CN107758994A - Advanced treatment process for gas station phenol water - Google Patents

Advanced treatment process for gas station phenol water Download PDF

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Publication number
CN107758994A
CN107758994A CN201610679752.4A CN201610679752A CN107758994A CN 107758994 A CN107758994 A CN 107758994A CN 201610679752 A CN201610679752 A CN 201610679752A CN 107758994 A CN107758994 A CN 107758994A
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parts
baf ponds
catalysis oxidation
oxidation pond
pond
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CN201610679752.4A
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Inventor
唐新亮
乐淑荣
宋小林
况定文
温文鹏
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ZHONGHAI ASPHALT (TAIZHOU) CO Ltd
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ZHONGHAI ASPHALT (TAIZHOU) CO Ltd
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Priority to CN201610679752.4A priority Critical patent/CN107758994A/en
Publication of CN107758994A publication Critical patent/CN107758994A/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C02F3/106—Carbonaceous materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • 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
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The present invention discloses a kind of advanced treatment process for gas station phenol water, the handling process is based on a special processor, the special processor includes catalysis oxidation pond, oxidation-stabilized pond, rear biochemical BAF ponds, clear water reserviors, the comprehensive tank of dilution, pretreated primary BAF ponds, pretreatment two level BAF ponds and discharge bay, the catalysis oxidation pond, oxidation-stabilized pond, rear biochemical BAF ponds and passes sequentially through back segment transfer conduit with clear water reserviors and connect；Ozone catalytic particle is made up of activated alumina particle, cupric oxide, titanium dioxide, polyethylene glycol, polyvinyl alcohol；The carrier is made up of the component of following parts by weight：60 ~ 70 parts of high density polyethylene (HDPE), 10 ~ 15 parts of acrylic resin, 6 ~ 8 parts of low density polyethylene (LDPE), 8 ~ 10 parts of bamboo carbon powder, 4 ~ 6 parts of wood powder, 2 ~ 3 parts of lignin, 2 ~ 3 parts of dichloromethane, 1 ~ 2 part of diethyl guanidine sulfate, N, 0.5 ~ 1 part of N' ethylene bis stearamides, 3 ~ 5 parts of maleic anhydride.Macromolecular hardly degraded organic substance is oxidized to the easily biochemical organic matter of small molecule by the present invention, and then is improved the biochemical of water outlet.

Description

Advanced treatment process for gas station phenol water
Technical field
The present invention relates to a kind of advanced treatment process for gas station phenol water, belong to technical field of waste water processing.
Background technology
The processing method for being presently used for phenol wastewater mainly has extraction, absorption method, chemical oxidization method, biochemical treatment process Deng.Extraction high energy consumption, extractant easily occurs and residues in follow-up waste water, influences follow-up processing procedure；Absorption method operation letter It is single, it is suitable for the relatively low waste water of amount containing phenol, but equipment one-time investment is larger, and adsorbent reactivation is difficult；Though chemical method energy Oxidation removes phenol, but direct oxidation operating cost is higher.
