CN111763103A - Process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater - Google Patents
Process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater Download PDFInfo
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- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
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Abstract
The invention provides a process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater, belonging to the technical field of sewage treatment. Comprises a desulfurization wastewater treatment unit, a landfill leachate treatment unit, a phosphorus-containing wastewater treatment unit and a calcium magnesium ammonium phosphate generation unit. The desulfurization wastewater treatment unit is used for treating desulfurization wastewater of a coal-fired power plant to obtain a calcium-containing solution; the landfill leachate treatment unit takes ammonia nitrogen escaping from the landfill leachate in the stripping deamination process as an ammonia nitrogen source; the phosphorus-containing wastewater treatment unit is used for treating the phosphorus-containing wastewater or the leakage liquid of the phosphogypsum slag yard to obtain a phosphorus-containing solution; the ammonium phosphate calcium magnesium generation unit is formed by mixing calcium/magnesium solution, ammonia nitrogen and phosphorus-containing solution, adjusting pH and reacting to obtain calcium phosphate, calcium fluoride, calcium hydrogen phosphate and ammonium phosphate precipitate. The invention carries out comprehensive treatment on industrial wastewater, and prepares the raw material of the compound fertilizer, namely calcium magnesium ammonium phosphate, by utilizing calcium and magnesium ions in the desulfurization wastewater, nitrogen and ammonia in the landfill leachate and phosphorus in the phosphorus-containing wastewater.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater.
Background
The magnesium calcium ammonium phosphate is a mixture of calcium hydrogen phosphate and magnesium ammonium phosphate, wherein the content of nitrogen and phosphorus is higher than 20 percent, and the magnesium calcium ammonium phosphate is a very ideal production raw material of a compound fertilizer. Wherein, magnesium ammonium phosphate (MAP, MgNH)4PO4·6H2O), commonly known as struvite, orthorhombic, with equiaxed, wedge-shaped, short columnar, thick plate crystals, colorless, white, yellowish or brown, glass-lustrous, hardness of 2, brittle nature, slightly soluble in water and dilute acid; calcium hydroxy phosphate (HAP) is also a water insoluble inorganic fertilizer.
More than 90% of coal-fired power plants in China adopt a limestone-gypsum method for wet desulphurization, and the process has high desulphurization efficiency, but inevitably generates high-hardness desulphurization wastewater. In which CaSO4、MgSO4Tend to saturate and contain a variety of heavy metal ions. The existing desulfurization wastewater treatment system of the coal-fired power plant is a triple box, and heavy metal, SS and hardness ions in wastewater can be removed to a certain degree. However, the existing process generally does not utilize the calcium element in the wastewater as a resource, can not remove chloride ions in the wastewater, and can not remove Ca which is easy to scale in the water2+The existing method often blocks an evaporation device when the evaporative crystallization process is adopted for desulfurization wastewater treatment, and the existing method of chloride ions can corrode a pipeline and reduce SO of an absorption tower2The absorption efficiency of (2).
The landfill leachate is mainly generated in a waste incineration treatment plant and a landfill, is high-concentration organic wastewater with complex components, high organic matter content and high treatment difficulty, contains various complex components, and has the main water quality characteristic of high-concentration ammonia nitrogen. This is particularly true for leachate from old landfill sites, where the excessive ammonia nitrogen content makes the old landfill sites spend enormous amounts of extra carbon sources of glucose to help solve the problem of unbalanced carbon/nitrogen ratio in leachate treatment systems. With the improvement of the technology and the improvement of the wastewater discharge standard, the main standard discharge treatment processes of the current landfill leachate are biochemical and double-membrane methods (nanofiltration and reverse osmosis) in order to ensure that the landfill leachate is discharged in standard. Wherein, the biochemical method is carried out by combining an anaerobic process and an aerobic process, and the anaerobic process can greatly reduce COD and BOD in water but can not remove nitrogen elements. Although the aerobic process can remove pollutants such as ammonia nitrogen, COD, BOD and the like to a certain degree, the aerobic process needs to consume a large amount of electric energy to aerate the leachate. In addition, the use of membrane filtration devices inevitably produces a concentrate. The treatment and disposal problems of the landfill leachate concentrated solution are the key points of the landfill leachate treatment. In the case of a primary energy supply (e.g. a refuse incineration plant), the concentrate of the percolate is usually treated by back-spraying in a furnace. The provision of primary energy sources is therefore a favourable factor in the treatment of the landfill concentrate.
