WO2022222173A1 - Procédé de production d'engrais par électrodialyse - Google Patents

Procédé de production d'engrais par électrodialyse Download PDF

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WO2022222173A1
WO2022222173A1 PCT/CN2021/090559 CN2021090559W WO2022222173A1 WO 2022222173 A1 WO2022222173 A1 WO 2022222173A1 CN 2021090559 W CN2021090559 W CN 2021090559W WO 2022222173 A1 WO2022222173 A1 WO 2022222173A1
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chamber
product
liquid
electrodialysis
tank
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PCT/CN2021/090559
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Chinese (zh)
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叶志隆
李叶楠
陈少华
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中国科学院城市环境研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/34—Magnesium phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the invention relates to water treatment technology, in particular to a method for producing fertilizer by electrodialysis.
  • biogas slurry After anaerobic fermentation of aquaculture wastewater, biogas slurry can degrade COD by 80-90%, but it still contains high levels of ammonia nitrogen, total nitrogen, total phosphorus and other pollutants, which cannot meet the standard of direct discharge; most anaerobic processes
  • the ammonia nitrogen content in the produced biogas slurry is too high, and it is not suitable for direct return to the field.
  • the direct return to the field is also limited by the absorption capacity of the surrounding farmland.
  • the biogas slurry cannot be effectively treated, which is likely to cause secondary pollution.
  • CN110550818A discloses a process for high-efficiency desalination treatment of biogas slurry after fermentation of dairy cattle breeding wastewater, including pretreatment; the biogas slurry is passed through a grid to filter impurities and then passed into a sedimentation tank for precipitation treatment.
  • the purpose of the present invention is to overcome the problems existing in the existing biogas slurry recycling and processing, and provide a method for producing fertilizer by electrodialysis, which utilizes the electrodialysis technology to separate and process the biogas slurry to obtain ions of different valence states and different charge types.
  • the enrichment liquid cleverly using the characteristics and correlation of these enrichment liquids, can efficiently produce fertilizers and realize the full utilization of biogas slurry resources.
  • biogas slurry contains a large amount of nutrients such as ammonia nitrogen and phosphate, as well as pathogenic pollutants such as manure residue and pathogenic bacteria, direct discharge can easily cause environmental pollution and eutrophication of water bodies.
  • pathogenic pollutants such as manure residue and pathogenic bacteria
  • direct discharge can easily cause environmental pollution and eutrophication of water bodies.
  • the average farmland can only consume 1-3 pigs to produce manure and biogas slurry, which severely limits the development of intensive farming.
  • the treatment of biogas slurry by selective electrodialysis can not only meet the discharge requirements of the biogas slurry, but also obtain a concentrated solution containing high concentration of nutrients, which greatly reduces the transportation cost and facilitates the subsequent preparation of various fertilizers.
  • the concentrated water contains a lot of impurity elements, and it is worthless to purify. Nor can it be used directly as fertilizer; the existing method is to transfer it to a treatment plant for treatment, but there is a problem of inconvenient liquid transportation.
  • the present invention adopts an ion exchange membrane set in a selective electrodialysis system, so that the raw water is separated by selective electrodialysis to obtain a divalent anion enrichment solution, a divalent cation enrichment solution, a monovalent ion enrichment solution and desalinated water, Among them, the desalinated water meets the discharge standards, and the enriched liquid is used to produce fertilizers.
  • the nutrient substances of different components such as phosphates, potassium salts, ammonium salts, etc. in the biogas slurry
  • the present invention can be differentiated according to the number of charges and electrical properties thereof, and the selective electrodialysis process is used to separate and concentrate, so as to realize the separation and concentration of different types of chemical fertilizers. separation.
  • the traditional method is difficult to achieve such separation requirements.
  • a divalent anion enrichment solution is obtained in the product 1 chamber, which is a phosphate enrichment solution, and a divalent cation enrichment solution is obtained in the product 2 chamber, which is rich in calcium, magnesium ions, and some ammonium salts , a part of potassium salt enrichment solution, monovalent ion enrichment solution is obtained in the concentrated water chamber, which is an enrichment solution rich in part of ammonium salt and part of potassium salt.
  • the above separation is the basis for the next step in fertilizer production.
