CN113292187A - Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater - Google Patents
Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater Download PDFInfo
- Publication number
- CN113292187A CN113292187A CN202011632124.3A CN202011632124A CN113292187A CN 113292187 A CN113292187 A CN 113292187A CN 202011632124 A CN202011632124 A CN 202011632124A CN 113292187 A CN113292187 A CN 113292187A
- Authority
- CN
- China
- Prior art keywords
- ammonia
- wastewater
- chemical
- ammonia nitrogen
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/10—Separation of ammonia from ammonia liquors, e.g. gas liquors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
Abstract
The invention discloses a resource treatment method of high-concentration ammonia nitrogen wastewater, which adopts a low-pressure steam stripping process and sequentially comprises the steps of pretreatment, chemical impurity removal, ammonia distillation, chemical denitrification and online cleaning; the treatment method comprises the steps of adopting a two-stage chemical precipitation method and a steam stripping method to carry out emission reduction and resource utilization on ammonia nitrogen wastewater, removing impurities such as fluorine, heavy metal ions, sulfate radicals and silicates in the wastewater by using a chemical precipitation-flocculation method, extracting ammonia gas and ammonium sulfate by using a steam stripping method to be directly utilized, and finally treating residual nitrogen in the wastewater by using a magnesium ammonium phosphate MAP precipitation method to meet the national emission standard; the method can treat high-concentration wastewater containing the harmful substances and obtain byproducts which can be directly recycled.
Description
Technical Field
The invention relates to a method and a device for recycling industrial wastewater, in particular to a method for treating high-concentration ammonia nitrogen wastewater.
Background
Ammonia Nitrogen (NH)4 +N) ammonia (NH) in water mainly in free form3) And ammonium ion (NH)4 +) The method has the advantages that the source is wide, and a large amount of high-concentration ammonia nitrogen wastewater can be generated in hazardous waste, chemical fertilizer, petrifaction, coal gas, metallurgy, pharmacy, food, agriculture and other industrial processes.
Aiming at high-concentration ammonia nitrogen wastewater (NH)3-N concentration greater than 500mg/L) generally include chemical methods including chemical precipitation, coagulation, oxidation, chemical and physical methods including membrane separation, stripping and stripping, ion exchange, adsorption, etc., and biological methods including a2O process, AO process, pre-denitrification biological denitrification and oxidation ditch process, etc.; in recent years, new technologies such as a microwave-activated carbon method, an MVR (mechanical vapor recompression) method, an electrochemical oxidation method and the like are used for treating ammonia nitrogen in wastewater.
At present, the high-concentration ammonia nitrogen wastewater with the ammonia nitrogen content of 500-10000mg/L generated in the treatment industry mostly adopts a steam stripping method, and the reaction process is to adjust the wastewater to be alkaline, NH4 +Formation of NH under basic conditions3·H2And O, introducing a stripping carrier gas into the device, and stripping ammonia nitrogen existing in the wastewater in the form of free ammonia into steam through gas-liquid contact. The stripping method is suitable for treating high-concentration ammonia nitrogen wastewater, the removal rate of ammonia nitrogen can reach more than 99%, the efficiency is very high, the technical maturity is good, but the traditional stripping deamination technology aims at the ammonia nitrogen wastewater with simple components, and the wastewater generated in the hazardous waste industry can not be directly treated by using the stripping technology.
Because the waste water generated in the hazardous waste industry also contains impurities such as fluorine, heavy metal ions, sulfate radicals, silicates and the like, the waste water is difficult to be effectively treated, for example, the concentration of the fluorine ions in the actual hazardous waste industry is usually 1000mg/L, the fluorine ions need to be removed in advance, and if the removal is not complete, the corrosion to subsequent equipment is very large; the impurity ions can influence the equipment and the stripping efficiency; adsorption of organic matter on equipment affects efficiency and energy consumption.
The components of the waste liquid are complex, the content of harmful substances in the waste water in the conventional treatment method cannot reach the national emission standard, and the pollution water source is directly emitted, so that the environment is greatly damaged; the cost for treating the ammonia nitrogen wastewater is higher, the device is not energy-saving, the operating cost is high, and enterprises are difficult to bear.
In the prior art, the treatment of wastewater containing heavy metals and high ammonia nitrogen is generally carried out by adopting ammonia distillation or combination of a precipitation method and a biochemical method, the MAP method is firstly used for carrying out ammonia distillation treatment or an ammonia distillation tower, and then the high ammonia nitrogen wastewater is biochemically treated to remove residual ammonia nitrogen, however, the wastewater treated by the method still has a certain amount of metal ions and harmful impurities, which cannot reach the discharge standard, and the biochemical method has the defects of complex flow, large equipment facility investment, high operation cost, large floor area, complex operation and maintenance and the like.
In the prior art, CN107814465A provides a high ammonia nitrogen heavy metal ion industrial wastewater treatment device, which comprises a pH adjusting device, a stripping tower, a stripping device and a pH adjusting device; the pH adjusting device is used for converting ammonium ions in the wastewater into ammonia molecules and generating redundant hydroxide ions, the stripping tower is connected with the pH adjusting device and used for removing heavy metal ions in the wastewater, the heavy metal complex is decomposed by using the stripping tower and combined with the hydroxide ions, and thereby the precipitate is generated to remove heavy metals in the wastewater. However, harmful impurities except heavy metal ions cannot be removed from the wastewater treated by the device, and the wastewater treated by only using a stripping method has high ammonia nitrogen content and cannot meet the requirement of discharge.
Disclosure of Invention
In order to reduce the pollution of heavy metal, organic matters and harmful impurities to the environment, treat and recycle valuable materials in the wastewater, save the dosage of medicaments, save energy, reduce emission and reduce cost, the invention provides a treatment method for reducing emission and recycling ammonia nitrogen wastewater by combining a two-stage chemical precipitation method and a steam stripping mode. The method removes impurities such as fluorine, heavy metal ions, sulfate radicals and silicates in the wastewater by using a chemical precipitation-flocculation method, extracts ammonia gas in a steam stripping mode for resource utilization, and treats the wastewater by using an ammonium magnesium phosphate MAP precipitation method so as to meet the national discharge standard.