The phosphorus-containing wastewater comprises phosphorus-containing wastewater generated in the coating process of industrial equipment, garbage leachate, anaerobic digestion sludge dewatering waste liquid of a municipal sewage treatment plant and the like. The recycling of phosphorus in the phosphating waste water and the landfill leachate is described below.
The phosphating waste water is generally generated in a phosphating process, which is a conventional treatment process for parts in the coating process of the mechanical equipment manufacturing industry to ensure the paint quality, and specifically refers to a process of immersing metal work into phosphate solution for chemical treatment and forming an insoluble phosphate film on the surface of the metal by using solution containing phosphoric acid or phosphate. In order to increase the corrosion resistance of the phosphating film and to increase the adhesion of the coating to the metal substrate, Mn is usually added to the phosphating solution2+，Ni2+，Cu2+The function of Ni is very obvious. The phosphorization wastewater generated by the process contains PO with higher concentration4 3-Phosphorus element (160-3000mg/L) and a large amount of Fe3+、Zn2+Ions. In addition, the use of Ni-containing compounds in the phosphating process is a highly toxic class of controlled pollutants that must be handled and discharged at standard levels at plant processing facilities.
The leakage liquid of the phosphogypsum slag field comes from a phosphogypsum storage yard generated in the wet preparation process of sulfuric acid of phosphoric acid, and 1 ton of phosphoric acid (P is used) is extracted every time2O5Meter) yields 4.8-5.0 tons of phosphogypsum. The pH value of a seepage liquid generated in the stacking process of a large amount of phosphogypsum as common industrial solid waste is extremely low, and the main components of the seepage liquid are calcium sulfate, a certain amount of metal elements such as calcium, magnesium, iron, manganese and the like and PO4 3-And fluorine ions. At present, the treatment technology of the leakage liquid of the national phosphogypsum storage yard is relatively simple, and the fluorine ions, the phosphate ions, the iron and the manganese elements in the leakage liquid cannot be effectively treated. With the increasing requirements of the country on water pollution control, zero discharge of industrial wastewater is imperative. At present, the process of concentrating and drying the wastewater gradually becomes a mainstream means for treating high-concentration industrial wastewater, the process flow of the scheme is simple, and zero emission of the desulfurization wastewater can be realized to a certain extent, but the process can generate waste salt which is difficult to treat and dispose.
In view of the above, the prior art does not disclose a comprehensive treatment technique for wastewater from various sources. The technology which can comprehensively treat the wastewater and fully recycle the useful elements in the wastewater is developed, and has important economic significance and environmental protection significance.
Disclosure of Invention
The invention aims to provide a process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater, which comprehensively treats desulfurization wastewater, landfill leachate and phosphorus-containing wastewater generated by a coal-fired power plant, and recycles useful substances in the three types of wastewater by combining the characteristics of the three types of wastewater, thereby realizing the preparation of calcium magnesium ammonium phosphate.
