CN113683186B - Iron-carbon fiber coupling filler and application thereof in sewage treatment - Google Patents

Iron-carbon fiber coupling filler and application thereof in sewage treatment Download PDF

Info

Publication number
CN113683186B
CN113683186B CN202111010015.2A CN202111010015A CN113683186B CN 113683186 B CN113683186 B CN 113683186B CN 202111010015 A CN202111010015 A CN 202111010015A CN 113683186 B CN113683186 B CN 113683186B
Authority
CN
China
Prior art keywords
iron
filler
carbon fiber
semicircular
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111010015.2A
Other languages
Chinese (zh)
Other versions
CN113683186A (en
Inventor
周佳恒
徐晓蕾
王涛
潘晨驰
富敏华
郭文福
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202111010015.2A priority Critical patent/CN113683186B/en
Publication of CN113683186A publication Critical patent/CN113683186A/en
Application granted granted Critical
Publication of CN113683186B publication Critical patent/CN113683186B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C02F3/005—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
    • 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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes 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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
    • 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
    • C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/15—N03-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/16—Total nitrogen (tkN-N)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/22—O2
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/38—Gas flow rate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/44—Time
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of 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

Abstract

The invention discloses an iron-carbon fiber coupling filler and application thereof in sewage treatment, wherein the iron-carbon fiber coupling filler consists of a filler shell, a surface filler and a core; the filler shell is a hollow cylinder which is fixed in a matched manner through a buckle roller; the surface layer filler is attached to the inner surface of the column body to form a cavity, and the iron-carbon composite is filled in the cavity to form an inner core; the surface layer filler is made of carbon fiber material; the iron-carbon composite is formed by mixing agar powder, an emulsifying agent, starch and iron powder with boiling water, stirring and solidifying. The invention prepares the iron-carbon fiber coupling filler for enhancing the denitrification, effectively enhances the nitrification denitrification effect, reduces the inhibition effect of the solid carbon source on autotrophic microorganisms, accelerates and enhances the attachment and fixation of the microorganisms, has simple and convenient implementation operation, high pollutant removal efficiency, low residual sludge yield and reduces the sludge treatment cost.