The content of the invention
It is an object of the present invention to provide a kind of advanced treatment process for gas station phenol water, this is used for the depth of gas station phenol water It is low, simple to operate, stable to spend handling process operating cost, and obtains the purpose of efficient degradation organic pollution, can be achieved The high saline sewage advanced treating of petroleum chemical industry and qualified discharge under low cost.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of depth science and engineering for gas station phenol water Skill, the handling process are based on a special processor, the special processor include catalysis oxidation pond, oxidation-stabilized pond, after Biochemical BAF ponds, clear water reserviors, the comprehensive tank of dilution, pretreated primary BAF ponds, pretreatment two level BAF ponds and discharge bay, the dilution Comprehensive tank, pretreated primary BAF ponds, pretreatment two level BAF ponds pass sequentially through leading portion transfer conduit with discharge bay and connected, described to urge Change oxidation pond, oxidation-stabilized pond, rear biochemical BAF ponds pass sequentially through back segment transfer conduit with clear water reserviors and connects, the discharge bay and Catalysis oxidation pond is connected to inside catalysis oxidation pond by inlet channel；
One ozone generator is connected to inside catalysis oxidation pond by gas pipeline, and the clear water reserviors are provided with inlet opening, water outlet Hole, the inlet opening of the clear water reserviors are connected with rear biochemical BAF ponds by back segment transfer conduit, and the clear water reserviors are connected to a backwash Pump one end, this backwashing pump other end is connected to catalysis oxidation pond, inside rear biochemical BAF ponds by back segment reflux line, described to urge Change oxidation pond and ozone catalytic particle is filled with fixed bed form, the comprehensive tank of dilution is provided with charge door and agitator；
The ozone catalytic particle is obtained by following steps：
Step 1: 88.7 ~ 91.3 parts of activated aluminas are cleaned for several times to remove the impurity on its surface with distilled water, and dry To quality constant weight, the particle diameter of the activated alumina is 2 ~ 4mm；
Step 2: 88.7 ~ 91.3 parts of activated aluminas and 1.4 ~ 1.6 parts of cupric oxide, titanium dioxide 0.8 that step 1 is obtained ~ 1.2 parts, 4 ~ 7 parts of polyethylene glycol, 1.9 ~ 2.1 parts of polyvinyl alcohol mix in stirring mixer so that uniform mixed oxidation 1.4 ~ 1.6 parts of copper, 0.8 ~ 1.2 part of titanium dioxide, 4 ~ 7 parts of polyethylene glycol, 1.9 ~ 2.1 parts of polyvinyl alcohol are covered in the active oxygen Change alumina particles surface and form catalyst mother bulb；
Step 3: taking out the catalyst mother bulb from stirring mixer, after drying at room temperature, baking oven is put into, 100~ Dried under the conditions of 120 DEG C and obtain dried catalyst mother bulb；
Step 4: dried catalyst mother bulb is put into Muffle furnace, the resistance to high salt of roasting acquisition is smelly under the conditions of 350 ~ 520 DEG C VPO catalysts；
Several biologic packing materials are placed with biochemical BAF ponds after described, the biologic packing material is overlying on carrier surface by carrier and extension Microbial film composition；
The carrier is made up of the component of following parts by weight：
60 ~ 70 parts of high density polyethylene (HDPE),
10 ~ 15 parts of acrylic resin,
6 ~ 8 parts of low density polyethylene (LDPE),
8 ~ 10 parts of bamboo carbon powder,
4 ~ 6 parts of wood powder,
2 ~ 3 parts of lignin,
2 ~ 3 parts of dichloromethane,
1 ~ 2 part of diethyl guanidine sulfate,
0.5 ~ 1 part of N, N'- ethylene bis stearamide,
3 ~ 5 parts of maleic anhydride,
0.2 ~ 0.6 part of cumyl peroxide,
1.5 ~ 3 parts of gelatin,
1 ~ 2 part of magnetic,
0.5 ~ 1 part of pentaerythritol stearate.
Further improved technical scheme is as follows in above-mentioned technical proposal：
Preferably, a dividing plate is vertically provided with the catalysis oxidation pond, it is left and right so as to which catalysis oxidation pond be divided into Chamber, catalysis oxidation pond lower horizontal are provided with a sieve plate, and the lower end of this dividing plate is installed to the upper surface of sieve plate, the ozone Catalysed particulate is located above sieve plate and is located at dividing plate both sides.
Preferably, also include the backwash sedimentation basin, leading portion supernatant liquid pool and pretreatment backwashing pump being sequentially connected, it is described anti- Wash sedimentation basin and pretreated primary BAF ponds, pretreatment two level BAF ponds, the pretreatment are connected to by the first pipeline, second pipe Backwashing pump is connected to pretreated primary BAF ponds, pretreatment two level BAF ponds by leading portion reflux line.
Preferably, the ozone generator is connected to the bottom in catalysis oxidation pond by gas pipeline.
Preferably, drying time is 4 ~ 6 hours under the conditions of 100 ~ 120 DEG C in the step 3.
Preferably, roasting time is 7 ~ 9 hours under the conditions of 350 ~ 520 DEG C in the step 4.
Preferably, the white lime and Tao Shi Powdered Activated Carbons and precipitated calcium carbonate are according to 1：1.2：0.9 parts by weight are mixed Close.