The purpose of the invention is realized by the following technical scheme:
the process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater comprises a desulfurization wastewater treatment unit, a landfill leachate treatment unit, a phosphorus-containing wastewater treatment unit and a calcium magnesium ammonium phosphate generation unit:
the desulfurization wastewater treatment unit is used for sequentially treating desulfurization wastewater of a coal-fired power plant through a triple box to remove heavy metals, ultrafiltering to remove suspended particle pollutants, nanofiltering to separate out divalent calcium and magnesium ions, then performing monovalent ion electrodialysis concentration, and feeding the generated concentrated water into a storage tank 1 to be used as a raw material for preparing calcium magnesium ammonium phosphate;
the landfill leachate treatment unit is used for sending ammonia nitrogen escaping from the landfill leachate in the stripping deamination process into a storage tank 2 to be used as a raw material for preparing calcium magnesium ammonium phosphate;
the phosphorus-containing wastewater treatment unit is used for treating phosphorus-containing wastewater or treating leakage liquid of a phosphogypsum slag yard: adding NaOH into the phosphating wastewater to adjust the pH value, then removing toxic heavy metals in the phosphating wastewater through standing and precipitating, and allowing alkaline phosphorus-containing wastewater obtained by ultrafiltration of supernatant to enter a storage tank 3 to serve as a raw material for preparing calcium magnesium ammonium phosphate; the leakage liquid treatment of the gypsum slag field is to carry out ultrafiltration on the raw water of the leakage liquid after coagulating sedimentation, and the generated concentrated water enters the storage tank 3 to be used as the raw material for preparing the ammonium phosphate calcium magnesium;
the ammonium phosphate calcium magnesium generating unit is characterized in that the solution containing calcium and magnesium in the storage tank 1 and the solution containing NH in the storage tank 23The feed liquid is mixed with the phosphorus-containing solution in the storage tank 3, and after the pH value is adjusted, the mixture reacts for a period of time to obtain calcium hydrogen phosphate and magnesium ammonium phosphate precipitates.
Further, the monovalent ion electrodialysis can selectively concentrate monovalent salt chloride ions and sodium ions and divalent salt SO4 2-And the water is intercepted on the fresh water side, and the produced water on the fresh water side is returned to the desulfurizing tower as the supplemented water of a desulfurizing system.
Further, the specific operation of landfill leachate treatment is as follows: sequentially carrying out steam stripping deamination, anaerobic fermentation, aerobic fermentation, ultrafiltration, nanofiltration and roll type reverse osmosis filtration on the landfill leachate, using the filtered clear liquid as open circulating cooling water of a power plant, using the concentrated solution for lime pulping, and sending ammonia nitrogen escaping in the steam stripping deamination process into a storage tank 2 as a raw material for preparing calcium magnesium ammonium phosphate.
Further, in the process of generating calcium and magnesium ammonium phosphate, the solution containing calcium and magnesium in the storage tank 1 and the solution containing NH in the storage tank 2 are mixed3When the feed liquid is mixed with the phosphorus-containing solution in the storage tank 3, the magnesium and the calcium are ensured to be added in excess。
Further, during the generation of calcium magnesium ammonium phosphate, Mg2+、PO4 3-And NH3The molar ratio of (A) is 1-1.5: 1-1.187: 1.0; ca2+And PO4 3-The molar ratio of (A) to (B) is 1-3: 2.
Further, in the step of generating calcium magnesium ammonium phosphate, the pH is 8.5-10, and the reaction time is 18-24 hours.
Further, in the step of generating calcium magnesium ammonium phosphate, the generated water is stripped and deaminated together with the landfill leachate.
Compared with the prior art, the invention has the following beneficial effects:
the proportion of carbon/nitrogen/phosphorus in the landfill leachate is extremely unbalanced, and excessive ammonia nitrogen influences the operation of a landfill leachate biochemical system, so that the burden is increased for the disposal of the landfill leachate. In leachate production sites where primary energy is scarce, it is not economical to establish a separate treatment for domestic landfill leachate, and the treatment of its concentrate is problematic. Similarly, in order to remove the pollutants contained in the conventional phosphate industrial wastewater treatment process, a large amount of precious phosphorus resources are converted into secondary pollutants, namely sludge, which needs to be treated again.
The invention comprehensively treats the pollutants such as desulfurization waste water of coal-fired power plants, landfill leachate, phosphorus-containing waste water and the like, and realizes a pollutant treatment mode of treating wastes with processes of wastes against one another. The divalent metal ions (calcium and magnesium) in the desulfurization wastewater, ammonia in the landfill leachate concentrated solution and phosphorus in the phosphorus-containing wastewater are utilized to prepare the compound fertilizer raw material calcium ammonium phosphate magnesium with high added value.
The process of the invention enables the thermal power plant to become a sewage treatment unit while utilizing the low-grade heat energy of the power plant, and can reduce the self-consumption water of the power plant, thereby improving the operation economic benefit of the power plant on the whole.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater of the invention is described in detail below with reference to specific principles and processes.
