CN101066802A - Prepn and application in industrial effluent treatment of biomembrane carrier - Google Patents

Prepn and application in industrial effluent treatment of biomembrane carrier Download PDF

Info

Publication number
CN101066802A
CN101066802A CNA2007101189415A CN200710118941A CN101066802A CN 101066802 A CN101066802 A CN 101066802A CN A2007101189415 A CNA2007101189415 A CN A2007101189415A CN 200710118941 A CN200710118941 A CN 200710118941A CN 101066802 A CN101066802 A CN 101066802A
Authority
CN
China
Prior art keywords
carrier
modification
temperature
fiber
concentration
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.)
Granted
Application number
CNA2007101189415A
Other languages
Chinese (zh)
Other versions
CN100488893C (en
Inventor
刘杰
杨琨
马兆昆
梁节英
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.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
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 Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CNB2007101189415A priority Critical patent/CN100488893C/en
Publication of CN101066802A publication Critical patent/CN101066802A/en
Application granted granted Critical
Publication of CN100488893C publication Critical patent/CN100488893C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The present invention relates to one kind of functional biological carbon fiber and its preparation process and application as biomembrane carrier. The biomembrane carrier is prepared with polyacrylonitrile carbon fiber, and through electrochemical surface treatment in 5-20 % concentration ammonium bicarbonate electrolyte to increase the surface acid oxygen containing functional groups and raise wettability, and gluing with water soluble epoxy resin in the amount 0.5-2 %. The biomembrane carrier can fix nitrobacteria, sulfate reducing bacteria and anaerobic methanogen. It may be used in treating high concentration acrylon waste water, and can eliminate sulfate, COD and ammonia nitrogen effectively. In addition, the biomembrane carrier is easy to regenerate and has no secondary pollution.