  • the first scheme is shown in Figure 1. It includes: Step 1) Mix the feed liquid obtained from the product 1 chamber with the feed liquid obtained from the product 2 chamber in proportion, adjust the pH, and obtain phosphoric acid The ammonium and magnesium are precipitated, and the clear liquid enters the next process; Step 2) mix the clear liquid obtained in step 1) with the feed liquid obtained in the concentrated water chamber, adjust pH, and evaporate, and the evaporated gas is absorbed by sulfuric acid to obtain ammonium sulfate, The evaporated liquid crystallized as potassium salt.
  • air blowing is used for denitrification during evaporation, that is, air is bubbling into the solution during the evaporation process, which is helpful for the removal of ammonia gas.
  • the second scheme is shown in Figure 2: it includes: step 1) adjusting the pH of the feed liquid obtained in the product 2 chamber, and evaporating, the evaporated gas is absorbed by sulfuric acid to obtain ammonium sulfate, and the evaporated solid enters the next process; step 2 ) adding the solid obtained in step 1) to the feed liquid obtained in the product 1 chamber, adjusting the pH, and the solid obtained by precipitation is calcium phosphate and magnesium phosphate; step 3) adjusting the pH of the feed liquid obtained in the concentrated water chamber, evaporating, evaporating The obtained gas is absorbed by sulfuric acid to obtain ammonium sulfate, and the evaporated liquid crystallizes into potassium salt.
  • air blowing is used for denitrification during evaporation, that is, air is bubbling into the solution during the evaporation process, which is helpful for the removal of ammonia gas.
  • the key is to integrate different enrichment materials to form the target product, and at the same time to effectively separate from other elements.
  • the present invention does not require additional additives, and can realize high-efficiency chemical fertilizer production only by adjusting pH. specific:
  • the pH should be adjusted to be greater than 8.00, and the reaction speed is faster when the pH is above 10.00.
  • step 1) pH should be maintained to be greater than 10.00 during the reaction, and ammonia nitrogen removal is more thorough when pH is greater than 12.00, so that the ammonium sulfate yield is high, and it is ensured that potassium salt does not contain ammonia nitrogen.
  • the method of evaporation is preferably reduced pressure evaporation, and the gas obtained by evaporation should first be passed into sulfuric acid to absorb the ammonia gas therein, and the evaporation temperature can be reduced by reduced pressure evaporation. , reduce heat loss, and greatly reduce energy consumption while accelerating the evaporation rate and ensuring the evaporation effect.
  • step 2) of scheme 2 the pH should be adjusted to be greater than 9.00, and the precipitation of calcium and magnesium ions is relatively thorough, thereby improving the yield of phosphate fertilizer.
  • a method for producing fertilizer by electrodialysis comprising pre-processing biogas slurry, removing suspended particulates and colloids in the biogas slurry to obtain raw water, and then passing the raw water into a selective electrodialysis system for operation, the selecting An ion exchange membrane is installed in the electrodialysis system, so that the raw water is separated to obtain a divalent anion enrichment solution, a divalent cation enrichment solution, a monovalent ion enrichment solution and desalinated water, wherein the desalinated water meets the discharge standard, and the enriched Liquid collection to produce fertilizers, including:
  • the pH of the monovalent ion enrichment solution is adjusted, followed by evaporation treatment, the evaporated gas is absorbed by sulfuric acid to obtain ammonium sulfate, and the evaporated liquid crystallizes to obtain solid potassium salt.
  • the biogas slurry is the biogas slurry after anaerobic fermentation
  • the conductivity is 2-50mS/cm
  • the ammonia nitrogen concentration is 100-5000mg/L
  • the total phosphorus concentration is 5-200mg/L
  • the potassium concentration is 50-1500mg /L.
  • the selective electrodialysis system comprises an anode electrode chamber, a cathode electrode chamber arranged oppositely, and a chamber arranged between the anode electrode chamber and the cathode electrode chamber;
  • the chamber includes N Units connected in parallel, N is a positive integer, and each unit has the same structure, including a product 1 room, a concentrated water room, a product 2 room and a desalination room arranged in sequence; the product 1 room and the concentrated water room are separated by a The valence anion selective exchange membrane MVA is separated, the concentrated water compartment and the product 2 compartment are separated by a monovalent cation selective exchange membrane MVK, and the product 2 compartment and the desalination compartment are separated by a cation exchange membrane SK , the desalination chamber is separated from the product 1 chamber of the next unit by an anion exchange membrane SA; each of the units is separated from the anode electrode chamber and the cathode electrode chamber by a polar film PC-SC;
  • the anode electrode chamber and the cathode electrode chamber are respectively connected to the positive electrode and the negative electrode of the DC power supply, and the anode electrode chamber, the cathode electrode chamber, the chamber and the DC power supply form a series loop, so that the chamber Under the action of the current, a divalent anion enrichment solution is obtained in the product 1 chamber, a divalent cation enrichment solution is obtained in the product 2 chamber, and a monovalent ion enrichment solution is obtained in the concentrated water chamber liquid, and desalinated water is obtained in the desalination chamber.