A process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater comprises a desulfurization wastewater treatment unit, a landfill leachate treatment unit, a phosphorus-containing wastewater treatment unit and a calcium magnesium ammonium phosphate generation unit.
The application selects the power plant desulfurization wastewater, landfill leachate and phosphorus-containing wastewater as raw materials to realize the production of calcium magnesium ammonium phosphate, and is based on the following consideration:
more than 90% of coal-fired power plants in China adopt a limestone-gypsum method for wet desulphurization, the process has high desulphurization efficiency, but can generate high-hardness desulphurization waste water with high salt concentration (TDS: 30000-4Tends to be saturated (Ca)2+The concentration is 400-800Mg/L), Mg2+The concentration is also up to 8000-30000 mg/L. The desulfurization wastewater is the terminal wastewater of a coal-fired power plant, belongs to typical high-salt refractory wastewater, is difficult to treat by using the traditional water treatment technology, and simultaneously has waste heat for gas stripping deamination.
The landfill leachate is high-concentration organic wastewater with complex components, high organic matter content and high treatment difficulty, and contains various complex components, and high-concentration ammonia nitrogen is the main water quality characteristic of the landfill leachate and is the key point and the difficulty of landfill leachate treatment. In order to make the landfill leachate reach the standard or be nearly zero-discharge, the existing treatment of the landfill leachate is mainly carried out by a biochemical process and a double-membrane process. The biochemical method combines an anaerobic process and an aerobic process, the anaerobic process can greatly reduce COD and BOD in water but can not remove nitrogen elements, and the aerobic process can remove pollutants such as ammonia nitrogen, COD, BOD and the like to a certain degree, but the aerobic process needs to consume a large amount of electric energy to aerate the percolate. In addition, the application of membrane filtration equipment inevitably produces concentrated liquid, and the membrane concentration liquid ammonia nitrogen concentration of the landfill leachate is extremely high and difficult to be effectively disposed.
Phosphorus is a very precious resource, and the phosphorus content in sewage, especially phosphorus-containing industrial wastewater, is high, such as phosphate industrial wastewater, and the phosphorus concentration can reach 1.8g/L, so that the phosphate is very necessary to be recycled.
Because the productivity is excessive, the economy is downslide, the domestic coal-fired thermal power plant benefit is downslide, and the center taking the thermal power plant as the core and being used for wastewater treatment has natural advantages: the coal-fired power plant has low-temperature waste heat which can be used for air stripping deamination, the benefit of the power plant can be increased by additionally treating percolate and phosphorus-containing industrial wastewater, and the ammonium phosphate calcium magnesium type byproduct is an advantageous fertilizer. Therefore, the preparation of calcium magnesium ammonium phosphate is jointly realized by the desulfurization wastewater of the power plant, the landfill leachate and the phosphorus-containing wastewater.
The desulfurization wastewater treatment unit is used for sequentially treating desulfurization wastewater of a coal-fired power plant through a triple box to remove heavy metals, ultrafiltering to remove suspended particle pollutants, nanofiltering to separate out divalent calcium and magnesium ions, then performing monovalent ion electrodialysis concentration, and enabling generated concentrated water to enter a storage tank 1 to serve as a raw material for preparing calcium magnesium ammonium phosphate.
Specifically, desulfurization wastewater of a coal-fired power plant is treated by a triple box (a neutralization box and a reaction box) to remove heavy metals, then is softened, suspended particle pollutants are removed by ultrafiltration, divalent calcium ions and magnesium ions are separated by nanofiltration, the load of subsequent electrodialysis treatment is reduced, finally monovalent ion electrodialysis concentration is carried out, monovalent salt chloride ions and sodium ions are selectively concentrated, and divalent salt SO is used for removing heavy metals4 2-And the concentrated water generated by electrodialysis concentration enters the storage tank 1 to be used as a raw material for preparing calcium magnesium ammonium phosphate, most chloride ions are removed from the fresh water side, and the concentrated water is used as a supplementary water of a desulfurization system and returns to the desulfurization tower.
