CN105645655A - Comprehensive treatment method of high-concentration ammonia-nitrogen wastewater containing S<2-> - Google Patents
Comprehensive treatment method of high-concentration ammonia-nitrogen wastewater containing S<2-> Download PDFInfo
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- CN105645655A CN105645655A CN201610105999.5A CN201610105999A CN105645655A CN 105645655 A CN105645655 A CN 105645655A CN 201610105999 A CN201610105999 A CN 201610105999A CN 105645655 A CN105645655 A CN 105645655A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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Abstract
The invention discloses a comprehensive treatment method of high-concentration ammonia-nitrogen wastewater containing S<2->. According to the method, the high-concentration ammonia-nitrogen wastewater containing S<2-> is pretreated, sulfur is removed, alkaline substances are added to the wastewater, ammonium ions are converted into molecular ammonia, the wastewater is heated by a heat source in a deamination conversion tower, ammonia in the wastewater enters a condenser from the tower top in a gas form and is cooled to form ammonia water, a part of ammonia water flows back, and the remaining part is recovered as a product; high-temperature water after deamination exchanges heat with to-be-treated wastewater and then enters a deamination wastewater tank, and the wastewater can be directly discharged when the content of ammonia nitrogen in the wastewater reaches the standard. S<2-> removal and deamination processes are combined, the 15%-28% high-concentration ammonia water can be obtained, no sulfur is contained in the ammonia water, the concentration of ammonia nitrogen in the treated wastewater is under 8 mg/L, the pollutant treatment rate and the resource recovery rate of high ammonia-nitrogen wastewater are larger than or equal to 99%, and good economic benefits are obtained while the wastewater reaches the standard required for the environment.
Description
Technical field
The present invention relates to field of waste water treatment, particularly relating to one will combine except negative divalent sulfur and deamination technique, to the processing method carrying out resource recovery containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater.
Background technology
In the production process of the industries such as oil refining, petrochemical industry, pharmacy, metallurgy, battery, plating, usually produce a large amount of containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, in this waste water, negative divalent sulfur content is more than 50mg/L, reach as high as 20000mg/L, and ammonia nitrogen concentration is more than 500mg/L, reach as high as more than 100000mg/L. Sulfide in waste water has toxicity, corrosivity; Ammonia-containing water, if easily caused " algae proliferation " after not being acted upon being directly discharged into water body, causes the eutrophication of water body, the mankind and environment causes great pollution, harm and threat, waste again resource simultaneously.
The technique of existing sulphur removal has chemical oxidization method, aeration, acidization, steam stripping method, chemical precipitation method etc.
Patent CN1326899A proposes air oxidation process and processes high strength sulfide-bearing wastewater and high-concentration sulfur-containing alkali residue waste liquid desulfurization deamination simultaneously, in this method, regulate waste liquor PH to 8��14, add desulfurizing agent generation desulphurization reaction, carrying out solid-liquid separation through depositor, settler water outlet sulfide content is less than 50mg/L, and ammonia content is less than 100mg/L, in discharge to sewage treatment plant, remaining ammonia is oxidized to nitrogen discharge in high temperature incineration device. Here there are three problems: one be water outlet sulfide content and ammonia content too high, produce secondary pollution problem, it is necessary to reprocessing, and sulfur and ammonia go process low; Two is after waste water is regulated pH, when adding reactive desulfurizing agent, has a large amount of ammonia and gets rid of, and contaminated environment is unfavorable for environmental protection; Three is that high temperature incineration needs fuel, plant construction and operating cost higher, and it cannot be guaranteed that completely up to standard.
Patent CN103102033A relates to the processing method of a kind of sulfur-bearing and ammonia waste water, in this method, first waste water is easily separated oil removing, add catalyst and carry out oxidation reaction sulphur removal, then through entering biomembrane reaction pond after device for absorbing tail gas.In the method, catalytic reaction temperature is 60��90 DEG C, catalyst need to be loaded with the activated carbon of catalytically-active metals, and catalyst need to carry with steam, needing to absorb tail gas with sodium hydroxide solution, saturated absorption liquid need to enter sewage treatment unit reprocessing, and this technological process is more complicated, require that operator's technical merit is high, and relatively costly. The method is suitable for sulfide concentration lower than 1500mg/L, the ammonia nitrogen concentration waste water lower than 4000mg/L, therefore a lot of high salt industrial wastewaters are inapplicable.
