decreases in the process of submerging from the water surface to the water, the center of buoyancy coincides with the center of stability after completely submerging into water, and the initial height of stability is the distance between the center of buoyancy and the center of gravity. Because the whole gravity center of the filler is lower and the floating center is upper, when the filler is skewed in water, the buoyancy and gravity can form new restoring moment, and the filler is righted and cannot be turned over, as shown in fig. 7.
Alternatively, the entire suspension carrier is hollow in its entirety.
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; all the blades are gradually increased along the vertical distance between the axial outer edge and the outer surface of the rotating body from the bottom of the rotating body to the direction of the connecting part; all the blades deflect spirally 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 bottoms of the rotating bodies, of all the blades; facilitating the entry of water flow.
As a more specific shape selection of the lower half, the lower half is in the shape of an arcuate gear cone.
Optionally, the connecting part is a connecting plate in a leo triangle shape; 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 part of the connecting part through the reinforcing rib.
The upper half part of the suspension carrier is a cone formed by a sheet structure and an umbrella-shaped structure connected with the connector through the reinforcing ribs, so that the structural strength is enhanced, and the suspension carrier also plays a role in buffering 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 coupling body in the shape of a Lailo triangle; the lower half part is a structure which is approximately in the shape of a spiral bevel gear and consists of blades, and can be in a self-rotation state under the impact of waste water flowing horizontally, so that each surface can be uniformly contacted with sewage, and meanwhile, the phenomenon of hardening and passivation between fillers can be avoided.
The lower part of the filler is larger in 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 suspend in water and keep stable balance; when the filler is inclined in water, a new restoring moment can be formed by buoyancy and gravity, and the filler is righted and cannot be turned over.
The invention also provides a suspension type iron-carbon micro-electrolysis filler, which comprises the suspension carrier and an iron-carbon micro-electrolysis layer loaded on the surface of the suspension carrier.
The invention also provides a preparation method of the suspension type iron-carbon micro-electrolysis filler, which comprises the following steps:
(1) Mixing the raw materials: sieving sponge iron powder, graphene powder, a catalyst and a pore-forming agent respectively, taking according to a preset proportion, adding water, uniformly mixing, and carrying out ultrasonic reinforcement in the mixing process to promote uniform distribution of all components so as to obtain an initial raw material a;
(2) Ball milling of raw materials: ball milling is carried out on the initial raw material a to obtain an initial raw material b with the grain diameter less than or equal to 100 mu m;
(3) And (3) electrostatic spraying: pretreating the suspension carrier to enable the suspension carrier to have conductivity, coating the whole suspension carrier skeleton 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) sintering a filler: and (3) placing the formed filler in a tube furnace, sintering at high temperature in an anaerobic atmosphere, naturally cooling to room temperature, and then soaking and cleaning for later use.
The invention couples the iron-carbon micro-electrolysis technology with the biomembrane method, and the surface-coated iron-carbon micro-electrolysis layer is rough enough, has large porosity and large specific surface area, has better hydrophilicity and biocompatibility, and ensures that the microbial film forming efficiency is high.
In step (1):
optionally, 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 catalyst and 9-12 parts of 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, 12% of nickel powder, 8% of manganese powder, 8% of cobalt powder, 8% of lanthanum powder, 6 9% of lead oxide and 6 9% 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 100-110 mesh sieve, so that the granularity is small, the contact between the raw materials is facilitated to be sufficient, and the micro-electrolysis efficiency is improved.
Optionally, the enhanced ultrasound 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 (the mass ratio of medium balls to materials) is 1-7: 1, the rotating speed is 300-500 r/min.
In the step (3):
optionally, the preprocessing is: firstly, spraying a layer of UV primer on the surface of the central carrier, drying, and then plating a layer of metal layer on the surface in a vacuum sputtering mode.
Optionally, the metal layer is a metal aluminum layer.
Optionally, the electrostatic spraying process uses a nozzle with the diameter of 14-18mm, the electrostatic pressure is set to be 30-70KV, the flow rate pressure is 0.3-0.5Mpa, the powder flow 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 heating of the tube furnace is gradually increased during high-temperature sintering, the heating rate is 15 ℃/min, and sintering is carried out for 4-5 h at the temperature of 700-950 ℃.
Optionally, the suspension carrier is made of cellulose nanofibre board; the overall density of the suspended carrier loaded with the iron-carbon micro-electrolysis layer is 0.96-0.98 g/cm 3 . The biological film is equivalent to water density after being coated.
The invention also provides application of the suspension type iron-carbon micro-electrolysis filler in wastewater purification.
As an implementation mode of the application, the suspension type iron-carbon micro-electrolysis filler is added into a wastewater body to be treated, wherein the addition 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 spiral gear shape, and can be caused to be in a self-rotation state under the impact of horizontally flowing wastewater, so that each surface can be uniformly contacted with the wastewater, and hardening passivation phenomenon among fillers can be avoided; the opening of each sector of the lower half part is beneficial to the extrusion of wastewater into the filler, so that the contact area of the filler is effectively increased.
