CN103102049B - High-nitrogen-concentration organic wastewater treatment method - Google Patents
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Abstract
The invention discloses a high-nitrogen-concentration organic wastewater treatment method which comprises the following steps: (1) PH value adjustment: adjusting the PH value of wastewater to be 8-9; (2) chemical oxidation treatment: carrying out chemical oxidated denitrification on the wastewater; (3) anoxic/aerobic biological treatment: removing pollutants containing nitrogen elements in the wastewater; (4) filtration and reverse osmosis treatment: carrying out filtration and reverse osmosis treatment on the wastewater, so that particles, inorganic salts, organic matters, hardness ions and bacteria and the like in the wastewater are separated from water; (5) ion exchange treatment: carrying out ion exchange on the wastewater subjected to reverse osmosis treatment so as to remove residual matters containing nitrogen elements, and then directly reusing the obtained product in production; and (6) triple-effect evaporation treatment: concentrating concentrated water subjected to reverse osmosis treatment by using a triple-effect evaporator. The method can be used for not only realizing the zero emission of wastewater treatment, but also realizing the cyclic utilization of wastewater through deep treatment, thereby meeting the requirements of energy conservation and emission reduction.
Description
Technical field
The present invention relates to a kind for the treatment of process of high nitrogenous organic waste water.
Background technology
Nitrogenous and organic content is very high, be difficult to biological degradation in chemical industry, the waste water butchering, produce in the industry production process such as food-processing, semi-conductor, be one of the difficult point of wastewater treatment both at home and abroad at present and focus.For a long time, the processing of sewage all be take and is removed organism (COD) and suspended solids (SS) be target, fails the removal of comprehensive consideration to nutritive substances such as nitrogens.After the Taihu Lake Blue Algae Event that nitrogen phosphorus eutrophication in 2007 causes, the principal contradiction of Chinese current environment problem has started to have been turned to by organic pollutant the problem of nitrogen.Nitrate pollution be cause in the important factor, particularly water of body eutrophication and Hypoxic water quality deterioration nitrogenous the most obvious on the impact of water quality.In recent years, aggravate rapidly nitrogenous first of many water bodys and the basin pollutent that exceeds standard that becomes containing polluted by nitrogen.In " the 12 " stage, nitrogen has become the important control index that the total amount of pollutant reduces discharging after COD, sulfurous gas.The efficient control of water body nitrogen becomes the important node that ensures water quality and Ecology safety.China is tending towards strict to entering the sewage drainage standard of major river valley.In the < of the up-to-date modification of China < urban wastewater treatment firm pollutant emission standard > > by the operative norm of urban wastewater treatment firm water outlet that enters major river valley by original one-level B standard upgrading to one-level A standard, require the nitrogenous 5mg/L of being less than of the last water outlet nitrogen content of all pollutant discharging units, total nitrogen is less than 15mg/L, and to China, newly-built and built Sewage Plant has proposed the technical requirements of sewage deep denitrogenation.In China developed area as Taihu Lake basin area requires to carry out the zero release of nitrogenous effluent especially to new project.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, providing a kind of processes chemical oxidation treatment+anoxia/aerobic biological processing+filtration treatment+reverse osmosis system processing+ion exchange treatment+triple effect evaporation to be applied to the treatment process in high nitrogenous organic waste water, the method treatment effect is stable, treatment effect is good, processing cost is low, operational condition is simple, realizes wastewater zero discharge, carries out the recycle that advanced treatment realizes waste water simultaneously.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A treatment process for high nitrogenous organic waste water, comprises the following steps:
(1), adjust pH value: according to the water quality characteristics of waste water, the pH value of described waste water is adjusted to 8 ~ 9;
(2), chemical oxidation treatment: described waste water, after step (1) is processed, enters chemical oxidation pond and carries out denitrogenation processing;
(3), anoxia/aerobic biological is processed: described waste water is after step (2) is processed, be introduced into anoxic pond reaction 13h ~ 16h, then enter Aerobic Pond reaction 8h ~ 10h, in described anoxic pond and described Aerobic Pond, the nitrogenous organic pollutant in described waste water is removed in and aerobic biological treatment biological by anoxic respectively, the described return of waste water of part in described Aerobic Pond is to described anoxic pond simultaneously, between described anoxic pond and described Aerobic Pond, form an internal recycle, the return current ratio of the mixed liquid of described internal recycle is 150% ~ 200%;
(4), filtration and reverse-osmosis treated: under pressure-driven, make the water outlet after step (3) is processed through mechanical filter, activated charcoal filter and cartridge filter, carry out filtration treatment successively, then enter into reverse osmosis membrane system and carry out separation, after described reverse osmosis membrane system, isolate two portions water outlet, a part is for producing water, another part is dense water, and producing water ratio is 65% ~ 70%.
