CN108773928A - A kind of waste water treatment process - Google Patents

A kind of waste water treatment process Download PDF

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Publication number
CN108773928A
CN108773928A CN201810590622.2A CN201810590622A CN108773928A CN 108773928 A CN108773928 A CN 108773928A CN 201810590622 A CN201810590622 A CN 201810590622A CN 108773928 A CN108773928 A CN 108773928A
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waste water
sent
obtains
reverse osmosis
added
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不公告发明人
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Li Delan
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Li Delan
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Priority to CN201610413801.XA priority Critical patent/CN105906104B/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The present invention relates to a kind of waste water treatment process, belong to water-treatment technology field.Include the following steps:Ammonia nitrogen waste water is sent into prefilter and is filtered, oil removal, then the waste water to obtaining is gone to carry out ozone Oxidation Treatment;Between the pH of obtained waste water is adjusted to 11 ~ 13 by the, it is sent into the adsorption tower for being filled with the first adsorbent and is adsorbed;Between the pH of obtained waste water is adjusted to 5 ~ 6, it is sent into the adsorption tower for being filled with the second adsorbent and is adsorbed;Obtained waste water is sent into reverse osmosis membrane and is filtered, the filtrate that obtains that treated.The technique of processing ammonia nitrogen waste water provided by the invention, has high treating effect, advantage simple for process.

Description

A kind of waste water treatment process
Technical field
The present invention relates to a kind of integrated techniques of processing ammonia nitrogen waste water, belong to water-treatment technology field.
Background technology
Many places use ammonium salt and ammonium hydroxide in the catalyst production process of petrochemical industry, therefore, in the containing wastewater from catalyst of discharge Containing a large amount of ammonia nitrogens, the ammonia nitrogen in waste water is mainly with ammonium ion(NH4+)In the presence of being to lead to body eutrophication and environmental pollution Important substance, easily cause algae and other microorganism mass propagations in water, oxygen in water can be made to decline when serious, fish are big Amount is dead, results even in the dry of lake;Ammonia nitrogen can also make to increase in water disinfection and industrial circulating water sterilisation process Chlorine dosage;In addition, ammonia nitrogen is to certain metals(Copper)With corrosivity, when reusing sewage, ammonia nitrogen can promote water delivery in recycled water The breeding of microorganism in pipeline and water equipment forms biofouling, blocks pipeline and water equipment, and influence heat exchange efficiency.
However the ammonia nitrogen waste water of high concentration has inhibiting effect to the activity of microorganism, constrains biochemical process and answers its processing With and effect, while degradation efficiency of the biochemical system to organic pollution can be reduced, be difficult to reach so as to cause processing water outlet and want It asks.Therefore one of key of this engineering is the removal of ammonia nitrogen, the main method for removing ammonia nitrogen has:Physical, chemical method, biology Method.Physical is containing treatment technologies such as reverse osmosis, distillation, soil irrigations;Chemical method contains ion exchange, ammonia aeration, break point chlorination, burns The treatment technologies such as burning, chemical precipitation, catalytic pyrolysis, electrodialysis, electrochemistry;Bioanalysis is containing algal culture, biological nitration, immobilization The treatment technologies such as biotechnology method practical at present has:Break point chlorination method, selective ion exchange method, ammonia aeration method, Bioanalysis and chemical precipitation method.