For many years, all having carried out substantial amounts of research both at home and abroad for the process of high-concentration ammonia nitrogenous wastewater, in existing process waste water, the method for ammonia nitrogen has air stripping method, break point chlorination method, biological nitration method, electrochemical oxidation process, vaporizing extract process. The kinds of processes such as oxidation and aeration, although ammonia nitrogen waste water treatment method is numerous, but it is big all to there is capital expenditure cost. The shortcomings such as operating cost is high, treating capacity is little, technological process is complicated, resource recovery is low, and after process, ammonia nitrogen concentration is extremely difficult to below 8mg/L, and the ammonia concn reclaimed is low.
Patent CN1367147A proposes the method that oxidation and aeration processes high-concentration ammonia nitrogenous wastewater, first adds alkalescence complexing agent in waste water, carries out aeration with aeration tower or Aeration tank after stirring, adds flocculant sedimentation, separates. The method technological process is simple, but can only process the ammonia nitrogen of below 6000mg/L, and aeration process intermediate ion state ammonium changes into amino molecule by stripping out, affects the mankind and environment, and without ammonia output, No Assets reclaims, and causes relatively costly.
Summary of the invention
For the deficiencies in the prior art, in order to solve containing the problem in negative divalent sulfur high-concentration ammonia nitrogenous wastewater processing procedure, the present invention proposes a kind of comprehensive utilization of resources technique sulphur removal and deamination technique combined, with optimizing process, saving process the time, turn waste into wealth, energy-saving and emission-reduction, realizing the deep removal of ammonium, ammonia nitrogen water outlet reaches below 8mg/L; The high concentration ammonia of recyclable 15��28%, and ammonia is born divalent sulfur content not higher than 0.5mg/L.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of integrated conduct method containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, comprises the steps:
(1) pretreatment sulphur removal will be carried out containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, remove most sulfur;
(2) high ammonia-nitrogen wastewater after step (1) sulphur removal is mixed with alkaline matter, ammonium ion is transformed into molecular state ammonia;
(3) being delivered in deamination converter by the material that step (2) obtains, thermal source passes into from tower reactor, and ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor;
(4) the ammonia steam separated from water is entered condenser by rectifying tower jacking, and is condensed into ammonia condensed fluid within the condenser, and ammonia condensed fluid partial reflux is to tower top, partly as ammonolysis product;
(5) high-temperature water after deamination flows out from tower reactor, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
The described pretreatment sulphur removal method of step (1) can be chemical precipitation method; Chemical precipitation method is to add chemical precipitation agent in waste water to generate sulfide precipitation.
Chemical precipitation agent used by described chemical precipitation method sulphur removal can be the combination of a kind of or at least two of mantoquita, lead salt, iron salt, zinc salt, manganese salt, and the response time is 1��7h;
Preferably, chemical precipitation agent is iron salt or mantoquita;
Preferably, the response time is 2��6h.
The described pretreatment desulfurization process of step (1) is after with chemical precipitation method sulphur removal, it is possible to obtain supernatant through gravitational settling or centrifugal sedimentation or flocculating sedimentation or filtering technique, i.e. high ammonia-nitrogen wastewater after sulphur removal;
Preferably, high ammonia-nitrogen wastewater after flocculating sedimentation technique obtains sulphur removal;
Preferably, the addition of flocculant is 0.1��2%;
It is further preferred that the addition of flocculant is 0.1��1%;
Preferably, the flocculation reaction time is 1��7h;
It is further preferred that the flocculation reaction time is 1��5h.
Step (2) adds alkaline matter in high ammonia-nitrogen wastewater after sulphur removal, and alkaline matter can be the combination of a kind of or at least two in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate;
Preferably, alkaline matter is sodium hydroxide.