Description

Iron-carbon fiber coupling filler and application thereof in sewage treatment
Field of the art
The invention belongs to the technical field of sewage treatment, and relates to an iron-carbon fiber coupling filler with enhanced denitrification performance and application thereof in sewage treatment.
(II) background art
The carbon source is one of important influencing factors in the biological denitrification process, and can provide an electron donor in the removal process of the biological nitrate to gradually convert the nitrate nitrogen into nitrogen so as to realize denitrification, but in the denitrification process, the phenomenon of insufficient carbon source generally exists, and the additional carbon source is required to be added to improve the denitrification efficiency. Many studies have proposed the addition of solid carbon sources to promote denitrification and thereby increase denitrification efficiency. For example, the aged landfill leachate contains a large amount of ammonia nitrogen and has low carbon nitrogen ratio, and a carbon source is usually required to be supplemented in the denitrification process.
In sewage treatment, autotrophic aerobic microorganisms (i.e., nitrifying bacteria) oxidize ammonia nitrogen to nitrate. Nitrifying bacteria can be classified into Ammonia Oxidizing Bacteria (AOB) and Nitrite Oxidizing Bacteria (NOB) according to the substrate. The nitration reaction involves two basic reaction steps: the first stage is NH by AOB 4 + Conversion of N to NO 2 - N, i.e. nitrosation; in the second stage, NOB converts NO 2 - -N is further oxidized to NO 3 - N, known as nitration. Nitrifying bacteria utilizing CO 2 、CO 3 2- 、HCO 3 - And an inorganic carbon component as a carbon source. Therefore, the added organic carbon source can inhibit autotrophic bacteria such as AOB and NOB.
The common biological fillers in the market at present are mainly made of traditional polypropylene, polyethylene, polyvinyl chloride or polyester and other materials, and in practical application, the fillers are found to have defects in film forming speed, film forming amount and film forming compactness between films and fillers. The invention adopts carbon fiber as surface filler, and has the advantages of high porosity, high adsorption capacity, easy film formation and the like compared with other fillers and films used in a contact oxidation pond. In addition, the surface of the carbon fiber is provided with hydrophilic oxygen-containing functional groups, such as carboxyl, carbonyl and the like, so that the hydrophilicity of the surface of the carrier is improved, the interaction with an aqueous solution is increased, the growth of microorganisms is promoted, the film forming rate is accelerated, and the wastewater treatment efficiency is improved.
In recent years, zero-valent iron has been widely used to degrade and remove organic and inorganic pollutants in the environment. The invention adopts zero-valent iron as one of the main components of the inner core, and has the advantages of low price, rich sources, convenient transportation, active chemical property, certain specific surface area and strong reducing capability. Is easily oxidized into ferrous iron and ferric iron, and continuously forms iron hydroxide and polymer under a certain pH value, so as to perform coagulation adsorption on pollutants to achieve the removal effect.
The catalytic enzymes involved in the nitration process are Ammonia Monooxidase (AMO) and hydroxylamine oxidase (HAO). And the coupling of the iron and carbon fibers can improve the activity of AMO and HAO. Can make up for the inhibition effect of the external solid organic carbon source on Ammonia Oxidizing Bacteria (AOB) and nitrous acid oxidizing bacteria (NOB). Moreover, the carbon fiber is used as biological filler, and has the advantages of high microorganism growth speed, large film forming amount, high wastewater treatment efficiency and the like. In addition, the zero-valent iron is subjected to chemical denitrification, so that the denitrification of the sewage treatment system is further promoted and the denitrification effect is further enhanced under the condition of externally adding a carbon source.
(III) summary of the invention
In order to solve the problem of nitrification inhibition caused by externally added organic carbon sources, the invention provides a novel sewage treatment carrier, namely the iron-carbon fiber coupling filler and application thereof in wastewater treatment.
The technical scheme adopted by the invention is as follows:
the invention provides an iron-carbon fiber coupling filler, which consists of a filler shell, a surface filler and an inner core; the filler shell is a hollow cylinder which is fixed in a matched manner through a buckle roller; the surface layer filler is attached to the inner surface of the column body to form a cavity, and the iron-carbon composite is filled in the cavity to form an inner core;
the surface layer filler is made of carbon fiber material; the iron-carbon composite is formed by mixing agar powder, an emulsifying agent, starch and iron powder with boiling water, stirring and solidifying.
Further, the carbon fiber material is a fibrous carbon material having a carbon content of more than 90%, a very high strength and elastic modulus (rigidity), and a density of 1.70 to 1.809 g.cm -3 The strength is 1200-7000 MPa, the elastic modulus is 200-400 GPa, and the thermal expansion coefficient is close to zero. More preferably T700 carbon fiber material with carbon content of 95% and density of 1.78g cm -3 The strength is 4960MPa, the elastic modulus is 245GPa, and the thermal expansion coefficient is close to zero.