Description

A kind of preparation of biomembrane carrier and in Application in Industrial Wastewater Treatment
Technical field:
The invention belongs to technical field of waste water processing, the high-performance bio membrane carrier PAN base of particularly a kind of novel treatment high-sulfate, high COD and refractory organic trade effluent has the preparation and the application of glue charcoal fiber.
Background technology:
Nitrilon waste water is the trade effluent that typically has high-sulfate, high COD and refractory organic.Nitrilon waste water mainly contains following 3 characteristics: the one, contain the high molecular polymer that is difficult to biological degradation and difficult natural subsidence, and biodegradability is relatively poor; The 2nd, produce sulfuric acid and sulfurous acid in the polymer manufacture process, cause the vitriol and the sulphite that contain high density in the waste water; The 3rd, contain organonitrogen and ammonia nitrogen in the waste water, cause ammonia and nitrogen pollution.Owing to above several aspects reason is brought all puzzlements to biological treatment, cause the waste water COD after the processing: 400-800mg/L, NH 3-N:80-150mg/L is away from country-level standard: COD<100mg/L, NH 3-N<15mg/L.
In the present wastewater processing technology that develops, biomembrance process has become countries in the world and has handled the main means that waste water control water pollutes.The core of biomembrance process water treatment is a carrier, and its performance directly influences and restricting treatment effect.The biofilm carrier material of broad research and application roughly is divided into two classes at present, i.e. mineral-type carrier and organic class carrier.The mineral-type carrier, major part is a bead-type substrate, as quartz sand, glass pellet, slag, gac, haydite etc.Most of mineral-type carrier physical strengths are better relatively, but self proportion is bigger, are not suitable for doing the fluidized motion.Organic class mainly is divided into two big classes: a kind of is the chemosynthesis macromolecular material, and as polymer plastics such as polyethylene, polystyrene, polypropylene, thermovyls, this class support strength height, chemical stability is good but mass-transfer performance is poor slightly, easily causes cell inactivation; Another kind of is natural macromolecular material, and as agar, sodium alginate etc., this type of mechanical strength is lower, and easily by microbiological degradation, the life-span is short.
Make a general survey of the present Research of biological treatment carrier, the special emphasis of the exploitation of carrier mainly concentrates on the physicals aspect of carrier at present, the biofilm carrier of current widespread use biocompatibility, stability, mechanical property, biofilm speed and again aspect such as processing exposed a lot of deficiencies, the microbial film of restriction is in the development of water technology.In view of the biofilm carrier material of present widespread use mostly is a bio-inert material, the good environment of microorganism growth can not initiatively be provided, biofilm speed is slow: therefore study the functional biomembrane carrier with the required microenvironment of active adjustment microorganism growth and represented biofilm speed and the reactor efficiency of the direction of biofilm carrier development for the raising carrier, it is significant to develop efficient, practical water processing establishment.
Japanese scholar's Ojima Zhaos in 1997 have carried out the correlative study of basic high strength carbon fibre of polyacrylonitrile (PAN) and aerobic microbiological relation, but only limit to natural wild aerobic microbiological, found that the charcoal fiber has the ability of gathering and fixation of microbe.People such as Sato have studied the relation between basic high strength carbon fibre of the PAN that is used for the natural water processing and the microorganism, find that also a large amount of microorganisms is adsorbed on the carbon fiber.
Research as biofilm carrier all is confined in natural microbial and the natural water processing investigator in the past for the basic high strength carbon fibre of polyacrylonitrile (PAN).Functional biomembrane carrier of the present invention is applied in the Industrial Wastewater Treatment, has carried out the correlative study of the aerobic and anaerobion relation of carrier and artificial screening, has more realistic meaning.
The used PAN base of the present invention has glue charcoal fiber biological consistency good, the intensity height, and advantage such as it is easy to regenerate is a kind of good wastewater treatment material and biofilm carrier.Be applicable to the biological treatment of the trade effluent of high-sulfate, high COD and refractory organics such as Nitrilon waste water, pulping and paper-making, the black phase of weaving, food, fermentation.
Summary of the invention:
The object of the present invention is to provide a kind of novel carbon-fiber biofilm carrier of handling high-sulfate, high COD and refractory organic trade effluent.This bioremediation can improve the activity of bacterium to hardly degraded organic substance, improves vitriol, COD and ammonia-N removal rate greatly.
Concrete grammar and step that usual method prepares the PAN based carbon fiber are as follows:
1) acrylonitrile monemer copolymer quality content is not less than 90% polyacrylonitrile fibre in air dielectric in 180~300 ℃, under the drawing-off of 0~20% elongation, carry out the preoxidation of 20~100min;