After step (2) adds alkaline matter, by the pH regulator of high ammonia-nitrogen wastewater after sulphur removal to 11��14;
Preferably, wastewater pH is regulated to 11.5��13.
Deamination converter described in step (3) can be packed tower, plate column, composite construction tower.
Thermal source described in step (3) can provide for high-temperature steam, electric heating, heat conduction oil machine;
Preferably, thermal source is provided by high-temperature steam.
The high concentration ammonia that ammonolysis product is 15��28% described in step (4), and the negative divalent sulfur content in ammonia is less than or equal to 0.5mg/L.
The ammonia-nitrogen content of the deamination tower reactor water outlet described in step (5), can reuse or arrange outward less than or equal to 15mg/L;
Containing the negative divalent sulfur content in negative divalent sulfur high-concentration ammonia nitrogenous wastewater higher than 50mg/L in step (1), reach as high as 20000mg/L, and ammonia nitrogen concentration is more than 500mg/L, reach as high as more than 100000mg/L.
Step (1) is pretreatment sulphur removal process, it is possible to for chemical oxidization method, aeration, chemical precipitation method, chemical oxidization method refers to that sulfide-oxidation is removed by the method with adding oxidant, and oxidant can be chlorine, ozone, hydrogen peroxide etc.; Aeration refers to the sulfide in the oxygen oxidation removal waste water in the device air adopting aeration, and the effusion of air simultaneously also can carry the sulfide in effluent part with the form of hydrogen sulfide; Chemical precipitation method is to add chemical precipitation agent in waste water to generate sulfide precipitation. For optimization process technique, it is preferred to use chemical precipitation method sulphur removal. Precipitant used by chemical precipitation method sulphur removal can be the combination of a kind of or at least two of mantoquita, lead salt, iron salt, zinc salt, manganese salt, for saving cost, it is preferred to iron salt or mantoquita, for instance for FeSO4��7H2O or CuCl2Deng. Response time is 1��7h; It is preferably 2��6h, for instance for 2h, 3h, 4h, 5h, 6h etc. After chemical precipitation method sulphur removal, it is possible to obtain supernatant through gravitational settling or centrifugal sedimentation or flocculating sedimentation or filtering technique, i.e. high ammonia-nitrogen wastewater after sulphur removal, for optimization process technique, it is preferred to high ammonia-nitrogen wastewater after flocculating sedimentation technique obtains sulphur removal. Needing to add flocculant in flocculating sedimentation technique, the addition of flocculant is 0.1��2%, it is preferred to the addition of flocculant is 0.1��1%, for instance 0.1%, 0.3%, 0.7%, 1% etc. The flocculation reaction time is 1��7h, it is preferred to 1��5h, for instance 1h, 3h, 5h.
Step (2) is that mixing adds alkali process. Adding alkaline matter after sulphur removal in high ammonia-nitrogen wastewater, alkaline matter can be the combination of a kind of or at least two in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, it is preferred to NaOH.Add after alkaline matter, by the pH regulator of high ammonia-nitrogen wastewater after sulphur removal to 11��14, it is preferred to 11.5��13, for instance be 11.5,12,12.5,13 etc.
Step (3) is the committed step that deamination converts, and deamination converter can be packed tower, plate column, composite construction tower. Deamination converts required thermal source and can be provided by high-temperature steam, electric heating, heat conduction oil machine, for saving cost, it is preferred to high-temperature steam provides thermal source.
Step (4) is to produce the main process of ammonia. Obtain the high concentration ammonia of 15��28%, and ammonia is born divalent sulfur content less than or equal to 0.5mg/L.
Step (5) is the final step of high-concentration ammonia nitrogenous wastewater deamination. From the water that tower reactor flows out, ammonia-nitrogen content is less than or equal to 8mg/L, can be back to production technology or arrange outward.