Because above-mentioned technical proposal is used, the present invention has following advantages and effect compared with prior art：
1st, the present invention is used for the advanced treatment process of gas station phenol water, and carrier biofilm speed is fast in biochemical BAF ponds thereafter, is not easy to take off Fall, treatment effeciency is high, the processing of low-concentration organic and ammonia nitrogen suitable for sewage, low-concentration organic waste water, life of the invention Thing filler has extremely strong hydrophily and bioaffinity, and filler has very strong adsorption strength to biomembrane in itself, favorably In the retention and accumulation of biomass on filling carrier, its ammonia nitrogen removal frank more than 92%, COD clearances more than 78%, therefore can be compared with Wastewater treatment under good adaptation low consistency conditions.
2nd, the present invention is used for the advanced treatment process of gas station phenol water, further in carrier compound in biochemical BAF ponds thereafter Using resin material based on 60 ~ 70 parts of high density polyethylene (HDPE) collocation, 10 ~ 15 parts of acrylic resin, 6 ~ 8 parts of low density polyethylene (LDPE)s, 3 ~ 5 parts of maleic anhydride, cumyl peroxide and gelatin are added, the contact angle of sewage and carrier is reduced, improves carrier Hydrophily and impact resistance, microorganism is set to be easier to be attached on carrier, hydrophilic bio-carrier specific surface area is big, adsorptivity pole By force, it can prevent the microbial film that carrier outer surface adheres to from being come off because being rubbed between carrier in water, it is short the time required to biofilm, improve Waste water treatment efficiency, ammonia nitrogen removal frank, more than 78%, therefore can well adapt to low consistency conditions more than 92%, COD clearances Under wastewater treatment；Secondly, 0.5 ~ 2 part of magnetic combines 0.5 ~ 1 part of pentaerythritol stearate during it is formulated, and is advantageous to improve load The biofilm amount of body biomembrane.
3rd, the present invention be used for gas station phenol water advanced treatment process, thereafter in biochemical BAF ponds carrier in high-density polyethylene Bamboo carbon powder, wood powder, lignin are further added in alkene, acrylic resin, low density polyethylene (LDPE), not only improves filler production Raw absorption affinity, the adsorbance on increase filler surface, it is also beneficial to microorganism and quickly colonizes growth in early days, and strengthens biomembrane absorption Intensity, it is difficult for drop-off.
4th, the present invention is used for the advanced treatment process of gas station phenol water, arranges in pairs or groups add in carrier system in biochemical BAF ponds thereafter Add methylene chloride, diethyl guanidine sulfate, N, N'- ethylene bis stearamides and magnetic, the porous space of specific structure can be formed, With magnetization effect is formed compared with ferromagnetism, Pollutants in Wastewater conversion rate and efficiency are improved, improves the activity of microorganism, in water Microorganism is after magnetization, and the microorganism for adapting to survive has bigger propagation and metabolic capability so that organic contamination Thing in the presence of low-intensity magnetic field, by the effect such as magnetic force key, magnetic force, Lorentz force and mangneto cavity effect through magnetic is poly-, absorption, It is enriched to magnetic biological filling material surface, oxygen is paramagnet, and it is attached to be adsorbed to biologic packing material under magnetic fields during aeration Closely, increase the oxygen concentration on filler surface, promote the breeding of aerobe, in addition activity of the low-intensity magnetic field also with inducing microbial and The effect of enzymatic activity, substantially reduce power stirring energy consumption, improve filler the effect of.
5th, the present invention is used for the advanced treatment process of gas station phenol water, is further added in carrier in biochemical BAF ponds thereafter 5 ~ 20 parts of Tao Shi Powdered Activated Carbons so that filler has excellent adsorption capacity, can make biological cell and organic matter adsorbent solid Surface, the high oxidization rate of local space is caused, break through the boundary of original concentration balance, extend contact of the microorganism with organic matter Time, organic matter is set activated carbon surface adsorption capacity is restored again by rapid, thorough degraded, biological oxidation.