2) with above-mentioned pre-oxidized fibers under the protection of inert atmosphere; under the drawing-off of-2~+ 10% elongations; handle through continuous low temperature carbonization, high temperature cabonization; wherein the temperature of carbonization at low temperature is 300~800 ℃; the temperature rise rate per minute of low temperature carbonization furnace is no more than 400 ℃; the temperature of high temperature cabonization is an a certain temperature in 1200~1600 ℃, keeps this temperature 0.2~5min and makes high-strength carbon fiber.
Above-mentioned polyacrylonitrile fibre tow can adopt the fiber of dry method of the prior art, wet method or dried wet method spinning, and the monofilament hole count is 0.1~400,000 in the bundle fiber, and filament number was 0.5~3.0 dawn.In the above-mentioned polyacrylonitrile fibre tow, also contain one or more following multipolymers of 10% mass content: vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl vinyl cyanide, hydroxyalkyl vinylformic acid and ester class thereof.This is that as long as the acrylonitrile monemer mass content is not less than 90% above-mentioned multipolymer in the precursor, the present invention is promptly applicable because the different methods of preparation precursor causes.
A kind of biomembrane carrier is to carry out modification and gluing makes on the charcoal fiber basis of above-mentioned usual method preparation, it is characterized in that, may further comprise the steps:
1) above-mentioned PAN based carbon fiber is carried out the anode electrochemical surface modification at the bicarbonate of ammonia electrolytic solution of quality percentage composition 5%~20%, under 20~100 ℃ the temperature, the electric weight of 100c/g~700c/g, modification 0.5~6 minute, fiber surface acidic functionality 0.051~0.186meq/g, equilibrium moisture content scope 2.0%~7.8% after the modification of acquisition electrochemical surface, then fiber is washed and drying, made modification PAN based carbon fiber;
2) above-mentioned charcoal fiber is entered the water-soluble epoxy resin glue through deflector roll and soak into, spread 0.5%~2% is reeled through deflector roll after the oven dry, finishes the gluing process.
The kind and the sorting technique of biofilm packing are various, and according to the materials classification of carrier, biofilm carrier is broadly divided into suspension type filler and suspension type fillers such as fixed filler, soft-filler, semi soft packing and compounded mix.The modification PAN base of above-mentioned preparation has glue charcoal fiber can select various ways as biofilm carrier.
Biomembrane carrier with above-mentioned method preparation is handled Nitrilon waste water.Adopt two anaerobism, anoxic-aerobic process, set sulphate reducing bacteria, methanogen and nitrobacteria shorten the reactor start-up time fast, effectively reduce and remove vitriol, COD and ammonia nitrogen.
Acidogenic reactor experiment condition in the diphasic anaerobic technique: temperature is at 30 ℃~35 ℃, and the pH value is in 5.5~6.5 scopes, and dissolved oxygen is less than 0.5mg/L, hydraulic detention time 4~8h.The methane-producing reactor experiment condition: about 30 ℃~35 ℃ of temperature, pH is in 6.0~7.5 scopes, and dissolved oxygen is less than 0.5mg/L, hydraulic detention time 8~12h.
Hypoxia response condition in the anoxic-aerobic process: temperature is controlled at 25~35 ℃, and pH is controlled in 7.0~8.0 scopes, and the concentration of dissolved oxygen is less than 0.5mg/l, hydraulic detention time 6~12h.The nitration reaction condition: temperature is controlled at 30~35 ℃, and pH is 6.0~8.0, and dissolved oxygen is controlled at 2~4mg/l, hydraulic detention time 6~12h.
Biomembrane carrier modification PAN base provided by the invention has glue charcoal fiber to have excellent biological compatibility, suitable wettability and surface acidity functional group, and the set microorganism promotes microbial growth fast.50~600 μ m reach stable substantially at 8~48h left and right sides microbial film thickness, and can promote microbial growth, shorten the domestication time of microorganism.Amount 0.5~3.0g/g carrier of its sessile organism dry film is 5~20 times of general carrier.An amount of wettability and surface acidity functional group can increase the affinity of charcoal fiber, fast the set microorganism.
Modification PAN base of the present invention has the renovation process of glue charcoal fiber simple, the alkali lye that needs regenerated charcoal fiber with 1mol/L is soaked 20~50min down at 30 ℃~80 ℃, charcoal fiber after water washes oven dry repeatedly can utilize again after the modification gluing repeatedly again, and regeneration PAN base has the treatment effect of glue charcoal fiber good.
Bio-modification PAN base of the present invention has glue charcoal fiber utilization diphasic anaerobic reaction unit to handle the high density Nitrilon waste water and has multiple effect: first, the diphasic anaerobic reaction unit has reduced the substrate competition of sulfatereducting bacteria and methanogen, improved the transformation efficiency of vitriol, weakened in the Nitrilon waste water high-sulfate concentration the treatment effect influence of COD; Second, the PAN base has glue charcoal fiber to have good biocompatibility, suitable wettability and surface acidity functional group, set sulfatereducting bacteria and product methane finish bacterium fast, promote microbial growth, shortened the domestication time of microorganism, biofilm speed is fast, and aging biofilm detachment is easy, anti impulsion load is high; The 3rd, the PAN base has glue charcoal fibre strength height, and recyclability is strong, and renovation process is simple, can repeatedly reuse, and has reduced cost of sewage disposal.