A kind of integrated conduct method containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, it comprises the following steps:
(1) FeSO is used4��7H2O or CuCl2To carry out pretreatment sulphur removal containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater as chemical precipitation agent, the pretreatment reaction time is 2��6h; After chemical precipitation method sulphur removal, then adding flocculant and carry out flocculating sedimentation and obtain high ammonia-nitrogen wastewater after sulphur removal, the addition of flocculant is 0.1��1%, and the flocculation reaction time is 1��5h;
(2) regulate to 11.5��13 by the NaOH wastewater pH that step (1) is obtained, make ammonium ion be transformed into molecular state ammonia;
(3) being delivered in packed tower, plate column or composite construction tower by the material that step (2) obtains, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor;
(4) the ammonia steam in step (3) is entered condenser by rectifying tower jacking after separating from water, and it is condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, remainder is as ammonia product, wherein ammonia is the high concentration ammonia of 15��28%, and the negative divalent sulfur content in ammonia is less than or equal to 0.5mg/L;
(5) high-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is less than or equal to 8mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Compared with prior art, the present invention has the effect that
(1) the invention discloses the new method of a kind of integrated treatment containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, the method will combine except negative divalent sulfur and deamination technique, simultaneously optimization process technique, turn waste into wealth, energy-saving and emission-reduction;
(2) deamination converter of the present invention, floor space is little, it may be achieved the deep removal of ammonia, tower reactor water outlet ammonia-nitrogen content, less than or equal to 8mg/L, can be back to production technology or arrange outward, and non-secondary pollution generates, technological operation is simple, and less costly, operational stability is higher. (3) ammonia reclaimed is the ammonia of the high concentration of 15��28%, and ammonia is born divalent sulfur content less than or equal to 0.5mg/L, the standard of ammonia chemical pure medium sulphide content content can be reached, ammonolysis product can return to FEOL and uses, control source, greatly reduce material consumption, add economic benefit.
Accompanying drawing explanation
Fig. 1 is the process chart of the inventive method.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, below the present invention is described in more detail. But following embodiment is only the simple and easy example of the present invention, not representing or restriction the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Embodiment 1
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 4.8g/L, and ammonia nitrogen concentration is 15g/L. Aoxidizing negative divalent sulfur with hydrogen peroxide as oxidant, the addition of hydrogen peroxide is 25g/L, and oxidization time is 8h; Adding NaOH in waste water after oxidation and regulate pH to 11, make ammonium ion be transformed into molecular state ammonia, then be delivered in plate column, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by plate column tower top after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 22%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 6mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 2
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 3.5g/L, and ammonia nitrogen concentration is 42g/L. Use CuCl2Carrying out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 2h, then adds the flocculant of 0.1% and carry out flocculating sedimentation, and the flocculation reaction time is 7h; Taking supernatant NaOH and regulate pH to 12, make ammonium ion be transformed into molecular state ammonia, then be delivered in packed tower, electric heating lifting supplying heat source pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by packed tower tower top after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 26%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 5mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 3
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 1g/L, and ammonia nitrogen concentration is 1g/L. Use FeSO4��7H2O carries out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 5h, again waste water is delivered in high-efficiency sedimentation device, the waste water time of staying in settler is 5h, takes supernatant addition KOH and regulates pH to 12.5, makes ammonium ion be transformed into molecular state ammonia, it is delivered in composite construction tower again, being thered is provided thermal source to pass into from tower reactor by high-temperature steam, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 15%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 5mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 4
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 12g/L, and ammonia nitrogen concentration is 76g/L.Use PbNO3Carrying out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 1h, then adds the flocculant of 0.7% and carry out flocculating sedimentation, and the flocculation reaction time is 5h; Taking supernatant CaO and regulate pH to 13, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, heat conduction oil machine provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 28%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 3mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 5
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 8g/L, and ammonia nitrogen concentration is 35g/L. Aoxidizing negative divalent sulfur with ozone as oxidant, wherein ozone intake is 12m3/ h, oxidation time of contact is 3h; Take waste water Na after oxidation2CO3Regulating pH to 11.5, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 25%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 8mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 6