(2) The invention adopts the ultrasonic strengthening means in the raw material preparation process, can promote the uniform distribution of each component, and also improves the porosity of the material to a certain extent.
(3) The suspension carrier designed by the invention is prepared from the cellulose nanofiber plate serving as a raw material, the production cost of the cellulose nanofiber plate is lower than that of most plastics, and the cellulose nanofiber plate has low density, excellent strength, toughness and thermal dimensional stability, and all the characteristics exceed those of the traditional metal, ceramic and polymer, so that the cellulose nanofiber plate 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 be made into an environment-friendly material.
(4) According to the invention, 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 method for preparing the iron-carbon micro-electrolysis filler from active carbon and other materials, the method has better reaction efficiency and pollutant removal rate.
(5) The iron-carbon micro-electrolysis layer coated by the outer layer of the suspension type iron-carbon micro-electrolysis filler prepared by the invention has high porosity and rough surface under the strengthening effect of ultrasound and the existence of pore-forming agents, and has higher microbial film-forming efficiency compared with the traditional regular and smooth-surface biological filler.
(6) The whole density of the suspension type iron-carbon micro-electrolysis filler prepared by the invention is 0.96-0.98 g/cm 3 The device can be in a suspended state in wastewater instead of sinking, improves the utilization efficiency of the filler, and reduces the probability of hardening of the filler.
Drawings
Fig. 1 to 3 are schematic perspective views of different angles of a suspension carrier according to 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 a force analysis of a suspended carrier in water;
fig. 7 is a schematic representation of the stability of a suspended carrier in water.
Reference numerals shown in the drawings are as follows:
10. an upper half part 11, a sheet-like structure;
20. a connection part;
30. the lower half part 31, the rotating body 32, the blades 33, the central hole 34 and the water passing hole;
40. a top cover;
50. reinforcing ribs.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the 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 herein in the description of the invention 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 perspective views of the suspension carrier according to the present invention at different angles, and fig. 4 and 5 are top and bottom views of the suspension carrier according to the present invention, respectively.
As shown in fig. 1, the suspension vehicle includes an upper half 10, a connection part 20, a lower half 30, and a top cover 40, the upper half 10 and the lower half 30 are connected by the connection part 20, the top cover 40 is positioned on top of the upper half 10, and the top cover 40 is connected with the connection part 20 by a reinforcing rib 50. The lower half part of the suspension carrier has larger 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 lower, 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 center of stability gradually decreases in the process of submerging from the water surface to the water, the center of buoyancy coincides with the center of stability after completely submerging into water, and the initial height of stability is the distance between the center of buoyancy and the center of gravity. Because the whole gravity center of the filler is lower and the floating center is upper, when the filler is skewed in water, the buoyancy and gravity can form new restoring moment, and the filler is righted and cannot be turned over, as shown in fig. 7.
Referring to fig. 1 and 4, the upper half 10 is substantially cone-shaped 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-like structure 11 has a substantially right-angled triangular shape, standing on the top surface of the connecting portion at right angles thereof near the geometric center of the connecting portion 20, the triangular sheet-like structure comprising a hypotenuse and two right-angle sides, one of which is fixed to the top surface of the connecting portion, the angle between the hypotenuse and the top surface of the connecting portion being between 20 and 40 °, more preferably 30 °; the height of the vertebral body may be set to 25-35 mm, preferably 30mm.
Referring to fig. 1, 2 and 5, the lower half 30 includes a rotating body 31 and a plurality of blades 32 distributed on the surface of the rotating body 31. As a specific option for 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 be 40-50 mm, and more preferably 45mm; the vanes 32 extend axially and are circumferentially spaced apart on the hollow cylindrical surface; the vertical distance between the axial outer edges of all the blades 32 and the outer surface of the rotating body 31 increases gradually from the bottom of the rotating body 31 toward the connecting portion 20, the width of the bottom of the blade (the vertical distance of the outer edge from the outer surface of the cylinder) may be set to 10 to 20mm, the width of the top of the blade may be set to 35 to 45mm, more 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 the same angle in the same direction, and the helix angle is 15-30 degrees, so that the blades can be in a self-rotation state under the impact of waste water flowing horizontally, each surface can be uniformly contacted with the waste water, and meanwhile, hardening passivation phenomenon among fillers can be avoided. All the blades 32 are provided with water holes 34 near the bottom of the rotating body 31, which is beneficial for water flow entering. As a more specific shape selection for the lower half, the lower half is in the shape of an arcuate gear cone.