6th, the present invention is used for the advanced treatment process of gas station phenol water, and its catalytic ozonation technology compares other chemical oxygens Change method, reaction rate is rapid, the hydroxyl radical free radical of a large amount of active non-selectivities of generation, the multiple pollutant in oxidized waste water, The biodegradability of waste water is improved, oxidation water outlet enters interior circulation BAF, made in the filtering of biological bed, bioflocculation and biological adsorption Under, the material such as organic matter contained in waste water is further adsorbed oxidation, and it is low that this method effectively combines biochemical treatment cost The advantages of honest and clean and advanced oxidation high efficiency, improve the feasibility of RO concentrated water advanced treatings；Secondly, improve to petrochemical industry The tolerance of high saline sewage so that in the catalytic oxidation treatment process to saline sewage, catalyst ozone produces work The hydroxyl radical free radical of jump, removal, decolouring to waste water COD, de- stench, degraded toxic pollutant and improves the biochemical of waste water Property keep good effect.
Brief description of the drawings
Accompanying drawing 1 be handling process of the present invention based on special processor structural representation.
In the figures above：1st, catalysis oxidation pond；2nd, oxidation-stabilized pond；3rd, rear biochemical BAF ponds；4th, clear water reserviors；41st, intake Hole；42nd, apopore；51st, leading portion transfer conduit；52nd, back segment transfer conduit；6th, elevator pump；7th, inlet channel；8th, ozone occurs Device；9th, gas pipeline；10th, back segment reflux line；11st, backwashing pump；12nd, ozone catalytic particle；15th, pretreated primary BAF ponds； 16th, two level BAF ponds are pre-processed；17th, discharge bay；18th, comprehensive tank is diluted；181st, charge door；182nd, agitator；19th, backwash precipitates Pond；201st, the first pipeline；202nd, backwash sedimentation basin；21st, leading portion supernatant liquid pool；22nd, backwashing pump is pre-processed；23rd, leading portion return duct Road.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1 ~ 4：A kind of advanced treatment process for gas station phenol water, the handling process are filled based on a dedicated processes Put, the special processor includes catalysis oxidation pond 1, oxidation-stabilized pond 2, rear biochemical BAF ponds 3, clear water reserviors 4, the comprehensive tank of dilution 18th, pretreated primary BAF ponds 15, pretreatment two level BAF ponds 16 and discharge bay 17, the dilution synthesis tank 18, pretreated primary BAF ponds 15, pretreatment two level BAF ponds 16 and discharge bay 17 pass sequentially through leading portion transfer conduit 51 and connected,
The catalysis oxidation pond 1, oxidation-stabilized pond 2, rear biochemical BAF ponds 3 and clear water reserviors 4 pass sequentially through back segment transfer conduit 52 and connected Connecing, the discharge bay 17 is connected to inside catalysis oxidation pond 1 with catalysis oxidation pond 1 by inlet channel 7,
One ozone generator 8 is connected to inside catalysis oxidation pond 1 by gas pipeline 9, and the clear water reserviors 4 are provided with inlet opening 41st, apopore 42, the inlet opening 41 of the clear water reserviors 4 are connected with rear biochemical BAF ponds 3 by back segment transfer conduit 52, described clear Pond 4 is connected to the one end of a backwashing pump 11, and this other end of backwashing pump 11 is connected to catalysis oxidation pond by back segment reflux line 10 1st, inside rear biochemical BAF ponds 3, the catalysis oxidation pond 1 is filled with ozone catalytic particle 12 with fixed bed form, and the dilution is comprehensive Close tank 18 and be provided with charge door 181 and agitator 182；
The ozone catalytic particle 12 is obtained by following steps：
Step 1: 88.7 ~ 91.3 parts of activated aluminas are cleaned for several times to remove the impurity on its surface with distilled water, and dry To quality constant weight, the particle diameter of the activated alumina is 2 ~ 4mm；
Step 2: 88.7 ~ 91.3 parts of activated aluminas and 1.4 ~ 1.6 parts of cupric oxide, titanium dioxide 0.8 that step 1 is obtained ~ 1.2 parts, 4 ~ 7 parts of polyethylene glycol, 1.9 ~ 2.1 parts of polyvinyl alcohol mix in stirring mixer so that uniform mixed oxidation 1.4 ~ 1.6 parts of copper, 0.8 ~ 1.2 part of titanium dioxide, 4 ~ 7 parts of polyethylene glycol, 1.9 ~ 2.1 parts of polyvinyl alcohol are covered in the active oxygen Change alumina particles surface and form catalyst mother bulb；
Step 3: taking out the catalyst mother bulb from stirring mixer, after drying at room temperature, baking oven is put into, 100~ Dried under the conditions of 120 DEG C and obtain dried catalyst mother bulb；
Step 4: dried catalyst mother bulb is put into Muffle furnace, the resistance to high salt of roasting acquisition is smelly under the conditions of 350 ~ 520 DEG C VPO catalysts.
