CN113087063A - Method for deeply removing phosphorus in high-salinity wastewater - Google Patents
Method for deeply removing phosphorus in high-salinity wastewater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/58—Use in a single column
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/18—PO4-P
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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Abstract
The invention relates to the technical field of sewage treatment, and discloses a method for deeply removing phosphorus in high-salinity wastewater, which comprises the following steps: s1: preparing a salt-tolerant phosphorus adsorption material, (1) placing strong-base anion resin into a FeCl3 solution, stirring for 2 hours until the resin is adsorbed and saturated, and then carrying out centrifugal dehydration on the obtained strong-base anion resin, and (2) quickly adding the prepared strong-base anion resin into a solution containing NaOH; s2: deep phosphorus removal of high-salt-content wastewater, (1) filling prepared salt-tolerant phosphorus adsorption resin into a resin column, enabling the phosphorus-containing wastewater to flow through the resin column, regulating the flow of inlet and outlet water, and controlling the hydraulic retention time, (2) when the adsorption capacity in an adsorption device is close to saturation, resolving the resin by using NaOH + NaCl regeneration solution, and transferring the adsorbed phosphorus into alkali liquor to realize the regeneration of the resin. The salt-tolerant phosphorus adsorption material prepared by the invention can keep large adsorption capacity for phosphorus in high-salinity wastewater, and has simple preparation process and convenient use.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for deeply removing phosphorus in high-salinity wastewater.
Background
Phosphorus is an indispensable nutrient element for life bodies and is a resource which is difficult to regenerate and is increasingly exhausted. Meanwhile, with the development of social economy and the improvement of the living standard of people, more and more phosphorus-containing sewage is discharged into the water body, so that the eutrophication of the water body is increasingly serious, the mass propagation of algae is caused, fishes die, and the water body smells. Therefore, a method for removing phosphorus from sewage and separating and recovering the phosphorus is actively sought, so that the water quality can be improved, the pollution is reduced, the phosphorus can be recycled, and the condition of phosphorus resource shortage is relieved.
At present, the technology for treating phosphate in sewage at home and abroad is mature, and mainly comprises a biological method and a chemical method. The biological phosphorus removal method is simple in operation, phosphorus-removing bacteria are alternately operated under aerobic and anaerobic conditions, and phosphorus removal is realized by sludge discharge, but the phosphorus removal efficiency is low. The chemical method mainly comprises the methods of chemical precipitation, resin adsorption, ion exchange, electrodialysis, reverse osmosis and the like, wherein the chemical precipitation has high phosphorus removal efficiency, the method of removing the phosphorus in the wastewater by mainly utilizing lime, aluminum salt, iron salt and the like and phosphate radicals to generate precipitates has good effect on the high-phosphorus wastewater, but the consumption of the medicament in the wastewater with lower phosphorus concentration is not economical, and in addition, the generated precipitates are difficult to dewater and treat, so that secondary pollution is easily caused. Anion resin has high specific surface area, excellent pore structure and multifunctional groups, and has been widely applied in the field of sewage treatment, but the adsorption selectivity of the adsorption resin to phosphorus is poor, and the application effect in high-salt-content wastewater of more than 3000mg/L is not ideal.