New function material of the present invention is handled the efficient height of waste water, and adaptability is strong, applied range, and floor space is little, and is low with the property expense, the carrier reproducible utilization, and renovation process is simple.Be applicable to the biological treatment of the trade effluent of high-sulfate, high COD and refractory organics such as Nitrilon waste water, pulping and paper-making, the black phase of weaving, food, fermentation.
Embodiment:
Embodiment 1
The commercially available Britain courtaulds company that selects wet method to spin produces, (its monofilament hole count is 3000 3K to contain the polyacrylonitrile copolymer fibre of 90% above acrylonitrile monemer component, 1.1 dawn of fiber number (1.22dtex), multipolymer is formed (by mass ratio): vinyl cyanide 96, propylenedicarboxylic acid 1, methyl acrylate 3), in air through 215 ℃, 240 ℃, 260 ℃, 280 ℃ of four joint pre-oxidation furnace handled, the residence time is respectively 7.5,15,15,15minn, amount to preoxidation time 52.5min, through low continuously, high temperature cabonization is handled, wherein temperature is 300~700 ℃ during carbonization at low temperature, temperature rise rate is 300 ℃ of per minutes, the high temperature cabonization temperature is 1350 ℃, keep this temperature 2min, make carbon fiber.60 ℃ of following modification 5min of electric weight with PAN based carbon fiber 100c/g in 5% bicarbonate of ammonia electrolytic solution of above-mentioned system.The charcoal fiber is soaked into to enter the water-soluble epoxy resin glue by deflector roll, and spread is 0.5%, reels through deflector roll after the oven dry, finishes the gluing process.It is 4.8% that above-mentioned PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.135meq/g.The charcoal fiber of above-mentioned preparation is distinguished set sulfatereducting bacteria and methanogen as biofilm carrier, the sulfatereducting bacteria of set reaches the thickness of 448 μ m at 24h, dry weight 1.9g/g carrier. the methanogen of set reaches the thickness of 223 μ m at 24h, dry weight 1.2g/g carrier. adopt diphasic anaerobic reaction unit concentration of treatment COD=1500~2000mg/L, SO 4 2-The high density Nitrilon waste water of=3000~5000mg/L.The acidogenic reactor experiment condition: temperature is controlled at 30 ℃~35 ℃, and pH is controlled in 5.5~6.5 scopes, and the concentration of dissolved oxygen is less than 0.5mg/L, hydraulic detention time 4~8h.The methane-producing reactor experiment condition: temperature is controlled at about 30 ℃~35 ℃, and pH is controlled in 6.0~7.5 scopes, and the concentration of dissolved oxygen is less than 0.5mg/L, hydraulic detention time 8~12h.Going out water concentration is COD<700mg/L, SO 4 2-<350mg/L, COD clearance>54%, SO 4 2-Clearance>88%.
Embodiment 2
The PAN based carbon fiber prepares with example 1,70 ℃ of following modification 3min of electric weight of 400c/g in 15% bicarbonate of ammonia electrolytic solution, and the gluing condition is with example 1.It is 5.1% that the modification PAN base that makes has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.186meq/g.Experimental installation, experiment condition be with example 1, and the sulfatereducting bacteria of set reaches the thickness of 500 μ m, dry weight 2.4g/g carrier at 24h.The methanogen of set reaches the thickness of 256 μ m, dry weight 1.3g/g carrier at 24h. and testing out water concentration is COD<630mg/L, SO 4 2-<300mg/L, COD clearance>58%, SO 4 2-Clearance>90%
Embodiment 3
The PAN based carbon fiber prepares with example 1,20 ℃ of following modification 2min of electric weight of 300c/g in 10% bicarbonate of ammonia electrolytic solution, and the gluing condition is with example 1.It is 7.8% that modification PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.152meq/g.Experimental installation, experiment condition be with example 1, and the sulfatereducting bacteria of set reaches the thickness of 465 μ m, dry weight 2.1g/g carrier at 24g.The methanogen of set reaches the thickness of 248 μ m, dry weight 1.2g/g carrier at 24g. and testing out water concentration is COD<650mg/L, SO 4 2-<330mg/L, COD clearance>57%, SO 4 2-Clearance>89%
Embodiment 4
Used PAN base among the embodiment 2 there be the Na of glue charcoal fiber with 1mol/L 2CO 3Solution soaks 20min down at 65 ℃, oven dry after water washes repeatedly.Charcoal fiber in 20% bicarbonate of ammonia electrolytic solution after 100 ℃ of following modification 3.5min. of electric weight modification of 500c/g soaks into through the water-soluble epoxy resin glue, spread 1.5%, and obtaining regenerated PAN base after the oven dry has glue charcoal fiber.Glue charcoal fiber equilibrium moisture content is arranged is 6.2% to the PAN base after the modification, and surface acidity functional group is 0.156meq/g.Experimental installation, experiment condition be with example 1, and the sulfatereducting bacteria of set reaches the thickness of 480 μ m, dry weight 2.3g/g carrier at 24h.The methanogen of set reaches the thickness of 250 μ m, dry weight 1.3g/g carrier at 24h. and testing out water concentration is COD<640mol/L, SO 4 2-<310mol/LCOD clearance>57%, SO 4 2-Clearance>90%
Embodiment 5