The invention provides a resourceful treatment method of high-concentration ammonia nitrogen wastewater, which sequentially comprises the following steps:
step one, pretreatment
The pretreatment is to pre-filter the ammonia nitrogen wastewater to remove solid particle impurities in the wastewater; the ammonia nitrogen wastewater is prefiltered by the method comprising the following steps: a 10-60 mesh prefilter is arranged at the feed end of the ammonia nitrogen wastewater;
the ammonia nitrogen wastewater filtered by the prefilter is lifted by a discharge pump to enter a filtered ammonia nitrogen wastewater storage tank, or directly enters a subsequent flow through an overrun pipeline arranged in the ammonia nitrogen wastewater storage tank;
step two, chemical impurity removal
The chemical impurity removal is to convey the pretreated ammonia nitrogen wastewater to a chemical precipitation tank, add a chemical precipitator to react with the ammonia nitrogen wastewater to form insoluble precipitated salt; then adding a flocculating agent, carrying out solid-liquid separation, and carrying out ammonia distillation on the separated liquid-phase ammonia nitrogen wastewater;
the chemical impurity removal process comprises a chemical precipitation method and a flocculation method: adding a chemical precipitator into the chemical precipitation tank, and then adding a flocculating agent into the precipitation tank;
further, the chemical precipitating agent comprises an inorganic impurity ion remover and a metal precipitating agent which are sequentially added;
furthermore, the inorganic impurity ion remover is one or more of calcium chloride and calcium hydroxide, and can form precipitates with fluoride ions, sulfate radicals, phosphate radicals and the like in the wastewater to achieve the purification effect;
further, the metal precipitator is sodium carbonate and a sulfur precipitator which is used in a matching way, and the sulfur precipitator is one or more of an organic sulfur precipitator and an inorganic sulfur precipitator which are used in a matching way;
further, the inorganic sulfur precipitating agent comprises sodium sulfide and sodium hydrosulfide; organic sulfur precipitants include SDD, TMT15, TMT 55; the metal precipitator forms precipitates with calcium, magnesium and other heavy metal ions in the water to achieve the removal effect; sodium carbonate can further reduce [ H + in ammonia nitrogen waste liquid]As the pH value rises, Cu, for example, can be removed2+、Ni2+、Cr3+、Zn2+Etc.; and because the dissolution grade constant of the sulfide is small, compared with hydroxide, the heavy metal ions are easier to precipitate, so that the heavy metal ions in the ammonia nitrogen waste liquid can be further removed by adding the sulfur precipitator. In addition, the metal precipitator comprises sodium carbonate, so that the function of alkali adjustment can be realized, the subsequent alkali adding amount can be reduced, the cost is saved, and the sludge yield is reduced.
Further, the flocculant is one or more of polyaluminium chloride (PAC), polyaluminium sulfate (PAS), polyferric chloride (PFC) or polyferric sulfate (PFS), Polyacrylamide (PAM); a flocculating agent is added, so that the generated flocculation effect can be utilized to quickly accumulate and settle the precipitate;
further, the solid-liquid separation selects a filter press to separate sludge, produced water enters an ammonia distillation stage, and the sludge is dewatered and then sent to a solidification landfill workshop for disposal; the filter press is preferably a chamber filter press;
step three, ammonia distillation
In the ammonia distillation process, liquid-phase ammonia nitrogen wastewater after chemical impurity removal is sent to an ammonia distillation tower for steam stripping, and deamination wastewater at the bottom of the ammonia distillation tower enters a chemical denitrification groove; ammonia gas at the top of the ammonia still enters an ammonia water absorption tower for cooling and absorption;
the ammonia distillation comprises steam stripping, ammonia water absorption and secondary absorption;
the steam stripping comprises the steps that liquid-phase ammonia nitrogen wastewater after solid-liquid separation is lifted into a heat exchanger at the top of an ammonia still by a pump to carry out heat exchange and heat rise to 110 ℃, the ammonia nitrogen wastewater enters an adjusting tank at the top of the ammonia still and is subjected to normal-pressure operation, then the ammonia nitrogen wastewater enters an adjusting tank at the top of the ammonia still, the pH value, the temperature and the flow are monitored in real time by an online pH meter and a thermometer which are arranged in the adjusting tank and a flow meter which is positioned at an ammonia nitrogen wastewater inlet of the ammonia still, and after 30% of liquid alkali in mass percentage is added on line to adjust the pH value of the ammonia nitrogen wastewater to be not less than 11, the ammonia nitrogen wastewater in the adjusting tank enters the ammonia still to carry out circular stripping; the ammonia nitrogen wastewater flows downwards step by step through the first stage tower plate in the tower, is heated by the lower layer hot steam and then enters the two-stage heating and stripping section, and the waste liquid and the stripping gas carry out turbulence and mass transfer on each stage tower plate in the tower. Based on the difference principle of relative volatility of ammonia and water molecules, the waste liquid is subjected to gas-liquid phase equilibrium for multiple times on each layer of tower plates in the deamination tower, and the removed ammonia gas rises together with steam and enters the upper section, so that conditions are provided for continuous and efficient removal of ammonia in the waste liquid while the partial pressure of ammonia in the tower is reduced.
Ammonia nitrogen in the ammonia nitrogen wastewater is removed into a gas phase at each stage of tower plates with different efficiencies; the generated ammonia gas enters a heat exchanger at the top of an ammonia still for heat exchange and temperature reduction; the automatic control system monitors deamination wastewater with ammonia nitrogen content lower than 200mg/L through an online component analyzer arranged at the bottom of the ammonia still, and controls the deamination wastewater to enter a chemical denitrification tank through a heat exchanger at the bottom of the ammonia still;
the ammonia water absorption comprises: ammonia gas which is subjected to heat exchange and temperature reduction through a heat exchanger at the top of the ammonia distillation tower enters an ammonia water absorption tower; the ammonia water absorption tower circularly absorbs process water under a cooling condition to improve the solubility of ammonia in water, after an automatic control system monitors that the concentration of ammonia water reaches the standard through an online component analyzer arranged at the bottom of the ammonia water absorption tower, the automatic control system controls the extraction amount of the ammonia water and sets an automatic extraction control program by using the physical parameter of set ammonia water density, and 5-15% ammonia water is usually extracted, wherein the density range of the ammonia water is 981.4-941.3 kg/m3。
Condensing by a tower top condenser, collecting high-concentration ammonia gas with the ammonia content of about 80-90%, sending the high-concentration ammonia gas to an ammonia gas absorption tower, and absorbing ammonia in a gas phase by using process water to prepare 5-15% ammonia water.
The produced ammonia water can be directly conveyed to a conventional flue gas denitration system to be used as a reducing agent, so that the aim of resource recycling is fulfilled.
And the residual ammonia gas in the air and the non-condensable gas exhausted from the tower top is considered, so that a secondary absorption tower is added in the ammonia water absorption tower, the overflowed ammonia gas is absorbed by sulfuric acid to generate ammonium sulfate, and the standard-reaching air is directly discharged. When the absorption ammonium sulfate is saturated, the ammonium sulfate is transported to other units for utilization.
Furthermore, after the automatic control system monitors that the air components meet the national emission standard, the air up to the standard is controlled to be directly emitted.
The concentration of the recovered ammonia water and the concentration of the fed ammonia are in a direct proportional relation, and the larger the concentration of the fed ammonia is, the larger the concentration of the recovered ammonia water is. When the concentration of the fed ammonia is 40000 mg/L-60000 mg/L, the strong ammonia water with the mass percent of 5% -15% can be obtained.
