CN102923902B - High-salt and low-carbon ammonia nitrogen wastewater treatment method - Google Patents
High-salt and low-carbon ammonia nitrogen wastewater treatment method Download PDFInfo
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Abstract
The invention provides a high-salt and low-carbon ammonia nitrogen wastewater treatment method. The method comprises the following steps: 1, letting an exhaust gas into high-salt and low-carbon ammonia nitrogen wastewater, and mixing to form an absorption liquid; 2, letting the exhaust gas into the absorption liquid obtained in step 1, mixing, and nitrosifying; and 3, carrying out anaerobic ammoxidation of the solution obtained in step 2, and discharging. According to the method provided by the invention, the high-concentration ammonia nitrogen wastewater absorbs the exhaust which is carbon dioxide as an inorganic carbon source without adding a carbon source, and simultaneously oxygen in the exhaust gas is an oxygen source provided for biochemical treatment, so the nitrogen removal efficiency of the treated water is high, and the water quality is good. The method has the advantages of substantial investment saving, wastewater treatment cost reduction, reaching of a purpose of treatment of wastes with processes of wastes against one another, and wide application and popularization values when the method is adopted to treat the high-concentration ammonia nitrogen wastewater.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment.More particularly, the present invention relates to one with CO in waste gas
2as inorganic carbon source, with the O in waste gas
2process the method for high salt low-carbon (LC) ammonia nitrogen waste water as the oxygen source of nitrosation reaction.
Background technology
The treatment process of ammonia nitrogen waste water mainly contains physico-chemical process and biological process both at home and abroad, has developed a lot of advanced oxidation processes nearly decades.
Physico-chemical process has break point chlorination, chemical precipitation method, ion exchange method, stripping/vaporizing extract process, membrane technique method, electroosmose process and crystallization process.There is the shortcoming such as severe reaction conditions, working cost height in physico-chemical process, its application also only limits to part industry and field.
Biological process is processed high-concentration ammonia nitrogenous wastewater various ways, mainly contains traditional nitration denitrification, Nitritation/denitrification process, Simultaneous Nitrification/denitrification, short distance nitration/anaerobic ammonia oxidation process; Wherein nitrite type biological denitrification process has advantages of that floor space is little, reduces investment outlay, oxygen-consumption is little, power consumption, carbon source and alkali number consumption few; But in this process, still need to add a certain amount of organic carbon source.Prove after further study, do not adding organic carbon source, also can realize nitrous acid approach ammonia nitrogen removal by biological autotrophy, but this method still needs to add certain inorganic carbon source, thereby guarantee normally carrying out of nitration denitrification.
High-level oxidation technology mainly comprises photochemical catalytic oxidation, supercritical catalyst oxidation, Wet Oxidation Process, Catalytic Wet Oxidation technology.These technology all have that facility investment is large, working cost is high, operational condition requires harsh feature, and ammonia nitrogen is converted to oxynitride after high-level oxidation technology, and total nitrogen still needs further processing.
In prior art, the open CN1359863A of Chinese patent discloses a kind of catalyzer ammonia nitrogen sewage processing method, mainly to adopt " method of physical chemistry-biotechnology catalytic cracking catalyst ammonia-nitrogen sewage ", the subject matter that the method exists has: 1. in biological nitrification process, need additional methyl alcohol as carbon source, cause the increase of processing cost increase and draining COD value.2. adopt biochemistry pool device processes ammonia nitrogen waste water reaction time long, occupation area of equipment is large, investment is large.3. do not solve the problem of denitrogenation of waste water.Chinese patent open CN1903752A, CN1978339C, CN101139134A disclose the improvement method of three kinds of high-concentration ammonia nitrogenous wastewaters, and their common feature is: the non-high salt low-carbon (LC) class ammonia nitrogen waste water of wastewater treatment; Take biochemical treatment as main, be aided with multiple physical chemistry preprocessing means, although these treatment process can effectively be processed high-concentration ammonia nitrogenous wastewater, but still need to add a certain amount of organic or inorganic carbon source, use equally the oxygen source of air as nitrosation reaction, thereby cause, in high-concentration ammonia nitrogenous wastewater is processed, causing the problem that working cost is high, and do not solve denitrogenation of waste water problem completely, be difficult to promote the use of.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, provides one to utilize CO in waste gas
2as inorganic carbon source, utilize O in waste gas
2as the treatment process of oxygen source, both thoroughly solved ammonia and nitrogen pollution problem and also subdued greenhouse gas emissions simultaneously, there is dual environmental benefit.
The invention provides a kind of high salt low-carbon (LC) ammonia nitrogen waste water treatment method, comprising:
A) waste gas is passed in high salt low-carbon (LC) ammonia nitrogen waste water, mixes and formation absorption liquid;
B) waste gas is passed in the water outlet in a step, after mixing, carries out nitrosification processing;
C) water outlet in b step is carried out after Anammox is processed discharge.