There is glue charcoal fiber to soak 50min down at 30 ℃ in used PAN base among the embodiment 2, washes oven dry repeatedly through water with the NaHCO3 solution of 1mol/L.Charcoal fiber in 10% bicarbonate of ammonia electrolytic solution after 50 ℃ of following modification 6min. of electric weight modification of 600c/g soaks into through the water-soluble epoxy resin glue, spread 1.5%, and obtaining regenerated PAN base after the oven dry has glue charcoal fiber.It is 2.0% that modification PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.051meq/g.Experimental installation, experiment condition are with example 1.The sulfatereducting bacteria of set reaches the thickness of 436 μ m, dry weight 1.8g/g carrier at 24h.The methanogen of set reaches the thickness of 202 μ m, dry weight 1g/g carrier at 24h. and testing out water concentration is COD<700mg/L, SO 4 2-<360mg/L.COD clearance>53%, SO 4 2-Clearance>88%
Embodiment 6
Adopt commercially available homemade Jilin Chemical Industry Company synthetic resin plant wet method spinning 3K fiber, the fiber multipolymer is formed (by mass ratio) and is: vinyl cyanide 92, methyl acrylate 6, propylenedicarboxylic acid 2.Preoxidation process is to handle in the pre-oxidation furnace at 220 ℃, 240 ℃, 260 ℃, 270 ℃ four joint, and the residence time is respectively 10,10,20,20min, amounts to preoxidation time 60min.Pre-oxidized fibers is carried out continuous carbonization to be handled.Wherein temperature is 300~700 ℃ during carbonization at low temperature, and temperature rise rate is 270 ℃ of per minutes, and the high temperature cabonization temperature is 1400 ℃, keeps this temperature 5min, makes the charcoal fiber.PAN based carbon fiber 90 ℃ of following modification 3min of 400c/g electric weight in 12% bicarbonate of ammonia electrolytic solution with above-mentioned system.The charcoal fiber is soaked into to enter the water-soluble epoxy resin glue by deflector roll, and spread is 0.5%, reels through deflector roll after the oven dry, finishes the gluing process.It is 7.0% that above-mentioned PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.161meq/g.Adopt anoxic~nitration processes concentration of treatment COD=400~700mg/L, NH 3The Nitrilon waste water of-N=300~500mg/L.Reach the thickness of 480 μ m in the anerobe 8h, dry weight 1.7g/g carrier, nitrobacteria 48h reaches the thickness of 220 μ m, dry weight 0.8g/g carrier.The hypoxia response condition: 25 ℃~35 ℃ of temperature, pH is in 7.0~8.0 scopes, and the concentration of dissolved oxygen is less than 0.5mg/l, hydraulic detention time 6~12h.Nitration reaction condition: 30~35 ℃ of temperature, pH6.0~8.0, dissolved oxygen 2~4mg/l, hydraulic detention time 6~12h.Water outlet concentration C OD<90mg/L, NH 3-N<1mg/L.
Embodiment 7
The PAN based carbon fiber prepares with example 6,70 ℃ of following modification 3min of electric weight of 400c/g in 18% bicarbonate of ammonia electrolytic solution, and gluing condition experiment device, experiment operational conditions are with example 6.It is 6.8% that the PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.145meq/g.The anerobe of set reaches the thickness of 600 μ m at 8h, dry weight 2.0g/g carrier, and nitrobacteria 48g reaches the thickness of 300 μ m, dry weight 1.1g/g carrier.Water outlet concentration C OD<80mg/L, NH 3-N<1mg/L.
Embodiment 8
Modification PAN base has glue charcoal fiber production with embodiment 2, experimental installation, experiment operational conditions are with example 6, and the anerobe of set reaches the thickness of 550 μ m, anerobe dry weight 1.9g/g carrier at 8h, nitrobacteria 48h reaches the thickness of 260 μ m, nitrobacteria dry weight 1.0g/g carrier.Water outlet concentration C OD<80mg/L, NH 3-N<1mg/L.
Embodiment 9
Used PAN base among the embodiment 6 there be the Na of glue charcoal fiber with 1mol/L 2CO 3Solution soaks 50min down at 50 ℃, oven dry after water washes repeatedly.Charcoal fiber in 15% bicarbonate of ammonia electrolytic solution after 30 ℃ of following modification 0.5min. of electric weight modification of 200c/g soaks into through the water-soluble epoxy resin glue, spread 1.5%, and obtaining regenerated PAN base after the oven dry has glue charcoal fiber.It is 3.8% that the PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.076meq/g.Experimental installation, experiment operational conditions are with example 6, and the anerobe of set reaches the thickness of 520 μ m at 8h, dry weight 1.8g/g carrier, and nitrifier 48h reaches the thickness of 270 μ m, dry weight 1.0g/g carrier.Water outlet concentration C OD<90mg/L, NH 3-N<10mg/L.
Embodiment 10
To use the PAN base that the NaHCO of glue charcoal fiber with 1mol/L arranged among the embodiment 6 3Solution under soak 40min, after water washes repeatedly the oven dry.Charcoal fiber in 8% bicarbonate of ammonia electrolytic solution after 50 ℃ of following modification 4min. of electric weight modification of 700c/g soaks into through the water-soluble epoxy resin glue, spread 1.5%, and obtaining regenerated PAN base after the oven dry has glue charcoal fiber.It is 2.5% that the PAN base has glue charcoal fiber equilibrium moisture content, and surface acidity functional group is 0.065meq/g.Experimental installation, experiment operational conditions are with example 6.The anerobe of set reaches the thickness of 430 μ m at 8h, dry weight 1.4g/g carrier, and nitrobacteria 48h reaches the thickness of 150 μ m, dry weight 0.6g/g carrier.Going out water concentration is COD<100mg/L, NH 3-N<10mg/L.
Embodiment 11
Modification PAN base has the preparation, experiment condition, experimental installation of glue charcoal fiber with example 1, handles COD=1800~2500mg/L, SO 4 2-The high density paper waste of=3000~5000mg/L.Testing out water concentration is COD<600mol/L, SO 4 2-<300mol/L, COD clearance>67%, SO 4 2-Clearance>90%
Embodiment 12
Modification PAN base has the preparation, experiment condition, experimental installation of glue charcoal fiber with example 6, handles COD=600~1000mg/L, NH 3The food wastewater of-N=500~800mg/L.Testing out water concentration is COD<100mg/L, NH 3-N<15mg/L.