Further, the iron-carbon composite mass composition: 8-9% of agar powder, 20-27% of starch, 4-5% of emulsifying agent, 3-4% of iron powder and the balance of water, wherein the total amount is 100%; the grain diameter of the iron powder is 30-50 mu m, and the purity is 99.95%; the starch isCommon starch, preferably cationic starch or acetate starch; the emulsifier is polyoxyethylene sorbitan monolaurate. The gel strength of the agar powder is 1000-1200g cm -2 Ash is less than or equal to 1.5%; the purity of the soluble starch is AR; the iron powder is high-purity zero-valent iron powder (commercial specification is 500g of high-purity superfine iron powder, and purity is 99.95%).
Further, it is preferable that the iron-carbon composite mass composition: 8% of agar powder, 24% of starch, 4% of emulsifying agent, 3% of iron powder and the balance of water, wherein the total amount is 100%.
The preparation method of the iron-carbon composite comprises the following steps: sequentially adding emulsifier, agar powder, starch and iron powder into a container, stirring, mixing, adding boiled pure water, and stirring for 50 rpm -1 Stirring for 30min, mixing with water, cooling at room temperature for solidification, and refrigerating at-4deg.C for 12 hr to obtain iron-carbon composite.
Further, the packing shell is a hollow cylinder formed by mutually matching and fixing two parts through a buckle and a roller, and preferably, the packing shell is a hollow cylinder formed by mutually matching and fixing two semi-cylinders through a buckle and a roller; each semi-cylinder consists of three semicircular rings 2, two semicircular bottoms 3 and three ribs 4, wherein the three semicircular rings are respectively fixed at two ends and the middle position of the two ribs, the semicircular bottoms are arranged between the two semicircular rings at the two ends and the ribs, the semicircular bottoms and the semicircular rings form a sealed plane bottom, and the outer side surfaces of the two semicircular bottoms are respectively provided with a hanging ring 5; two buckles 6 are arranged at two ends of one rib of the fixed semicircular ring, a third rib is vertically fixed on the other rib of the fixed semicircular ring, two rollers 7 which are mutually matched and spliced with the buckles 6 are arranged on the 3 rd rib, and the buckles 6 and the rollers 7 are respectively fixed at the upper end and the lower end of the rib through screws 8.
The width of the surface layer filler is matched with the arc length of the semicircular ring of the filler shell to cover the inner surface of the semi-cylinder, and the length of the surface layer filler is larger than the sum of the diameter of the semicircular bottom and the length of the rib; the surface layer filler is attached to the inner surface of the semi-cylinder of the filler shell and extends out of two ends of the filler shell to form a cavity; the chamber is filled with iron-carbon composite to form an inner core.
The filler shell is made of polyvinyl chloride Plastic (PVC); the rib is 1-10cm wide, 0.1-1.5cm thick and 10-40cm high, and the two ends of the rib are respectively provided with a buckle 6 and a roller 7 1-6cm away; the width of the semicircular rings is 1-5cm, the thickness is 0.1-1.5cm, and the radius is 1-20cm. The screw is a polyvinylidene fluoride (PVDF) plastic screw. The surface layer filler has a length of 16-84 cm, a width of 3-63 cm and a thickness of 0.2-0.5 cm.
Preferably, the filler shell is made of polyvinyl chloride Plastic (PVC); the width of the ribs is 2cm, the wall thickness is 0.2cm, the height is 16cm, and the buckles 6 and the rollers 7 are respectively arranged 2cm away from the two ends of the ribs; the width of the semicircular rings is 2cm, the thickness of the semicircular rings is 0.2cm, and the radius of the semicircular rings is 4cm. The screw is a polyvinylidene fluoride (PVDF) plastic screw. The hanging ring is rectangular, is made of polyvinyl chloride (PVC), and has a length of 1.1cm, a width of 0.8cm and a height of 0.8cm.
The invention also provides application of the iron-carbon fiber coupling filler in wastewater treatment, wherein the application is as follows: adopting a fixed bed biomembrane reactor (preferably a novel tail gas backflow type biomembrane reactor, refer to patent application 201910975827.7), fixing hanging rings of the iron-carbon fiber coupling fillers into groups through nylon ties, fixing each group of iron-carbon fiber coupling fillers into the reactor, inoculating sludge, introducing wastewater, and controlling the hydraulic retention time to be 8 hours and the aeration intensity to be 4.0+/-0.2 L.min -1 Realizing the degradation of sewage.
COD concentration of the wastewater inflow water is 180mg.L -1 Ammonia nitrogen concentration 47.37 mg.L -1 The carbon-nitrogen ratio is 3.8, and the water inlet speed is 4.374cm 3 ·s -1 . The sludge inoculation amount is 2000 mg.L calculated by mixed liquor suspended solid particles (MLSS) -1 。