The metal material taking the anion exchange resin as the support shows stronger adsorption capacity and better selectivity. CN 110560012A reports a method for removing phosphorus by hydrated iron oxide-resin composite resin, but the preparation process of the adsorbent is complex and the cost is high. Based on the thought, the efficient phosphorus removal material which is simple in production process, salt-resistant, large in phosphorus adsorption capacity, good in selectivity, certain in strength and chemical stability and small in water flow resistance is developed and applied to the adsorption phosphorus removal processes of various sewage to enrich and separate phosphorus in the sewage, and the efficient phosphorus removal material is an important means for ensuring the phosphorus removal effect of the sewage and realizing the recycling of phosphorus resources.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for deeply removing phosphorus in high-salinity wastewater, and solves the technical problems that the consumption of a medicinal preparation in the wastewater with lower phosphorus concentration is not economical, and in addition, the generated precipitate is difficult to dewater and treat, is easy to cause secondary pollution, and has a complex process and high cost.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a method for deeply removing phosphorus in high-salinity wastewater comprises the following steps: s1: preparing a salt-tolerant phosphorus adsorption material, (1) placing strong-base anion resin in FeCl3 solution, stirring for 2 hours until the resin is adsorbed and saturated, and then carrying out centrifugal dehydration on the obtained strong-base anion resin, (2) quickly adding the prepared strong-base anion resin into the solution containing NaOH, and carrying out centrifugal dehydration after the reaction is finished; s2: the method comprises the steps of (1) deeply removing phosphorus from high-salt-content wastewater, (1) filling prepared salt-tolerant phosphorus adsorption resin into a resin column, enabling the phosphorus-containing wastewater to flow through the resin column, adjusting water flow in and out to control hydraulic retention time, enabling the resin to be fully contacted with the phosphorus-containing wastewater to adsorb and fix phosphorus in the resin, and (2) when adsorption capacity in an adsorption device is close to saturation, resolving the resin by using NaOH + NaCl regeneration solution, transferring the adsorbed phosphorus into alkali liquor to realize regeneration of the resin, and then entering the next adsorption phosphorus removal operation.
Preferably, in step S1, the concentration of the FeCl3 solution is 0.05-5 mol/L.
Preferably, in step S1, the concentration of the FeCl3 solution is preferably 1-3 mol/L, and the solubility of FeCl3 can be increased by adding HCl solution, wherein the HCl concentration is 0.5-3 mol/L.
Preferably, in step S1, the concentration of the NaOH solution is 5-30%.
Preferably, in step S1, the volume ratio of the strongly basic anion exchange resin to the FeCL3 solution is 1:2 to 1: 5.
Preferably, in step S1, the volume ratio of the strongly basic anion exchange resin to the NaOH solution is 1:5-1: 10.
Preferably, the content of Fe in the prepared salt-tolerant phosphorus adsorption resin is 7-35%.
Preferably, the prepared salt-tolerant phosphorus adsorption resin is not dried, and can be directly used for phosphorus removal treatment of high-salt wastewater after transformation of NaCl solution.
Preferably, the concentration of the NaCl solution is 2-8%.
Preferably, in the step S2, the concentration of phosphorus in the phosphorus-containing wastewater is 2-10 ppm, and the hydraulic retention time of the device is 2-20 min.
Preferably, in step S2, the concentration of the NaOH + NaCl regeneration solution is NaOH: 1-2%, NaCl: 4-8%, the volume consumption of the adsorbent is 2-3 times of the volume of the adsorbent, and the regeneration time is 1-4 hours.
(III) advantageous effects
According to the salt-tolerant phosphorus adsorption material prepared by the invention, the loaded hydrated iron oxide exists mainly in the form of Fe-OH functional groups in an aqueous solution due to protonation to form a positive charge distribution center, and the surface hydroxyl groups of the hydrated iron oxide can exchange ions with anions H2PO4-, HPO 42-and PO 43-in water, compared with the anions such as C1-, HCO 3-and SO 42-which are commonly existing in water, the hydrated iron oxide has high selectivity on phosphate ions, SO that the high-salinity wastewater can keep large adsorption capacity on phosphorus, and the preparation process is simple and convenient to use.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
adding 50g of strong basic resin into 250ml of 60% ferric chloride solution, stirring at 120rpm for 2h, performing suction filtration, then putting 50g of the resin processed in the previous step into NaOH solution for reaction, wherein the concentration of NaOH in the solution is 10%, stirring at 120rpm/min for reaction for 3h, and performing suction filtration to obtain the salt-tolerant phosphorus adsorption resin, wherein the content of simple substance iron in the prepared resin is 15%. 50ml of prepared salt-tolerant phosphorus adsorption resin is filled into a resin column, certain biochemical effluent containing phosphorus is taken, the total phosphorus concentration in the wastewater is 3mg/L, the pH value is 7-8, the salt content is 10000 mg/L, the phosphorus-containing wastewater flows through the device, the water conservancy retention time is 6min, and the total phosphorus content in the effluent is less than 0.2 mg/L. Stopping water inflow when the total phosphorus in the effluent reaches 0.5mg/L, and calculating to obtain the phosphorus adsorption capacity of the salt-tolerant phosphorus adsorption resin of 2.5 mg/g. And (3) resolving the resin by using a NaOH-NaCl regeneration solution, wherein the concentration of NaOH in the regeneration solution is 1 percent, the concentration of NaCl in the regeneration solution is 8 percent, reversely introducing the regeneration solution, the water conservancy retention time is 1h, and introducing water for washing to be neutral after the volume of the regeneration solution is 2 times of the numerical value calculation volume. The adsorption and process experiment is repeated for 50 times, so that the total phosphorus in the effluent is not more than 0.1mg/L, and the adsorption capacity of the resin is more than 2.0 mg/g.