(5), ion exchange treatment: the described product water of generation enters into ion-exchanger after step (4) is processed, and recycles after removing Nitrogen element pollutent residual in described product water by ion exchange resin;
(6), triple effect evaporation is processed: the described dense water producing after step (4) is processed enters into triple-effect evaporator and processes, after processing, a gained part is crystallization concentrated solution, described crystallization concentrated solution enters in supercentrifuge through centrifugation, the clear liquid that centrifugation produces reenters circulating and evaporating in triple-effect evaporator and processes, it is phlegma that described triple-effect evaporator is processed gained another part, described phlegma reenters described anoxic pond, and the described waste water after processing with step (2) carries out step (3) to be processed.
Preferably, in step (2), the oxygenant in described chemical oxidation pond adopts aqueous sodium hypochlorite solution, and the mol ratio of nitrogen and clorox is 1:2 ~ 2.5, and the reaction times is 45min ~ 60min.
Preferably, the PH of the waste water after step (2) is processed is adjusted to the processing of carrying out again step (3) after 7 ~ 8.
Preferably, in step (3), a part of sludge reflux that described Aerobic Pond produces is to described anoxic pond, and another part mud enters into sludge thickener.
Preferably, in step (4), described reverse osmosis membrane system adopts crosslinked aromatic polymeric amide anti-pollution reverse osmosis membrane, and its ratio of desalinization is greater than 98%.
Particularly, in step (4), the producing water ratio of described reverse osmosis membrane system is 68% ~ 70%.
Preferably, in step (4), the outer disposal of solid waste committee that described supercentrifuge centrifugation produces.
The processing of the nitrogenous organic waste water of all kinds of height of the industry production such as the present invention is applicable to chemical industry, butchers, food-processing, semi-conductor, can realize wastewater zero discharge, is also applicable to the Treatment for Reuse of other high nitrogenous organic waste waters.
Due to the employing of technique scheme, the present invention compared with prior art tool has the following advantages:
The present invention is by technique unit organic combinations such as chemical oxidation treatment, anoxia/aerobic biological processing, filtration treatment, reverse osmosis system processing, ion exchange treatment, triple effect evaporation processing, bring into play the synergy of each technique, nitrogenous organic pollutant in waste water and other organic pollutants significantly reduce the most at last, finally realize the process water of waste water recycling in producing and the object of wastewater zero discharge.Wherein, waste water first passes through chemical oxidation pre-treatment denitrogenation, more further by anoxia/aerobic biological treatment process, carries out biochemical denitrification, reduces processing cost.The present invention is first separated with water by materials such as the particulate matter in waste water, inorganic salt, organism, hardness ions, bacteriums by reverse osmosis system, and the water outlet of reverse osmosis system is divided into produces water and dense water two portions: producing water can the reuse water of direct reuse in producing after ion exchange resin is removed remaining Nitrogen element material, dense water is processed through energy-efficient triple-effect evaporator, it is fast that triple-effect evaporator has velocity of evaporation, heated time is short, circulation degree and steam capability are large, and material can be in lower temperature evaporation, meet the concentrated requirement of heat-sensitive material, and evaporative crystallization is integrated, treatment process is not subject to the impact of saltiness height, crystallization concentrated solution after triple-effect evaporator enters into supercentrifuge, be easy to can not introduce new pollutent by solid-liquid separation and in water, clear liquid after separation is got back in triple-effect evaporator, phlegma after triple-effect evaporator pumps in anoxic pond to be processed, realize wastewater zero discharge.Usage range of the present invention is wide, and technique is simple, simple to operate, and working cost is lower, and producer is acceptant, easy to utilize.