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 20g/L, and ammonia nitrogen concentration is 55g/L. Use NiCl2Carrying out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 4h, is centrifuged sedimentation with sedimentation centrifuge, takes supernatant Ca (OH)2Regulating pH to 11.5, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 23%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 6mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 7
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 6g/L, and ammonia nitrogen concentration is 115g/L. Use FeSO4��7H2O carries out pretreatment sulphur removal as chemical precipitation agent, and the pretreatment reaction time is 4h, then adds the flocculant of 0.3% and carry out flocculating sedimentation, and the flocculation reaction time is 7h;Taking supernatant NaOH and regulate pH to 13, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 21%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 4mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 8
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 3g/L, and ammonia nitrogen concentration is 18g/L. Aoxidizing negative divalent sulfur with chlorine as oxidant, wherein chlorine intake is 23m3/ h, oxidation time of contact is 5h; After taking oxidation, waste water NaOH regulates pH to 12, makes ammonium ion be transformed into molecular state ammonia, then is delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, and ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 19%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 5mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 9
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 5g/L, and ammonia nitrogen concentration is 29g/L. Use ZnNO3Carrying out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 7h, then adds the flocculant of 1% and carry out flocculating sedimentation, and the flocculation reaction time is 3h; Taking supernatant NaOH and regulate pH to 12.5, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 22%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 6mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 10
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 6.5g/L, and ammonia nitrogen concentration is 45g/L. Being passed into by waste water in Aeration tank, carry out aeration with aerator, negative divalent sulfur part is oxidized, and other parts are blown with the form of hydrogen sulfide; After taking oxidation, waste water NaOH regulates pH to 13, makes ammonium ion be transformed into molecular state ammonia, then is delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, and ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 26%, and bears divalent sulfur content in ammonia less than 0.5mg/L;High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 6mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 11
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 2.6g/L, and ammonia nitrogen concentration is 13g/L. Use MnNO3Carrying out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 6h, then adds the flocculant of 2% and carry out flocculating sedimentation, and the flocculation reaction time is 1h; Taking supernatant NaOH and regulate pH to 14, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn is 28%, and bears divalent sulfur content in ammonia less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 4mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Embodiment 12
Certain factory provides a kind of high-concentration ammonia nitrogenous wastewater containing negative divalent sulfur, and wherein negative divalent sulfur content is 6.4g/L, and ammonia nitrogen concentration is 22g/L. Use MnNO3Carrying out pretreatment sulphur removal as chemical precipitation agent, the pretreatment reaction time is 6h, enters back into filter press and is filtered; Taking filtrate and regulate pH to 12 with NaOH, make ammonium ion be transformed into molecular state ammonia, then be delivered in composite construction tower, high-temperature steam provide thermal source to pass into from tower reactor, ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor; Ammonia steam is entered condenser by composite construction column overhead after separating from water, and it being condensed into ammonia condensed fluid within the condenser, ammonia condensed fluid partial reflux is to tower top, and remainder is ammonia product, wherein ammonia concn 23%, and negative divalent sulfur content is less than 0.5mg/L; High-temperature water after deamination flows out from tower reactor, and in high-temperature water, ammonia-nitrogen content is 3mg/L, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
Applicant states, the method that the present invention illustrates the present invention by above-described embodiment, but the invention is not limited in aforesaid operations step, does not namely mean that the present invention has to rely on aforesaid operations step and could implement. The equivalence of raw material selected by the present invention it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc., is all fallen within protection scope of the present invention and open scope by person of ordinary skill in the field.
Claims (10)
1. the integrated conduct method containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, it is characterised in that comprise the steps:
(1) pretreatment sulphur removal will be carried out containing negative divalent sulfur high-concentration ammonia nitrogenous wastewater, remove most sulfur;
(2) high ammonia-nitrogen wastewater after step (1) sulphur removal is mixed with alkaline matter, ammonium ion is transformed into molecular state ammonia;
(3) being delivered in deamination converter by the material that step (2) obtains, thermal source passes into from tower reactor, and ammonia and water separate under the action of heat, and the ammonia steam of formation rises to tower top from tower reactor;
(4) the ammonia steam separated from water is entered condenser by rectifying tower jacking, and is condensed into ammonia condensed fluid within the condenser, and ammonia condensed fluid partial reflux is to tower top, partly as ammonolysis product;
(5) high-temperature water after deamination flows out from tower reactor, after pending waste water heat-shift, enters deamination waste water tank, can be back to production technology or direct outer row.