In aforesaid method, CO in described waste gas
2content be 2～8%, O
2content be 16～18%.Described waste gas is from the industrial gaseous waste of producing molecular sieve or catalyzer roasting furnace etc.Ammonia nitrogen concentration 300～500mg/L in described high salt low-carbon (LC) ammonia nitrogen waste water, TOC is 5.0～10.5mg/L, SO
4 -concentration be 5000～20000mg/L, pH value is 7.0～12.0, the concentration of suspended substance is 200～800mg/L.
In aforesaid method, in described a) step, described waste gas is lowered the temperature, after pre-treatment, be passed in high salt low-carbon (LC) ammonia nitrogen waste water after dedusting etc.CO in waste gas
2after being absorbed by waste water, generate HCO
3 -and CO
3 2-, and be dissolved in waste water.Vapour-liquid ratio 60: 1～120: 1, temperature is 20～40 ℃.In a specific embodiment, waste gas carried out with mixing in absorption tower of waste water, and waste water is contrary with the traffic direction of waste gas, waste gas flows from lower to upper, and waste water flows from top to bottom, and waste water adopts the mode of spray, can increase the contact area of waste water and waste gas, be conducive to absorb CO
2.
In aforesaid method, in described a) step, described absorption liquid carries out precipitate and separate.The method that ammonia nitrogen waste water adopts part circulation to absorb, the part of the supernatant liquid after precipitate and separate continues the CO in blended absorbent waste gas with waste gas
2, improve HCO in absorption liquid
3 -and CO
3 2-content.Another part supernatant liquid carries out next step nitrosification processing.In a specific embodiment, in homogeneous groove, carry out homogeneous, precipitate and separate, partially absorb liquid and be back to absorption tower and absorb CO with circulation
2, another part supernatant liquid is squeezed in next step nitrosation reaction device with volume pump.
In aforesaid method, described b) in, the ammonia nitrogen in waste water utilizes nitrosification flora to carry out nitrosification processing, Partial Conversion is nitrite nitrogen.Wherein hydraulic detention time is 8～12h, dissolved oxygen 1.5～2.5mg/L, 20～35 ℃ of temperature.Ammonia nitrogen concentration 300～500mg/L in described high salt low-carbon (LC) ammonia nitrogen waste water.In described step, also add as required nutritive salt and regulate pH value, described nutritive salt is as Ca
2+, Mg
2+, Fe
3+, KH
2pO
4deng; The acid, the alkali that regulate the pH value of waste water to use are compound conventional in technique, as sodium carbonate etc., and the pH value 6.5～8.5 of adjusting waste water.By waste gas after pre-treatment, through being again passed in the water outlet in a step and mixing after cooling, continuing as on the one hand nitrosification processing provides inorganic carbon source, regulates pH value, can provide oxygen for ammonia nitrogen nitrosification on the other hand.The nitrous rate of ammonia nitrogen is 50～60%.Described nitrosification waste water after treatment carries out precipitate and separate, and the clear liquid on upper strata carries out Anammox processing, and the sludge reflux of lower floor is to guarantee sludge concentration in reactor.In a specific embodiment, in bio-aeration pool, carry out nitrosification processing, after pre-treatment, waste gas is introduced the air feed of bio-aeration pool as aerating system simultaneously, in settling tank, carry out precipitate and separate, supernatant liquid after separation enters next step Anammox processing, and mud is back to bio-aeration pool.Ammonia nitrogen concentration 300～500mg/L in described high salt low-carbon (LC) ammonia nitrogen waste water;
In aforesaid method, described c) in, in waste water, nitrite nitrogen, ammonia nitrogen utilize Anammox flora to be converted into nitrogen in anaerobic reactor; Hydraulic detention time 6～8h, dissolved oxygen is less than 0.2mg/L, 20～38 ℃ of temperature.In described step, also add as required nutritive salt and regulate pH value, described nutritive salt is as Ca
2+, Mg
2+, Fe
3+, KH
2pO
4deng; The acid, the alkali that regulate the pH value of waste water to use are compound conventional in technique, as sodium carbonate etc., and the pH value 7.0～8.5 of adjusting waste water.Described Anammox waste water after treatment is through precipitate and separate, and supernatant liquid is discharged, and lower floor's sludge reflux is to guarantee sludge concentration in reactor.In a specific embodiment, in anaerobic reactor, carry out Anammox processing, in settling tank, carry out precipitate and separate, the supernatant liquid after separation is discharged, and mud is back to anaerobic reactor.Discharge total clearance of ammonia nitrogen in water for being greater than 98.0%, the clearance of nitrite nitrogen is greater than 96.5%, and the clearance of total nitrogen is greater than 76.5%.