Accompanying drawing explanation
Fig. 1 is according to the process flow sheet of the treatment process of the nitrogenous organic waste water of height of the present invention.
Embodiment
COD can be used as an overall target of organic substance relative content in water, and COD value is larger, represents that water body is subject to organic pollution more serious, and the testing method of COD has multiple, and present embodiment adopts potassium dichromate standard method, and the COD value calculating is designated as COD
cr.
In technical process of the present invention, if before anoxia/aerobic biological treatment process is placed in to chemical oxidation treatment, nitric efficiency declines 40% ~ 50%, this is because the C/N < 7 in former water, can not meet the demand of denitrification process to carbon source, if adopt the method for supplementary carbon source, will cause the significantly raising of processing cost again, so first chemical oxidation pre-treatment denitrogenation in technical process of the present invention, more further by anoxia/aerobic biological, process denitrogenation, if before triple effect evaporation processing is placed in to the processing of reverse osmosis (RO) system, to cause processing cost to increase by 3～4 times, this is mainly because if all waste water directly enters triple-effect evaporator, the cost that a large amount of consumption of heat energy cause increases, so first process pollutant removals such as the salinity in waste water and organism by reverse osmosis (RO) system in technical process of the present invention, produce water after ion-exchange direct reuse in production technique, dense water is by triple-effect evaporator evaporation concentration, phlegma is back to anoxic pond, a small amount of crystallization concentrated solution that triple-effect evaporator produces is disposed outside solid waste committee after centrifuge dehydration, clear liquid circulating and evaporating is processed, realize wastewater zero discharge.
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be further described in detail.
Embodiment 1
The high nitrogenous factory effluent of certain semi-conductor is carried out to sampling analysis, and the essential property of its waste water is: ammonia nitrogen: 300～350mg/L, total nitrogen: 422～473mg/L, COD
cr: 1000～1500mg/L, PH is 8～10, SS:40～60mg/L, specific conductivity: 3500～4000us/cm, waste water generation is 240m
3/ d.
According to following steps, this waste water is processed:
(1), adjust pH value: the nitrogenous organic waste water of the height in wastewater equalization pond is pumped into PH with lift pump and adjusts in pond 1, then according to the water quality characteristics of waste water, the pH value of described waste water is regulated whole to 8 ~ 9;
(2), chemical oxidation treatment: described waste water is after step (1) is processed, enter and in chemical oxidation pond, carry out denitrogenation processing, oxygenant in chemical oxidation pond adopts aqueous sodium hypochlorite solution, and the mol ratio of nitrogen and clorox is 1:2 ~ 2.5, and the reaction times is 45min ~ 60min;
(3), anoxia/aerobic biological is processed: after the PH of the waste water after step (2) is processed is adjusted to 7 ~ 8, then entering anoxia/aerobic biological processes, the water outlet that PH adjusts pond 2 is introduced into anoxic pond reaction 13h ~ 16h, then enter Aerobic Pond reaction 8h ~ 10h, nitrogenous organic pollutant remove described waste water by anoxic biology and aerobic biological treatment respectively in described anoxic pond and described Aerobic Pond in, the described return of waste water of part in described Aerobic Pond is to described anoxic pond simultaneously, between described anoxic pond and described Aerobic Pond, form an internal recycle, the return current ratio of the mixed liquid of internal recycle is 150% ~ 200%, in described Aerobic Pond, can produce mud, a described mud part is back to described anoxic pond, described mud another part enters into sludge thickener,
(4), filtration and reverse-osmosis treated: under pressure-driven, make the water outlet after step (3) is processed through mechanical filter, activated charcoal filter and cartridge filter, carry out filtration treatment successively, then enter into reverse osmosis membrane system and carry out separation, described reverse osmosis membrane selects to have the crosslinked aromatic polymeric amide anti-pollution reverse osmosis membrane of highly selective, the de-rate of its salt is greater than 98%, after described reverse osmosis membrane system, isolate two portions water outlet, a part is for producing water, another part is dense water, and producing water ratio is 68% ~ 70%;
(5), ion exchange treatment: the described product water after step (4) is processed enters into ion-exchanger, recycles after removing Nitrogen element pollutent residual in described product water by ion exchange resin;
(6), triple effect evaporation is processed: the described dense water after step (4) is processed enters into triple-effect evaporator and processes, after processing, a gained part is crystallization concentrated solution, described crystallization concentrated solution enters in supercentrifuge through centrifugation, the clear liquid that centrifugation produces reenters circulating and evaporating in triple-effect evaporator and processes, the outer disposal of solid waste committee that centrifugation produces; It is phlegma that triple-effect evaporator is processed gained another part, and described phlegma reenters described anoxic pond, and the waste water after processing with step (2) carries out step (3) to be processed.