2. processing method as claimed in claim 1, it is characterised in that the described pretreatment sulphur removal method of step (1) can be chemical precipitation method, chemical oxidization method or aeration;
Preferably, described pretreatment sulphur removal method can be chemical precipitation method.
3. processing method as claimed in claim 2, it is characterised in that the chemical precipitation agent used by described chemical precipitation method sulphur removal can be the combination of a kind of or at least two of mantoquita, lead salt, iron salt, zinc salt, manganese salt, and the response time is 1��7h;
Preferably, chemical precipitation agent is iron salt or mantoquita;
Preferably, the response time is 2��6h.
4. processing method as described in any claim in claim 1-3, it is characterized in that, the described pretreatment desulfurization process of step (1) is after with chemical precipitation method sulphur removal, supernatant can be obtained, i.e. high ammonia-nitrogen wastewater after sulphur removal through gravitational settling or centrifugal sedimentation or flocculating sedimentation or filtering technique;
Preferably, high ammonia-nitrogen wastewater after flocculating sedimentation technique obtains sulphur removal;
Preferably, the addition of flocculant is 0.1��2%;
It is further preferred that the addition of flocculant is 0.1��1%;
Preferably, the flocculation reaction time is 1��7h;
It is further preferred that the flocculation reaction time is 1��5h.
5. processing method as claimed in claim 1, it is characterized in that, step (2) adds alkaline matter in high ammonia-nitrogen wastewater after sulphur removal, and alkaline matter can be the combination of a kind of or at least two in sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate;
Preferably, alkaline matter is sodium hydroxide.
6. processing method as claimed in claim 5, it is characterised in that after step (2) adds alkaline matter, by the pH regulator of high ammonia-nitrogen wastewater after sulphur removal to 11��14;
Preferably, wastewater pH is regulated to 11.5��13.
7. processing method as claimed in claim 1, it is characterised in that the deamination converter described in step (3) can be packed tower, plate column, composite construction tower.
8. processing method as claimed in claim 7, it is characterised in that the thermal source described in step (3) can provide for high-temperature steam, electric heating, heat conduction oil machine;
Preferably, thermal source is provided by high-temperature steam.
9. processing method as described in any claim in claim 1-8, it is characterised in that the high concentration ammonia that ammonolysis product is 15��28% described in step (4), and the negative divalent sulfur content in ammonia is less than or equal to 0.5mg/L.
10. processing method as claimed in claim 9, it is characterised in that the ammonia-nitrogen content of the deamination tower reactor water outlet described in step (5), can reuse or arrange outward less than or equal to 8mg/L.
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| CN107986498A (en) * | 2017-12-20 | 2018-05-04 | 北京科技大学 | The method of sulphion in a kind of precipitation-biological adsorption combination removing waste water |
| CN108439646A (en) * | 2018-04-17 | 2018-08-24 | 中南大学 | A kind of preprocess method of organic wastewater with high concentration during sulfhydryl heterocycle class production of chemicals |
| CN109626694A (en) * | 2019-01-23 | 2019-04-16 | 杭州卧特松环保科技有限公司 | High ammonia-nitrogen wastewater purifying technique with high salt |
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| CN106830487A (en) * | 2017-03-21 | 2017-06-13 | 北京中科康仑环境科技研究院有限公司 | A kind of comprehensive processing technique of the high-concentration ammonia nitrogenous wastewater containing organic matter thiocarbamide |
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| CN109626694A (en) * | 2019-01-23 | 2019-04-16 | 杭州卧特松环保科技有限公司 | High ammonia-nitrogen wastewater purifying technique with high salt |
| CN114477584A (en) * | 2021-12-29 | 2022-05-13 | 国家能源集团煤焦化有限责任公司 | Benzene hydrogenation sewage treatment system |
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