The online cleaning of the ammonia still comprises the following steps: because of TDS in the waste liquid is higher, long-time use can be at cooler and ammonia still tower plate scale deposit, influences and blows off the effect. Therefore, the process is provided with a cleaning device which can wash tower plates in a cooler and an ammonia still, the cleaning water can be used as treated discharge water, and the cleaned wastewater is discharged to a subsequent treatment system; when the blow-off system stops working, the system starts a cleaning device, and sludge adhered to the wall in the pipeline is washed in time in the tower after cleaning; after normal operation for a certain period, stopping water inflow for half an hour, and starting a cleaning device in the tower to timely wash the sludge adhered to the inner wall of the tower.
Step four, chemical denitrification;
and the chemical denitrification comprises the steps of introducing the deamination wastewater of the ammonia distillation process into a chemical denitrification tank, and adding magnesium salt and phosphate to ensure that the molar ratio of magnesium, phosphorus and nitrogen in the solution is (Mg): (N): (P) 1-1.2: 1: 1-1.2, adjusting the pH to 9-11, under the action of mechanical stirring, generating magnesium ammonium phosphate (MAP struvite) by residual ammonia nitrogen in the wastewater, feeding effluent of a chemical denitrification tank into a filter press, feeding filtrate of the filter press into an effluent observation pool, and when an online component analyzer arranged in the effluent observation pool monitors that water quality parameters meet the effluent quality index of a physical and chemical workshop, sending a signal by an automatic control system to control the denitrified wastewater in the effluent observation pool to enter a water collecting pool for discharging or recycling; the adding proportion of magnesium salt and phosphate is controlled through online analysis, so that the ammonia nitrogen can be efficiently removed (the removal rate is 90-98%), and the content of other components in the wastewater is not increased.
The effluent of the chemical denitrification tank is lifted by a hose pump to enter a filter press, a return pipeline is arranged on the filter press and is connected to the chemical denitrification tank, the filtrate 5-10 minutes before the filter press operation is started flows back to the chemical denitrification tank at the front end until a sludge layer is formed on the filter cloth, and then the filtrate of the filter press is sent to an effluent observation tank; the filtrate enters an effluent observation pool, and after analysis and test, the water quality parameters meet the effluent quality index of the materialization workshop and then enter a water collecting pool; and returning to the reaction tank for secondary treatment when the water quality parameters do not meet the effluent quality index of the materialization workshop.
Further, when an online component analyzer arranged in the effluent observation pool monitors that the water quality parameters do not meet the effluent quality index of the materialization workshop, the automatic control system sends a signal to control the denitrified wastewater in the effluent observation pool to return to the chemical denitrification tank for treatment in a circulating manner; and collecting the mud cakes filtered out by the filter press and then sending the mud cakes to a subsequent process for disposal.
Step five, online cleaning:
the on-line cleaning is to control the cleaning of the equipment in the steps of pretreatment, chemical impurity removal, ammonia evaporation and chemical denitrification through the automatic control system by continuously detecting the parameters of the equipment and the water inlet and outlet pipelines by the analysis instrument of the automatic control system.
The automatic cleaning process is mainly used for preventing the scaling phenomena of a prefilter, an ammonia still and a heat exchanger, and the equipment must be thoroughly cleaned by water within a certain time. The certain time is obtained by calculating according to the stored mathematical model after the automatic control system receives the real-time equipment parameters monitored on line.
Cleaning the pre-filter in the pretreatment step, sending a signal in time by an automatic control system after each batch of high-concentration ammonia nitrogen wastewater is discharged and is subjected to pre-filtration, controlling a cleaning device to clean and clean the pre-filter, and sending filtered insoluble substances to an incineration workshop for harmless treatment;
cleaning the heat exchanger and the tower plate of the ammonia still in the ammonia still step, and controlling to start a cleaning device by an automatic control system when the heat exchangers of the ammonia still and the top of the ammonia still stop to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline; and after the ammonia still normally runs for a certain period, the automatic control system controls the ammonia still and the heat exchanger to stop water feeding for half an hour, and controls to start the cleaning device to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline.
The cleaning device can use the discharged water treated in the water collecting tank as cleaning water, and the cleaned wastewater is discharged to a subsequent treatment system.
The ammonia nitrogen wastewater contains ammonia nitrogen, fluorine, heavy metal ions, sulfate radicals, silicate and other impurities, the ammonia nitrogen wastewater is high-concentration ammonia nitrogen wastewater with ammonia nitrogen content of 500-10000mg/L, and the ammonia concentration in the high-concentration ammonia nitrogen wastewater is higher than 40000mg/L (containing 40000 mg/L).
The invention provides an ammonia nitrogen wastewater recycling treatment device for the treatment method, which comprises a pre-filtering device, a chemical precipitation-flocculation system, an ammonia distillation system, a chemical denitrification system and an automatic control system:
the pre-filtering device comprises a pre-filter and an ammonia nitrogen waste liquid storage tank;
the chemical precipitation-flocculation system comprises a chemical precipitation tank and a chamber type filter press; the chemical sedimentation tank is provided with a waste liquid inlet, a precipitator adding inlet, a flocculating agent adding inlet and a stirring device;
the ammonia distillation system comprises a circulating heat exchanger, an ammonia distillation tower, an ammonia water absorption tower and a secondary absorption tower; the ammonia still comprises a plurality of layers of tower plates, and the circulating heat exchanger is arranged at the top of the ammonia still;
the chemical denitrification system comprises a chemical denitrification groove, a filter press, an effluent observation pool and a water collecting pool; the chemical denitrification tank is provided with a wastewater inlet, a reactant feeding port, an online pH meter, a stirring device and a water outlet device;
the automatic control system is electrically connected to the pre-filtering device, the chemical precipitation-flocculation system, the ammonia distillation system, the chemical denitrification system and the online cleaning device;
the automatic control system uses a control system based on a single chip microcomputer, a control system based on a microprocessor and taking an ARM as a core or a control system based on a PLC.
Furthermore, the automatic control system is preferably a PLC-based control system, the PLC program is simple, the collected monitoring and analyzing data can be simply processed or the data can be transmitted to an upper computer for processing through serial port communication, the performance is stable, and the maintenance cost is low; the method has the advantages of small workload, low cost and strong interference resistance when being applied to the framework of a wastewater treatment system.
The invention has the beneficial effects that:
according to the invention, harmful impurities such as fluorine ions, heavy metal ions and organic matters in the ammonia nitrogen wastewater are removed by a pre-filtration and chemical precipitation-flocculation method, so that not only can ammonia water recovered by a subsequent ammonia distillation tower be directly reused in a flue gas denitration device of a factory or sold after being treated and packaged; but also ensures that the struvite produced by the MAP method in the chemical denitrification can be directly used as a high-quality fertilizer for recycling; the recycling rate of resources is extremely high, ammonia nitrogen in waste liquid is generated into ammonia water, a small amount of ammonium sulfate and struvite are recycled through the circular stripping of the ammonia still and the reflux denitrification of the chemical denitrification groove, and the resource recycling rate is more than or equal to 98.75 percent.