In aforesaid method, ammonia nitrogen concentration≤15mg/L in Anammox discharge water after treatment; Nitrite nitrogen concentration≤15mg/L; TOC≤10mg/L.
The invention provides a kind for the treatment of process of high salt low-carbon (LC) ammonia nitrogen waste water, utilize CO in waste gas
2as inorganic carbon source, utilize the O in waste gas
2as oxygen source, by ammonia nitrogen partial nitrification in high-concentration ammonia nitrogenous wastewater, then under anaerobic environment, carry out the method for Anammox denitrogenation processing.Method provided by the invention has the following advantages: CO in waste gas
2as sole carbon source, and utilize O in waste gas
2as the oxygen source of nitrosation reaction; Utilize CO in waste gas
2as all right Effective Regulation wastewater pH of inorganic carbon source, thereby reduce the required soda acid dosage of pH regulator; Both solved ammonia and nitrogen pollution problem and also subdued greenhouse gas emissions, reached treatment of wastes with processes of wastes against one another object, there is dual environmental benefit simultaneously; Do not need additional carbon, greatly saved investment, thereby reduced cost for wastewater treatment; After ammonia nitrogen partial nitrification, carry out Anammox processing, avoid traditional process to process the problem that needs to add organic carbon source in low-carbon (LC) ammonia nitrogen waste water denitrification process; Solved the problem of high salt low-carbon (LC) class ammonia nitrogen waste water biochemical treatment difficulty by this technique.
According to method provided by the invention, in the situation that not adding carbon source, high-concentration ammonia nitrogenous wastewater absorbs carbonic acid gas in waste gas as inorganic carbon source, and the oxygen in waste gas provides oxygen source for nitrosification processing simultaneously, the nitric efficiency of water outlet is after treatment high, and water quality is good.Adopt the present invention to process high-concentration ammonia nitrogenous wastewater, can greatly reduce investment outlay, reduce cost for wastewater treatment, reach the object of the treatment of wastes with processes of wastes against one another, be widely used and promotional value.The present invention can be applicable to the technique that need to process low-carbon (LC) ammonia nitrogen waste water, concrete as Catalyst waste water, nitrogen fertilizer industry wastewater treatment etc.
Accompanying drawing explanation
Fig. 1 is process flow diagram according to an embodiment of the invention.
Embodiment:
Fig. 1 is process flow diagram according to an embodiment of the invention.In figure, device comprises absorption tower 1, homogeneous pond 2, aeration and biological pond 3, heavy pond 4, anaerobic reactor 5 and a second pond 6.Take catalyst production waste water as example, from the waste gas 8 of producing molecular sieve or catalyzer roasting furnace after comprising the pre-treatment of washing, dedusting, cooling step, enter from 1 bottom, absorption tower, enter the waste gas on absorption tower discharging from top, absorption tower in tower after ammonia nitrogen waste water 7 counter-current absorption, absorbed CO in waste gas
2waste water enter homogeneous pond 2 and carry out homogeneous, precipitate and separate, the liquid that partially absorbs in homogeneous pond 2 is back to absorption tower and absorbs CO with circulation
2, can improve HCO in absorption liquid
3 -and CO
3 2-content.Upper strata CO in homogeneous pond
2absorption liquid arrives BAF 3 through pump delivery.Pretreated waste gas is due to O
2concentration is higher, therefore it is directly introduced to BAF 3 by aerating system, continuing as nitrococcus provides inorganic carbon source on the one hand, on the other hand for ammonia nitrogen nitrosification provides O
2; Add the sodium carbonate and the required nutritive salt 9 of microorganism growth that regulate BAF pH value, BAF 3 water outlets enter heavy pond 4 precipitate and separate, sludge reflux 10, and ammonia nitrogen partial nitrification waste water is introduced anaerobic reactor 5 by pump; In anaerobic reactor 5, waste water ph is mainly controlled by dilute sulphuric acid and sodium bicarbonate, reactor is airtight, oxygen dissolving value is controlled at below 0.2mg/L, temperature is by heating and the control of jacket for heat exchange device certainly, anaerobic reactor 5 water outlets enter second pond 6 precipitate and separate, sludge reflux 10, and supernatant liquid can directly discharge.
Adopt the treatment scheme shown in Fig. 1, in absorption tower, waste gas flows from lower to upper, and waste water adopts the mode of spray to flow from top to bottom.
The water quality of refining catalytic agent production waste water: ammonia nitrogen 420～450mg/L, suspended substance 560mg/L, SO
4 2-28 ℃ of 12500mg/L, pH9.0～9.5, water temperature.
A, Zeolite Calciner waste gas carry out after dedusting, cooling flue gas by material filling type water spray scrubber, suspended particulate 0.5～1mg/m
3, CO
23.3%, O
216.2%, temperature 50 C.
Absorb agitation condition: waste water specific liquid rate 3.5～6.5m
3/ m
2.h, flue gas flux 350～520m
3/ m
2.h.