Compared with the prior art, the invention has the following main beneficial effects: the invention prepares the iron-carbon fiber coupling filler for enhancing denitrification, wherein agar wrapping and a hydrophobic emulsifier are adopted, so that the carbon release effect is stable, and the denitrification effect can be effectively enhanced. The coupling of iron and carbon fibers can improve the activity of autotrophic microorganisms (AOB and NOB), effectively strengthen the nitrification and denitrification effect and reduce the inhibition of solid carbon sources on the autotrophic microorganisms; the coupling of iron and carbon fibers can increase the surface area of the filler and the hydrophilicity of the surface of the carrier, and promote the interaction between the carbon fibers and the aqueous solution. Accelerating and enhancing the attachment and immobilization of microorganisms. The invention has simple operation, high concentration microbe content, high capacity load of the treating device, small occupied area, high pollutant eliminating efficiency, low residual sludge yield and low sludge treating cost.
(IV) description of the drawings
Fig. 1 is a schematic view of a packing casing, in which 1 packing casing, 2 semicircular rings, 3 semicircular bottom surfaces, 4 ribs, 5 hanging rings, 6 buckles, 7 rollers, 8 screws.
Fig. 2 is a partial schematic view of the clasp (b) and roller (a) of the packing casing.
Fig. 3 is a schematic plan view of the clasp (b) and roller (a) of the packing casing.
Fig. 4 is a side view of the snap rollers of the packing casing, in which the snap rollers are matched, spliced and fixed, and in the figure, the snap rollers with ribs 4 and the snap rollers with ribs 6 and the snap rollers with ribs 7.
Fig. 5 is an assembly schematic diagram of the iron-carbon fiber coupling filler, 9 surface layer filler, 10 inner core.
Fig. 6 is a schematic diagram of the iron-carbon fiber coupled filler after being spliced and fixed.
Fig. 7 is a series detail view of the packing casing, in which 5 rings, 11 nylon ties are shown.
Fig. 8 is a diagram of the iron-carbon fiber coupled filler lifting ring azimuth, in which l1=1.3 cm, l2=0.8 cm, l3=1.8 cm, l4=0.8 cm, l5=1.1 cm;
fig. 9 is a schematic diagram of a series combination of iron carbon fiber coupled fillers.
FIG. 10 is a side view of a biofilm reactor, illustrating 304 a stainless steel rack 12.
(fifth) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
example 1, iron carbon fiber coupling Filler
Referring to fig. 1 to 10, the iron-carbon fiber coupling filler consists of a filler shell 1, a surface layer filler 9 and an inner core 10; the packing shell is a hollow cylinder formed by mutually matching and fixing two semi-cylinders through a buckle 6 and a roller 7; each semi-cylinder consists of three semicircular rings 2, two semicircular bottoms 3 and three ribs 4, wherein the three semicircular rings are respectively fixed at two ends and the middle position of the two ribs, the semicircular bottoms are arranged between the two semicircular rings at the two ends and the ribs, the semicircular bottoms and the semicircular rings form a sealed plane bottom, and the outer side surfaces of the two semicircular bottoms at the two ends are respectively provided with a hanging ring 5; two buckles 6 are arranged at two ends of one rib of the fixed semicircular ring, a third rib is vertically fixed on the other rib of the fixed semicircular ring, two rollers 7 which are mutually matched and spliced with the buckles 6 are arranged on the 3 rd rib, and the buckles 6 and the rollers 7 are respectively fixed at the upper end and the lower end of the rib through screws 8.
The surface layer filler is made of carbon fiber material, the width of the carbon fiber material is matched with the arc length of the semicircular ring of the filler shell to cover the inner surface of the semicircular cylinder, and the length of the surface layer filler is larger than the sum of the diameters of the two semicircular bottoms and the length of the rib; the surface layer filler is attached to the inner surface of the semi-cylinder of the filler shell and extends out of two ends of the filler shell to form a cavity; the chamber is filled with iron-carbon composite to form an inner core.
The filler shell is made of polyvinyl chloride Plastic (PVC); the rib is 2cm wide, 0.2cm thick and 16cm high, and the buckles 6 and the rollers 7 are respectively arranged 2cm away from the two ends of the rib; the width of the semicircular rings is 2cm, the thickness of the semicircular rings is 0.2cm, and the radius of the semicircular rings is 4cm. The screw is a polyvinylidene fluoride (PVDF) plastic screw. The hanging ring is rectangular, is made of polyvinyl chloride (PVC), and has a length of 1.1cm, a width of 0.8cm and a height of 0.8cm.
Preparation of the iron-carbon composite: sequentially adding 0.5kg of emulsifying agent, 1kg of agar powder, 3kg of soluble starch and 0.375kg of iron powder into a container, stirring, mixing, adding 7.625L of boiled pure water, and stirring at 50 rpm -1 Stirring for 30min, mixing with water, cooling at room temperature for solidification, and refrigerating at-4deg.C for 12 hr to obtain iron-carbon composite.
The gel strength of the agar powder is1000-1200g·cm -2 Ash less than or equal to 1.5%, purchased from Hangzhou Pont chemical industry Co., ltd., CAS:9002-18-0, product number A800728-1kg; soluble starch was purchased from Hangzhou Poncirus chemical Co., ltd, purity AR, CAS:9005-84-9, number S817547-500g; the emulsifier was polyoxyethylene sorbitan monolaurate with a purity of 99.9%, purchased from national pharmaceutical chemicals, inc., CAS:9005-64-5, commodity specification 500g; the iron powder was high purity iron powder, 99.95% purity, purchased from archer: 500g of Lijia metal material and commodity specification.