CN104445725A a kind of exhaust gas disclosed and high-concentration ammonia nitrogenous wastewater processing integrated apparatus include ammonia-nitrogen blowing desorption zone, Gas collection area, cleaning dust area, demister, activated carbon adsorption layer and exhaust fan;Ammonia-nitrogen blowing desorption zone is equipped with sediment discharge valve, air Air inlet pipe, gas distribution pipe, wastewater inlet pipe, water distributor, three phase separator and outlet pipe, wastewater inlet pipe connect lye addition and meter Measure device;Gas collection area is equipped with gas-liquid separator, gas gathering mask, gas collecting tube and stripping gas air pump, and gas collecting tube is connected with stripping gas air pump Sulfuric acid absorption pond;Exhaust gas cleaning dust area is equipped with processing water spray system, exhaust inlet pipe, exhaust gas gas distribution pipe and processing water cycle Pump;Integrated apparatus centre is cylindrical, upper and lower ends are conical tank body, using vertical vertical placement, the circular cone of topmost Exhaust fan is installed at shape tank body.CN103449584A discloses a kind of ammonia nitrogen waste water treatment method, is related to wastewater processing technology neck Domain handles ammonia nitrogen waste water using guanite method, and the method is that waste I and waste II are added in ammonia nitrogen waste water to mix, Wherein I is the waste of the compound containing magnesium ion;II is the waste of phosphorus-containing acid ion compound.CN103183393A is disclosed A kind of technique handling ammonia nitrogen waste water using vacuum outgas membrane technology, it is characterized in that including the following steps:1)What is be discharged contains ammonia The waste water of the impurity such as nitrogen removes most suspended matter into ammonia nitrogen waste water pond by pre-processing;2)Subsequently into cycle Soda bath and steam is added in pond in circulating water pool;3)In the case where recycling pumping action, waste water is de- into vacuum through filter The side of film in air film device, in vacuum outgas film device, the free ammonia in waste water is separated into the another of film Side;4)It is extracted under the action of vacuum system.After recycling several times, the free ammonia in waste water is constantly removed.
But there is complex process, the not high problems for the treatment of effect for above-mentioned method.
Invention content
The purpose of the present invention is:There is provided a kind for the treatment of process of efficiently industrial ammonia nitrogen waste water, it is necessary to have at low cost, places Manage the good advantage of effect.
Technical solution is:
A kind of technique efficiently handling industrial ammonia nitrogen waste water, includes the following steps:
Ammonia nitrogen waste water is sent into prefilter and is filtered by the 1st step, and oil removal, then the waste water to obtaining is gone to carry out ozone Oxidation processes;
2nd step, between the pH for the waste water that the 1st step obtains is adjusted to 11~13, feeding is filled in the adsorption tower of the first adsorbent It is adsorbed;
3rd step, between the pH for the waste water that the 2nd step obtains is adjusted to 5~6, be sent into be filled in the adsorption tower of the second adsorbent into Row absorption;
4th step, the waste water obtained to the 3rd step are sent into reverse osmosis membrane and are filtered, the filtrate that obtains that treated.
In one embodiment, reverse osmosis concentrate is sent into the ozone process processing in the 1st step.
In one embodiment, the water quality situation of the ammonia nitrogen waste water described in the 1st step is:PH8.5~10, conductance 5~ 50mS/cm, CODcr200~400mg/L, Na+1500~6000mg/L, NO3-5000~7000mg/L, NH4-500~ 10000mg/L。
In one embodiment, the addition of ozone is 500mg/L in the 1st step.
In one embodiment, the first adsorbent is activated carbon in the 2nd step.
In one embodiment, the second adsorbent is macroporous absorbent resin in the 3rd step.
In one embodiment, reverse osmosis pressure is 2.0~3.5Mpa in the 4th step, and reverse osmosis temperature is 25~30, is used Be polyamide reverse osmose membrane.
In one embodiment, the preparation method of macroporous absorbent resin is as follows:
1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres carrier (PS-acyl-Cl), and 60ml tetrahydrochysene furans are added Mutter swelling 12h, 40ml methanol is added, then according to weight ratio (PS-acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1: 8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to be stirred to react for 24 hours at 80 DEG C, after reaction, product is poured into sand In core funnel, neutrality is washed to distillation, methanol filter wash is dried under vacuum to constant weight 3 times, and it is microsphere supported to obtain crosslinking EDA;
2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, after dimethylformamide swelling 12h is added, adds It is double to enter 2- acrylamido -2- methyl propane sulfonic acids (AMPS) 16g, N- butoxy methyl acrylamide (NBMA) 3g, acrylic acid Cyclopentene base ester(DCPA), K2CO35g, tetrabutylammonium bromide(TBAB)12g flows back instead under stirring in the oil bath of certain temperature It answers, reaction product is transferred in sintered filter funnel after reaction, after cleaning 4 times with the HC1 of 5wt% with distilled water diafiltration into Property, finally with being drained after methanol filter wash, it is dried under vacuum to constant weight, obtains macroporous resin adsorption agent.
