CN117427616B - Dephosphorization agent and preparation method thereof - Google Patents

Dephosphorization agent and preparation method thereof Download PDF

Info

Publication number
CN117427616B
CN117427616B CN202311764009.5A CN202311764009A CN117427616B CN 117427616 B CN117427616 B CN 117427616B CN 202311764009 A CN202311764009 A CN 202311764009A CN 117427616 B CN117427616 B CN 117427616B
Authority
CN
China
Prior art keywords
agent
salt
ferrous
precursor
deionized water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311764009.5A
Other languages
Chinese (zh)
Other versions
CN117427616A (en
Inventor
刘旭
李玉善
肖永厚
安博星
梁正奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panjin Institute of Industrial Technology Dalian University of Technology DUT
Original Assignee
Panjin Institute of Industrial Technology Dalian University of Technology DUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panjin Institute of Industrial Technology Dalian University of Technology DUT filed Critical Panjin Institute of Industrial Technology Dalian University of Technology DUT
Priority to CN202311764009.5A priority Critical patent/CN117427616B/en
Publication of CN117427616A publication Critical patent/CN117427616A/en
Application granted granted Critical
Publication of CN117427616B publication Critical patent/CN117427616B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention relates to the technical field of wastewater treatment, and discloses a dephosphorization agent and a preparation method thereof. Thus, the dephosphorizing agent has the following advantages: (1) The phosphorus removal agent prepared by sludge recycling has high adsorption capacity to phosphorus-containing components in sewage, the highest adsorption capacity can reach 89.25mg P/g, and the sewage discharge standard requirement that the total phosphorus content is less than 0.5mg/L can be met; (2) The water-based magnetic particle has paramagnetism, can be rapidly separated from water under the magnetic field condition, and is easy to recycle.