The carbon fiber material is a T700 carbon fiber material, and is purchased from Yixing City Ci Yi Ji carbon fiber products Co., ltd., and has a carbon content of 95% and a density of 1.78g cm -3 The strength is 4960MPa, the elastic modulus is 245GPa, and the thermal expansion coefficient is close to zero.
Example 2 treatment of wastewater with iron carbon fiber coupled fillers
1. Reactor arrangement
The reactor is a fixed bed biomembrane reactor (namely a novel tail gas backflow type biomembrane reactor, refer to patent application 201910975827.7), the main body is made of organic glass materials, and the dimensions, length, width and height are respectively 80cm, 40cm and 50cm, and the effective volume is 144L.
Denitrification experiment sets up 4 groups of reactors: r1 and R3 are added blank filler; r2 and R4 are iron-carbon fiber coupling filler prepared by the method of the adding example 1, and the operation parameters are the same. The hollow white filler R1 and R3 is prepared by removing iron powder in the iron-carbon composite in the example 1, and other structures and preparation methods are the same as in the example 1.
The R2 reactor filler adding method comprises the following steps: the slings 5 of the iron-carbon fiber coupling filler prepared in each 2 examples 1 are connected in series into a group by using a nylon ribbon 11, 42 groups are fixed on a 304 stainless steel frame 12, then the stainless steel frame 12 is fixed on a reactor top cover and hung in a reactor, the filler is immersed in water during the reaction, and the total volume of the filler is 67522.6cm 3 The filling rate was 46.89%. The nylon ribbon is a self-locking nylon ribbon, and is 200mm long and 3mm wide, and is made of PA66 nylon material. The R1, R3 and R4 fillers are serially fixed by adopting the same method.
2. Sludge inoculation and reactor operation
Taking sludge of oxidation ditch aeration tank of Hangzhou sewage treatment plant, acclimating, and then respectively inoculating into two reactors (R1 and R2) to make MLSS value of each reactor be 2000 mg.L -1 . At 4.374cm 3 ·s -1 Is introduced into the reactor from the water inlet of the reactor to simulate the organic wastewater (table 1), and the COD concentration of the inflow water is 180 mg.L -1 Ammonia nitrogen concentration 47.37 mg.L -1 The carbon-nitrogen ratio is 3.8, the HRT is 8h, and the aeration intensity is 4.0+/-0.2 L.min -1 . The experiment was run for 80 days.
R3 and R4 were not inoculated with sludge and the other experiments were performed identically.
Table 1 artificially simulating organic wastewater composition (Water as solvent)
Figure BDA0003238576670000061
3. Reactor operating parameter detection
Sampling from the water outlet every 2 days, measuring pH, chemical Oxygen Demand (COD), ammonia Nitrogen (NH) 4 + -N), nitrite nitrogen (NO 2 - -N), nitrate nitrogen (NO 3 - -N), total Nitrogen (TN). The biofilm was taken from the packing every 5 days to determine the amount of sludge. The total iron content was detected by sampling from the water outlet every 5 days. The remaining carbon content was measured by sampling from the filler every 5 days. Ammonia Monooxygenase (AMO) and hydroxylamine oxidase (HAO) were sampled from the fillers every 10 days, and the effect of each filler on the denitrification performance of the reactor was examined.
COD was measured using potassium dichromate, NH 4 + N is determined photometrically by Naviet reagent, NO 3 - -N is determined by UV spectrophotometry, NO 2 - N is measured by adopting an N- (1-naphthyl) -ethylenediamine photometry, total nitrogen is measured by adopting an alkaline potassium persulfate digestion ultraviolet spectrophotometry, and carbon content is measured by adopting an anthrone colorimetry; the sludge amount is measured by a gravimetric method. Enzyme kit (purchased from Nanjsen Bei Ga Biotechnology Co., ltd.) for AMO activity and enzyme kit (purchased from Nanjsen Bei Ga Biotechnology Co., ltd.) for HAO activityDriver) for detection.
(1) COD and ammonia nitrogen removal rate
Because the slow-release carbon source is arranged in the filler, the COD of the effluent at the initial starting stage of the two groups of R1 and R2 reactors is higher. After the R1 reactor runs for 7 days, the COD of the effluent reaches stability, and the COD removal rate is 88.58%. After the R2 reactor runs for 9 days, the COD of the effluent reaches stability, and the COD removal rate is 98.10%.
And within 7 days of starting, the ammonia nitrogen removal rate of the two groups of R1 and R2 is lower, and when the residual carbon source in the filler is less, the ammonia nitrogen removal rate of the two groups of R1 and R2 starts to rise. After the R1 reactor runs for 15 days, the ammonia nitrogen in the effluent reaches stability, and the ammonia nitrogen removal rate is 78.66%. After the R2 reactor runs for 9 days, the ammonia nitrogen in the effluent reaches stability, and the ammonia nitrogen removal rate is 87.65%. When the COD and ammonia nitrogen concentration of the effluent reach stability, the film formation of the filler is successful, and the film formation of R1 and R2 respectively passes through 15 days and 9 days, so that the film formation speed of the iron-carbon fiber filler is high.