The invention also can treat the high-concentration ammonia nitrogen waste liquid by combining the ammonia evaporation method and the MAP method, has no limit to the concentration of the ammonia nitrogen inlet, and can accept the waste liquid with the ammonia concentration of 40000mg/L and above; through the combination of the technical means, the ammonia is thoroughly removed, and the effluent can meet the discharge requirement of general industrial wastewater.
The device of the invention uses an automatic control system such as a PLC program to carry out automatic control in the whole process, and has reasonable arrangement and high automation degree. Through the use of the automatic control system and the monitoring and analyzing instrument, the reaction condition and the reaction duration of steam stripping can be reasonably controlled, and meanwhile, the addition of the medicament of the MAP method with high cost can be accurately controlled, so that the cost increase caused by excessive medicament and the water eutrophication caused by phosphorus entering sewage are prevented.
The invention provides a safer, more economical and more efficient treatment and recovery technology suitable for high-concentration ammonia nitrogen wastewater containing heavy metal ions, fluoride ions and organic matters, realizes the recycling of industrial wastewater, reaches the zero discharge of waste, and has important strategic and practical significance for environmental protection, improvement of the living standard of people and development of enterprises.
Drawings
FIG. 1 is a schematic diagram of a general process route of a resource treatment method of high-concentration ammonia nitrogen wastewater in embodiment 1 of the invention.
FIG. 2 is a schematic flow chart of a deamination process scheme of the resource treatment method of high-concentration ammonia-nitrogen wastewater in embodiment 1 of the present invention.
Fig. 3 is a schematic flow chart of a general process scheme of the resource treatment method of the high-concentration nitrogen wastewater in example 1 of the present invention.
Detailed Description
For better understanding of the present invention, the following detailed description will be given of the process and effect of the present invention with reference to the accompanying drawings.
Example 1
A resource treatment method for high-concentration ammonia nitrogen wastewater is shown in figure 1, the used ammonia nitrogen wastewater contains ammonia nitrogen, fluorine, heavy metal ions, sulfate radicals, silicate and other impurities, the ammonia concentration of the high-concentration ammonia nitrogen wastewater produced in the industry is 40000mg/L, the average fluorine ion concentration is 1000mg/L, and the high-concentration ammonia nitrogen wastewater is sequentially treated according to the following steps:
step one, pretreatment:
a 30-mesh prefilter is arranged at the feed end of the ammonia nitrogen wastewater and is used for removing solid particle impurities in the wastewater; the ammonia nitrogen wastewater filtered by the prefilter is lifted by a discharge pump to enter a filtered ammonia nitrogen wastewater storage tank, or directly enters a subsequent flow through an overrun pipeline arranged in the ammonia nitrogen wastewater storage tank;
step two, chemical impurity removal
The chemical impurity removal comprises chemical precipitation, flocculation and solid-liquid separation:
the ammonia nitrogen waste liquid after the pretreatment stage enters a chemical sedimentation tank, and insoluble precipitated salt is formed by adding chemical precipitant calcium chloride, sodium carbonate, SDD and NaHS in sequence, adjusting the pH value of the waste liquid to 7.0-9.0, and heavy metal ions, calcium and magnesium ions and the like in water;
the organic sulfide SDD can effectively remove heavy metal impurities such as Ni, Co and the like, and the formed large-particle chelate sediment is easy to separate by filter pressing; the solubility of the precipitate is larger than that of heavy metal ions in the waste liquid by controlling the dosage of NaHS.
Then adding flocculant polyaluminium phosphate chloride into the sedimentation tank to assist the generation of sediment so as to remove small-particle sediment and adsorb fluoride ions, organic matters and toxic substances; when the flocculating agent is one or more of poly-phosphorus aluminum chloride, poly-aluminum sulfate (PAS), poly-ferric chloride (PFC) or poly-ferric sulfate (PFS), because the flocculating agent can also remove the fluoride ions in the waste liquid, no fluoride ion precipitator can be added, the cost is only slightly higher than that of calcium chloride and the like, but the process is simplified, and the equipment investment and the production cost are reduced.
The solid-liquid separation is to separate sludge from the ammonia nitrogen waste liquid subjected to chemical impurity removal through a box type filter press, the produced water enters an ammonia distillation stage, and the sludge is dewatered and then sent to a solidification landfill workshop for disposal;
step three, ammonia distillation
The ammonia distillation comprises three stages of steam stripping, ammonia water absorption, online cleaning and the like;
the steam stripping comprises: lifting the ammonia nitrogen waste liquid subjected to chemical impurity removal and solid-liquid separation stages into a finned heat exchanger at an air outlet of an ammonia still by a pump for heat exchange, and simultaneously supplementing 30% of liquid caustic soda on line to adjust the pH value and then feeding the adjusted liquid caustic soda into the ammonia still; the waste liquid flows downwards step by step through the first stage tower plate in the tower, is heated by the lower layer hot steam and then enters the two-stage heating and stripping section, and the waste liquid and the stripping gas carry out turbulence and mass transfer on the tower plates in all stages in the tower. Based on the difference principle of relative volatility of ammonia and water molecules, the waste liquid is subjected to gas-liquid phase equilibrium for multiple times on each layer of tower plates in the deamination tower, and the removed ammonia gas rises together with steam and enters the upper section, so that conditions are provided for continuous and efficient removal of ammonia in the waste liquid while the partial pressure of ammonia in the tower is reduced. Ammonia nitrogen in the waste liquid is removed into gas phase at different levels of tower plates with different efficiencies until the ammonia-removed waste water with the ammonia nitrogen content lower than 200mg/L is obtained at the bottom of an ammonia still and then enters a subsequent treatment system after passing through a heat exchanger. And the ammonia gas at the tower top enters a fin heat exchanger at the air outlet of the ammonia still to be cooled. The high-temperature ammonia gas at the air outlet in the ammonia still exchanges heat with the low-temperature ammonia nitrogen wastewater at the wastewater inlet, and the cyclic utilization of the waste heat obviously reduces the energy consumption.
The ammonia water absorption comprises: and the ammonia gas subjected to heat exchange and temperature reduction in the finned heat exchanger at the air outlet of the ammonia still enters an ammonia water absorption tower. The ammonia water absorption tower utilizes the process water to circularly absorb under the cooling condition so as to improve the solubility of ammonia in water, after the concentration of the ammonia water reaches the standard, the produced amount of the ammonia water is controlled by utilizing the density of the ammonia water, and the produced ammonia water is conveyed to the incineration denitration system for use. The residual ammonia gas in the air and the non-condensable gas exhausted from the tower top is considered, so that secondary absorption is subsequently added in the ammonia water absorption tower, the overflowed ammonia gas is absorbed by sulfuric acid to generate ammonium sulfate, and the air reaching the standard is directly discharged. When the absorption of ammonium sulfate reaches saturation, the ammonium sulfate is transferred to other units for utilization.