Ozone catalytic particle 12 is made up of the component of following parts by weight in embodiment 1 ~ 4, as shown in table 1：
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Activated alumina particle 90 parts 89.5 parts 89 parts 91 parts
Cupric oxide 1.55 part 1.4 part 1.6 part 1.5 part
Titanium dioxide 1.2 part 0.85 part 0.95 part 1.1 part
Polyethylene glycol 5.5 part 4.8 part 6 parts 6.5 part
Polyvinyl alcohol 2 parts 1.9 part 1.95 part 2.1 part
A dividing plate 13 is vertically provided with above-mentioned catalysis oxidation pond 1, it is described so as to which catalysis oxidation pond is divided into left and right chamber The lower horizontal of catalysis oxidation pond 1 is provided with a sieve plate 14, and the lower end of this dividing plate 13 is installed to the upper surface of sieve plate 14, the ozone Catalysed particulate 12 is located at the top of sieve plate 14 and is located at the both sides of dividing plate 13.
Also include the backwash sedimentation basin 19, leading portion supernatant liquid pool 21 and pretreatment backwashing pump 22 being sequentially connected, the backwash Sedimentation basin 19 is connected to pretreated primary BAF ponds 15, pretreatment two level BAF ponds 16 by the first pipeline 201, second pipe 201, The pretreatment backwashing pump 22 is connected to pretreated primary BAF ponds 15, pretreatment two level BAF ponds by leading portion reflux line 23 16。
Several biologic packing materials are placed with biochemical BAF ponds 3 after described, the biologic packing material is overlying on carrier by carrier and extension The microbial film composition on surface；
The carrier is made up of the component of following parts by weight, as shown in table 4：
Table 4
The density of above-mentioned use in waste water treatment suspension microorganism filler is 0.96~0.98g/cm3。
Above-mentioned white lime is with Tao Shi Powdered Activated Carbons and precipitated calcium carbonate according to 1：1.2：0.9 parts by weight mix.
Note：The magnetic of embodiment 1 is ferroso-ferric oxide magnetic；The magnetic of embodiment 2 is ferroso-ferric oxide magnetic, manganese-zinc ferrite installation 1：1 mixing；The magnetic of embodiment 3 is manganese-zinc ferrite and nickel-zinc ferrite according to 1：2 mixing；The magnetic of embodiment 4 is manganese-zinc ferrite Body.
A kind of manufacture method for above-mentioned suspension microorganism filler, comprise the following steps：
Step 1: take 60 ~ 70 parts of high density polyethylene (HDPE), 10 ~ 15 parts of acrylic resin, 6 ~ 8 parts of low density polyethylene (LDPE), dichloromethane 2 ~ 3 parts of alkane, 1 ~ 2 part of diethyl guanidine sulfate, N, 0.5 ~ 1 part of N'- ethylene bis stearamides, 3 ~ 5 parts of maleic anhydride, peroxidating two 0.2 ~ 0.6 part of isopropylbenzene, 1.5 ~ 3 parts of gelatin, 1 ~ 2 part of magnetic, 0.5 ~ 1 part of pentaerythritol stearate, it is placed in mixer high Speed stirs, and after temperature is slowly raised to 120 DEG C, stirring at low speed is cooled to 40 DEG C, adds 5 ~ 10 parts of bamboo carbon powder, timber 4 ~ 6 parts of powder, 5 ~ 8 parts of lignin are evenly stirred until room temperature；
Step 2: above-mentioned solid material is put into double screw extruder, melting extrusion is granulated；
Step 3: again putting into the particle produced above in 45 type single screw extrusion machines, by extrusion die extrusion forming, obtain Filler be cylinder, axial cross reinforcing rib is set in it, sets axially radial fin on cylinder outer wall.
Above-mentioned ozone generator 8 is connected to the bottom in catalysis oxidation pond 1 by gas pipeline 9.
Drying time is 5 hours under the conditions of 100 ~ 120 DEG C in above-mentioned steps three；At 350 ~ 520 DEG C in above-mentioned steps four Under the conditions of roasting time be 8 hours.