Adopt aforesaid method to process waste water, waste water containing nitrogen removal efficiency more than 99.9%, the clearance of COD is more than 98%, the water-quality guideline of water outlet reaches enterprise's water of productive use water quality standard.
The water quality situation of concrete effluent reuse water is as follows:
Total nitrogen and ammonia nitrogen cannot detect, COD
cr: 12～18mg/L, pH is 7～8, specific conductivity <10 μ s/cm, water quality meets the zero emission requirement of this enterprise's production technique water and nitrogenous effluent; Solid waste Chan Sheng Liang≤1.0% of triple-effect evaporator.
These were more than 2 years from 2011 to 2012 for this project actual motion, and processing wastewater flow rate is 240m
3/ d, processing cost mainly comprises: 1. the electricity charge are 22.5 yuan/ton, and 2. medicament expense is with 4.8 yuan/ton, and 3. gas fired-boiler Sweet natural gas expense is 35.0 yuan/ton, and 4. labour cost is 2.8 yuan/ton, and more than adding up to ton cost of water treatment is 65.1 yuan/ton.
Embodiment 2
Certain Production in Chemical Plant waste water is carried out to sampling analysis, and the essential property of its waste water is: ammonia nitrogen: 200～260mg/L, total nitrogen: 341～385mg/L, COD
cr: 1140～1480mg/L, PH is 4～11, SS:36～80mg/L, specific conductivity: 4100～4960us/cm, waste water generation is 160m
3/ d.
According to following steps, this waste water is processed:
(1), adjust pH value: the nitrogenous organic waste water of the height in wastewater equalization pond is pumped into PH with lift pump and adjusts in pond 1, then according to the water quality characteristics of waste water, the pH value of described waste water is regulated whole to 8 ~ 9;
(2), chemical oxidation treatment: described waste water is after step (1) is processed, enter and in chemical oxidation pond, carry out denitrogenation processing, oxygenant in chemical oxidation pond adopts aqueous sodium hypochlorite solution, and the mol ratio of nitrogen and clorox is 1:2 ~ 2.5, and the reaction times is 45min ~ 60min;
(3), anoxia/aerobic biological is processed: after the PH of the waste water after step (2) is processed is adjusted to 7 ~ 8, then entering anoxia/aerobic biological processes, the water outlet that PH adjusts pond 2 is introduced into anoxic pond reaction 13h ~ 16h, then enter Aerobic Pond reaction 8h ~ 10h, nitrogenous organic pollutant remove described waste water by anoxic biology and aerobic biological treatment respectively in described anoxic pond and described Aerobic Pond in, the described return of waste water of part in described Aerobic Pond is to described anoxic pond simultaneously, between described anoxic pond and described Aerobic Pond, form an internal recycle, the return current ratio of the mixed liquid of internal recycle is 150% ~ 200%, in described Aerobic Pond, can produce mud, a described mud part is back to described anoxic pond, described mud another part enters into sludge thickener,
(4), filtration and reverse-osmosis treated: under pressure-driven, make the water outlet after step (3) is processed through mechanical filter, activated charcoal filter and cartridge filter, carry out filtration treatment successively, then enter into reverse osmosis membrane system and carry out separation, described reverse osmosis membrane selects to have the crosslinked aromatic polymeric amide anti-pollution reverse osmosis membrane of highly selective, the de-rate of its salt is greater than 98%, after described reverse osmosis membrane system, isolate two portions water outlet, a part is for producing water, another part is dense water, and producing water ratio is 68% ~ 70%;
(5), ion exchange treatment: the described product water after step (4) is processed enters into ion-exchanger, recycles after removing Nitrogen element pollutent residual in described product water by ion exchange resin;
(6), triple effect evaporation is processed: the described dense water after step (4) is processed enters into triple-effect evaporator and processes, after processing, a gained part is crystallization concentrated solution, described crystallization concentrated solution enters in supercentrifuge through centrifugation, the clear liquid that centrifugation produces reenters circulating and evaporating in triple-effect evaporator and processes, the outer disposal of solid waste committee that centrifugation produces; It is phlegma that triple-effect evaporator is processed gained another part, and described phlegma reenters described anoxic pond, and the waste water after processing with step (2) carries out step (3) to be processed.