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 may be set to be about 15mm, and as a specific scheme of the connecting portion, as shown in fig. 1, 4 and 5, the connecting portion 20 is a connecting plate in a leo triangle shape; the upper sheet structure 11 is fixed on the top surface of the connecting plate, and the tops of the cylinders of the lower half and the tops of all the blades are fixed on the bottom surface of the connecting plate; the web has a through hole in its geometric center that is aligned with the central hole 33 of the hollow cylinder that forms the lower half.
As shown in fig. 1, the top cover 40 has an umbrella-shaped structure and is connected with the connecting portion 20 through the reinforcing ribs 50, and when the connecting portion 20 adopts a leo triangle shape, the top cover is connected with three corners of the connecting portion through the reinforcing ribs 50. Preferably, the umbrella-like structure has a coverage area which is 50% of the top area of the connection portion as projected onto the connection portion.
The suspended iron-carbon micro-electrolysis filler comprises the suspended carrier and the iron-carbon micro-electrolysis layer loaded on the surface of the suspended carrier, wherein the iron-carbon micro-electrolysis layer is loaded on the suspended carrier in an electrostatic spraying mode. The iron-carbon micro-electrolysis technology is combined with the biomembrane method to prepare the iron-carbon micro-electrolysis filler which can be used as suspended biological filler, the special structure of the iron-carbon micro-electrolysis filler enables the iron-carbon micro-electrolysis filler to be suspended in wastewater and keep autorotation under the impact of water flow, hardening and passivation of the filler are avoided, the specific surface area is large, the surface is rough, the porosity is high, the microbial film forming efficiency is improved, and the water quality of effluent is improved.
The following is a description of specific examples:
example 1:
the preparation method of the suspended iron-carbon micro-electrolysis filler comprises the following steps:
(1) Preparing a suspension carrier: preparing a cellulose nanofiber plate into a structure shown in figures 1-5 by mechanical cutting, wherein the structure is used as a center carrier of suspended iron-carbon micro-electrolysis;
(2) Mixing the 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 carrying out ultrasonic strengthening by using ultrasonic waves with the frequency of 80kHz in the mixing process to promote uniform distribution of all components 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 drum ball mill, the ball milling time was set to 90min at a ball milling frequency of 270Hz, and the ball-to-material ratio (mass ratio of medium balls to material) was 6: 1. ball milling is carried out on the initial raw material a under the condition of the rotating speed of 450r/min to obtain an initial raw material b with the particle size of 100 mu m;
(4) And (3) electrostatic spraying: spraying a layer of UV primer on the surface of the central carrier, drying, then plating a layer of metal Al layer on the surface by using a vacuum sputtering mode to enable the surface to have conductivity, coating the whole carrier skeleton with the obtained initial raw material b by using an electrostatic spraying mode, and forming an iron-carbon micro-electrolysis layer with the thickness of 5mm on the surface of the carrier. Wherein, a nozzle with the diameter of 15mm is used for electrostatic spraying, the electrostatic pressure is set to be 70KV, the flow velocity pressure is set to be 0.5Mpa, the powder flow is set to be 160g/min, and the distance between the nozzle and the central carrier is controlled to be 250mm;
(5) And (3) sintering a filler: and (3) placing the formed filler in a tube furnace, gradually heating and sintering in an anaerobic atmosphere, wherein the heating rate is 15 ℃/min, sintering for 5 hours at 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 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, COD of the inlet water is 200mg/L, ammonia nitrogen is 30mg/L, the removal rate of the filler and the ammonia nitrogen in the bioreactor combined with the filler reaches more than 90 percent in 90 minutes, the outlet water can reach the first grade A standard of pollutant emission standard of urban sewage treatment plant, and microorganisms can be producedThe efficiency of film formation on the surface of the filler is high, inoculated sludge can be effectively intercepted, and the amount of discharged water sludge is reduced.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (3)
1. A suspended iron-carbon micro-electrolysis filler is characterized by comprising a suspended carrier and an iron-carbon micro-electrolysis layer loaded on the surface of the suspended carrier, wherein the suspended carrier is made of cellulose nanofiber plates, and the overall density of the suspended carrier loaded with the iron-carbon micro-electrolysis layer is 0.96-0.98 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The suspension carrier comprises:
the upper half part is a cone formed by a plurality of sheet structures 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 and the lower half;
the top cover is in 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 gravity center and the floating center of the suspension carrier are positioned on the same vertical line; the gravity center of the suspension carrier is positioned at the lower half part;
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 edges of all the blades along the axial direction and the outer surface of the rotating body gradually increases from the bottom of the rotating body to the direction of the connecting part; all the blades deflect spirally in the same direction and at the same angle;
all blades are provided with water holes near the bottom of the rotating body, so that wastewater can enter the blades through the water holes.
2. The suspended iron-carbon micro-electrolysis filler according to claim 1, wherein the connecting portion is a connecting plate in the shape of a leo 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 part of the connecting part through the reinforcing rib.
3. Use of the suspended iron-carbon micro-electrolysis filler according to claim 1 or 2 in wastewater purification.
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