The concentration of the recovered ammonia water and the concentration of the fed ammonia are in a direct proportional relation, and the larger the concentration of the fed ammonia is, the larger the concentration of the recovered ammonia water is. In the embodiment, the concentration of the fed ammonia is 40000mg/L, and the strong ammonia water with the mass fraction of 5% is obtained. The concentration of ammonia nitrogen discharged from the bottom of the ammonia distillation tower is less than or equal to 200mg/L, the resource recovery rate is more than or equal to 95 percent, and the steam consumption of the stripping deamination ton is less than or equal to 200kg (the saturated steam pressure is more than or equal to 0.4 MPa).
The ammonia still needs to be cleaned on line periodically: because of TDS in the waste liquid is higher, long-time use can be at cooler and ammonia still tower plate scale deposit, influences and blows off the effect. Therefore, the process is provided with a cleaning device controlled by an automatic control system, the tower plates in a cooler and an ammonia still can be washed, the cleaning water can be used as the treated discharge water, and the cleaned wastewater is discharged to a subsequent treatment system; when the blow-off system stops working, the system starts a cleaning device, and sludge adhered to the wall in the pipeline is washed in time in the tower after cleaning; after normal operation for a certain period, the system controls to stop water feeding for half an hour, and a cleaning device in the tower is started to timely wash the sludge adhered to the inner wall of the tower.
Step four, chemical denitrification;
the chemical denitrification stage comprises: lifting the effluent of the ammonia distillation process by a pump, feeding the effluent into a chemical denitrification tank, and adding magnesium salt and phosphate to ensure that the molar ratio of magnesium, phosphorus and nitrogen in the solution is (Mg): (N): adjusting the pH value to 9.5 and generating struvite (MAP magnesium ammonium phosphate) by residual ammonia nitrogen in the wastewater under the action of mechanical stirring when the pH value is 1:1: 1.2; the effluent of the chemical denitrification groove is lifted by a hose pump (provided with a return pipeline) and enters a filter press.
And (3) refluxing the filtrate 8 minutes before the start of the filter pressing operation to the front-end reaction tank so as to form a sludge layer on the filter cloth and ensure the quality of the effluent. The filtrate enters an effluent observation pool, and after analysis and test, the water quality parameters meet the effluent quality index of the materialization workshop and then enter a water collecting pool; and the water quality parameters do not meet the effluent quality index of the materialization workshop, and the effluent is returned to the reaction tank for secondary treatment.
And the mud cake is collected and then sent to a subsequent process for further treatment.
Step five, online cleaning:
the on-line cleaning is to control the cleaning of the equipment in the steps of pretreatment, chemical impurity removal, ammonia evaporation and chemical denitrification through the automatic control system by continuously detecting the parameters of the equipment and the water inlet and outlet pipelines by the analysis instrument of the automatic control system.
The automatic cleaning process is mainly used for preventing the scaling phenomena of a prefilter, an ammonia still and a heat exchanger, and the equipment must be thoroughly cleaned by water within a certain time. The certain time is obtained by calculating according to the stored mathematical model after the automatic control system receives the real-time equipment parameters monitored on line.
Cleaning the pre-filter in the pretreatment step, sending a signal in time by an automatic control system after each batch of high-concentration ammonia nitrogen wastewater is discharged and is subjected to pre-filtration, controlling a cleaning device to clean and clean the pre-filter, and sending filtered insoluble substances to an incineration workshop for harmless treatment;
cleaning the heat exchanger and the tower plate of the ammonia still in the ammonia still step, and controlling to start a cleaning device by an automatic control system when the heat exchangers of the ammonia still and the top of the ammonia still stop to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline; and after the ammonia still normally runs for a certain period, the automatic control system controls the ammonia still and the heat exchanger to stop water feeding for half an hour, and controls to start the cleaning device to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline.
The cleaning device can use the discharged water treated in the water collecting tank as cleaning water, and the cleaned wastewater is discharged to a subsequent treatment system.
The cost accounting for this example is shown in the following table:
it can be seen that through pretreatment and on-line real-time measurement, the cost, especially the medicament consumption, of the embodiment is reduced by at least 30% compared with the prior art, while the cost of 40000mg/L wastewater treatment is only 472.556 yuan/ton, the impurity content, especially the heavy metal content, in the struvite which is the target product of the MAP method is very low, and the struvite can be directly treated and packaged to be sold as a high-quality fertilizer.
Example 2: the treatment capacity of the waste liquid of a certain factory is 30t/d, the ammonia nitrogen content of the waste liquid is usually more than 4 ten thousand mg/L, usually between 4 and 6 ten thousand mg/L, and the technical scheme of the invention is used in the factory:
step one, pretreatment:
a 60-mesh prefilter is arranged at the feed end of the ammonia nitrogen wastewater and is used for removing solid particle impurities in the waste liquid; the ammonia nitrogen wastewater filtered by the prefilter is lifted by a discharge pump to enter a filtered ammonia nitrogen wastewater storage tank, or directly enters a subsequent flow through an overrun pipeline arranged in the ammonia nitrogen wastewater storage tank;
step two, chemical impurity removal
The chemical impurity removal comprises chemical precipitation, flocculation and solid-liquid separation:
the ammonia nitrogen waste liquid after the pretreatment stage enters a chemical sedimentation tank, and insoluble precipitated salt is formed by sequentially adding chemical precipitants such as calcium hydroxide, sodium sulfide and sodium carbonate with heavy metal ions, calcium magnesium ions and the like in water; then adding polyacrylamide serving as a flocculating agent into the sedimentation tank for adsorbing fluoride ions, organic matters and toxic substances;
the solid-liquid separation is to separate sludge from the ammonia nitrogen waste liquid subjected to chemical impurity removal through a box type filter press, the produced water enters an ammonia distillation stage, and the sludge is dewatered and then sent to a solidification landfill workshop for disposal;
step three, ammonia distillation
The ammonia distillation comprises three stages of steam stripping, ammonia water absorption, online cleaning and the like;
the steam stripping comprises: lifting the ammonia nitrogen waste liquid subjected to chemical impurity removal and solid-liquid separation stages into a finned heat exchanger at an air outlet of an ammonia still by a pump for heat exchange, and simultaneously supplementing 30% of liquid caustic soda on line to adjust the pH value and then feeding the adjusted liquid caustic soda into the ammonia still; the waste liquid flows downwards step by step through the first stage tower plate in the tower, is heated by the lower layer hot steam and then enters the two-stage heating and stripping section, and the waste liquid and the stripping gas carry out turbulence and mass transfer on the tower plates in all stages in the tower. Based on the difference principle of relative volatility of ammonia and water molecules, the waste liquid is subjected to gas-liquid phase equilibrium for multiple times on each layer of tower plates in the deamination tower, and the removed ammonia gas rises together with steam and enters the upper section, so that conditions are provided for continuous and efficient removal of ammonia in the waste liquid while the partial pressure of ammonia in the tower is reduced. Ammonia nitrogen in the waste liquid is removed into gas phase at different levels of tower plates with different efficiencies until the ammonia-removed waste water with the ammonia nitrogen content lower than 200mg/L is obtained at the bottom of an ammonia still and then enters a subsequent treatment system after passing through a heat exchanger. And the ammonia gas at the tower top enters a fin heat exchanger at the air outlet of the ammonia still to be cooled. The high-temperature ammonia gas at the air outlet in the ammonia still exchanges heat with the low-temperature ammonia nitrogen wastewater at the wastewater inlet, and the cyclic utilization of the waste heat obviously reduces the energy consumption.