Ozone catalytic particulate catalytic effect assessment of the present invention, experimental method and data are shown in Table 2：
In the experiment of dynamic continuous flow catalytic ozonation, catalyst amountses 1.5L, ozone dosage 100mg/L, waterpower are stopped Time 1h is stayed, using gas flowmeter control ozone dosage in experiment, passes through peristaltic pump continuum micromeehanics.3 cycles of operation urge After changing effect stability, COD is repeatedly measured by sampling, averages.
Experiment condition：Dynamic continuous flow operational mode, the h of ozone dosage 100mg/L, HRT=1.
Intake source：Certain factory RO concentrated waters, COD about 350 mg/L, TDS 3500mg/L.
It is resistance to relative to Zhonghai Asphalt's conventional alumina ozone catalyst from table 2 it was found from data High salt ozone catalyst catalysis oxidation RO concentrated waters, it is 100mg/L in ozone dosage, hydraulic detention time is 1 h service conditions Under, COD clearances are up to 31%, and ozone efficiency is 1.03, far superior to conventional ozone catalyst.
The present invention be used for gas station phenol water advanced treatment process based on special processor, the course of work is as follows, bag Include following step：
（1）High saliferous phenol wastewater squeezes into interior circulation BAF systems by pump, and sewage is lifted along aeration tube, then by biological bed, is formed Recycle stream.Water velocity inside packing layer reaches 20~30m/h, improves the mass transfer velocity between biomembrane and aqueous phase, improves The treatment efficiency and impact resistance of reactor, while prevent and gas caused by the channel to be formed directly is aerated to packing layer Water short circuit phenomenon occurs.The biochemical component of high saliferous phenol wastewater is degraded by the BAF systems of pretreatment, so as to drop Low bio-chemical effluent COD；
（2）Biochemistry pre-processes water outlet gravity flow into catalytic ozonation, rear biochemical interior circulation BAF coupling technique processing systems, should System carries out catalytic oxidation first with ozone, using a part of refractory organic of ozone oxidation, makes macromolecular Oxidation operation can improve the biodegradability of pretreatment water outlet into small organic molecule；
（3）Circulation BAF advanced treatment systems in catalytic ozonation water outlet is biochemical after entering, the biochemical reaction tank utilize domestication Mushroom carries out biodegradation to the small organic molecule of ozone oxidation water outlet, water outlet COD is further reduced.
Wherein, step（1）In in order to ensure pretreatment IRBAF devices in microorganism growth, total dissolved solid is dense Degree control is 1.3% to 2.5%；
Step（2）In middle catalytic ozonation technique, control ozone dosage is not more than 100mg/L, to be followed in biochemistry after satisfaction Ring BAF demands.Catalyst exists as a fixed bed in catalytic ozonation pond, and the present embodiment catalyst is that metal ion is born Supported catalyst, can catalysis ozone produce hydroxyl radical free radical, while reduce the activation energy of hydroxyl radical free radical oxidation reaction, make to contain The organic matter of difficult degradation is mineralized removal in phenol sewage.
Step（3）Circulation BAF advanced treatment systems in middle catalytic ozonation water outlet gravity flow is biochemical after entering, utilize micro- life Thing carries out biodegradation to the organic matter after catalytic ozonation, to reduce processing cost.
Table 3 implements the water analysis data of embodiment
When influent COD is 1100-1300mg/L, it is less than 120mg/L by pre-processing the water outlet of IRBAF biochemical systems, COD is removed Rate is up to 90%, it can be seen that high efficiency of the interior circulation BAF reactors to high saliferous phenol wastewater；For pre-processing biochemical treatment Waste water difficult for biological degradation afterwards, using catalytic ozonation high-level oxidation technology, it is catalyzed using metal ion loaded catalyst Ozone produces the hydroxyl radical free radical of strong oxidizing property, the organic matter of bio-refractory is aoxidized, on the one hand by organic matter Mineralising can reduce water outlet COD, learn that water outlet COD is less than 60mg/L by table 3；On the other hand can be macromolecular hardly degraded organic substance The easily biochemical organic matter of small molecule is oxidized to, and then is improved the biochemical of water outlet.Pass through rear biochemical interior circulation BAF systems again Mineralising is carried out to the organic matter in water, final outflow water is less than 30mg/L, embodies economy, the high efficiency of the group technology.