As the filler slow-release carbon source is more in the initial operation period (the first 14 days), the R1 reactor has obvious ammonia nitrogen accumulation phenomenon, and the concentration range of the ammonia nitrogen in the effluent is 45.82 +/-0.24-10.11+/-0.75 mg.L -1 L, the inhibition of the nitration process by the carbon source. While the R2 reactor was operated for 10 days, NH 4 + The H concentration can be reduced to 5.82+/-0.25 mg.L -1 The coupling of iron and carbon fiber can improve the activity of autotrophic microorganisms (AOB and NOB), effectively strengthen the nitrification and denitrification effect and reduce the inhibition of solid carbon sources on the autotrophic microorganisms. In addition, the total nitrogen removal rate of the R1 reactor is below 68.75%, and the total nitrogen removal rate of the R2 reactor is above 80%. The method shows that the synchronous nitrification and denitrification effect in the R2 reactor is good, and the total nitrogen removal capacity is high.
(2) Sludge and biomass on filler
Measuring the sludge amount on a single filler, wherein the average increase speed of the sludge amount on the R1 and R2 fillers is 87.97 mgVSS.g within 20 days before experimental operation -1 ·d -1 And 103.82 mgVSS.g -1 ·d -1 The film forming speed of the R2 filler is higher. After the reactor is stable, biomass on a single filler is measured, R1 and R2 are 215.11 +/-10.75 mgVSS.g respectively -1 、345.37±18.46mgVSS·g -1 The individual filler biomass of R2 is significantly higher than R1, indicating that the iron carbon fiber coupled filler can promote adsorption and growth of microorganisms on the filler.
(3) Residual content of carbon source
The carbon source content of the fillers in R1, R2, R3 and R4 was measured on a colorimetric method using anthrone, and the average initial carbon content of each filler was 48.087g, 48.656g, 48.189g and 48.487g. The carbon source content in the filling materials of the R1, R2, R3 and R4 reactors is slowly reduced along with time, but the slow release carbon source of the R2 reactor is faster, the carbon source is exhausted in the R1 at the 51 th day, the carbon source is exhausted in the R2 at the 34 th day, the carbon source is exhausted in the R3 at the 75 th day, and the carbon source is exhausted in the R4 at the 57 th day. The effluent COD detection shows that the effluent COD of the R1 and R2 reactors is always lower than 50mg.L -1 The slow-release carbon source filler is shown to not adversely affect the quality of the effluent.
The difference between the initial carbon content and the residual carbon content of the filler of R1, R3, R2 and R4 is calculated to obtain the carbon source amounts which can be utilized by microorganisms in the biomembrane on the single R1 filler and the single R2 filler of 28.260g and 35.649g respectively, and the consumption rates of the carbon sources of the microorganisms are 2.577 mg.mgVSS respectively -1 ·d -1 And 3.039 mg.mgVSS -1 ·d -1 Accounting for 58.77 percent and 74.13 percent of the carbon source.
(4) Total iron in effluent
The experiment is carried out by sampling from the R2 reactor at regular intervals, and the total iron in the effluent of the R2 reactor is measured by adopting a phenanthroline spectrophotometry method so as to analyze the slow-release iron effect, and the result shows that the total iron concentration in the effluent of the R2 reactor is wholly in a descending trend. The average value of the initial iron content of each filler of the R2 reactor is 6.124g, and the total iron concentration of effluent water of the first day of running the reactor is 10.335 mg.L -1 After 10 days of operation, the total iron concentration of the effluent is 4.307 mg.L -1 After 30 days of operation, the total iron concentration of the effluent is 2.645 mg.L -1 The total iron concentration of the effluent in day 45R 2 is close to the total iron concentration of the inlet water: 0.238 mg.L -1 Indicating exhaustion of the R2 iron powder. The method shows that the iron-carbon fiber coupling filler has long iron release time and stable iron release effect.
(5) Ammonia Monooxygenase (AMO) and hydroxylamine oxidase (HAO)
In general, the removal of contaminants is highly dependent on microbial activity. Thus, experiments were carried out while periodically measuring the key enzyme activity of microorganisms to remove contaminants. Ammonia Monooxygenase (AMO) and hydroxylamine oxidase (HAO) are NH 4 + The key enzymes in the oxidative nitration of N, in the R1 reactor, AMO and HAO contents on day 10 were 64.932. Mu. Mol. Min, respectively -1 ·g -1 And 132.514. Mu. Mol.min -1 ·g -1 On day 30, the temperature was decreased to 19.959. Mu. Mol.min -1 ·g -1 And 102.284. Mu. Mol.min -1 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the In the R2 reactor, the contents of AMO and HAO on day 10 were 70.748. Mu. Mol.min, respectively -1 ·g -1 And 140.887. Mu. Mol.min -1 ·g -1 Respectively rise to 80.431 mu mol min on day 30 -1 ·g -1 And 163.807. Mu. Mol.min -1 ·g -1 . With the carbon source released, only 7% of the carbon source remained for the R1 reactor single packing after 40 days of start-up, and AMO and HAO began to rise. On day 50, AMO and HAO in R1 increased to 43.788. Mu. Mol.min, respectively -1 ·g -1 And 131.787. Mu. Mol.min -1 ·g -1 . After 40 days of operation of the R2 reactor, the relative activities of AMO and HAO in the R2 reactor were reduced due to the lower balance of iron release, but were always significantly higher than in the R1 reactor. Obviously, the change trend of the key enzyme activity and NH in the R1-R2 reactor 4 + The removal of N results in good agreement. Indicating that the iron-carbon fiber coupling filler has higher NH 4 + -N removal capability.