Claims (4)

1. the preparation method of a biomembrane carrier carries out modification and gluing on the PAN-based carbon fiber basis, it is characterized in that, may further comprise the steps:
1) above-mentioned PAN-based carbon fiber is carried out the anode electrochemical surface modification at the bicarbonate of ammonia electrolytic solution of quality percentage composition 5%~20%, under 20~100 ℃ the temperature, the electric weight of 100c/g~700c/g, modification 0.5~6 minute, fiber surface acidic functionality 0.051~0.186meq/g, equilibrium moisture content scope 2.0%~7.8% after the modification of acquisition electrochemical surface, then fiber is washed and drying, made modification PAN based carbon fiber;
2) above-mentioned charcoal fiber is entered the water-soluble epoxy resin glue through deflector roll and soak into, spread 0.5%~2% is reeled through deflector roll after the oven dry, finishes the gluing process.
2. the manipulation of regeneration of the biofilm carrier of method preparation according to claim 1 is characterized in that, the alkali lye that needs regenerated charcoal fiber with 1mol/L is soaked 20~50min down at 30 ℃~80 ℃, washes repeatedly also through water and utilizes after the drying again.
3. handle Nitrilon waste water according to the functional biological membrane carrier of the described method preparation of claim 1, it is characterized in that following three aspects:
Diphasic anaerobic, anoxic-aerobic process are adopted in experiment;
Acidogenic reactor experiment condition in the diphasic anaerobic technique: temperature is at 30 ℃~35 ℃, and the pH value is in 5.5~6.5 scopes, and the concentration of dissolved oxygen is less than 0.5mg/l, hydraulic detention time 4~8h; The methane-producing reactor experiment condition: about 30 ℃~35 ℃ of temperature, pH is in 6.0~7.5 scopes, and the concentration of dissolved oxygen is less than 0.5mg/l, hydraulic detention time 8~12h;
Hypoxia response condition in the anoxic-aerobic process: temperature is controlled at about 25~35 ℃, and pH is controlled in 7.0~8.0 scopes, and the concentration of dissolved oxygen is less than 0.5mg/l, hydraulic detention time 6~12h; The nitration reaction condition: temperature is controlled at 30~35 ℃, and pH is 6.0~8.0, and dissolved oxygen is controlled at 2~4mg/l, hydraulic detention time 6~12h.
4. use according to the functional biological membrane carrier of the described method preparation of claim 1, it is characterized in that it is applicable to the biological treatment of the trade effluent of high-sulfate, high COD and refractory organics such as Nitrilon waste water, pulping and paper-making, the black phase of weaving, food, fermentation.
CNB2007101189415A 2007-06-15 2007-06-15 Preparation and application in industrial effluent treatment of biomembrane carrier Expired - Fee Related CN100488893C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007101189415A CN100488893C (en) 2007-06-15 2007-06-15 Preparation and application in industrial effluent treatment of biomembrane carrier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007101189415A CN100488893C (en) 2007-06-15 2007-06-15 Preparation and application in industrial effluent treatment of biomembrane carrier