  • the two sides of the product 1 chamber are a monovalent selective anion exchange membrane MVA and an anion exchange membrane SA, and a divalent anion enrichment solution is obtained in the product 1 chamber, which is a phosphate enrichment solution;
  • the product 2 Both sides of the chamber are monovalent selective cation exchange membrane MVK and cation exchange membrane SK, and the divalent cation enrichment solution is obtained in the product 2 chamber, which is rich in calcium, magnesium ions, and part of ammonium salts and part of potassium salts.
  • Collecting liquid; both sides of the concentrated water chamber are anion exchange membrane SA and cation exchange membrane SK, and monovalent ion enrichment solution is obtained in the concentrated water chamber, which is enriched solution rich in part of ammonium salt and part of potassium salt.
  • the product 1 chamber of each unit is connected to the product 1 chamber feed tank, and the product 2 chamber of each unit is connected to the product 2 chamber feed liquid.
  • the concentrated water chamber of each of the units is connected to the concentrated water chamber material tank, and the desalination chamber of each of the units is connected to the desalination chamber material tank, so as to realize the selective electrodialysis system.
  • All the circulation of the feed liquid in the product 1 chamber, all the circulation of the feed liquid in the product 2 chamber, all the circulation of the feed liquid in the concentrated water chamber, and all the circulation of the feed liquid in the desalination chamber; the anode electrode chamber and The cathode electrode chamber is connected to the electrode liquid tank to realize the circulation of the electrode liquid, with a total of 5 circulation loops, wherein the feed liquid in the desalination chamber, the product 1 chamber, the product 2 chamber and the concentrated water chamber The flow is in parallel in the same direction, and the flow of the electrode liquid in the anode electrode chamber and the cathode electrode chamber is in reverse series.
  • the raw water is added to the feed liquid tank of the desalination chamber for circulation, and an equal volume of a strong electrolyte solution with an electrical conductivity of not less than 5mS/cm is added to the feed liquid tank of the product 1 chamber and the product 2 chamber respectively.
  • Circulation is carried out in the feed liquid tank and the feed liquid tank of the concentrated water chamber feed liquid tank, and the electrode liquid with an electrical conductivity of not less than 5mS/cm is added to the electrode liquid tank, and the anode electrode chamber and the cathode electrode are placed in the anode electrode chamber and the cathode electrode.
  • Circulation is performed in the chamber; DC current is applied to the selective electrodialysis system through the DC power supply to carry out the selective electrodialysis process, and finally the desalinated water is obtained in the feed liquid tank of the desalination chamber, and the product 1 chamber Divalent anion enrichment solution, divalent cation enrichment solution, and monovalent ion enrichment solution are obtained from the feed solution tank, the product 2-chamber feed solution tank and the feed solution tank of the concentrated water chamber feed solution tank, respectively.
  • the use of the enriched liquid to produce chemical fertilizers includes: step 1) mixing the feed liquid obtained in the product 1 room with the feed liquid obtained in the product 2 room in proportion, adjusting the pH, and obtaining the precipitation of magnesium ammonium phosphate, and the clear liquid enters the next step.
  • Procedure Step 2) mix the clear liquid obtained in step 1) with the feed liquid obtained in the concentrated water chamber, adjust pH, and evaporate, and the evaporated gas is absorbed by sulfuric acid to obtain ammonium sulfate, and the evaporated liquid crystallizes into potassium salt.
  • step 1) the pH is adjusted to be greater than or equal to 8.00, preferably 10.00-14.00;
  • step 2) the pH is adjusted to be greater than or equal to 10.00, preferably 12.00-14.00;
  • step 2) the evaporation is reduced pressure evaporation, the gas obtained by evaporation is passed into sulfuric acid to absorb the ammonia gas therein, and the evaporated liquid crystallizes into potassium salt.
  • the use of the enriched liquid to produce chemical fertilizer includes: step 1) adjusting the pH of the feed liquid obtained in the product 2 chamber, and evaporating, the evaporated gas is absorbed by sulfuric acid to obtain ammonium sulfate, and the evaporated solid enters the next process; Step 2) Add the solid obtained in step 1) to the feed liquid obtained in the product 1 chamber, adjust the pH, and precipitate the solid obtained as calcium phosphate and magnesium phosphate; step 3) Adjust the pH of the feed liquid obtained in the concentrated water chamber, and evaporate , the gas obtained by evaporation is absorbed by sulfuric acid to obtain ammonium sulfate, and the liquid crystallized after evaporation is potassium salt.