Product A, B, C, the D for taking same amount of embodiment to obtain, are placed in 4 parallel bioreactors and are tested.It is dirty Mud and waste water are certain chemical engineering sewage processing unit bio-chemical effluent, are carried out wherein testing in MBBR, are suspended Media-filling rate is 40%, pH 6.3-7.6, and temperature is 20-30 DEG C, C/N/P=100：5：Under conditions of 1, DO=1.5 ~ 3mg/L, Hydraulic detention time 5h, as a result as shown in table 2.
The filler A- D of table 5 result of the test
Filling kind Biofilm time (d） Water outlet COD（mg/L) Water outlet ammonia nitrogen (mg/L) COD clearances（%） Ammonia nitrogen removal frank（%）
Embodiment 1 11 37 3 80.5 94
Embodiment 2 10 36 2 81 96
Embodiment 3 11 37 3 80.5 94
Embodiment 4 10 35 2 80 95
From table 5, the carrier biofilm time prepared by the inventive method substantially shortens, and the clearance of COD and ammonia nitrogen significantly improves.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.

Claims (7)

  1. A kind of 1. advanced treatment process for gas station phenol water, it is characterised in that：The handling process is based on a dedicated processes Device, the special processor include catalysis oxidation pond（1）, oxidation-stabilized pond（2）, rear biochemical BAF ponds（3）, clear water reserviors（4）、 The comprehensive tank of dilution（18）, pretreated primary BAF ponds（15）, pretreatment two level BAF ponds（16）And discharge bay（17）, it is described dilution it is comprehensive Close tank（18）, pretreated primary BAF ponds（15）, pretreatment two level BAF ponds（16）And discharge bay（17）Pass sequentially through leading portion transmission Pipeline（51）Connection；
    The catalysis oxidation pond（1）, oxidation-stabilized pond（2）, rear biochemical BAF ponds（3）And clear water reserviors（4）Pass sequentially through back segment transmission Pipeline（52）Connection, the discharge bay（17）With catalysis oxidation pond（1）Pass through inlet channel（7）It is connected to catalysis oxidation pond（1） It is internal；
    One ozone generator（8）Pass through gas pipeline（9）It is connected to catalysis oxidation pond（1）Inside, the clear water reserviors（4）It is provided with Inlet opening（41）, apopore（42）, the clear water reserviors（4）Inlet opening（41）With rear biochemical BAF ponds（3）Pass through back segment transfer tube Road（52）Connection, the clear water reserviors（4）It is connected to a backwashing pump（11）One end, this backwashing pump（11）The other end is flowed back by back segment Pipeline（10）It is connected to catalysis oxidation pond（1）, rear biochemical BAF ponds（3）Inside, the catalysis oxidation pond（1）With fixed bed form Filled with ozone catalytic particle（12）, the comprehensive tank of dilution（18）It is provided with charge door（181）And agitator（182）；
    The ozone catalytic particle（12）Obtained by following steps：
    Step 1: 88.7 ~ 91.3 parts of activated aluminas are cleaned for several times to remove the impurity on its surface with distilled water, and dry To quality constant weight, the particle diameter of the activated alumina is 2 ~ 4mm；
    Step 2: 88.7 ~ 91.3 parts of activated aluminas and 1.4 ~ 1.6 parts of cupric oxide, titanium dioxide 0.8 that step 1 is obtained ~ 1.2 parts, 4 ~ 7 parts of polyethylene glycol, 1.9 ~ 2.1 parts of polyvinyl alcohol mix in stirring mixer so that uniform mixed oxidation 1.4 ~ 1.6 parts of copper, 0.8 ~ 1.2 part of titanium dioxide, 4 ~ 7 parts of polyethylene glycol, 1.9 ~ 2.1 parts of polyvinyl alcohol are covered in the active oxygen Change alumina particles surface and form catalyst mother bulb；
    Step 3: taking out the catalyst mother bulb from stirring mixer, after drying at room temperature, baking oven is put into, 100~ Dried under the conditions of 120 DEG C and obtain dried catalyst mother bulb；
    Step 4: dried catalyst mother bulb is put into Muffle furnace, the resistance to high salt of roasting acquisition is smelly under the conditions of 350 ~ 520 DEG C VPO catalysts；
    Biochemical BAF ponds after described（3）Several biologic packing materials are inside placed with, the biologic packing material is overlying on carrier table by carrier and extension The microbial film composition in face；
    The carrier is made up of the component of following parts by weight：
    60 ~ 70 parts of high density polyethylene (HDPE),
    10 ~ 15 parts of acrylic resin,
    6 ~ 8 parts of low density polyethylene (LDPE),
    8 ~ 10 parts of bamboo carbon powder,
    4 ~ 6 parts of wood powder,
    2 ~ 3 parts of lignin,
    2 ~ 3 parts of dichloromethane,
    1 ~ 2 part of diethyl guanidine sulfate,
    0.5 ~ 1 part of N, N'- ethylene bis stearamide,
    3 ~ 5 parts of maleic anhydride,
    0.2 ~ 0.6 part of cumyl peroxide,
    1.5 ~ 3 parts of gelatin,
    1 ~ 2 part of magnetic,
    0.5 ~ 1 part of pentaerythritol stearate.