A kind of integrating device of processing ammonia nitrogen waste water, includes sequentially connected prefilter, ozone treatment apparatus, filling There are the adsorption tower, the adsorption tower filled with the second adsorbent, reverse osmosis membrane of the first adsorbent.
Advantageous effect
The technique of processing ammonia nitrogen waste water provided by the invention, has high treating effect, advantage simple for process.
Specific implementation mode
Embodiment 1
A kind of technique efficiently handling industrial ammonia nitrogen waste water, includes the following steps:
Ammonia nitrogen waste water is sent into prefilter and is filtered by the 1st step, and the water quality situation of the ammonia nitrogen waste water is wrapped in component It has included:PH9, conductance 30mS/cm, CODcr300mg/L, Na+4330mg/L, NO3-6500mg/L, NH4-1285mg/L, removal Suspended matter, then the waste water to obtaining carry out ozone Oxidation Treatment, and the addition of ozone is 500mg/L;
The pH for the waste water that 1st step obtains is adjusted to 11, is sent into the adsorption tower for being filled with activated carbon and is adsorbed by the 2nd step;
The pH for the waste water that 2nd step obtains is adjusted to 5, is sent into the adsorption tower for being filled with macroporous absorbent resin and is inhaled by the 3rd step It is attached;
4th step is sent into reverse osmosis membrane the waste water that 3 steps obtain and is filtered, and reverse osmosis pressure is 2.0Mpa, reverse osmosis temperature It it is 25 DEG C, using polyamide reverse osmose membrane, the filtrate that obtains that treated, reverse osmosis concentrate is sent into smelly in the 1st step The processing of oxygen process.
The preparation method of macroporous absorbent resin is as follows:
1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres carrier (PS-acyl-Cl), and 60ml tetrahydrochysene furans are added Mutter swelling 12h, 40ml methanol is added, then according to weight ratio (PS-acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1: 8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to be stirred to react for 24 hours at 80 DEG C, after reaction, product is poured into sand In core funnel, neutrality is washed to distillation, methanol filter wash is dried under vacuum to constant weight 3 times, and it is microsphere supported to obtain crosslinking EDA;
2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, after dimethylformamide swelling 12h is added, adds It is double to enter 2- acrylamido -2- methyl propane sulfonic acids (AMPS) 16g, N- butoxy methyl acrylamide (NBMA) 3g, acrylic acid Cyclopentene base ester(DCPA), K2CO35g, tetrabutylammonium bromide(TBAB)12g flows back instead under stirring in the oil bath of certain temperature It answers, reaction product is transferred in sintered filter funnel after reaction, after cleaning 4 times with the HC1 of 5wt% with distilled water diafiltration into Property, finally with being drained after methanol filter wash, it is dried under vacuum to constant weight, obtains macroporous resin adsorption agent.
Embodiment 2
A kind of technique efficiently handling industrial ammonia nitrogen waste water, includes the following steps:
Ammonia nitrogen waste water is sent into prefilter and is filtered by the 1st step, and the water quality situation of the ammonia nitrogen waste water is wrapped in component It has included:PH9, conductance 30mS/cm, CODcr300mg/L, Na+4330mg/L, NO3-6500mg/L, NH4-1285mg/L, removal Suspended matter, then the waste water to obtaining carry out ozone Oxidation Treatment, and the addition of ozone is 500mg/L;
The pH for the waste water that 1st step obtains is adjusted to 13, is sent into the adsorption tower for being filled with activated carbon and is adsorbed by the 2nd step;
The pH for the waste water that 2nd step obtains is adjusted to 6, is sent into the adsorption tower for being filled with macroporous absorbent resin and is inhaled by the 3rd step It is attached;
4th step is sent into reverse osmosis membrane the waste water that the 3rd step obtains and is filtered, and reverse osmosis pressure is 3.5Mpa, reverse osmosis temperature Degree is 30 DEG C, and using polyamide reverse osmose membrane, the filtrate that obtains that treated, reverse osmosis concentrate is sent into the 1st step The processing of ozone process.