Claims (9)

1. The iron-carbon fiber coupling filler for reinforced denitrification is characterized by comprising a filler shell, a surface filler and an inner core; the filler shell is a hollow cylinder which is fixed in a matched manner through a buckle roller; the surface filler is attached to the inner surface of the column body to form a cavity, and the cavity is filled with iron-carbon composite to form an inner core;
the surface layer filler is made of carbon fiber material; the iron-carbon compound is formed by mixing agar powder, an emulsifying agent, starch and iron powder with boiling water, stirring and solidifying;
the iron-carbon composite material comprises the following components in parts by weight: 8-9% of agar powder, 20-27% of starch, 4-5% of emulsifying agent, 3-4% of iron powder and the balance of water, wherein the total amount is 100%; the emulsifier is polyoxyethylene sorbitan monolaurate.
2. The iron carbon fiber coupling filler for enhanced denitrification as claimed in claim 1, wherein the carbon fiber material is T700 carbon fiber material.
3. The iron-carbon fiber coupling filler for enhanced denitrification as claimed in claim 1, wherein the iron-carbon composite is prepared by the following steps: sequentially adding the emulsifier, the agar powder, the starch and the iron powder into a container according to the formula amount, stirring and mixing uniformly, adding boiled pure water, stirring for 30min at 50 r/min < -1 >, fully mixing with water, cooling and solidifying at room temperature, and refrigerating at-4 ℃ for 12h to obtain the iron-carbon composite.
4. The iron-carbon fiber coupling filler for enhancing denitrification as claimed in claim 1, wherein the filler housing is a hollow cylinder formed by mutually fixing two semi-cylinders through a buckle and a roller; each semi-cylinder consists of three semicircular rings, two semicircular bottoms and three ribs, wherein the three semicircular rings are respectively fixed at two ends and the middle position of the two ribs, the semicircular bottoms are arranged between the two semicircular rings at the two ends and the ribs, the semicircular bottoms and the semicircular rings form a sealed plane bottom, and the outer side surfaces of the two semicircular bottoms are respectively provided with a hanging ring; two buckles are arranged at two ends of one rib of the fixed semicircular ring, a third rib is vertically fixed on the other rib of the fixed semicircular ring, two rollers which are mutually matched and spliced with the buckles are arranged on the third rib, and the buckles and the rollers are respectively fixed at the upper end and the lower end of the rib through screws.
5. The iron-carbon fiber coupling filler for enhanced denitrification as claimed in claim 4, wherein the width of the surface filler is matched with the arc length of the semicircular ring of the filler shell to cover the inner surface of the semicircular cylinder, and the length is greater than the sum of the diameter of the semicircular bottom and the length of the rib; the surface layer filler is attached to the inner surface of the semi-cylinder of the filler shell and extends out of two ends of the filler shell to form a cavity; the chamber is filled with iron-carbon composite to form an inner core.
6. The iron-carbon fiber coupling packing for enhanced denitrification as set forth in claim 5, wherein the buckle and the roller are respectively provided 1-6cm apart from both ends of the rib.
7. The iron-carbon fiber coupling filler for reinforced denitrification as claimed in claim 6, wherein said filler shell material is polyvinyl chloride plastic; the width of the rib is 1-10cm, the wall thickness is 0.1-1.5cm, the height is 10-40cm, and the two ends of the rib are respectively provided with a buckle and a roller 1-6cm away from each other; the width of the semicircular rings is 1-5cm, the thickness of the semicircular rings is 0.1-1.5cm, and the radius of the semicircular rings is 1-20cm.
8. Use of the iron-carbon fiber coupling filler for enhanced denitrification according to claim 1 for treating wastewater.
9. The application of claim 8, wherein the application is: adopting a fixed bed biomembrane reactor, fixing the hanging rings of the iron-carbon fiber coupling fillers into groups through nylon ties, fixing each group of iron-carbon fiber coupling fillers into the reactor, inoculating sludge, introducing wastewater, and controlling the hydraulic retention time to be 8 hours and the aeration intensity to be 4.0+/-0. L.min -1 Degradation of sewage is realized; the COD concentration of the wastewater inlet is 180 mg.L-1, the ammonia nitrogen concentration is 47.37 mg.L-1, the carbon nitrogen ratio is 3.8, and the water inlet speed is 4.374cm 3 ·s -1 The method comprises the steps of carrying out a first treatment on the surface of the The sludge inoculation amount is 2000 mg.L based on the mixed solution suspended solid particles -1 。
CN202111010015.2A 2021-08-31 2021-08-31 Iron-carbon fiber coupling filler and application thereof in sewage treatment Active CN113683186B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111010015.2A CN113683186B (en) 2021-08-31 2021-08-31 Iron-carbon fiber coupling filler and application thereof in sewage treatment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111010015.2A CN113683186B (en) 2021-08-31 2021-08-31 Iron-carbon fiber coupling filler and application thereof in sewage treatment