Example 2:
adding 50g of strong basic resin into 250ml of 50% ferric chloride solution, stirring at 120rpm for 3h, carrying out suction filtration, then putting 50g of the resin processed in the previous step into NaOH solution for reaction, wherein the concentration of NaOH in the solution is 20%, stirring at 120rpm/min for reaction for 3h, and carrying out suction filtration to obtain the salt-tolerant phosphorus adsorption resin, wherein the content of simple substance iron in the prepared resin is 13.5%. 50ml of prepared salt-tolerant phosphorus adsorption resin is filled into a resin column, certain phosphorus-containing biochemical effluent is taken, the total phosphorus concentration in the wastewater is 10mg/L, the pH value is 7-8, the salt content is 8000mg/L, the phosphorus-containing wastewater flows through the device, the water conservancy residence time is 6min, and the total phosphorus content in the effluent is less than 0.2 mg/L. Stopping water inflow when the total phosphorus in the effluent reaches 0.5mg/L, and calculating to obtain the phosphorus adsorption capacity of the salt-tolerant phosphorus adsorption resin of 2.5 mg/g. And (3) resolving the resin by using a NaOH-NaCl regeneration solution, wherein the concentration of NaOH in the regeneration solution is 1 percent, the concentration of NaCl in the regeneration solution is 8 percent, reversely introducing the regeneration solution, the water conservancy retention time is 1h, and introducing water for washing to be neutral after the volume of the regeneration solution is 3 times of the numerical value calculation volume. The adsorption and process experiment is repeated for 50 times, so that the total phosphorus in the effluent is not more than 0.1mg/L, and the adsorption capacity of the resin is more than 2.2 mg/g.
Comparative example 1
50ml of salt-tolerant phosphorus adsorption resin prepared in example 1 is filled into a resin column, certain phosphorus-containing biochemical effluent is taken, the total phosphorus concentration in the wastewater is 5mg/L, the pH value is 7-8, the salt content is 9000mg/L, the phosphorus-containing wastewater flows through the device, the water conservancy residence time is 6min, and the total phosphorus content in the effluent is less than 0.2 mg/L. Stopping water inflow when the total phosphorus in the effluent reaches 0.5mg/L, and calculating to obtain the phosphorus adsorption capacity of the salt-tolerant phosphorus adsorption resin of 2.4 mg/g. And (3) resolving the resin by using a NaOH-NaCl regeneration solution, wherein the concentration of NaOH in the regeneration solution is 1 percent, the concentration of NaCl in the regeneration solution is 8 percent, reversely introducing the regeneration solution, the water conservancy retention time is 1h, and introducing water for washing to be neutral after the volume of the regeneration solution is 3 times of the numerical value calculation volume. The adsorption and process experiment is repeated for 50 times, so that the total phosphorus in the effluent is not more than 0.1mg/L, and the adsorption capacity of the resin is more than 2.1 mg/g.