The preparation method of macroporous absorbent resin is as follows:
1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres carrier (PS-acyl-Cl), and 60ml tetrahydrochysene furans are added Mutter swelling 12h, 40ml methanol is added, then according to weight ratio (PS-acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1: 8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to be stirred to react for 24 hours at 80 DEG C, after reaction, product is poured into sand In core funnel, neutrality is washed to distillation, methanol filter wash is dried under vacuum to constant weight 3 times, and it is microsphere supported to obtain crosslinking EDA;
2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, after dimethylformamide swelling 12h is added, adds It is double to enter 2- acrylamido -2- methyl propane sulfonic acids (AMPS) 16g, N- butoxy methyl acrylamide (NBMA) 3g, acrylic acid Cyclopentene base ester(DCPA), K2CO35g, tetrabutylammonium bromide(TBAB)12g flows back instead under stirring in the oil bath of certain temperature It answers, reaction product is transferred in sintered filter funnel after reaction, after cleaning 4 times with the HC1 of 5wt% with distilled water diafiltration into Property, finally with being drained after methanol filter wash, it is dried under vacuum to constant weight, obtains macroporous resin adsorption agent.
Embodiment 3
A kind of technique efficiently handling industrial ammonia nitrogen waste water, includes the following steps:
Ammonia nitrogen waste water is sent into prefilter and is filtered by the 1st step, and the water quality situation of the ammonia nitrogen waste water is wrapped in component It has included:PH9, conductance 30mS/cm, CODcr300mg/L, Na+4330mg/L, NO3-6500mg/L, NH4-1285mg/L, removal Suspended matter, then the waste water to obtaining carry out ozone Oxidation Treatment, and the addition of ozone is 500mg/L;
2nd step between the pH for the waste water that the 1st step obtains is adjusted to 12, is sent into the adsorption tower for being filled with activated carbon and is adsorbed;
3rd step, between the pH for the waste water that the 2nd step obtains is adjusted to 5.5, be sent into be filled in the adsorption tower of macroporous absorbent resin into Row absorption;
4th step is sent into reverse osmosis membrane the waste water that the 3rd step obtains and is filtered, and reverse osmosis pressure is 3.0Mpa, reverse osmosis temperature Degree is 27 DEG C, and using polyamide reverse osmose membrane, the filtrate that obtains that treated, reverse osmosis concentrate is sent into the 1st step The processing of ozone process.
The preparation method of macroporous absorbent resin is as follows:
1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres carrier (PS-acyl-Cl), and 60ml tetrahydrochysene furans are added Mutter swelling 12h, 40ml methanol is added, then according to weight ratio (PS-acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1: 8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to be stirred to react for 24 hours at 80 DEG C, after reaction, product is poured into sand In core funnel, neutrality is washed to distillation, methanol filter wash is dried under vacuum to constant weight 3 times, and it is microsphere supported to obtain crosslinking EDA;
2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, after dimethylformamide swelling 12h is added, adds It is double to enter 2- acrylamido -2- methyl propane sulfonic acids (AMPS) 16g, N- butoxy methyl acrylamide (NBMA) 3g, acrylic acid Cyclopentene base ester(DCPA), K2CO35g, tetrabutylammonium bromide(TBAB)12g flows back instead under stirring in the oil bath of certain temperature It answers, reaction product is transferred in sintered filter funnel after reaction, after cleaning 4 times with the HC1 of 5wt% with distilled water diafiltration into Property, finally with being drained after methanol filter wash, it is dried under vacuum to constant weight, obtains macroporous resin adsorption agent.
Reference examples 1
With embodiment 3 difference lies in:The use sequence of first adsorbent and the second adsorbent is opposite.