The treatment of the desulfurization wastewater can be carried out by concentrating metal salt ions in the desulfurization wastewater by using an electrodialysis technology, and the salt content of the outlet water at the concentrated water end can reach 20%; the effluent water has low chloride ion content, and can be reused in the FGD desulfurization pulping system.
The landfill leachate treatment unit is used for sending ammonia nitrogen escaping from the landfill leachate in the stripping deamination process into the storage tank 2 to be used as a raw material for preparing calcium magnesium ammonium phosphate.
Specifically, the landfill leachate is sequentially subjected to stripping deamination, anaerobic fermentation, aerobic fermentation, ultrafiltration, nanofiltration and roll type reverse osmosis filtration, the filtered clear liquid is used as open circulating cooling water of a power plant, the concentrated solution is used for lime pulping, and ammonia nitrogen escaping in the stripping deamination process is sent to a storage tank 2 to be used as a raw material for preparing calcium magnesium ammonium phosphate.
For gas stripping deamination, in order to save energy, a heat exchange device is added on a methane combustion system, and the waste heat of desulfurization tail gas of a power plant is properly supplemented, so that a steam heat source is provided for a gas stripping deamination system (the temperature of the gas stripping deamination is only 80-90 ℃), the ammonia nitrogen in percolate is effectively removed by the gas stripping deamination system under the condition that a chemical agent is not added to adjust the pH value, the water quality is adjusted, the pollutant concentration is reduced, and the efficiency of a subsequent biochemical treatment system is obviously improved.
For nanofiltration, the nanofiltration concentrated solution is further concentrated by reverse osmosis of high-pressure disc filtration to obtain concentrated solution, the concentrated solution is sprayed back to the incinerator, and clear water enters the roll-type reverse osmosis filtration.
The phosphorus-containing wastewater treatment unit is used for treating phosphorus-containing wastewater or treating leakage liquid of a phosphogypsum slag yard.
And the phosphorization wastewater treatment comprises the steps of adding NaOH into the phosphorization wastewater to adjust the pH value to 9-11, then removing toxic heavy metals in the phosphorization wastewater through standing and precipitation, and enabling alkaline phosphorus-containing wastewater obtained by ultrafiltration of supernatant to enter a storage tank 3 to be used as a raw material for preparing calcium magnesium ammonium phosphate.
Further, the toxic heavy metal in the phosphorization wastewater is removed to be Ni, and the toxic heavy metal which needs to be particularly removed in the phosphorization wastewater is Ni; the ultrafiltration is carried out by passing the filtrate through an ultrafiltration system under the pressure of 0.1-0.5MPa, intercepting the precipitated fine particulate matters in the filtrate, and passing the solution through a filter membrane to obtain the alkaline phosphorus-containing wastewater.
The phosphogypsum slag yard leakage liquid treatment is that raw leakage liquid is subjected to coagulation sedimentation and then is subjected to ultrafiltration, clear liquid enters a high-pressure disc filtration type reverse osmosis device, generated concentrated water enters a storage tank 3 to be used as a raw material for preparing calcium magnesium ammonium phosphate, and filtrate is recovered to be used as desulfurization wastewater.
The ammonium phosphate calcium and magnesium is generated into the storage tank 1Of the solution containing calcium, NH contained in the reservoir 23The feed liquid is mixed with the phosphorus-containing solution in the storage tank 3, and after the pH value is adjusted, the mixture reacts for a period of time to obtain calcium hydrogen phosphate and magnesium ammonium phosphate precipitates. The specific chemical reaction is as follows:
CaSO4+H3PO4+2NH3+2H2O＝CaHPO4·2H2O↓+(NH4)2SO4
CaCl2+H3PO4+2NH3+2H2O＝CaHPO4·2H2O↓+2NH4Cl
MgSO4+H3PO4+3NH3+H2O＝MgNH4PO4·H2O↓+(NH4)2SO4
MgCl2+H3PO4+3NH3+H2O＝MgNH4PO4·H2O↓+2NH4Cl
further, in the process of generating calcium magnesium ammonium phosphate, the solution containing calcium in the storage tank 1 and the solution containing NH in the storage tank 2 are mixed3It is easy for those skilled in the art to ensure that the magnesium and calcium are added in excess when the feed solution is mixed with the phosphorus-containing solution in the reservoir 3.