Adopt aforesaid method to process waste water, waste water containing nitrogen removal efficiency more than 99.8%, the clearance of COD is more than 96%, the water-quality guideline of water outlet reaches enterprise's water of productive use water quality standard.
The water quality situation of concrete effluent reuse water is as follows:
Total nitrogen and ammonia nitrogen cannot detect, COD
cr: 16～22mg/L, PH is 7～9, specific conductivity <30 μ s/cm, water quality meets the zero emission requirement of this enterprise's production technique water and nitrogenous effluent; Solid waste Chan Sheng Liang≤1.2% of triple-effect evaporator.
This project actual motion 2012 this one year over, processing wastewater flow rate is 160m
3/ d, processing cost mainly comprises: 1. the electricity charge are 26.1 yuan/ton, and 2. medicament expense is with 5.5 yuan/ton, and 3. gas fired-boiler Sweet natural gas expense is 37.2 yuan/ton, and 4. labour cost is 3.1 yuan/ton, and more than adding up to ton cost of water treatment is 71.9 yuan/ton.
Above-described embodiment is only explanation technical conceive of the present invention and feature; its object is to allow person skilled in the art can understand content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (3)
1. a treatment process for high nitrogenous organic waste water, is characterized in that: said method comprising the steps of:
(1), adjust pH value: according to the water quality characteristics of waste water, the pH value of described waste water is adjusted to 8 ~ 9;
(2), chemical oxidation treatment: described waste water is after step (1) is processed, enter chemical oxidation pond and carry out denitrogenation processing, wherein, the oxygenant in described chemical oxidation pond adopts aqueous sodium hypochlorite solution, the mol ratio of nitrogen and clorox is 1:2 ~ 2.5, and the reaction times is 45min ~ 60min;
(3), anoxia/aerobic biological is processed: described waste water is after step (2) is processed, the pH value of described waste water is adjusted to 7 ~ 8, be introduced into anoxic pond reaction 13h ~ 16h, then enter Aerobic Pond reaction 8h ~ 10h, in described anoxic pond and described Aerobic Pond, the nitrogenous organic pollutant in described waste water is removed in and aerobic biological treatment biological by anoxic respectively, the described return of waste water of part in described Aerobic Pond is to described anoxic pond simultaneously, between described anoxic pond and described Aerobic Pond, form an internal recycle, the return current ratio of the mixed liquid of described internal recycle is 150% ~ 200%;
(4), filtration and reverse-osmosis treated: under pressure-driven, make the water outlet after step (3) is processed through mechanical filter, activated charcoal filter and cartridge filter, carry out filtration treatment successively, then enter into reverse osmosis membrane system and carry out separation, after described reverse osmosis membrane system, isolate two portions water outlet, a part is for producing water, another part is dense water, and producing water ratio is 68% ~ 70%; Described reverse osmosis membrane system adopts crosslinked aromatic polymeric amide anti-pollution reverse osmosis membrane, and its ratio of desalinization is greater than 98%;
(5), ion exchange treatment: the described product water of generation enters into ion-exchanger after step (4) is processed, and recycles after removing Nitrogen element pollutent residual in described product water by ion exchange resin;
(6), triple effect evaporation is processed: the described dense water producing after step (4) is processed enters into triple-effect evaporator and processes, after processing, a gained part is crystallization concentrated solution, described crystallization concentrated solution enters in supercentrifuge through centrifugation, the clear liquid that centrifugation produces reenters circulating and evaporating in triple-effect evaporator and processes, it is phlegma that described triple-effect evaporator is processed gained another part, described phlegma reenters described anoxic pond, and the described waste water after processing with step (2) carries out step (3) to be processed.