Ammonia nitrogen waste water is sent into prefilter and is filtered by the 1st step, and the water quality situation of the ammonia nitrogen waste water is component In include:PH9, conductance 30mS/cm, CODcr300mg/L, Na+4330mg/L, NO3-6500mg/L, NH4-1285mg/L, Oil removal, then the waste water to obtaining is gone to carry out ozone Oxidation Treatment, the addition of ozone is 500mg/L;
2nd step, between the pH for the waste water that the 1st step obtains is adjusted to 5.5, be sent into be filled in the adsorption tower of macroporous absorbent resin into Row absorption;
3rd step between the pH for the waste water that the 2nd step obtains is adjusted to 12, is sent into the adsorption tower for being filled with activated carbon and is adsorbed;
4th step is sent into reverse osmosis membrane the waste water that the 3rd step obtains and is filtered, and reverse osmosis pressure is 3.0Mpa, reverse osmosis temperature Degree is 27 DEG C, and using polyamide reverse osmose membrane, the filtrate that obtains that treated, reverse osmosis concentrate is sent into the 1st step The processing of ozone process.
The preparation method of macroporous absorbent resin is as follows:
1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres carrier (PS-acyl-Cl), and 60ml tetrahydrochysene furans are added Mutter swelling 12h, 40ml methanol is added, then according to weight ratio (PS-acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1: 8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to be stirred to react for 24 hours at 80 DEG C, after reaction, product is poured into sand In core funnel, neutrality is washed to distillation, methanol filter wash is dried under vacuum to constant weight 3 times, and it is microsphere supported to obtain crosslinking EDA;
2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, after dimethylformamide swelling 12h is added, adds It is double to enter 2- acrylamido -2- methyl propane sulfonic acids (AMPS) 16g, N- butoxy methyl acrylamide (NBMA) 3g, acrylic acid Cyclopentene base ester(DCPA), K2CO35g, tetrabutylammonium bromide(TBAB)12g flows back instead under stirring in the oil bath of certain temperature It answers, reaction product is transferred in sintered filter funnel after reaction, after cleaning 4 times with the HC1 of 5wt% with distilled water diafiltration into Property, finally with being drained after methanol filter wash, it is dried under vacuum to constant weight, obtains macroporous resin adsorption agent.
Reference examples 2
With embodiment 3 difference lies in:N- butoxy methyl acrylamides are not added in the preparation method of macroporous absorbent resin (NBMA) monomer.
Ammonia nitrogen waste water is sent into prefilter and is filtered by the 1st step, and the water quality situation of the ammonia nitrogen waste water is component In include:PH9, conductance 30mS/cm, CODcr300mg/L, Na+4330mg/L, NO3-6500mg/L, NH4-1285mg/L, Oil removal, then the waste water to obtaining is gone to carry out ozone Oxidation Treatment, the addition of ozone is 500mg/L;
2nd step between the pH for the waste water that the 1st step obtains is adjusted to 12, is sent into the adsorption tower for being filled with activated carbon and is adsorbed;
3rd step, between the pH for the waste water that the 2nd step obtains is adjusted to 5.5, be sent into be filled in the adsorption tower of macroporous absorbent resin into Row absorption;
4th step is sent into reverse osmosis membrane the waste water that the 3rd step obtains and is filtered, and reverse osmosis pressure is 3.0Mpa, reverse osmosis temperature Degree is 27 DEG C, and using polyamide reverse osmose membrane, the filtrate that obtains that treated, reverse osmosis concentrate is sent into the 1st step The processing of ozone process.
The preparation method of macroporous absorbent resin is as follows:
1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres carrier (PS-acyl-Cl), and 60ml tetrahydrochysene furans are added Mutter swelling 12h, 40ml methanol is added, then according to weight ratio (PS-acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1: 8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to be stirred to react for 24 hours at 80 DEG C, after reaction, product is poured into sand In core funnel, neutrality is washed to distillation, methanol filter wash is dried under vacuum to constant weight 3 times, and it is microsphere supported to obtain crosslinking EDA;
2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, after dimethylformamide swelling 12h is added, adds Enter 2- acrylamido -2- methyl propane sulfonic acids (AMPS) 16g, acrylic acid double cyclopentenyl ester(DCPA), K2CO35g, four fourths Base ammonium bromide(TBAB)12g, under stirring in the oil bath of certain temperature back flow reaction, reaction product is transferred to after reaction In sintered filter funnel, with distilled water diafiltration to neutrality after cleaning 4 times with the HC1 of 5wt%, finally with being drained after methanol filter wash, vacuum is dry It is dry to constant weight, obtain macroporous resin adsorption agent.