The ammonia water absorption comprises: and the ammonia gas subjected to heat exchange and temperature reduction in the finned heat exchanger at the air outlet of the ammonia still enters an ammonia water absorption tower. The ammonia water absorption tower utilizes the process water to circularly absorb under the cooling condition so as to improve the solubility of ammonia in water, after the concentration of the ammonia water reaches the standard, the produced amount of the ammonia water is controlled by utilizing the density of the ammonia water, and the produced ammonia water is conveyed to the incineration denitration system for use. The residual ammonia gas in the air and the non-condensable gas exhausted from the tower top is considered, so that secondary absorption is subsequently added in the ammonia water absorption tower, the overflowed ammonia gas is absorbed by sulfuric acid to generate ammonium sulfate, and the air reaching the standard is directly discharged. When the absorption of ammonium sulfate reaches saturation, the ammonium sulfate is transferred to other units for utilization.
The concentration of the recovered ammonia water and the concentration of the fed ammonia are in a direct proportional relation, and the larger the concentration of the fed ammonia is, the larger the concentration of the recovered ammonia water is. The ammonia still needs to be cleaned on line periodically: because of TDS in the waste liquid is higher, long-time use can be at cooler and ammonia still tower plate scale deposit, influences and blows off the effect. Therefore, the process is provided with a cleaning device controlled by an automatic control system, the tower plates in a cooler and an ammonia still can be washed, the cleaning water can be used as the treated discharge water, and the cleaned wastewater is discharged to a subsequent treatment system; when the blow-off system stops working, the system starts a cleaning device, and sludge adhered to the wall in the pipeline is washed in time in the tower after cleaning; after normal operation for a certain period, the system controls to stop water feeding for half an hour, and a cleaning device in the tower is started to timely wash the sludge adhered to the inner wall of the tower.
Step four, chemical denitrification;
the chemical denitrification stage comprises: lifting the effluent of the ammonia distillation process by a pump, feeding the effluent into a chemical denitrification tank, and adding magnesium salt and phosphate to ensure that the molar ratio of magnesium, phosphorus and nitrogen in the solution is (Mg): (N): adjusting the pH value to 9.0-11, and generating struvite (MAP magnesium ammonium phosphate) from residual ammonia nitrogen in the wastewater under the action of mechanical stirring; the effluent of the chemical denitrification groove is lifted by a hose pump (provided with a return pipeline) and enters a filter press.
And (3) refluxing the filtrate 8 minutes before the start of the filter pressing operation to the front-end reaction tank so as to form a sludge layer on the filter cloth and ensure the quality of the effluent. The filtrate enters an effluent observation pool, and after analysis and test, the water quality parameters meet the effluent quality index of the materialization workshop and then enter a water collecting pool; and the water quality parameters do not meet the effluent quality index of the materialization workshop, and the effluent is returned to the reaction tank for secondary treatment.
And the mud cake is collected and then sent to a subsequent process for further treatment.
Step five, online cleaning:
the on-line cleaning is to control the cleaning of the equipment in the steps of pretreatment, chemical impurity removal, ammonia evaporation and chemical denitrification through the automatic control system by continuously detecting the parameters of the equipment and the water inlet and outlet pipelines by the analysis instrument of the automatic control system.
The automatic cleaning process is mainly used for preventing the scaling phenomena of a prefilter, an ammonia still and a heat exchanger, and the equipment must be thoroughly cleaned by water within a certain time. The certain time is obtained by calculating according to the stored mathematical model after the automatic control system receives the real-time equipment parameters monitored on line.
Cleaning the pre-filter in the pretreatment step, sending a signal in time by an automatic control system after each batch of high-concentration ammonia nitrogen wastewater is discharged and is subjected to pre-filtration, controlling a cleaning device to clean and clean the pre-filter, and sending filtered insoluble substances to an incineration workshop for harmless treatment;
cleaning the heat exchanger and the tower plate of the ammonia still in the ammonia still step, and controlling to start a cleaning device by an automatic control system when the heat exchangers of the ammonia still and the top of the ammonia still stop to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline; and after the ammonia still normally runs for a certain period, the automatic control system controls the ammonia still and the heat exchanger to stop water feeding for half an hour, and controls to start the cleaning device to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline.
The cleaning device can use the discharged water treated in the water collecting tank as cleaning water, and the cleaned wastewater is discharged to a subsequent treatment system.
In the embodiment, when the concentration of the waste liquid entering the ammonia still is 4-6 mg/L, the concentration of the produced ammonia water is usually 5-15%; no matter the concentration of the waste liquid entering the ammonia still, the ammonia nitrogen in the effluent is lower than 200mg/L through the gradual reduction of the tower plate of the ammonia still; the resource recovery rate in the ammonia still is more than or equal to 95 percent, and the steam consumption of the stripping deamination ton is less than or equal to 200kg (the saturated steam pressure is more than or equal to 0.4 MPa).
Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the specific details of the above-described embodiments, and those skilled in the art, having the benefit of the present inventive concepts, may make further alterations and modifications to these embodiments within the scope of the inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A resourceful treatment method of high-concentration ammonia nitrogen wastewater adopts a low-pressure steam stripping process, and is characterized in that the method sequentially comprises the steps of pretreatment, chemical impurity removal, ammonia distillation, chemical denitrification and online cleaning;
the method comprises the following steps of firstly, pre-filtering ammonia nitrogen wastewater by using a pre-filter to remove solid particle impurities in the wastewater;
step two, the chemical impurity removal is to convey the pretreated ammonia nitrogen wastewater to a chemical precipitation tank, add a chemical precipitator to react with the ammonia nitrogen wastewater, and form insoluble precipitated salt; then adding a flocculating agent, carrying out solid-liquid separation, and carrying out ammonia distillation on the separated liquid-phase ammonia nitrogen wastewater;
step three, in the ammonia distillation process, sending the liquid-phase ammonia nitrogen wastewater subjected to chemical impurity removal into an ammonia distillation tower for steam stripping, and sending the deamination wastewater at the bottom of the ammonia distillation tower into a chemical denitrification groove; ammonia gas at the top of the ammonia still enters an ammonia water absorption tower for cooling and absorption;
step four, the chemical denitrification is to introduce the deamination wastewater of the ammonia distillation process into a chemical denitrification tank, add magnesium salt and phosphate and adjust the pH to 9-11, under the action of mechanical stirring, the residual ammonia nitrogen in the wastewater generates magnesium ammonium phosphate, the effluent of the chemical denitrification tank enters a filter press, the filtrate of the filter press is sent into an effluent observation pool, when an online component analyzer arranged in the effluent observation pool monitors that the water quality parameters meet the effluent quality index of a physical and chemical workshop, an automatic control system sends a signal to control the denitrogenation wastewater in the effluent observation pool to enter a water collecting pool for discharge or reuse;
and fifthly, the online cleaning is to continuously detect the parameters of the equipment and the water inlet and outlet pipelines through an analysis instrument of the automatic control system, and the automatic control system is used for controlling the cleaning of the equipment in the steps of pretreatment, chemical impurity removal, ammonia evaporation and chemical denitrification.