2. the treatment process of the nitrogenous organic waste water of height according to claim 1, is characterized in that: in step (3), a part of sludge reflux that described Aerobic Pond produces is to described anoxic pond, and another part mud enters into sludge thickener.
3. the treatment process of the nitrogenous organic waste water of height according to claim 1, is characterized in that: in step (4), outside the solid waste committee that described supercentrifuge centrifugation produces, dispose.
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| CN103693788B (en) * | 2014-01-06 | 2015-10-21 | 昆山工研院华科生物高分子材料研究所有限公司 | A kind of Industrial Waste Water Treatments integrative machine |
| CN105776700B (en) * | 2016-03-24 | 2018-10-26 | 华东理工大学 | A kind of waste water nitrogen phosphorus " zero-emission " technology |
| CN106167342A (en) * | 2016-09-29 | 2016-11-30 | 环境保护部南京环境科学研究所 | A kind of biological medicine waste water nitrogen phosphorus processing means and processing method thereof |
| CN106495401A (en) * | 2016-11-24 | 2017-03-15 | 天津市联合环保工程设计有限公司 | A kind of coal chemical industry enterprises reverse osmosis concentrated water become zero-emission method and complexes |
| CN106946397A (en) * | 2017-05-18 | 2017-07-14 | 伟泰科技（无锡）有限公司 | A kind of wastewater zero discharge system |
| CN108083552B (en) * | 2017-06-02 | 2020-10-09 | 苏州苏净环保工程有限公司 | Treatment method of textile industry wastewater |
| CN110759579A (en) * | 2018-07-26 | 2020-02-07 | 上海易湃富得环保科技有限公司 | Method for recycling pharmaceutical wastewater |
| CN109111020A (en) * | 2018-08-21 | 2019-01-01 | 重庆渝茁科技有限公司 | City sewage deep treatment method |
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| CN100336737C (en) * | 2005-11-18 | 2007-09-12 | 哈尔滨工业大学 | Method of removing ammonia nitrogen in water by using electrodialysis |
| CN100569676C (en) * | 2007-11-23 | 2009-12-16 | 陈伟雄 | A kind of treatment process of percolate |
| CN101549907A (en) * | 2008-04-02 | 2009-10-07 | 天津膜天膜工程技术有限公司 | Membrane biologic reaction equipment and processing method for processing industrial waste water with high ammoniac nitrogen |
| CN102107958B (en) * | 2009-12-25 | 2012-06-20 | 上海亚同环保实业股份有限公司 | Method for performing advanced treatment and reuse on oil-refining sewage and matched device |
| CN102001786B (en) * | 2010-10-22 | 2013-04-10 | 中国瑞林工程技术有限公司 | New high-nitrogen organic sewage treatment biochemical denitrification process |
| CN102557339B (en) * | 2011-12-19 | 2014-10-01 | 北京昊业怡生科技有限公司 | Treatment method of landfill leachate |
| CN102718363B (en) * | 2012-06-21 | 2014-05-07 | 浙江晶泉水处理设备有限公司 | Coking wastewater comprehensive treatment method and system thereof |
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