Publications (2)

Publication Number Publication Date
CN101066802A true CN101066802A (en) 2007-11-07
CN100488893C CN100488893C (en) 2009-05-20

Family

ID=38879525

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007101189415A Expired - Fee Related CN100488893C (en) 2007-06-15 2007-06-15 Preparation and application in industrial effluent treatment of biomembrane carrier

Country Status (1)

Country Link
CN (1) CN100488893C (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102627375A (en) * 2012-04-01 2012-08-08 北京工业大学 Integrated treatment method and integrated treatment device for polluted river and lake water
CN101544449B (en) * 2009-05-14 2012-10-31 北京化工大学 Application of carbon-fiber biofilm carrier in wastewater treatment
WO2014127501A1 (en) * 2013-02-19 2014-08-28 中国海洋大学 Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof
CN105237793A (en) * 2015-10-30 2016-01-13 南京工业大学 Macro-molecular material for improving rate of biogas production of anaerobic fermentation system and preparation method for macro-molecular material and application of macro-molecular material
CN109336211A (en) * 2018-09-11 2019-02-15 湖北理工学院 A kind of corrosion-resistant carbon fiber artificial aquatic weed brick and preparation method thereof
CN109962209A (en) * 2017-12-22 2019-07-02 中国电子科技集团公司第十八研究所 Preparation method of high-efficiency oxygen catalytic active carbon fiber electrode
CN111439839A (en) * 2020-04-09 2020-07-24 贵州省绿洲海环保有限责任公司 Unpowered sewage treatment method adopting surface modified carbon fiber material
CN112811573A (en) * 2019-11-18 2021-05-18 贵州通用水务技术发展有限公司 Sewage treatment method, sewage treatment device and application
CN115321679A (en) * 2022-10-13 2022-11-11 广州市华绿环保科技有限公司 Anaerobic ammonia oxidation treatment process for degrading landfill leachate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104652131B (en) * 2015-01-23 2017-06-16 北京京阳环保工程有限公司 A kind of bio-active carbon fibre, the complex ecological film filler assembly including it and preparation method thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101544449B (en) * 2009-05-14 2012-10-31 北京化工大学 Application of carbon-fiber biofilm carrier in wastewater treatment
CN102627375A (en) * 2012-04-01 2012-08-08 北京工业大学 Integrated treatment method and integrated treatment device for polluted river and lake water
WO2014127501A1 (en) * 2013-02-19 2014-08-28 中国海洋大学 Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof
CN104838051A (en) * 2013-02-19 2015-08-12 中国海洋大学 Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof
US9683314B2 (en) 2013-02-19 2017-06-20 Ocean University Of China Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof
CN105237793A (en) * 2015-10-30 2016-01-13 南京工业大学 Macro-molecular material for improving rate of biogas production of anaerobic fermentation system and preparation method for macro-molecular material and application of macro-molecular material
CN109962209A (en) * 2017-12-22 2019-07-02 中国电子科技集团公司第十八研究所 Preparation method of high-efficiency oxygen catalytic active carbon fiber electrode
CN109336211A (en) * 2018-09-11 2019-02-15 湖北理工学院 A kind of corrosion-resistant carbon fiber artificial aquatic weed brick and preparation method thereof
CN109336211B (en) * 2018-09-11 2021-11-23 湖北理工学院 Corrosion-resistant carbon fiber artificial waterweed brick and preparation method thereof
CN112811573A (en) * 2019-11-18 2021-05-18 贵州通用水务技术发展有限公司 Sewage treatment method, sewage treatment device and application
CN111439839A (en) * 2020-04-09 2020-07-24 贵州省绿洲海环保有限责任公司 Unpowered sewage treatment method adopting surface modified carbon fiber material
CN115321679A (en) * 2022-10-13 2022-11-11 广州市华绿环保科技有限公司 Anaerobic ammonia oxidation treatment process for degrading landfill leachate
CN115321679B (en) * 2022-10-13 2023-01-24 广州市华绿环保科技有限公司 Anaerobic ammonia oxidation treatment process for degrading landfill leachate