Further, in the process of generating calcium magnesium ammonium phosphate, the molar ratio of magnesium to phosphorus to nitrogen is 1-1.5: 1-1.187: 1.0; ca2+And PO4 3-The molar ratio of (A) to (B) is 1-3: 2.
Further, in the step of generating calcium magnesium ammonium phosphate, the pH is 8.5-10, and the reaction time is 15-30 min; the generated water is stripped and deaminated together with the landfill leachate.
The invention provides an optimized desulfurization wastewater zero-discharge treatment process. By comprehensively treating phosphorus-containing waste liquid such as desulfurization waste water, domestic garbage leachate, phosphorization waste water/phosphogypsum yard leakage liquid and the like, a large amount of calcium and magnesium ions in the desulfurization waste water are fully utilized to generate raw materials of a high-efficiency compound fertilizer, and meanwhile, a coal-fired thermal power plant can obtain benefits by treating the garbage leachate and the phosphorus-containing industrial waste water. The reclaimed water generated in the sewage treatment process can be used for lime pulping and circulating cooling water replenishing of a power plant, so that the water consumption of fresh water of the power plant is reduced.
The desulfurization wastewater treatment unit, the landfill leachate treatment unit, the phosphorus-containing wastewater treatment unit and the ammonium phosphate calcium magnesium generation unit are all conventional devices in the prior art, and the skilled person can select the devices conventionally.
Example 1
Desulfurization waste water from a certain thermal power plant is pumped into a neutralization box and a reaction box through a waste water pump. Adding Ca (OH) into the neutralization box2And adjusting the pH value of the wastewater to 7-9 to precipitate part of heavy metals. Then enters a reaction box, organic sulfur (TMT15) is added into the reaction box, and Hg which cannot be precipitated by hydroxide is further precipitated2+、Cu2+、Pb2+And (3) heavy metal ions. Then the wastewater directly enters an ultrafiltration device, and then divalent calcium ions and magnesium ions are separated out through nanofiltration, so that the load of subsequent electrodialysis treatment is reduced, and the generated clear water enters a monovalent ion electrodialysis device for treatment. The main metal ions of the side effluent of the monovalent ion electrodialysis concentrated water are calcium, magnesium, sodium, chloride ions and a small amount of sulfate ions, TDS>18000mg/L, the outlet water of the concentrated water side enters the storage tank 1 for preparing magnesium calcium ammonium phosphate, and the concentration of chloride ions in the produced water of the fresh water side is as low as below 1500 mg/L. The water quality data of the desulfurization waste water, the electrodialytic water and the concentrated water are shown in the following table 1:
TABLE 1 Water quality data for desulfurized waste water (FGD), electrodialytic produced water, and concentrate
In an ammonia supply system, domestic garbage leachate is taken as a main source of ammonia. Because the total nitrogen of the leachate is high, the carbon-nitrogen ratio is seriously disordered, if the water quality is adjusted by a conventional carbon source adding mode, the phase change can increase the concentration of pollutants, the existing water tank can not meet the scale requirement of biochemical treatment, and the cost of the carbon source is high. Therefore, after the leachate is subjected to grating removal of larger suspended matters, the leachate is pumped into a stripping deamination device by a waste water pump under the condition that the pH is adjusted without adding chemical agents, ammonia nitrogen in the leachate is removed by the stripping deamination device, and generated ammonia-containing steam is condensed and then enters an ammonia water storage tank 2. By stripping deamination, the concentration of pollutants is reduced while the water quality of the percolate is adjusted, so that the biochemical treatment capacity of a biochemical reaction system can be obviously improved. The stripping deamination device supplies heat to the deamination device by using the dedusting waste heat of the thermal power plant and the biogas generated by the anaerobic UASB device so as to maintain the temperature of the system at 80-90 ℃. Because the IC reactor has the characteristics of strong impact load resistance and good operation stability, the deaminated percolate can directly enter the IC reactor (anaerobic fermentation methane production unit) and can generate a large amount of methane, carbon dioxide and other gases in the process of decomposing organic matters by anaerobic microorganisms in the IC reactor, wherein the methane accounts for 75-85 percent and can be recycled. The upper part of the reactor is provided with a gas-collecting hood which collects the generated methane gas and supplies heat to a deamination device or a biochemical unit. In addition, the heat source for maintaining the temperature of the IC reactor system (about 40 ℃) can also be maintained by low-value waste heat of a power plant. Anaerobic effluent enters a secondary A/O biochemical reaction unit adopting an external MBR process. Compared with the traditional biochemical unit, the concentration of the activated sludge in the external MBR process can reach 15-30g/L, and the pollutant removal efficiency is high. The quality of the effluent water after the MBR produced water is treated by combining a nanofiltration device and a reverse osmosis device meets the water quality standard of open type circulating cooling water in Table 1 in the urban sewage recycling-industrial water quality (GB/T19923-2005), and can be used for supplementing circulating cooling water of a power plant. And (4) further concentrating the concentrated solution generated by nanofiltration by using a secondary material membrane, feeding the concentrated solution into a roll type reverse osmosis device, and spraying the concentrated solution back to the incinerator. The concentrated solution produced by the roll type reverse osmosis device is used for lime pulping.