It is small below by way of the NH4+ rejections of reverse osmosis membrane, water outlet conductivity, water outlet COD, the operation 10 of reverse osmosis membrane flux When in average flux technique characterized.
As can be seen from the above table, it is preferable can be obtained water quality after treatment by method provided by the invention for higher nitrogen nitrogen waste water Production water, have the advantages that simple for process, high treating effect;Due to being first to be carried out at absorption with the second adsorbent in reference examples 1 Reason, resulting in cannot be in advance by a part of organic matter removal, under the absorption property that the first adsorbent is made so as to cause organic matter Drop, causes the first adsorbent that cannot play preferable effect, reverse osmosis flux is made to decline;Reference examples 2 are relative to embodiment 3 It says, due to not modified using N- butoxy methyl acrylamides macroporous absorbent resin, causes under its adsorption effect to nitrogen nitrogen Drop.

Claims (1)

1. a kind of waste water treatment process, which is characterized in that include the following steps:Ammonia nitrogen waste water is sent into prefilter by the 1st step It is filtered, goes oil removal, then the waste water to obtaining to carry out ozone Oxidation Treatment, the addition of ozone is 500mg/L;
The pH for the waste water that 1st step obtains is adjusted to 13, is sent into the adsorption tower for being filled with activated carbon and is adsorbed by the 2nd step;
The pH for the waste water that 2nd step obtains is adjusted to 6, is sent into the adsorption tower for being filled with macroporous absorbent resin and is inhaled by the 3rd step It is attached;
4th step is sent into reverse osmosis membrane the waste water that the 3rd step obtains and is filtered, and reverse osmosis pressure is 3.5Mpa, reverse osmosis temperature Degree is 30 DEG C, the filtrate that obtains that treated, and reverse osmosis concentrate is sent into the ozone process processing in the 1st step;
Wherein, the water quality situation of the ammonia nitrogen waste water described in the 1st step is:PH9, conductance 30mS/cm, CODcr300mg/L, Na+ 4330mg/L, NO3-6500mg/L, NH4-1285mg/L;
The preparation method of the macroporous absorbent resin is as follows:1st step takes 10g chloracetylated polystyrenes-divinylbenzene microspheres Carrier (PS-acyl-Cl) is added 60ml tetrahydrofurans and is swollen 12h, 40ml methanol added, then according to weight ratio (PS- acyl-Cl):Ethylenediamine(EDA):Sodium bicarbonate is 1:8:0.7, ethylenediamine and sodium bicarbonate are sequentially added, is to stir at 80 DEG C It mixes reaction for 24 hours, after reaction, product is poured into sand core funnel, be washed to neutrality with distillation, 3 times vacuum of methanol filter wash are dry It is dry to constant weight, it is microsphere supported to obtain crosslinking EDA;2nd step claims 60g to take crosslinking EDA microsphere supported, is placed in three-neck flask, is added After dimethylformamide is swollen 12h, 2- acrylamido -2- methyl propane sulfonic acid (AMPS) 16g, N- butoxymethyl third is added Acrylamide (NBMA) 3g, acrylic acid double cyclopentenyl ester(DCPA), K2CO35g, tetrabutylammonium bromide(TBAB)12g, under stirring Reaction product, is transferred in sintered filter funnel by the back flow reaction in the oil bath of certain temperature after reaction, clear with the HC1 of 5wt% , finally with being drained after methanol filter wash, it is dried under vacuum to constant weight to neutrality with distilled water diafiltration after washing 4 times, obtains macroreticular resin suction Attached dose.
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