Also Published As

Publication number Publication date
CN100488893C (en) 2009-05-20

Similar Documents

Publication Publication Date Title
CN100488893C (en) Preparation and application in industrial effluent treatment of biomembrane carrier
CN110127972B (en) Method for improving anaerobic digestion efficiency of sludge and simultaneously reducing heavy metal ecotoxicity
CN101544449B (en) Application of carbon-fiber biofilm carrier in wastewater treatment
CN102660813B (en) Biological activated carbon fibe, ecological carbon fiber composite comprising same and preparation method thereof
CN108467118B (en) Method for removing nitrogen and phosphorus in aquaculture wastewater by using immobilized algae bacteria
CN102491498B (en) Ecological carbon-fiber composite, preparation method thereof and sewage treatment reactor containing ecological carbon-fiber composite
CN102181421A (en) Method for strengthening activity of anaerobic ammoxidized microorganisms through polyvinyl alcohol-sodium alginate-activated carbon embedment
CN101402489A (en) Process for treating chemical industry tail water with immobilized microorganism-artificial wet land
CN109734199A (en) Immobilized microorganism structural body and preparation method thereof
CN104652131A (en) Bioactive carbon fiber, composite ecological film packing component comprising bioactive carbon fiber and preparation method of bioactive carbon fiber
CN103497908A (en) Pseudomonas stutzeri and its culture, immobilization and use
CN108862574A (en) Denitrifying artificial wet land system and its sewage denitrification method are cooperateed with based on reduction-state Fe autotrophy/sawdust heterotrophism
CN113511723A (en) Preparation method and application of novel LDHs-based slow-release carbon source filler
CN110699347A (en) Immobilized microbial inoculum and preparation method and application thereof
Li et al. Granulation of filamentous microorganisms in a sequencing batch reactor with saline wastewater
Liu et al. Buffered loofah supported Microalgae-Bacteria symbiotic (MBS) system for enhanced nitrogen removal from rare earth element tailings (REEs) wastewater: Performance and functional gene analysis
CN112142189A (en) Carbon fiber biological filler for industrial wastewater treatment and preparation method thereof
Bhatti et al. Treatment performance and microbial structure of a granular consortium handling methanolic waste
CN113213632B (en) Nano-hydroxyapatite loofah sponge composite filler and preparation method and application thereof
CN115057526A (en) Preparation method and application of modified basalt fiber biological filler
CN109126896A (en) It is a kind of to prepare g-C3N4With the method for carbon fiber complex carrier
CN110565364B (en) Quinone modified basalt fiber carrier and preparation method and application thereof
CN112266074B (en) Method for enhancing denitrification of heterotrophic nitrification-aerobic denitrification strain by magnesium salt modified biomass charcoal
CN113526676A (en) Artificial wetland system capable of enhancing denitrification
Wu et al. Comparison of rod-versus filament-type methanogenic granules: microbial population and reactor performance

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090520

Termination date: 20170615