Absorb CO in flue gas
2the water quality of oil refining catalyst waste water: ammonia nitrogen 420～450mg/L, suspended substance 760mg/L, SO
4 2-: 12500mg/L, pH:8.5～9.5,33 ℃ of water temperatures.
B, in aeration and biological pond, add biological respinse nutritive substance: Ca
2+15mg/L, Mg
2+15mg/L, Fe
3+40mg/L, KH
2pO
4550mg/L; Regulate pH to 8.5.
Aeration and biological pond operational condition: pH6.5-8.5, dissolved oxygen 0.5～2.0mg/L, 25～35 ℃ of service temperatures.
C, in anaerobic ammonia oxidation reactor, add biological respinse nutritive substance: Fe
2+12mg/L, Mg
2++ 20mg/L, P (KH
2pO
4) 65mg/L; Regulate pH to 8.0.
Anaerobic ammonia oxidation reactor operational condition: 25～38 ℃ of pH7.0～8.5, dissolved oxygen≤0.2mg/L, service temperature.
Result is in table 1.
Table 1
Adopt the treatment scheme shown in Fig. 1.In absorption tower, waste gas flows from lower to upper, and waste water adopts the mode of spray to flow from top to bottom.
The water quality of refining catalytic agent production waste water: ammonia nitrogen 350～370mg/L, suspended substance 430mg/L, SO
4 2-35 ℃ of 19500mg/L, pH7.0～8.5, water temperature;
A, Zeolite Calciner waste gas carry out after dedusting, cooling flue gas by material filling type water spray scrubber, CO
25.3%, O
213.2%, 47 ℃ of temperature;
Absorb agitation condition: waste water specific liquid rate 5.5～7.5m
3/ m
2.h, flue gas flux 320～450m
3/ m
2.h.
Absorb CO in flue gas
2the water quality of oil refining catalyst waste water: ammonia nitrogen 320～350mg/L, 8O
4 2-: 37 ℃ of 19500mg/L, pH:8.5～10.0, water temperature.
B, in BAF, add biological respinse nutritive substance: Ca
2+20mg/L, Mg
2+15mg/L, Fe
3+35mg/L, KH
2pO
4350mg/L; Regulate pH to 8.3.
BAF operational condition: reactor load 0.55Kg ammonia nitrogen/dm
3, 25～38 ℃ of dissolved oxygen 0.5～2.0mg/L, service temperature.
C, in anaerobic ammonia oxidation reactor, add biological respinse nutritive substance: Fe
2+10mg/L, Mg
2+15mg/L, P (KH
2pO
4) 50mg/L; Regulate pH to 8.2.
Anaerobic ammonia oxidation reactor operational condition: 25～38 ℃ of pH7.0～8.5, dissolved oxygen≤0.2mg/L, service temperature.
Result is in table 2.
Table 2
Conclusion: data can be learnt from table 1 and table 2, after method provided by the invention is processed, water outlet nitric efficiency is high, and water quality is good.
Claims (1)
1. a treatment process for high salt low-carbon (LC) ammonia nitrogen waste water, comprising:
A) waste gas is passed in high salt low-carbon (LC) ammonia nitrogen waste water, mixes and formation absorption liquid, described absorption liquid carries out precipitate and separate; In described high salt low-carbon (LC) waste water, the concentration of ammonia nitrogen is 300～500mg/L, and TOC is 5.0～10.5mg/L, SO
4 2-concentration be 5000～20000mg/L, pH value is 7.0～12.0, the concentration of suspended substance is 200～800mg/L; Vapour-liquid ratio 60:1～120:1, temperature is 20～40 ℃; CO in described waste gas
2content be 2～8%, O
2content be 16～18%;
B) waste gas is passed in the water outlet in a step, carries out nitrosification processing after mixing, described nitrosification waste water after treatment carries out precipitate and separate; Wherein, hydraulic detention time is 8～12h, pH value 6.5～8.5, dissolved oxygen 1.5～2.5mg/L, 20～35 ℃ of temperature;
C) water outlet in b step is carried out after Anammox processing, waste water after treatment is through precipitate and separate, and supernatant liquid is discharged; Wherein, hydraulic detention time 6～8h, pH value 7.0～8.5, dissolved oxygen is less than 0.2mg/L, 20～38 ℃ of temperature;
Wherein, in the water of described discharge, ammonia nitrogen concentration≤15mg/L, nitrite nitrogen concentration≤15mg/L; TOC value≤10mg/L.
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| 厌氧氨氧化影响因素实验研究;游少鸿等;《工业水处理》;20091031;第29卷(第10期);第27-29页，第2.1节 * |
| 游少鸿等.厌氧氨氧化影响因素实验研究.《工业水处理》.2009,第29卷(第10期),第27-29页，第2.1节. |
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