In the phosphorus supply system, the phosphorization wastewater generated in the metal surface treatment process is taken as PO4 3-The main source of P. Adjusting the pH of the phosphorization wastewater to 10 in a chemical precipitation tank by using lime milk from a power plant desulfurization system, fully reacting for 10 minutes, standing for precipitation to remove toxic noble metals in the phosphorization wastewaterAnd Ni, pumping the supernatant into an ultrafiltration device by using a pump, and discharging water. As the Ni-containing compound belongs to highly toxic substances, an online Ni ion monitor is arranged, and an operator ensures that the Ni content of the effluent of the working section reaches the standard by controlling the pH value and the precipitation reaction time. And if the Ni content does not reach the standard, returning the effluent to the sedimentation tank until the Ni content of the effluent reaches the standard. The effluent passing through the chemical sedimentation tank is an alkaline standby solution containing elements such as phosphorus, iron, Mn and the like, wherein the elements such as iron and Mn are beneficial metal ions in soil and have no toxic action on animals. The subsequent synthesis of calcium magnesium ammonium phosphate also needs to be carried out under alkaline conditions. Therefore, the water discharged from the section is directly fed into the storage tank 3 as phosphorus-containing feed liquid for standby.
In the ammonium phosphate calcium magnesium synthesis system, the calcium and magnesium feed liquid from the storage tank 1 and the PO4 of the storage tank 3 are comprehensively treated3--NH content of P feed liquid and storage tank 33And (4) feed liquid. Controlling Mg in the reaction tank under the condition that the pH value is 9.52+:PO4 3-:NH31.5:1.187:1.0 (molar ratio); ca2+:PO4 3-The reaction time was 20min at a stirring speed of about 200rpm (molar ratio) of 1.5: 1.187. After the reaction is finished, mixed effluent enters an aging box for aging for 30 min. PO under the above conditions4 3-the-P removal rate was 99.53%, NH3The removal rate of-N is 87.56%, and the treated effluent PO4 3-P content is 6.79mg/L, NH3The N content was 76.12 mg/L. The effluent enters a biochemical treatment system of the percolate.