  • step 1) and/or step 3 the pH is adjusted to be greater than or equal to 10.00, preferably 12.00-14.00;
  • step 2) the pH is adjusted to be greater than or equal to 9.00, preferably 10.00-14.00;
  • step 1) and/or step 3 the evaporation is reduced pressure evaporation, and the gas obtained by evaporation is passed into sulfuric acid to absorb the ammonia gas therein.
  • the method for producing fertilizer by electrodialysis of the present invention uses selective electrodialysis to obtain different types of high-salinity concentrates from anaerobic biogas slurry, and realizes the multi-stage recycling of different components, and it is difficult to directly
  • the anaerobic biogas slurry used is prepared into a variety of high-value fertilizers to fully utilize the biogas slurry resources.
  • Fig. 1 is a schematic flow chart of scheme one provided by the invention
  • Fig. 2 is the schematic flow chart of scheme two provided by the present invention.
  • FIG. 3 is a schematic diagram of the principle of a selective electrodialysis system provided by an embodiment of the present invention.
  • FIG. 4 is a schematic structural diagram of a continuous processing device provided in Embodiment 2 of the present invention.
  • a continuous method for selective electrodialysis of biogas slurry comprising the following steps: pretreatment of biogas slurry to remove suspended particulate matter and colloid in the biogas slurry to obtain raw water.
  • the way of pretreatment can include coagulation sedimentation, filtration, ultrafiltration/microfiltration.
  • the selective electrodialysis system includes an anode electrode chamber, a cathode electrode chamber, and a chamber disposed between the anode electrode chamber and the cathode electrode chamber.
  • the chamber includes N parallel units, and N is a positive integer.
  • Each unit has the same structure, including product 1 chamber, concentrated water chamber, product 2 chamber and desalination chamber arranged in sequence; product 1 chamber and concentrated water chamber are separated by a monovalent anion selective exchange membrane MVA, and concentrated water chamber and product
  • the 2 compartment is separated by a monovalent cation selective exchange membrane MVK, the product 2 compartment is separated from the desalination compartment by a cation exchange membrane SK, and the desalination compartment is separated from the product 1 compartment of the next unit by an anion exchange membrane SA; each unit is It is separated from the anode electrode chamber and the cathode electrode chamber by the polar film PC-SC;
  • the anode electrode chamber and the cathode electrode chamber are respectively connected to the positive electrode and the negative electrode of the DC power supply.
  • the anode electrode chamber, the cathode electrode chamber, the chamber and the DC power supply form a series circuit, so that the current passes through the chamber, and under the action of the current, in the product 1 chamber Divalent anion enrichment solution is obtained, divalent cation enrichment solution is obtained in the product 2 chamber, monovalent ion enrichment solution is obtained in the concentrated water chamber, and after the conductivity is ⁇ 0.5mS/cm in the desalination chamber, the ammonia nitrogen concentration is ⁇ 20mg/ L, desalinated water with total phosphorus concentration ⁇ 5mg/L.
  • the system can process the biogas slurry after anaerobic fermentation, the conductivity is 2-50mS/cm, the ammonia nitrogen concentration is 100-5000mg/L, and the total phosphorus concentration is 5-200mg/L, preferably: the conductivity is 10-50mS/L cm, ammonia nitrogen concentration is 1000-5000mg/L, and total phosphorus concentration is 20-200mg/L.
  • Fig. 4 design a continuous treatment device, including a screw stacker, a filter tank and a desalination chamber feed tank F, and the three are connected in sequence, wherein the inlet of the screw stacker is connected to the biogas slurry, The desalination chamber feed tank F is connected to the selective electrodialyser SED.
  • the selective electrodialyser SED includes an anode electrode chamber, a cathode electrode chamber, and a chamber disposed between the anode electrode chamber and the cathode electrode chamber.
  • the chamber includes N parallel units, and N is a positive integer.
  • N is a positive integer of 10-1000, preferably a positive integer of 100-800.
  • the chamber in the selective electrodialyzer SED includes product 1 chamber, concentrated water chamber, product 2 chamber and desalination chamber; the product 1 chamber and the concentrated water chamber are separated by a monovalent anion selective exchange membrane MVA, and the concentrated water chamber and the product
  • the 2 compartment is separated by a monovalent cation selective exchange membrane MVK, and the product 2 compartment and the desalination compartment are separated by a cation exchange membrane SK.
  • the product 1 chamber is connected to the product 1 chamber feed tank AP, the product 2 chamber is connected to the product 2 chamber feed tank CP, the concentrated water chamber is connected to the concentrated water chamber feed tank B, and the desalination chamber is connected to the desalination chamber feed tank F.
  • the anode electrode chamber and the cathode electrode chamber are respectively connected to the electrode liquid tank R, and the electrode liquid tank is used for storing and circulating the electrode liquid.
  • the selective electrodialysis device SED is also connected to the acid cleaning tank AC, which is used for storing the acid solution for cleaning the electrodialysis membrane module.
  • the use method of the above device is as follows: the biogas slurry enters the screw stacker after coagulation to remove suspended solids and insoluble substances therein, and then secondary filtration in the filter tank obtains raw water suitable for electrodialysis treatment, and the raw water enters the desalination chamber. Slot pending.
  • the raw water enters the desalination chamber of the selective electrodialyser SED in the feed tank of the desalination chamber for circulation, and an equal volume of strong electrolyte solution with a conductivity of not less than 5mS/cm is added to the feed liquid tank of product 1 chamber and the material of product 2 chamber respectively.
  • the above-mentioned circulation means that the feed liquid circulates between the feed liquid tank and the corresponding chamber.
  • the circulation is between N units, that is, the circulation of the feed liquid in all products 1 in the selective electrodialysis system, the circulation of feed liquid in all products 2, and the feed liquid in all concentrated water. circulation, as well as the circulation of all liquids in the desalination chamber.
  • the anode electrode chamber and the cathode electrode chamber are connected to the electrode liquid tank to realize the circulation of the electrode liquid, a total of 5 circulation loops, among which the flow of the feed liquid in the desalination chamber, the product 1 chamber, the product 2 chamber and the concentrated water chamber is parallel in the same direction. , the flow of the electrode liquid in the anode electrode chamber and the cathode electrode chamber is reverse series.
  • the discharging method of the system is described below.
  • the conductivity of the biogas slurry in the feed tank of the desalination chamber drops to 0.5 mS/cm
  • part of the solution in the feed tank of the desalination chamber (the discharged part is the desalinated water) is discharged.
  • the relative speed of the feed liquid added and the discharged feed liquid is adjusted to retain 10-20 volume% of the feed liquid in the selective electrodialysis system.
  • the raw water contains 1900 mg/L ammonia nitrogen, 25 mg/L phosphate, 890 mg/L potassium, 75 mg/L calcium, and 30 mg/L magnesium.
  • the continuous concentration and separation of ions is carried out at a constant voltage.
  • each desalination chamber When the conductivity of the solution in the feed tank of the desalination chamber is less than 0.5mS/cm, since the feed tank of the desalination chamber is connected to each desalination chamber of the electrodialysis system, each desalination chamber has produced desalinated water that meets the discharge requirements and can be discharged Part of the solution in the feed tank of the desalination chamber is added, and the next batch of raw water is added for electrodialysis. At this time, by detecting the phosphate concentration in the feed tank of the product 1 chamber, the phosphate concentration in the product 1 chamber can be obtained, which is 226 mg/L. Similarly, it can be known from the detection that the ammonia concentration in the concentrated water chamber is 9680 mg/L.
  • the potassium concentration is 4586mg/L
  • the calcium ion concentration in the product 2 chamber is 358mg/L
  • the magnesium ion concentration is 114mg/L, which have basically reached the goal of concentration and enrichment, and can be discharged in time, or at the next batch processing.
  • the anaerobic biogas slurry is continuously fed into the screw stacker to remove suspended solids and insoluble substances therein, and then secondary filtration is performed in the filter tank to obtain raw water suitable for electrodialysis treatment. It acts as a temporary storage tank for raw water.
  • a valve is set between the filter tank and the desalination chamber material tank. The supernatant in the filter tank is controlled by the valve to enter the desalination chamber material tank in batches, so as to enter the electrodialysis system for circulating treatment. , the process is as follows:
  • the DC power supply applies a constant DC voltage to the selective electrodialysis system to carry out the selective electrodialysis process to separate and concentrate the nutrient ions such as phosphate, ammonia nitrogen and potassium salt in the biogas slurry.