2. The resource treatment method of the high-concentration ammonia nitrogen wastewater as recited in claim 1, characterized in that:
in the third step, the steam stripping comprises the steps that liquid-phase ammonia nitrogen wastewater after solid-liquid separation is lifted into a heat exchanger at the top of an ammonia still by a pump to carry out heat exchange and raise the temperature to 110 ℃, then the ammonia nitrogen wastewater enters an adjusting tank at the top of the ammonia still, the pH value, the temperature and the flow rate are monitored in real time by an online pH meter and a thermometer which are arranged in the adjusting tank and a flow meter which is positioned at an ammonia nitrogen wastewater inlet of the ammonia still, and after 30% of liquid alkali in mass percent is added on line to adjust the pH value of the ammonia nitrogen wastewater to be more than or equal to 11, the ammonia nitrogen wastewater in the adjusting tank enters the ammonia still to carry out circular stripping; the ammonia nitrogen wastewater flows downwards step by step through a first stage tower plate in the tower, is heated by lower layer hot steam and then enters a two-stage heating and stripping section, and ammonia nitrogen in the ammonia nitrogen wastewater is removed at each stage tower plate with different efficiency and enters a gas phase; the generated ammonia gas enters a heat exchanger at the top of an ammonia still for heat exchange and temperature reduction; when the automatic control system monitors that the ammonia nitrogen content of the deamination wastewater is lower than 200mg/L through an online component analyzer arranged at the bottom of the ammonia still, the deamination wastewater is controlled to enter a chemical denitrification tank through a heat exchanger at the bottom of the ammonia still;
in step three, the ammonia absorption comprises: ammonia gas which is subjected to heat exchange and temperature reduction through a heat exchanger at the top of the ammonia distillation tower enters an ammonia water absorption tower; the ammonia water absorption tower utilizes the process water to circularly absorb under the cooling condition so as to improve the solubility of ammonia in water, and the automatic control system utilizes the physical parameter ammonia water density to control the produced quantity of ammonia water after monitoring the ammonia water concentration to reach the standard through an online component analyzer arranged at the bottom of the ammonia water absorption tower.
3. The method for recycling high-concentration ammonia nitrogen wastewater as set forth in claim 1, wherein the chemical denitrification stage in the fourth step comprises: lifting the effluent of the chemical denitrification tank into a filter press through a hose pump, refluxing the filtrate 5-10 minutes before the start of filter pressing operation to the front-end chemical denitrification tank until a sludge layer is formed on the filter cloth, and then sending the filtrate of the filter press into an effluent observation tank; when an online component analyzer arranged in the effluent observation tank monitors that the water quality parameters do not meet the effluent quality index of the materialization workshop, the automatic control system sends a signal to control the denitrified wastewater in the effluent observation tank to return to the chemical denitrification tank for treatment in a circulating manner.
4. The method for recycling high-concentration ammonia nitrogen wastewater as set forth in any one of claims 1-3, wherein the on-line cleaning in the fifth step comprises:
cleaning the pre-filter in the pretreatment step, sending a signal in time by an automatic control system after each batch of high-concentration ammonia nitrogen wastewater is discharged and is subjected to pre-filtration, controlling a cleaning device to clean and clean the pre-filter, and sending filtered insoluble substances to an incineration workshop for harmless treatment;
cleaning the heat exchanger and the tower plate of the ammonia still in the ammonia still step, and controlling to start a cleaning device by an automatic control system when the heat exchangers of the ammonia still and the top of the ammonia still stop to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline; and after the ammonia still normally runs for a certain period, the automatic control system controls the ammonia still and the heat exchanger to stop water feeding for half an hour, and controls to start the cleaning device to flush the wall-sticking sludge in the ammonia still, the heat exchanger and the connecting pipeline.
5. A resource treatment method for high-concentration ammonia nitrogen wastewater as claimed in any one of claims 1-3, characterized in that in step three, a secondary absorption tower is connected with the ammonia water absorption tower, the overflowed ammonia gas is absorbed by sulfuric acid to generate ammonium sulfate, and after the automatic control system monitors that the air meets the national emission standard, the standard air is controlled to be directly discharged.
6. The method for recycling high-concentration ammonia nitrogen wastewater as recited in claim 4, wherein the cleaning device uses the discharge water treated in the collecting tank as cleaning water, and the cleaned wastewater is discharged to a subsequent treatment system.
7. A high-concentration ammonia nitrogen wastewater treatment device for implementing the resource treatment method of the high-concentration ammonia nitrogen wastewater in claim 1, wherein the treatment device comprises a pre-filtering device, a chemical precipitation-flocculation system, an ammonia distillation system, a chemical denitrification system and an automatic control system:
the pre-filtering device comprises a pre-filter and an ammonia nitrogen waste liquid storage tank;
the chemical precipitation-flocculation system comprises a chemical precipitation tank and a chamber type filter press; the chemical sedimentation tank is provided with a waste liquid inlet, a precipitator adding inlet, a flocculating agent adding inlet and a stirring device;
the ammonia distillation system comprises a circulating heat exchanger, an ammonia distillation tower, an ammonia water absorption tower and a secondary absorption tower; the ammonia still comprises a plurality of layers of tower plates, and the circulating heat exchanger is arranged at the top of the ammonia still;
the chemical denitrification system comprises a chemical denitrification groove, a filter press, an effluent observation pool and a water collecting pool; the chemical denitrification tank is provided with a wastewater inlet, a reactant feeding port, an online pH meter, a stirring device and a water outlet device;
the automatic control system is connected to the pre-filtering device, the chemical precipitation-flocculation system, the ammonia distillation system, the chemical denitrification system and the online cleaning device.