Publications (2)

Publication Number Publication Date
CN113683186A CN113683186A (en) 2021-11-23
CN113683186B true CN113683186B (en) 2023-07-14

Family

ID=78584315

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111010015.2A Active CN113683186B (en) 2021-08-31 2021-08-31 Iron-carbon fiber coupling filler and application thereof in sewage treatment

Country Status (1)

Country Link
CN (1) CN113683186B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115353194B (en) * 2022-09-20 2023-08-08 上海泓济环保科技股份有限公司 Multi-element electrochemical integrated filler and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014047520A1 (en) * 2012-09-20 2014-03-27 Danisco Us Inc. Microtiter plates for controlled release of culture components to cell cultures
WO2016100903A2 (en) * 2014-12-19 2016-06-23 The Texas A&M University System Hybrid activated iron-biological water treatment system and method
CN107935202B (en) * 2017-12-21 2020-02-11 环境保护部华南环境科学研究所 Biodegradable slow-release carbon source filler and preparation method thereof
CN109704457A (en) * 2019-02-25 2019-05-03 常功法 A kind of fluidisation bed fillers and preparation method thereof with strengthened denitrification function
CN110606563B (en) * 2019-10-17 2024-04-16 浙江工业大学 Sustained-release carbon source filler for strengthening denitrification and preparation method thereof
CN112678950A (en) * 2020-12-30 2021-04-20 山东大学 Method for synchronously strengthening anaerobic ammonium oxidation bacteria culture and enhancing stability by coupling nano zero-valent iron with magnetic field

Also Published As

Publication number Publication date
CN113683186A (en) 2021-11-23

Similar Documents

Publication Publication Date Title
CN106277589B (en) A kind of system and method using iron carbon Fenton pretreatment-UBF-A/O processing waste water from dyestuff
Timberlake et al. Combined aerobic heterotrophic oxidation, nitrification and denitrification in a permeable-support biofilm
US5599451A (en) Anaerobic and aerobic integrated system for biotreatment of toxic wastes (canoxis)
Yao et al. Simultaneous removal of organic matter and nitrogen by a heterotrophic nitrifying–aerobic denitrifying bacterial strain in a membrane bioreactor
AU2004213273B2 (en) Method for treating water containing ammonia nitrogen
Garrido et al. Simultaneous urea hydrolysis, formaldehyde removal and denitrification in a multifed upflow filter under anoxic and anaerobic conditions
CN107487847A (en) A kind of method of integral anaerobic ammoxidation enhanced endogenesis denitrification SBBR advanced nitrogens
CN110697895A (en) Wastewater treatment method and device for simultaneously removing ammonia nitrogen, nitrate nitrogen and phosphate
CN105753155B (en) A kind of optimization denitrogenation method of municipal sewage SNAD biomembrane process
CN113683186B (en) Iron-carbon fiber coupling filler and application thereof in sewage treatment
WO2006022539A1 (en) Progress for the biological denitrification of ammonium containing wastewater
Dangcong et al. Simultaneous organic carbon and nitrogen removal in an SBR controlled at low dissolved oxygen concentration
Garrido et al. Nitrous oxide production by nitrifying biofilms in a biofilm airlift suspension reactor
Lacalle et al. Combined anaerobic/aerobic (UASB+ UBAF) system for organic matter and nitrogen removal from a high strength industrial wastewater
CN108163978A (en) A kind of method that the basicity realization efficient nitrosation of high-concentration ammonia nitrogenous wastewater is provided with sodium carbonate
CN112645446A (en) Starting method of one-stage SBR-anammox denitrification system
CN102101740B (en) Treatment method of high-concentration organic wastewater in electronic industry
Fang et al. Removal of COD and nitrogen in wastewater using sequencing batch reactor with fibrous packing
Rittmann Biofilms in the water industry
CN116282543A (en) Composite biological directional conversion system and method for purifying inorganic nitrogen in mariculture tail water
Feng et al. Nitrogen removal characteristics in a biofilm system for recirculating aquaculture wastewater treatment under high-salinity conditions and oligotrophic stress
JP2002143888A (en) Method for accumulating autotrophic denitrifying microorganism and biological method for removing nitrogen
KR20110059692A (en) Apparatus for removing nitrogen from anaerobic digested waste water
KR101045975B1 (en) Method for removing nitrogen from anaerobic digested waste water
CN108545827B (en) Process for realizing stable short-cut nitrification of town wastewater

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant