CN111892229B - Method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water - Google Patents
Method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention relates to a method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water, which comprises the steps of removing organic matters in the biochemical tail water by using high-crosslinking adsorption resin, and adsorbing the phosphorus in the biochemical tail water by using a selective phosphorus removal composite material to realize the deep removal of the trace phosphorus in the biochemical tail water; the phosphorus-rich desorption solution containing high-concentration phosphorus is obtained by desorbing the phosphorus-removing composite material with saturated adsorption, and the phosphorus is converted into magnesium ammonium phosphate by crystallization and precipitation and is separated out, so that the trace phosphorus in the biochemical tail water is efficiently recovered. The method can realize deep removal of trace phosphorus in the biochemical tail water, and the recovered magnesium ammonium phosphate has high purity, can be used as a fertilizer, and can generate good environmental benefit and economic benefit.
Description
Technical Field
The invention relates to the field of deep treatment of biochemical tail water, in particular to a method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water.
Background
The eutrophication of water is one of the main environmental problems facing countries in the world, which is mainly caused by excessive nutrient substances such as nitrogen, phosphorus and the like in water, wherein phosphorus is the main limiting factor of the eutrophication of water, and it is generally considered that when the concentration of phosphorus in water exceeds 0.02mg/L, the water can be judged to enter the eutrophication state. On the other hand, phosphorus is also a strategic resource and is one of the indispensable elements for human life activities and modern agriculture. At present, the human society is facing the dilemma of shortage of phosphorus resources but serious shortage of phosphorus pollution, and more scholars and experts have recognized that advanced treatment of phosphorus in sewage and recycling of phosphate must be performed simultaneously. Phosphate fertilizers are an indispensable important component of modern agriculture, but only 20% of phosphorus consumed worldwide every year enters a food chain nowadays, and most of phosphorus is lost along with soil leaching and sewage discharge. The method for recovering phosphorus from the phosphorus-containing sewage can relieve the eutrophication pressure of the receiving water body and solve the problem of phosphorus resource shortage, and is an important way for closing phosphorus circulation.
After domestic sewage in cities is collected in a sewage plant, the sewage plant usually adopts a biochemical method (i.e. a process combining biology and chemistry) to treat the sewage, and the obtained tail water is called biochemical tail water.
The biochemical tail water cannot be directly discharged, the biochemical tail water contains overproof phosphorus, and the phosphorus mainly exists in the biochemical tail water in the form of phosphate, so that the biochemical tail water can obtain liquid meeting the discharge standard after deep phosphorus removal. The conventional deep phosphorus removal method is an adsorption method, has the characteristics of simple and stable operation, good deep treatment effect and the like, can realize phosphorus enrichment, has good potential of phosphorus recovery, and is a good way for realizing deep treatment and recovery of phosphorus. The iron, zirconium, lanthanum and other metal oxides are phosphorus-specific adsorbents which are widely concerned by people in recent years, the materials can realize selective adsorption of phosphorus through internal coordination and complexation, still show excellent phosphorus removal performance under the background of high-concentration competitive ions, and have good application prospects. However, the metal oxide has small particle size, and has technical bottlenecks of difficult solid-liquid separation, overlarge head loss and the like when being directly applied to biochemical tail water treatment engineering.
In the prior art, loading metal oxide nanoparticles such as iron, zirconium, lanthanum and the like in a porous material is an important means for realizing engineering application of the porous material. The patent document with application number 200810124787.7 discloses a method for deeply purifying trace phosphorus in a water body by using composite resin with nano iron oxide or manganese oxide particles loaded on the surface as an adsorbent, which can reduce the phosphorus content in the effluent from 0.05-20 ppm (ppm is the concentration per million) to below 20ppb (ppb is the concentration per billion), but the patent does not relate to the recovery of phosphorus. The patent document with the application number of 201910861894.6 discloses a resin-based nano lanthanum material, a preparation method and application thereof, and the invention also does not relate to a method for recovering phosphorus after adsorption. The patent document with the application number of 201810868976.9 discloses a system and a method for removing phosphorus and recovering phosphorus from tail water of a municipal sewage plant, but in the patent, a phosphorus removal adsorption filter material APM is metal oxide particles, and the filter material has a fine particle size and is easy to run off and block; calcium phosphate crystallization recovery is directly carried out on the phosphorus-rich regenerated alkali liquor by adopting calcium salt, the crystallization product has fine particles, solid-liquid separation is difficult, the purity of the recovered product is not high, the phosphorus content is low, and subsequent recovery and utilization are not facilitated.
In conclusion, aiming at the dilemma of the coexistence of two problems of phosphorus resource shortage and serious phosphorus pollution faced by human society, the biochemical tail water containing phosphorus can be deeply removed (especially, the biochemical tail water containing trace phosphorus is deeply removed, wherein the definition of the trace phosphorus is that the content of phosphorus in the biochemical tail water is less than or equal to 5mg/L) and the efficient recycling of phosphorus resources is realized, and the problem faced by the technology in the field is still solved.
Disclosure of Invention
The applicant aims at the defects in the prior art and provides a method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water, so that the trace phosphorus in the biochemical tail water can be deeply removed and recovered for reuse.
The technical scheme adopted by the invention is as follows:
a method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water comprises the following steps:
(A) introducing the biochemical tail water into a filter for filtering, and removing suspended pollutants in the sewage to obtain a filtrate;
(B) introducing the filtrate obtained in the step (A) into a first adsorption tower, filling high-crosslinking adsorption resin for adsorbing residual organic matters in the filtrate into the first adsorption tower, adsorbing by the first adsorption tower to obtain first adsorption effluent, detecting the first adsorption effluent, and stopping introducing the filtrate into the first adsorption tower when COD (chemical oxygen demand) of the first adsorption effluent is more than or equal to 15 mg/L;
(C) introducing the first adsorption effluent obtained in the step (B) into a second adsorption tower, wherein a selective phosphorus removal composite material is filled in the second adsorption tower, the selective phosphorus removal composite material is macroporous strong base anion exchange resin with pore channels loaded with metal oxide nanoparticles, the content of the metal oxide nanoparticles in the macroporous strong base anion exchange resin is 10-30% (weight percentage), a second adsorption device adsorbs the metal oxide nanoparticles to obtain second adsorption effluent, and simultaneously detecting the second adsorption effluent, wherein the second adsorption effluent meets the emission standard when the concentration of TP (total phosphorus) in the second adsorption effluent is less than 0.1mg/L, and the second adsorption tower stops introducing the first adsorption effluent into the second adsorption tower when the concentration of TP (total phosphorus) in the second adsorption effluent is more than or equal to 0.1 mg/L;
(D) after the introduction of the first adsorption effluent into the second adsorption tower is stopped in the step (C), introducing a NaOH (sodium hydroxide) solution with the concentration of 1-2 mol/L into the second adsorption tower by using an alkali liquor storage tank to perform desorption regeneration on the selective phosphorus removal composite material to obtain a phosphorus-containing desorption solution, wherein the phosphorus-containing desorption solution with high concentration is also called as a phosphorus-rich desorption solution and can be used for subsequent phosphorus recovery, and the phosphorus-containing desorption solution with low concentration can be returned to the alkali liquor storage tank to be used for preparing a NaOH solution;
(E) introducing the phosphorus-rich desorption solution obtained in the step (D) into a pH adjusting tank, adding a sulfuric acid solution with the concentration of 20-30% into the pH adjusting tank by an acid solution storage tank, and adjusting the pH of the phosphorus-rich desorption solution to 9-11;
(F) introducing the phosphorus-rich desorption solution with the pH adjusted in the step (E) into a crystallization reaction tank, and simultaneously adding magnesium chloride (MgCl) into the crystallization reaction tank2) Ammonium chloride (NH)4Cl) and magnetic powder (Fe)3O4) A stirrer is arranged in the crystallization reaction tank for stirring, so that phosphate in the phosphorus-rich desorption solution is made into magnetic powder (Fe)3O4) Formation of high density magnesium ammonium phosphate (MgNH) for condensation nuclei4PO4) Crystallizing the precipitate to obtain a crystallization mixed solution after crystallization reaction;
(G) introducing the crystallization mixed solution obtained in the step (F) into an inclined tube sedimentation tank for solid-liquid separation, returning supernatant formed after sedimentation into an alkali liquor storage tank for preparing NaOH solution, introducing the crystallization precipitate into a high-speed shearing machine, and shearing magnesium ammonium phosphate (MgNH) by the high-speed shearing machine4PO4) Magnetic powder (Fe) of floc3O4) Is stripped off and then MgNH is carried out4PO4Flocs and magnetic powder (Fe)3O4) The mixture is separated in a magnetic separator which magnetically separates magnetic powder (Fe)3O4) Absorbing and recovering, and separating magnesium ammonium phosphate (MgNH)4PO4) Is led out of the magnetic separator and collected, and can be subsequently used as slow release fertilizer for comprehensive utilization.
Further, the high-crosslinking adsorption resin is aminated high-crosslinking adsorption resin.
Further, the aminated high-crosslinking adsorption resin is a high-crosslinking polystyrene microsphere with a dimethylamino group modified on the surface,the content of amido in the high-crosslinked polystyrene microspheres is 1.5-2.5 mmol/g, the average pore diameter of the high-crosslinked polystyrene microspheres is 1-10 nm, and the specific surface area of the high-crosslinked polystyrene microspheres is 600-900 m2/g。
Furthermore, the content of the amino group in the high-crosslinked polystyrene microsphere is 2.0mmol/g, and the average pore diameter of the high-crosslinked polystyrene microsphere is 1-5 nm.
Further, the metal oxide nanoparticles in step (C) are one of HFO (ferric oxide hydrate) nanoparticles, HZO (zirconium oxide hydrate) nanoparticles or HLO (lanthanum oxide hydrate) nanoparticles, the macroporous strongly basic anion exchange resin is D201 resin, and the macroporous strongly basic anion exchange resin loaded with HFO nanoparticles, HZO nanoparticles or HLO nanoparticles is respectively called resin-based nano ferric oxide, resin-based nano zirconium oxide or resin-based nano lanthanum oxide, and the above resin-based nano ferric oxide, resin-based nano zirconium oxide or resin-based nano lanthanum oxide are all developed and produced by the university of nanjing.
Further, the phosphorus-rich desorption solution (i.e. the high-concentration phosphorus-containing desorption solution) in the step (D) or the step (E) refers to a phosphorus-containing desorption solution with a phosphorus concentration of more than or equal to 300mg/L, and the low-concentration phosphorus-containing desorption solution refers to a phosphorus-containing desorption solution with a phosphorus concentration of less than or equal to 10 mg/L.
Further, in the crystallization reaction tank in the step (F), magnesium chloride (MgCl) is determined according to the phosphorus concentration in the phosphorus-rich desorption solution2) And ammonium chloride (NH)4Cl), Phosphate (PO) after addition4 3+) Ammonium radical (NH)4 +) Magnesium ion (Mg)2+) In a molar ratio of 1: 2-6: 1 to 2 (i.e., 1mol of phosphorus ion: 2 to 6mol of ammonium group: 1 to 2mol of magnesium ion), and magnetic powder (Fe)3O4) The particle size of the crystal is 15-100 μm, the adding amount is 300-100 mg/L, the rotating speed of a stirring paddle of a stirrer is 150-250 rpm (revolutions per minute), and the crystallization reaction time is 15-30 minutes (min).
Further, magnesium chloride (MgCl) is determined according to the phosphorus concentration in the phosphorus-rich desorption solution2) And ammonium chloride (NH)4Cl), Phosphate (PO) after addition4 3+) Ammonium radical (NH)4 +) Magnesium ion (Mg)2+) In a molar ratio of 1: 3-5: 1.2 to 1.8 (i.e., 1mol of phosphorus ion, 3 to 5mol of ammonium group, and 1 to 2mol of magnesium ion).
Further, magnetic powder (Fe)3O4) The particle size of the particles is 20 to 40 μm, and the dosage is 400 to 800 mg/L.
Further, in the step (G), the surface load of the inclined tube sedimentation tank is controlled to be 5-10 m3/m2H; the rotating speed of the high-speed shearing machine is more than or equal to 4000rpm (revolutions per minute), the strong magnetic area of the magnetic separator is more than or equal to 5000GS (gauss, high for short), and magnetic powder (Fe)3O4) The recovery rate is more than 99 percent; MgNH obtained after high-speed shearing and magnetic separation4PO4The content of the product P is more than or equal to 15 percent.
Further, the method also comprises the step (H): when the first adsorption effluent reaches a first penetration point (COD is more than or equal to 15mg/L), introducing NaOH solution into the first adsorption tower by an alkali liquor storage tank for desorption and regeneration, discharging the obtained organic desorption solution out of the first adsorption tower, and concentrating the organic desorption solution and then burning the concentrated organic desorption solution.
Further, the pH of the phosphorus-rich desorption solution is adjusted to 10 in the step (E).
Further, the magnetic powder (Fe) recovered by the magnetic separator in the step (G) is adsorbed3O4) Can be put into the crystallization reaction tank again for use.
Further, the filter is a quartz sand filter, the TP (total phosphorus) content of the biochemical tail water is 0.5-5 mg/L, the COD (chemical oxygen demand) is 30-60 mg/L, and the concentration of the obtained SS (suspended substance) in the filtrate is less than or equal to 5 mg/L.
The invention has the following beneficial effects:
the first adsorption material is high-crosslinking adsorption resin or aminated high-crosslinking adsorption resin, so that organic matters in the biochemical tail water can be effectively removed, and interference of organic matter impurities on a subsequent process is eliminated; the aminated high-crosslinking adsorption resin can achieve a better effect of removing organic matters, and although dimethylamino can absorb trace phosphorus theoretically, because dimethylamino is a weak electric group, the aminated high-crosslinking adsorption resin has weak phosphorus adsorption effect in a solution in which organic matters, sulfate radicals, chloride ions and carbonate radicals coexist, so that the aminated high-crosslinking adsorption resin is a better choice.
The method has compact and reasonable steps, removes organic matters in the biochemical tail water by using the first adsorption material, and then adsorbs phosphorus in the first adsorption effluent by using the selective phosphorus removal composite material, so that trace phosphorus in the first adsorption effluent is deeply removed, and a second adsorption effluent meeting the emission standard is obtained; the metal oxide nano particles realize the selective adsorption of phosphorus through the internal coordination complexation, so that the selective phosphorus removal composite material can adsorb and enrich the phosphate in the biochemical tail water, and the phosphorus-enriched desorption solution, namely MgCl, enriched in phosphorus is obtained after the selective phosphorus removal composite material is desorbed2、NH4Cl reacts with phosphate in the phosphorus-rich desorption solution to form MgNH4PO4Forming crystal precipitate favorable to separation by using magnetic powder as condensation nucleus, and finally separating MgNH by using separation technology4PO4Separating MgNH from magnetic powder4PO4The low-concentration liquid can be used for preparing NaOH solution, so that the operation cost is reduced, and the unification of environmental benefits and economic benefits is really achieved.
In conclusion, the method has the advantages of simple operation process and low operation cost, can realize deep removal of trace phosphorus in the biochemical tail water and recycle of the phosphorus after the method is used, and generates environmental benefits and economic benefits simultaneously.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a schematic view of the structure of HFO (resin-based nano iron oxide) in the present invention.
FIG. 3 is a schematic view of the structure of HZO (resin-based nano zirconia) in the present invention.
FIG. 4 is a schematic structural diagram of HLO (resin-based nano lanthanum oxide) in the present invention.
Wherein: 1. a filter; 2. a first adsorption tower; 3. an alkali liquor storage tank; 4. a second adsorption column; 5. an acid liquor storage tank; 6. a pH adjusting tank; 7. a crystallization reaction tank; 701. a stirrer; 8. an inclined tube sedimentation tank; 9. a high-speed shearing machine; 10. a magnetic separator; 11. a D201 resin; 1101. a duct; 1102. iron oxide nanoparticles; 1103. zirconia nanoparticles; 1104. lanthanum oxide nanoparticles.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
A method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water comprises the following steps:
(A) introducing biochemical tail water with TP (total phosphorus) content of 0.5-5 mg/L, COD (chemical oxygen demand) of 30-60 mg/L into a filter 1 for filtering, wherein the filter 1 is a quartz sand filter, and the filter 1 removes suspended pollutants in sewage to obtain filtrate with SS (suspended matter) concentration less than or equal to 5 mg/L;
(B) introducing the filtrate obtained in the step (A) into a first adsorption tower 2, wherein the first adsorption tower 2 is filled with high-crosslinked polystyrene microspheres with the surface modified with dimethylamine groups, the content of the dimethylamine groups in the high-crosslinked polystyrene microspheres is 1.5-2.5 mmol/g, the average pore diameter of the high-crosslinked polystyrene microspheres is 1-10 nm, and the specific surface area of the high-crosslinked polystyrene microspheres is 600-900 m2The first adsorption effluent is obtained after the first adsorption device adsorbs the first effluent, the first adsorption effluent is detected, and when COD (chemical oxygen demand) in the first adsorption effluent is more than or equal to 15mg/L, the introduction of the filtrate into the first adsorption tower 2 is stopped;
(C) introducing the first adsorption effluent obtained in the step (B) into a second adsorption tower 4, wherein the second adsorption tower 4 is filled with one of resin-based nano-iron oxide, resin-based nano-zirconia or resin-based nano-lanthanum oxide, as shown in fig. 2 to 4, the resin-based nano-iron oxide, resin-based nano-zirconia and resin-based nano-lanthanum oxide are resins using D201 resin 11 as a carrier, the resin-based nano-iron oxide is obtained by loading HFO (hydrated iron oxide) nanoparticles 1102 in a pore canal 1101 of the D201 resin 11, the resin-based nano-zirconia is obtained by loading HZO (hydrated zirconium oxide) nanoparticles 1103 in the pore canal 1101 of the D201 resin 11, the resin-based nano-lanthanum oxide is obtained by loading HLO (hydrated lanthanum oxide) nanoparticles 1104 in the pore canal 1101 of the D201 resin 11, the HFO nanoparticles 1102, HZO nanoparticles 1103 or HLO nanoparticles 1104 account for 10 to 30% by weight in the D201 resin 11, obtaining second adsorbed effluent after adsorption by a second adsorption device, and detecting the second adsorbed effluent, wherein the second adsorbed effluent meets the emission standard when the concentration of TP (total phosphorus) in the second adsorbed effluent is less than 0.1mg/L, and the first adsorbed effluent is stopped being led into a second adsorption tower 4 when the concentration of TP (total phosphorus) in the second adsorbed effluent is more than or equal to 0.1 mg/L;
(D) after the introduction of the first adsorption effluent into the second adsorption tower 4 is stopped in the step (C), the alkali liquor storage tank 3 introduces a NaOH solution with a concentration of 1-2 mol/L into the second adsorption tower 4 to perform desorption regeneration on the second desorption device, so as to obtain a phosphorus-containing desorption solution, the high-concentration phosphorus-containing desorption solution is also called a phosphorus-rich desorption solution, the phosphorus-rich desorption solution is a phosphorus-containing desorption solution with a phosphorus concentration of more than or equal to 300mg/L and can be used for subsequent phosphorus recovery, the low-concentration phosphorus-containing desorption solution is a phosphorus-containing desorption solution with a phosphorus concentration of less than or equal to 10mg/L, and the low-concentration phosphorus-containing desorption solution can be returned to the alkali liquor storage tank 3 to be used for preparing a NaOH solution;
(E) introducing the phosphorus-rich desorption solution obtained in the step (D) into a pH adjusting tank 6, adding a sulfuric acid solution with the concentration of 20-30% into the pH adjusting tank 6 by an acid solution storage tank 5, and adjusting the pH of the phosphorus-rich desorption solution to 9-11;
(F) introducing the phosphorus-rich desorption solution with the pH adjusted in the step (E) into a crystallization reaction tank 7, and simultaneously adding magnesium chloride (MgCl) into the crystallization reaction tank 7 according to the phosphorus concentration in the phosphorus-rich desorption solution2) Ammonium chloride (NH)4Cl) and magnetic powder (Fe)3O4) Adding MgCl2、NH4Control of P: NH in post-Cl solution4Mg in a molar ratio of 1: 2-6: 1-2, the particle size of the magnetic powder is 15-100 mu m, the adding amount is 300-100 mg/L, a stirrer is arranged in a crystallization reaction tank 7 for stirring, the rotating speed of a stirring paddle of the stirrer is 150-250 rpm, and the crystallization reaction time is 15-30 minutes (min), so that phosphate in the phosphorus-rich desorption solution forms high-density magnesium ammonium phosphate (MgNH) by taking the magnetic powder as a condensation nucleus4PO4) Crystallizing the precipitate to obtain a crystallization mixed solution after crystallization reaction;
(G) introducing the crystallization mixed solution obtained in the step (F) into an inclined tube sedimentation tank 8 for solid-liquid separation, wherein the inclined tube sedimentation tank 8The surface load is controlled to be 5-10 m3/m2H, the supernatant formed after precipitation can be led back to the alkali liquor storage tank 3 for preparing NaOH solution, the crystallized precipitate enters a high-speed shearing machine 9, the rotating speed of the high-speed shearing machine 9 is more than or equal to 4000rpm (revolutions per minute), and the high-speed shearing machine 9 is used for shearing magnesium ammonium phosphate (MgNH)4PO4) Magnetic powder (Fe) of floc3O4) Is stripped off and then MgNH is carried out4PO4Flocs and magnetic powder (Fe)3O4) The mixture enters a magnetic separator 10 for separation, the strong magnetic area of the magnetic separator 10 is more than or equal to 5000GS (Gauss, high for short), and the magnetic separator 10 magnetically separates magnetic powder (Fe)3O4) Adsorbing and recovering magnetic powder (Fe)3O4) The recovery rate is more than 99 percent, and the recovered magnetic powder can be put into the crystallization reaction tank 7 again for use; separated magnesium ammonium phosphate (MgNH)4PO4) The phosphorus content of the product is more than or equal to 15 percent, and the product is led out of the magnetic separator 10 and collected, and can be subsequently used as a slow release fertilizer for comprehensive utilization.
Since the ultra-high crosslinked polystyrene in the first adsorption tower 2 can be recycled in the present invention, the present invention may further include the step (H): when COD (chemical oxygen demand) in the first adsorption effluent is not less than 15mg/L, introducing NaOH solution into the first adsorption tower 2 by the alkali liquor storage tank 3 for desorption regeneration, discharging the obtained organic desorption solution out of the first adsorption tower 2, and carrying out subsequent concentration and incineration treatment on the organic desorption solution.
The invention is illustrated below with reference to examples:
example 1
Passing sewage with TP concentration of 2.47mg/L and COD of 43.5mg/L through a quartz sand filter to obtain filtrate with SS less than or equal to 5 mg/L; introducing the filtrate into a first adsorption tower 2, and filling ultrahigh cross-linked polystyrene (developed and produced by Nanjing university) with a dimethylamine group modified surface into a first adsorption device in the first adsorption tower 2 to obtain first adsorption effluent with COD (chemical oxygen demand) less than or equal to 15 mg/L; the first adsorption effluent is led into a second adsorption tower 4, resin-based nano zirconia (developed and produced by Nanjing university) is filled in the second adsorption tower 4, the resin-based nano zirconia is D201 resin 11 with HZO nano particles 1103 loaded in a pore channel 1101, and second adsorption effluent with TP concentration less than or equal to 0.1mg/L is obtained after adsorption by a second adsorption device and discharged.
When the concentration of TP of the second adsorption effluent is more than 0.1mg/L, stopping introducing the first adsorption effluent into the second adsorption tower 4, inputting a NaOH solution with the concentration of 1.5mol/L into the alkali liquor storage tank 3 to the second adsorption tower 4 for desorbing the second adsorption device with saturated adsorption to generate a phosphorus-rich desorption solution with the phosphorus concentration of about 421.3mg P/L and a low-concentration phosphorus-containing desorption solution with the phosphorus concentration of 6.9mg P/L, wherein the phosphorus-rich desorption solution can be used for subsequent phosphorus recovery, and the low-concentration phosphorus-containing desorption solution flows back to the alkali liquor storage tank 3 for preparing the NaOH solution for use; and (3) introducing the phosphorus-rich desorption solution into a pH adjusting tank 6, and adding a 25% sulfuric acid solution into the pH adjusting tank 6 by an acid solution storage tank 5 to adjust the pH of the phosphorus-rich desorption solution to about 10.5.
The phosphorus-rich desorption solution after the pH value is adjusted is led into a crystallization reaction tank 7, and a proper amount of MgCl is added2、NH4Cl and magnetic powder (Fe)3O4) Control P to NH4Mg is added in a molar ratio of 1:4:1.5, the addition amount of magnetic powder is 600Mg/L, the rotation speed of a stirring paddle of a stirrer 701 in a crystallization reaction tank 7 is controlled to be 200rpm, and the crystallization reaction time is controlled to be 22 minutes (min). Introducing the crystallization mixed solution into an inclined tube sedimentation tank 8 for solid-liquid separation, and controlling the surface load of the sedimentation tank to be 8m3/m2H; supernatant formed after precipitation flows back to an alkali liquor storage tank 3 for preparing NaOH solution, and MgNH is formed after the precipitate enters a high-speed shearing machine 94PO4Peeling off from the magnetic powder, and then MgNH4PO4And the mixture of the magnetic powder and the magnetic powder enters a magnetic separator 10, the magnetic separator 10 recovers the magnetic powder (the recovery rate of the magnetic powder is more than 99 percent), the recovered magnetic powder can be put into the crystallization reaction tank 7 again to continue to react, and the stripped MgNH4PO4 (the content of P is more than or equal to 15 percent) is used as the slow release fertilizer for comprehensive utilization.
Example 2
Passing sewage with TP concentration of 4.38mg/L and COD of 56.3mg/L through a quartz sand filter to obtain filtrate with SS less than or equal to 5 mg/L; introducing the filtrate into a first adsorption tower 2, and filling ultrahigh cross-linked polystyrene (developed and produced by Nanjing university) with a dimethylamine group modified surface into a first adsorption device in the first adsorption tower 2 to obtain first adsorption effluent with COD (chemical oxygen demand) less than or equal to 15 mg/L; and introducing the first adsorption effluent into a second adsorption tower 4, introducing the second adsorption tower 4 into the second adsorption tower 4, and filling resin-based nano iron oxide (developed and produced by Nanjing university), wherein the resin-based nano iron oxide is D201 resin 11 loaded with HFO nano particles 1102 in a pore channel 1101, and adsorbing by a second adsorption device to obtain second adsorption effluent with the concentration of TP (total TP) less than or equal to 0.1mg/L and discharging the second adsorption effluent. .
When the concentration of TP of the second adsorption effluent is greater than 0.1mg/L, stopping introducing the first adsorption effluent into the second adsorption tower 4, inputting a NaOH solution with the concentration of 2.0mol/L into the alkali liquor storage tank 3 to the second adsorption tower 4 for desorbing the second adsorption device with saturated adsorption, so as to generate a phosphorus-rich desorption solution with the phosphorus concentration of about 583.7mg P/L and a low-concentration phosphorus-containing desorption solution with the phosphorus concentration of 9.3mg P/L, wherein the phosphorus-rich desorption solution can be used for subsequent phosphorus recovery, and the low-concentration phosphorus-containing desorption solution flows back to the alkali liquor storage tank 3 for preparing the NaOH solution for use; and (3) introducing the phosphorus-rich desorption solution into a pH adjusting tank 6, and adding a 25% sulfuric acid solution into the pH adjusting tank 6 by an acid solution storage tank 5 to adjust the pH of the phosphorus-rich desorption solution to about 10.8.
The phosphorus-rich desorption solution after the pH value is adjusted is led into a crystallization reaction tank 7, and a proper amount of MgCl is added2、NH4Cl and magnetic powder (Fe)3O4) The molar ratio of P to NH4 to Mg is controlled to be 1:5:1.8, the adding amount of magnetic powder is 800Mg/L, the rotating speed of a stirring paddle of a stirrer 701 in a crystallization reaction tank 7 is controlled to be 250rpm, and the crystallization reaction time is controlled to be 15 minutes (min). Introducing the crystallization mixed solution into an inclined tube sedimentation tank 8 for solid-liquid separation, and controlling the surface load of the sedimentation tank to be 6m3/m2H; supernatant formed after precipitation flows back to an alkali liquor storage tank 3 for preparing NaOH solution, and MgNH is formed after the precipitate enters a high-speed shearing machine 94PO4Peeling off from the magnetic powder, and then MgNH4PO4And the mixture of the magnetic powder and the magnetic powder enters a magnetic separator 10, the magnetic separator 10 recovers the magnetic powder (the recovery rate of the magnetic powder is more than 99 percent), the recovered magnetic powder can be put into the crystallization reaction tank 7 again to continue to react, and the stripped MgNH4PO4 (the content of P is more than or equal to 15 percent) is used as the slow release fertilizer for comprehensive utilization.
Example 3
Passing sewage with TP concentration of 1.25mg/L and COD of 35.6mg/L through a quartz sand filter to obtain filtrate with SS less than or equal to 5 mg/L; introducing the filtrate into a first adsorption tower 2, and filling ultrahigh cross-linked polystyrene (developed and produced by Nanjing university) with a dimethylamine group modified surface into a first adsorption device in the first adsorption tower 2 to obtain first adsorption effluent with COD (chemical oxygen demand) less than or equal to 15 mg/L; and introducing the first adsorption effluent into a second adsorption tower 4, introducing the second adsorption tower 4 into a resin-based nano lanthanum oxide (developed and produced by Nanjing university), wherein the resin-based nano lanthanum oxide is D201 resin 11 loaded with HLO nano particles 1104 in a pore channel 1101, and adsorbing by a second adsorption device to obtain second adsorption effluent with TP concentration less than or equal to 0.1mg/L and discharging the second adsorption effluent.
When the concentration of TP of the second adsorption effluent is more than 0.1mg/L, stopping introducing the first adsorption effluent into the second adsorption tower 4, inputting a NaOH solution with the concentration of 1.0mol/L into the alkali liquor storage tank 3 to the second adsorption tower 4 for desorbing the second adsorption device with saturated adsorption to generate a phosphorus-rich desorption solution with the phosphorus concentration of about 314.7mg P/L and a low-concentration phosphorus-containing desorption solution with the phosphorus concentration of 6.2mg P/L, wherein the phosphorus-rich desorption solution can be used for subsequent phosphorus recovery, and the low-concentration phosphorus-containing desorption solution flows back to the alkali liquor storage tank 3 for preparing the NaOH solution for use; and (3) introducing the phosphorus-rich desorption solution into a pH adjusting tank 6, and adding a 25% sulfuric acid solution into the pH adjusting tank 6 by an acid solution storage tank 5 to adjust the pH of the phosphorus-rich desorption solution to about 10.2.
The phosphorus-rich desorption solution after the pH value is adjusted is led into a crystallization reaction tank 7, and a proper amount of MgCl is added2、NH4Cl and magnetic powder (Fe)3O4) Control P to NH4Mg is added in a molar ratio of 1:3:1.2, the addition amount of magnetic powder is 400Mg/L, the rotation speed of a stirring paddle of a stirrer 701 in a crystallization reaction tank 7 is controlled to be 150rpm, and the crystallization reaction time is controlled to be 30 minutes (min). Introducing the crystallization mixed solution into an inclined tube sedimentation tank 8 for solid-liquid separation, and controlling the surface load of the sedimentation tank to be 10m3/m2H; supernatant formed after precipitation flows back to an alkali liquor storage tank 3 for preparing NaOH solution, and MgNH is formed after the precipitate enters a high-speed shearing machine 94PO4Peeling off from the magnetic powder, and then MgNH4PO4The mixture with the magnetic powder enters a magnetic separator 10, the magnetic separator 10 recovers the magnetic powder (the recovery rate of the magnetic powder is more than 99 percent), the recovered magnetic powder can be put into a crystallization reaction tank 7 again to continue to react, and the stripped MgNH4PO4 (the P content is more than or equal to 15 percent) is used as the slow release fertilizer for comprehensive utilization.
The above description is intended to be illustrative and not restrictive, and the scope of the invention is defined by the appended claims, which may be modified in any manner within the scope of the invention.
Claims (9)
1. A method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water comprises the following steps:
(A) introducing the biochemical tail water into a filter for filtering, and removing suspended pollutants in the sewage to obtain filtrate with the suspended matter concentration less than or equal to 5 mg/L;
(B) introducing the filtrate obtained in the step (A) into a first adsorption tower, wherein amination high-crosslinking adsorption resin for adsorbing residual organic matters in the filtrate is filled in the first adsorption tower, the amination high-crosslinking adsorption resin is used for removing the organic matters in the biochemical tail water, the content of amino in the high-crosslinking adsorption resin is 1.5-2.5 mmol/g, first adsorption effluent is obtained after adsorption in the first adsorption tower, and when the Chemical Oxygen Demand (COD) in each liter of the first adsorption effluent is more than or equal to 15mg, the introduction of the filtrate into the first adsorption tower is stopped;
(C) introducing the first adsorption effluent obtained in the step (B) into a second adsorption tower, wherein a selective phosphorus removal composite material is filled in the second adsorption tower, the selective phosphorus removal composite material is macroporous strong base anion exchange resin with pore channels loaded with metal oxide nanoparticles, the content of the metal oxide nanoparticles in the macroporous strong base anion exchange resin is 10-30% (weight percentage), the metal oxide nanoparticles are utilized to realize selective adsorption of phosphorus through internal coordination and complexation, a second adsorption effluent is obtained after adsorption by a second adsorption device, and when the concentration of Total Phosphorus (TP) in each liter of the second adsorption effluent is more than or equal to 0.1mg, the introduction of the first adsorption effluent into the second adsorption tower is stopped;
(D) after the introduction of the first adsorption effluent into the second adsorption tower is stopped in the step (C), introducing a sodium hydroxide (NaOH) solution with the concentration of 1-2 mol/L into the second adsorption tower by using an alkali liquor storage tank to perform desorption regeneration on the selective phosphorus removal composite material, so as to obtain a phosphorus-rich desorption solution with the phosphorus concentration of more than or equal to 300 mg/L;
(E) introducing the phosphorus-rich desorption solution obtained in the step (D) into a pH adjusting tank, adding a sulfuric acid solution with the mass concentration of 20-30% into the pH adjusting tank by an acid solution storage tank, and adjusting the pH of the phosphorus-rich desorption solution to 9-11;
(F) introducing the phosphorus-rich desorption solution with the pH adjusted in the step (E) into a crystallization reaction tank, and simultaneously adding magnesium chloride (MgCl) into the crystallization reaction tank according to the phosphorus concentration in the phosphorus-rich desorption solution2) Ammonium chloride (NH)4Cl) and ferroferric oxide (Fe)3O4) Granulated, added Phosphate (PO)4 3+) Ammonium radical (NH)4 +) Magnesium ion (Mg)2+) In a molar ratio of 1: 2-6: 1-2 (namely 1mol of phosphorus ions: 2-6 mol of ammonium radicals: 1-2 mol of magnesium ions), the particle size of the ferroferric oxide particles is 15-100 mu m, the adding amount is 300-100 mg per liter of the phosphorus-rich desorption solution, a stirrer is arranged in a crystallization reaction tank for stirring, the rotating speed of a stirring paddle of the stirrer is 150-250 revolutions per minute (rpm), the crystallization reaction time is 15-30 minutes (min), and the phosphate in the phosphorus-rich desorption solution forms high-density magnesium ammonium phosphate (MgNH) by taking the ferroferric oxide particles as condensation nuclei4PO4) Crystallizing the precipitate to obtain a crystallization mixed solution after crystallization reaction;
(G) introducing the crystallization mixed liquor obtained in the step (F) into an inclined tube sedimentation tank for solid-liquid separation, introducing the crystallization precipitate into a high-speed shearing machine, wherein the rotating speed of the high-speed shearing machine is more than or equal to 4000 revolutions per minute (rpm), and allowing the high-speed shearing machine to perform MgNH (magnesium ammonium hydroxide) treatment4PO4The flocs are stripped from the ferroferric oxide particles and then MgNH is carried out4PO4And (3) separating the mixture of the flocs and the ferroferric oxide particles in a magnetic separator, wherein the strong magnetic area of the magnetic separator is more than or equal to 5000GS, the ferroferric oxide particles are adsorbed and recovered by the magnetic separator through magnetic force, and the ammonium magnesium phosphate is led out of the magnetic separator and collected.
2. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 1, which is characterized in that: the surface of the aminated high-crosslinking adsorption resin is modified with dimethylaminoThe high-crosslinked polystyrene microsphere is characterized by comprising a mass, wherein the average pore diameter of the high-crosslinked polystyrene microsphere is 1-10 nm, and the specific surface area of the high-crosslinked polystyrene microsphere is 600-900 m2/g。
3. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 2, which is characterized in that: the content of the amino in the high-crosslinked polystyrene microspheres is 2.0mmol/g, and the average pore diameter of the high-crosslinked polystyrene microspheres is 1-5 nm.
4. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 1, which is characterized in that: the metal oxide nanoparticles in step (C) are one of hydrated iron oxide (HFO) nanoparticles, Hydrated Zirconium Oxide (HZO) nanoparticles or Hydrated Lanthanum Oxide (HLO) nanoparticles, and the macroporous strong base anion exchange resin is D201 resin (11).
5. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 1, which is characterized in that: controlling Phosphate (PO) in step (F)4 3+) Ammonium radical (NH)4 +) Magnesium ion (Mg)2+) In a molar ratio of 1: 3-5: 1.2 to 1.8 (i.e., 1mol of phosphorus ion, 3 to 5mol of ammonium group, and 1 to 2mol of magnesium ion).
6. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 1, which is characterized in that: ferroferric oxide particles (Fe)3O4) The particle size of the phosphorus-rich desorption solution is 20-40 mu m, and the adding amount is 400-800 mg per liter of the phosphorus-rich desorption solution.
7. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 1, which is characterized in that: and (E) adjusting the pH value of the phosphorus-rich desorption solution to 10.
8. The method for deeply purifying and efficiently recovering trace phosphorus in biochemical tail water according to claim 1, further comprising the step (H): and when the Chemical Oxygen Demand (COD) in each liter of first adsorption effluent is more than or equal to 15mg, introducing NaOH solution into the first adsorption tower by using the alkali liquor storage tank for desorption regeneration to obtain organic desorption solution, discharging the organic desorption solution out of the first adsorption tower, and concentrating the organic desorption solution and then burning the concentrated organic desorption solution.
9. The method for deeply purifying and efficiently recovering the trace phosphorus in the biochemical tail water according to the claim 1, which is characterized in that: the ferroferric oxide (Fe) absorbed and recovered by the magnetic separator in the step (G)3O4) The granules can be put into the crystallization reaction tank again for use.
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