  2. 2. the advanced treatment process according to claim 1 for gas station phenol water, it is characterised in that：The catalysis oxidation Pond（1）Inside vertically it is provided with a dividing plate（13）, so as to which catalysis oxidation pond is divided into left and right chamber, the catalysis oxidation pond（1） Lower horizontal is provided with a sieve plate（14）, this dividing plate（13）Lower end be installed to sieve plate（14）Upper surface, the ozone catalytic Particle（12）Positioned at sieve plate（14）Top and it is located at dividing plate（13）Both sides.
  3. 3. the advanced treatment process according to claim 1 for gas station phenol water, it is characterised in that：Also include connecting successively The backwash sedimentation basin connect（19）, leading portion supernatant liquid pool（21）With pretreatment backwashing pump（22）, the backwash sedimentation basin（19）Pass through First pipeline（201）, second pipe（201）It is connected to pretreated primary BAF ponds（15）, pretreatment two level BAF ponds（16）, it is described Pre-process backwashing pump（22）Pass through leading portion reflux line（23）It is connected to pretreated primary BAF ponds（15）, pretreatment two level BAF ponds （16）.
  4. 4. the advanced treatment process according to claim 1 for gas station phenol water, it is characterised in that：The ozone occurs Device（8）Pass through gas pipeline（9）It is connected to catalysis oxidation pond（1）Bottom.
  5. 5. the advanced treatment process according to claim 1 for gas station phenol water, it is characterised in that：In the step 3 Drying time is 4 ~ 6 hours under the conditions of 100 ~ 120 DEG C.
  6. 6. the advanced treatment process according to claim 1 for gas station phenol water, it is characterised in that：In the step 4 Roasting time is 7 ~ 9 hours under the conditions of 350 ~ 520 DEG C.
  7. 7. the advanced treatment process according to claim 1 for gas station phenol water, it is characterised in that：The white lime with Tao Shi Powdered Activated Carbons and precipitated calcium carbonate are according to 1：1.2：0.9 parts by weight mix.
CN201610679752.4A 2016-08-17 2016-08-17 Advanced treatment process for gas station phenol water Pending CN107758994A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN204874211U (en) * 2015-08-24 2015-12-16 苏州科环环保科技有限公司 A synthesize processing apparatus for high salt industrial waste water that contains
CN105481177A (en) * 2015-12-27 2016-04-13 苏州科环环保科技有限公司 Low-consumption nitrification and denitrification coal chemical wastewater advanced treatment device
CN105621595A (en) * 2016-01-27 2016-06-01 苏州科环环保科技有限公司 Hydrophilic carrier for microbial biofilm formation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN204874211U (en) * 2015-08-24 2015-12-16 苏州科环环保科技有限公司 A synthesize processing apparatus for high salt industrial waste water that contains
CN105481177A (en) * 2015-12-27 2016-04-13 苏州科环环保科技有限公司 Low-consumption nitrification and denitrification coal chemical wastewater advanced treatment device
CN105621595A (en) * 2016-01-27 2016-06-01 苏州科环环保科技有限公司 Hydrophilic carrier for microbial biofilm formation

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