Filling commercially available strong-base anion resin into a resin column, taking the same phosphorus-containing biochemical effluent, wherein the total phosphorus concentration in the wastewater is 5mg/L, the pH value is 7-8, the salt content is 9000mg/L, allowing the phosphorus-containing wastewater to flow through the device, the water conservancy retention time is 6min, and the total phosphorus content in the effluent is less than 0.2 mg/L. Stopping water inflow when the total phosphorus in the effluent reaches 0.5mg/L, and calculating to obtain that the adsorption capacity of the commercial strong-base anion resin to the phosphorus is 0.6 mg/g. And (3) resolving the resin by using a NaOH-NaCl regeneration solution, wherein the concentration of NaOH in the regeneration solution is 1 percent, the concentration of NaCl in the regeneration solution is 8 percent, reversely introducing the regeneration solution, the water conservancy retention time is 1h, and introducing water for washing to be neutral after the volume of the regeneration solution is 3 times of the numerical value calculation volume.
The adsorption and process experiment is repeated for 50 times, so that the total phosphorus in the effluent is not more than 0.1mg/L, and the adsorption capacity of the resin is 0.45 mg/g.
The invention aims to provide a high-efficiency phosphorus adsorption material which is simple in preparation process and salt-resistant and is applied to deep phosphorus removal of high-salt wastewater.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (11)
1. A method for deeply removing phosphorus in high-salinity wastewater is characterized by comprising the following steps:
s1: preparing a salt-tolerant phosphorus adsorption material, (1) placing strong-base anion resin in FeCl3 solution, stirring for 2 hours until the resin is adsorbed and saturated, and then carrying out centrifugal dehydration on the obtained strong-base anion resin, (2) quickly adding the prepared strong-base anion resin into the solution containing NaOH, and carrying out centrifugal dehydration after the reaction is finished;
s2: the method comprises the steps of (1) deeply removing phosphorus from high-salt-content wastewater, (1) filling prepared salt-tolerant phosphorus adsorption resin into a resin column, enabling the phosphorus-containing wastewater to flow through the resin column, adjusting water flow in and out to control hydraulic retention time, enabling the resin to be fully contacted with the phosphorus-containing wastewater to adsorb and fix phosphorus in the resin, and (2) when adsorption capacity in an adsorption device is close to saturation, resolving the resin by using NaOH + NaCl regeneration solution, transferring the adsorbed phosphorus into alkali liquor to realize regeneration of the resin, and then entering the next adsorption phosphorus removal operation.
2. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in step S1, the concentration of the FeCl3 solution is 0.05-5 mol/L.
3. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in the step S1, the concentration of the FeCl3 solution is preferably 1-3 mol/L, and the solubility of FeCl3 can be increased by adding HCl solution, wherein the HCl concentration is 0.5-3 mol/L.
4. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in step S1, the concentration of the NaOH solution is 5-30%.
5. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in step S1, the volume ratio of the strongly basic anion exchange resin to the FeCl3 solution is 1:2-1: 5.
6. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in step S1, the volume ratio of the strongly basic anion exchange resin to the NaOH solution is 1:5 to 1: 10.
7. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: the Fe content in the prepared salt-tolerant phosphorus adsorption resin is 7-35%.
8. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: the prepared salt-tolerant phosphorus adsorption resin can be directly used for dephosphorization treatment of high-salt wastewater after transformation of NaCl solution without drying treatment.
9. The method for deeply removing phosphorus in high salinity wastewater according to claim 8, characterized in that: the concentration of the NaCl solution is 2% -8%.
10. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in step S2, the concentration of phosphorus in the phosphorus-containing wastewater is 2-10 ppm, and the hydraulic retention time of the device is 2-20 min.
11. The method for deeply removing phosphorus in high salinity wastewater according to claim 1, characterized in that: in step S2, the concentration of the NaOH + NaCl regeneration solution is NaOH: 1-2%, NaCl: 4-8%, the volume consumption of the adsorbent is 2-3 times of the volume of the adsorbent, and the regeneration time is 1-4 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314908A (en) * | 2021-12-17 | 2022-04-12 | 安道麦股份有限公司 | Device and method for treating phosphorus-containing wastewater from production of acephate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114314908A (en) * | 2021-12-17 | 2022-04-12 | 安道麦股份有限公司 | Device and method for treating phosphorus-containing wastewater from production of acephate |
| CN114314908B (en) * | 2021-12-17 | 2023-05-30 | 安道麦股份有限公司 | Treatment device and method for phosphorus-containing wastewater from acephate production |
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