Example 2
Comprehensively treating desulfurization wastewater, landfill leachate and phosphogypsum leakage liquid:
the calcium and magnesium supply units and the ammonia supply unit were the same as in example 1. In the phosphorus supply unit, the phosphogypsum leakage liquid is used as a raw material in the embodiment. After the phosphogypsum ore leakage liquid is combined with the added polyaluminium sulfate and cationic polyacrylamide in the coagulation reaction tank, fine suspended matters in the acidic leachate are precipitated. The effluent enters an ultrafiltration device and a high-pressure reverse osmosis device which can tolerate acidic materials. The ultrafiltration and the reverse osmosis both adopt constant-pressure operation, the ultrafiltration membrane inlet pressure is 2bar, and the membrane outlet pressure is 1.7 bar. The reverse osmosis membrane inlet pressure was 10bar and the membrane outlet pressure was 9 bar. The reverse osmosis concentrated water enters the storage tank 3, and the filtrate enters the electrodialysis device.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater is characterized by comprising a desulfurization wastewater treatment unit, a landfill leachate treatment unit, a phosphorus-containing wastewater treatment unit and a calcium magnesium ammonium phosphate generation unit:
the desulfurization wastewater treatment unit is used for sequentially treating desulfurization wastewater of a coal-fired power plant through a triple box to remove heavy metals, ultrafiltering to remove suspended particle pollutants, nanofiltering to separate out divalent calcium and magnesium ions, then performing monovalent ion electrodialysis concentration, and feeding the generated concentrated water into a storage tank 1 to be used as a raw material for preparing calcium magnesium ammonium phosphate;
the landfill leachate treatment unit is used for sending ammonia nitrogen escaping from the landfill leachate in the stripping deamination process into a storage tank 2 to be used as a raw material for preparing calcium magnesium ammonium phosphate;
the phosphorus-containing wastewater treatment unit is used for treating phosphorus-containing wastewater or treating leakage liquid of a phosphogypsum slag yard: adding NaOH into the phosphating wastewater to adjust the pH value, then removing toxic heavy metals in the phosphating wastewater through standing and precipitating, and allowing alkaline phosphorus-containing wastewater obtained by ultrafiltration of supernatant to enter a storage tank 3 to serve as a raw material for preparing calcium magnesium ammonium phosphate; the leakage liquid treatment of the gypsum slag field is to carry out ultrafiltration on the raw water of the leakage liquid after coagulating sedimentation, and the generated concentrated water enters the storage tank 3 to be used as the raw material for preparing the ammonium phosphate calcium magnesium;
the ammonium phosphate calcium magnesium generating unit is characterized in that the solution containing calcium and magnesium in the storage tank 1 and the solution containing NH in the storage tank 23The feed liquid is mixed with the phosphorus-containing solution in the storage tank 3, and after the pH value is adjusted, the mixture reacts for a period of time to obtain calcium hydrogen phosphate and magnesium ammonium phosphate precipitates.
2. Preparation of phosphorus from desulfurization wastewater-landfill leachate-phosphorus-containing wastewaterThe process of ammonium calcium magnesium is characterized in that monovalent ion electrodialysis is used for selectively concentrating monovalent salt chloride ions and sodium ions and divalent salt SO4 2-And the water is intercepted on the fresh water side, and the produced water on the fresh water side is returned to the desulfurizing tower as the supplemented water of a desulfurizing system.
3. The process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater is characterized by comprising the following specific operations of treating the landfill leachate: sequentially carrying out steam stripping deamination, anaerobic fermentation, aerobic fermentation, ultrafiltration, nanofiltration and roll type reverse osmosis filtration on the landfill leachate, using the filtered clear liquid as open circulating cooling water of a power plant, using the concentrated solution for lime pulping, and sending ammonia nitrogen escaping in the steam stripping deamination process into a storage tank 2 as a raw material for preparing calcium magnesium ammonium phosphate.
4. A process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater is characterized in that in the process of generating calcium magnesium ammonium phosphate, a solution containing calcium and magnesium in a storage tank 1 and a solution containing NH in a storage tank 2 are mixed3When the feed liquid is mixed with the phosphorus-containing solution in the storage tank 3, the magnesium and calcium are added in excess.
5. A process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater is characterized in that Mg is added in the process of generating the calcium magnesium ammonium phosphate2+、PO4 3-And NH3The molar ratio of (A) is 1-1.5: 1-1.187: 1.0; ca2+And PO4 3-The molar ratio of (A) to (B) is 1-3: 2.
6. The process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater is characterized in that in the step of generating the calcium magnesium ammonium phosphate, the pH value is 8.5-10, and the reaction time is 15-30 min.
7. A process for preparing calcium magnesium ammonium phosphate from desulfurization wastewater, landfill leachate and phosphorus-containing wastewater is characterized in that in the step of generating calcium magnesium ammonium phosphate, generated water is stripped and deaminated together with landfill leachate.
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