  • the density of the direct current is 10-200 A/m 2 , preferably 100 A/m 2 .
  • the discharge rules for other chambers are as follows: when the volume ratio of the raw water entering the selective electrodialysis system to the volume ratio of the solution in the feed liquid tank of the product 1 chamber reaches more than 10, the solution in the feed liquid tank of the product 1 chamber is discharged, and the same The fresh strong electrolyte solution of the same volume of the solution is discharged; when the volume ratio of the raw water entering the selective electrodialysis system to the volume ratio of the solution in the feed liquid tank of the product 2 chamber reaches more than 10, the solution in the feed liquid tank of the product 2 chamber is discharged, And add fresh strong electrolyte solution with the same volume as the discharged solution; when the conductivity of the solution in the feed tank of the concentrated water chamber is > 90mS/cm, discharge the solution in the feed tank of the concentrated water chamber, and add the same volume of fresh solution as the discharged solution. Strong electrolyte solution to ensure continuous operation of selective electrodialysis system.
  • Example 3 Utilize the enrichment solution obtained in Example 3, namely discharge the 2L enriched solution produced from the feed liquid tank of product 1 chamber, the feed liquid tank of product 2 chamber, and the feed liquid tank of concentrated water chamber, wherein the material of product 1 chamber is
  • the liquid contains 226 mg/L of phosphate
  • the feed liquid of the concentrated water chamber contains 9680 mg/L of ammonia
  • 4586 mg/L of potassium the feed liquid of the product 2 chamber contains 358 mg/L of calcium ions and 114 mg/L of magnesium ions.
  • the obtained solid is NH 4 MgPO 4 ⁇ 6H 2 O, and the recovery efficiency of phosphate is greater than 96.70%.
  • the supernatant adjust the pH to 11.09, perform rotary evaporation under a water bath at 80°C, and absorb the evaporated gas in 200 mL of 10% sulfuric acid.
  • the solid obtained by evaporation is NaCl by XRD analysis, and the solid obtained by concentrating and crystallizing the absorption liquid is (NH 4 ) 2 SO 4 by XRD analysis.
  • the 2L enriched solution produced is discharged from the feed liquid tank of product 1 room, the material liquid tank of product 2 room, and the feed liquid tank of concentrated water chamber, wherein the feed liquid of product 1 room is discharged It contains 226 mg/L of phosphate, 9680 mg/L of ammonia and 4586 mg/L of potassium in the feed liquid of the concentrated water chamber, 358 mg/L of calcium ions and 114 mg/L of magnesium ions in the feed liquid of the product 2 chamber.
  • the pH of 200 mL of the feed liquid in the product 2 chamber was adjusted to 11.00, and it was rotary evaporated in a water bath at 80°C, and the gas generated by evaporation was absorbed by 200 mL of 10% sulfuric acid.
  • the solid obtained by evaporation was added to 400 mL of product 1-chamber feed solution to dissolve, the pH was adjusted to 9.00, and the mixture was left to stand and centrifuge for precipitation.
  • the precipitate was analyzed by XRD as a mixture of calcium phosphate and magnesium phosphate.

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  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

L'invention concerne un procédé de production d'un engrais par électrodialyse, consistant à : prétraiter une suspension de biogaz, éliminer des matières particulaires et des colloïdes en suspension dans la suspension de biogaz pour obtenir de l'eau brute et introduire l'eau brute dans un système d'électrodialyse sélective, une membrane échangeuse d'ions étant agencée dans le système d'électrodialyse sélective ; et séparer l'eau brute pour obtenir un liquide enrichi en anions divalents, un liquide enrichi en cations divalents, un liquide enrichi en ions monovalents et de l'eau dessalée, l'eau dessalée répondant à une norme d'évacuation. Un engrais chimique est produit à l'aide du liquide enrichi et la production consiste à : ajuster la valeur de pH du liquide enrichi en ions monovalents, puis effectuer un traitement d'évaporation, absorber le gaz évaporé à l'aide d'acide sulfurique pour obtenir du sulfate d'ammonium et cristalliser le liquide évaporé pour obtenir un sel de potassium solide. Le procédé résout efficacement le problème de l'utilisation des ressources de la solution concentrée à salinité élevée après le traitement d'une suspension anaérobie de biogaz au moyen d'une électrodialyse sélective et fournit un schéma réalisable pour la récupération de ressources de suspension de biogaz.
PCT/CN2021/090559 2021-04-19 2021-04-28 Procédé de production d'engrais par électrodialyse WO2022222173A1 (fr)

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