8. The high-concentration ammonia-nitrogen wastewater treatment device of claim 7, characterized in that: the automatic control system uses a control system based on a single chip microcomputer, a control system based on a microprocessor and taking an ARM as a core or a control system based on a PLC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011632124.3A CN113292187A (en) | 2020-12-31 | 2020-12-31 | Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011632124.3A CN113292187A (en) | 2020-12-31 | 2020-12-31 | Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113292187A true CN113292187A (en) | 2021-08-24 |
Family
ID=77318700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011632124.3A Pending CN113292187A (en) | 2020-12-31 | 2020-12-31 | Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113292187A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114604998A (en) * | 2022-03-08 | 2022-06-10 | 广东南方碱业股份有限公司 | System and process for reducing ammonia nitrogen in clear waste liquid |
| CN115259466A (en) * | 2022-08-05 | 2022-11-01 | 广东先导稀材股份有限公司 | Method for treating nickel in high-ammonia-nitrogen high-salt wastewater |
| CN116282688A (en) * | 2023-02-28 | 2023-06-23 | 大唐环境产业集团股份有限公司 | System and method for recycling urea hydrolysis wastewater |
| CN117566982A (en) * | 2024-01-17 | 2024-02-20 | 惠州金茂源环保科技有限公司 | Treatment and recycling recovery method for ammonia nitrogen in electroplating wastewater |
| CN117566982B (en) * | 2024-01-17 | 2024-04-26 | 惠州金茂源环保科技有限公司 | Treatment and recycling recovery method for ammonia nitrogen in electroplating wastewater |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958471A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for treating ammonia nitrogen wastewater |
| CN101066822A (en) * | 2007-05-24 | 2007-11-07 | 上海大学 | Combined treatment process for high-concentration ammonia nitrogen waste water |
| CN102910788A (en) * | 2012-11-13 | 2013-02-06 | 南京大学 | Deep denitrification process for wastewater |
| CN103508618A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Method for treating high-concentration ammonia nitrogen wastewater |
| US20140197111A1 (en) * | 2013-01-11 | 2014-07-17 | Chinese Research Academy Of Environmental Sciences | Methods and systems for wastewater treatment and resource recovery |
| CN104628206A (en) * | 2015-02-11 | 2015-05-20 | 北京赛科康仑环保科技有限公司 | Recycling technique of lithium iron phosphate production wastewater |
| CN110668600A (en) * | 2019-09-19 | 2020-01-10 | 浙江理工大学上虞工业技术研究院有限公司 | Comprehensive treatment method for phosphorus-containing wastewater and ammonia nitrogen wastewater |
-
2020
- 2020-12-31 CN CN202011632124.3A patent/CN113292187A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958471A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for treating ammonia nitrogen wastewater |
| CN101066822A (en) * | 2007-05-24 | 2007-11-07 | 上海大学 | Combined treatment process for high-concentration ammonia nitrogen waste water |
| CN103508618A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Method for treating high-concentration ammonia nitrogen wastewater |
| CN102910788A (en) * | 2012-11-13 | 2013-02-06 | 南京大学 | Deep denitrification process for wastewater |
| US20140197111A1 (en) * | 2013-01-11 | 2014-07-17 | Chinese Research Academy Of Environmental Sciences | Methods and systems for wastewater treatment and resource recovery |
| CN104628206A (en) * | 2015-02-11 | 2015-05-20 | 北京赛科康仑环保科技有限公司 | Recycling technique of lithium iron phosphate production wastewater |
| CN110668600A (en) * | 2019-09-19 | 2020-01-10 | 浙江理工大学上虞工业技术研究院有限公司 | Comprehensive treatment method for phosphorus-containing wastewater and ammonia nitrogen wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 竹涛等: "《矿山固体废物处理与处置工程》", 30 June 2016 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114604998A (en) * | 2022-03-08 | 2022-06-10 | 广东南方碱业股份有限公司 | System and process for reducing ammonia nitrogen in clear waste liquid |
| CN115259466A (en) * | 2022-08-05 | 2022-11-01 | 广东先导稀材股份有限公司 | Method for treating nickel in high-ammonia-nitrogen high-salt wastewater |
| CN115259466B (en) * | 2022-08-05 | 2023-12-22 | 湖南先导新材料科技有限公司 | Treatment method for nickel in high ammonia nitrogen and high salt wastewater |
| CN116282688A (en) * | 2023-02-28 | 2023-06-23 | 大唐环境产业集团股份有限公司 | System and method for recycling urea hydrolysis wastewater |
| CN116282688B (en) * | 2023-02-28 | 2023-10-27 | 大唐环境产业集团股份有限公司 | System and method for recycling urea hydrolysis wastewater |
| CN117566982A (en) * | 2024-01-17 | 2024-02-20 | 惠州金茂源环保科技有限公司 | Treatment and recycling recovery method for ammonia nitrogen in electroplating wastewater |
| CN117566982B (en) * | 2024-01-17 | 2024-04-26 | 惠州金茂源环保科技有限公司 | Treatment and recycling recovery method for ammonia nitrogen in electroplating wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113292187A (en) | Resourceful treatment method and device for high-concentration ammonia nitrogen wastewater | |
| CN102079601B (en) | Resource recovery and zero discharge process for treating rare-earth wet-method smelting wastewater | |
| CN107129094B (en) | Zero discharge system based on multi-heat-source evaporation desulfurization waste water | |
| CN102107978B (en) | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry | |
| CN102603097B (en) | Advanced treatment and recycling process for wastewater containing heavy metal ions | |
| CN107399876B (en) | A kind of processing method of high ammonia-nitrogen wastewater | |
| CN109879507B (en) | Process and device for resource utilization of coking high-salinity wastewater | |
| CN106746102A (en) | A kind of handling process of fluorine-containing ammonia nitrogen waste water | |
| CN110981065A (en) | Treatment method of lithium battery industrial wastewater | |
| CN218665656U (en) | System for recycling materialized heavy metal sewage of dangerous waste plant | |
| CN205241427U (en) | Desulfurization wastewater treatment system | |
| CN110818000B (en) | Garbage leachate membrane concentrated solution reduction and recycling treatment system and method | |
| CN107151072B (en) | Treatment process of desulfurization wastewater | |
| CN110818158B (en) | Comprehensive treatment method for waste hydrochloric acid and sludge containing heavy metals | |
| CN110697939A (en) | Thermal power plant flue gas desulfurization wastewater chlorine reduction recycling system and process | |
| CN104860465B (en) | Double-tower catalysis thermal-coupling reflux deamination method and deamination device thereof | |
| CN211445448U (en) | Sewage recovery processing system of steel pipe factory | |
| CN117185527A (en) | Chemical industry incineration flue gas high-ammonium salt spray wastewater recycling method and system for simultaneously recycling magnesium ammonium phosphate and ammonium sulfate | |
| CN111453795A (en) | High-magnesium desulfurization wastewater concentration and reduction treatment system and process | |
| CN101503257B (en) | Method and apparatus for recovering and treating ammonium nitrate condensate liquid wastewater | |
| CN207108723U (en) | A kind of zero-discharge treatment system of nuclear power plant evaporator sewer | |
| CN206927750U (en) | A kind of power plant waste water processing system | |
| CN210711126U (en) | Sintering furnace flue gas desulfurization denitration acid-making wastewater recycling system | |
| CN113277660A (en) | Desulfurization wastewater concentration and zero-emission treatment process based on flue gas evaporation | |
| CN114605017A (en) | Treatment process of ammonia nitrogen wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210824 |