Description

Dephosphorization agent and preparation method thereof
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a dephosphorization agent and a preparation method thereof.
Background
Along with the rapid development of industry and the continuous improvement of living standard of residents, phosphorus is widely used as industrial raw materials and chemical elements commonly used in daily life, and the phenomenon of eutrophication of water body is caused by the discharge of phosphorus into rivers, so that the ecological environment is seriously affected. Therefore, the removal of phosphate from sewage has been a major problem in the field of environmental protection. At present, the phosphate in the sewage is mainly removed by adopting a biological method and a chemical method, the biological method relies on the metabolism of microorganisms, the absorption and release functions of the phosphorus accumulating bacteria microorganisms on the phosphate are changed by regulating and controlling the dissolved oxygen concentration of the sewage, and the phosphate is removed from the sewage in an activated sludge mode; the chemical method converts phosphate into inorganic compound through the charge and adsorption bridging action of metal ions so as to separate the phosphate from sewage. The microbial phosphorus removal economy is good but is influenced by the ambient temperature and the microbial activity, the phosphorus removal efficiency is low, and the chemical method can remove phosphate efficiently, but can also produce a large amount of sludge at the same time, so that secondary pollution is caused. In view of the above, the development of an easily recyclable adsorbent product with a high adsorption capacity has become critical in solving the bottleneck in the phosphate removal field.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present invention is to propose a dephosphorizing agent and a method for preparing the same, whereby the dephosphorizing agent has the following advantages: (1) The phosphorus removal agent prepared by sludge recycling has high adsorption capacity to phosphorus-containing components in sewage, the highest adsorption capacity can reach 89.25mg P/g, and the sewage discharge standard requirement that the total phosphorus content is less than 0.5mg/L can be met; (2) The water-based magnetic particle has paramagnetism, can be rapidly separated from water under the magnetic field condition, and is easy to recycle.
In one aspect of the invention, a method of preparing a phosphorous removal agent is provided. According to an embodiment of the invention, the method comprises:
(1) Dissolving ferric salt in deionized water, sequentially adding divalent calcium salt and divalent ferrous salt, uniformly stirring, adding sludge powder, and uniformly mixing to obtain a precursor solution;
(2) After regulating the pH value of the precursor solution, reacting in a reaction kettle, and obtaining a dephosphorizing agent precursor after first treatment;
(3) And (3) dissolving ferrous salt in deionized water, mixing with the phosphorus removing agent precursor, adding a 2-methylimidazole solution, and performing second treatment to obtain the phosphorus removing agent.
In a second aspect of the invention, the invention provides a dephosphorizing agent. According to an embodiment of the invention, the dephosphorizing agent is prepared by the method described in the first aspect of the invention.
The dephosphorizing agent and the preparation method thereof provided by the invention have the advantages that:
(1) The phosphorus removal agent prepared by recycling sludge has high adsorption capacity to phosphate in sewage, the highest adsorption capacity can reach 89.25mg P/g, and the sewage discharge standard requirement that the total phosphorus content is less than 0.5mg/L can be met;
(2) The magnetic separation type water purifier has paramagnetism, can be rapidly separated from water under the magnetic field condition, and is easy to recycle;
(3) The preparation method adopts a hydrothermal method and a chemical precipitation method, and has the advantages of mild and controllable conditions, low production cost and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is an ASM characterization of phosphorus removal agent and sewage sludge obtained according to example 1 of the present invention;
FIG. 2 is an XPS characterization diagram of the dephosphorizing agent obtained in the embodiment 1 of the present invention, wherein FIG. 2A is the existence form of Ca element in the dephosphorizing agent, FIG. 2B is the existence form of Fe element in the dephosphorizing agent, and FIG. 2C is the variation before and after the adsorption of P element in the dephosphorizing agent;
FIG. 3 is an XRD characterization of the phosphorus removal agents obtained in examples 1-5 according to the present invention;
FIG. 4 is an XRD characterization of the phosphorus removal agent obtained in examples 1, 6-7, according to the present invention;
FIG. 5 shows the adsorption effect of the dephosphorizing agent obtained in examples 1 to 5 according to the present invention applied to sewage treatment;
FIG. 6 shows the adsorption effect of the dephosphorizing agent obtained in examples 6 to 7 according to the present invention applied to sewage treatment.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
Furthermore, the terms "first," second, "" third, "" fourth, "" fifth, "and sixth" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "first", "second", "third", "fourth", "fifth" and "sixth" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The content of the effective substances of the ferric salt, the ferrous ferrite, the ferrous calcium salt, the sodium hydroxide and the 2-methylimidazole chemical is more than or equal to 99 weight percent.
In one aspect of the invention, a method of preparing a phosphorous removal agent is provided. According to an embodiment of the invention, the method comprises:
s100: and (3) dissolving ferric salt in deionized water, sequentially adding divalent calcium salt and divalent ferrous salt, uniformly stirring, adding sludge powder, and uniformly mixing to obtain a precursor solution.
In the step, ferric salt is dissolved in deionized water, divalent calcium salt and divalent ferrous salt are sequentially added, dried sludge powder is added after uniform stirring, and precursor solution is obtained after uniform mixing. Experiments show that a precursor material with good magnetism can be formed by adding ferric salt and then adding ferrous salt, and if the ferric salt and ferrous salt are exchanged and added sequentially, the prepared material is weak in magnetism.
In some embodiments, the mixing ratio of the ferric salt, the deionized water, the divalent calcium salt, the divalent ferrous salt and the sludge powder is (1-2) mol:50mL: (0.2-1) mol: (0.5 to 1.5) mol:10g. Further, the molar ratio of the trivalent ferric salt to the divalent ferrous salt is 1.5 (0.5-1.0). The inventors found that a precursor material with good magnetic properties can be obtained by conforming the molar ratio of the trivalent iron salt to the divalent iron salt to this ratio range.
S200: and (3) after regulating the pH value of the precursor solution, reacting in a reaction kettle, and obtaining the phosphorus removing agent precursor after the first treatment.
In the step, after the pH value of the precursor solution is regulated, the precursor solution reacts in a reaction kettle, and the phosphorus removing agent precursor is obtained after the first treatment. Through regulating the pH value, ferric iron ions and ferrous iron ions in the solution can quickly form a ferroferric oxide magnetic material, further, sludge in a reaction kettle is gradually converted into a biochar material, and ferroferric oxide crystals and calcium crystals in the solution are gradually grown in a pore canal of the biochar material, so that a phosphorus removing agent precursor is obtained.
In some embodiments, the precursor solution is adjusted to a pH of 9-12, e.g., 9.5, 10, 10.5, 11, 11.5, etc.
In some embodiments, the reaction conditions in the reaction vessel are 150-220 ℃ for 24-48 hours. The inventor finds that the excessive high reaction temperature and the excessive long reaction time can cause the collapse of the framework of the biochar material, and influence the adsorption effect of the dephosphorizing agent on the phosphate; too low temperature and too short reaction time can not lead the sludge to form a framework material of the biochar, and the adsorption effect on the phosphate is greatly reduced.
In some embodiments, the first process comprises: and filtering, washing, neutralizing and drying a reaction product obtained by the reaction in the reaction kettle to obtain a phosphorus removing agent precursor.
S300: and (3) dissolving ferrous salt in deionized water, mixing with the phosphorus removing agent precursor, adding a 2-methylimidazole solution, and performing second treatment to obtain the phosphorus removing agent.
In the step, ferrous salt is dissolved in deionized water and mixed with the dephosphorizing agent precursor, then 2-methylimidazole solution is added, and the dephosphorizing agent is obtained after the second treatment. The inventor finds that the ferrous salt and 2-methylimidazole react to obtain the ZIF, on one hand, the ZIF can regulate and control the pore structure of the material, and phosphate in sewage is physically adsorbed, and on the other hand, ferrous ions can further adsorb phosphate in the water based on the chemical charge adsorption effect, so that the ZIF has the functions of physical and chemical adsorption of phosphate.
In some embodiments, the mixing ratio of the divalent ferrous salt, deionized water, the dephosphorizing agent precursor, and the 2-methylimidazole is (0.01-0.04) mol:20mL: (0.1 to 1.0) g: (0.01 to 0.12) mol. Further, the molar ratio of ferrous salt to 2-methylimidazole is 1 (1-3). The inventor finds that the proportion of ferrous salt and 2-methylimidazole is too high, so that the aperture of the ZIF material is too dense, the regulation and control of the pore channel structure of the ZIF material are not facilitated, in addition, the proportion is too high, the residual amount of the 2-methylimidazole is increased, and a powdery material is difficult to form in the drying stage; too low a ratio, insufficient ferrous ions are in solution, which results in reduced ZIF material yield and increased production costs.
In some embodiments, the second process comprises: and (3) dissolving ferrous salt in deionized water, and then dispersing, cleaning, solid-liquid separating and drying the mixture mixed with the phosphorus removing agent precursor to obtain the phosphorus removing agent.
In a second aspect of the invention, the invention provides a dephosphorizing agent. According to the embodiment of the invention, the dephosphorizing agent is prepared by adopting the method. The dephosphorizing agent takes sludge as a carrier, and ferroferric oxide, calcium oxide and ZIF are loaded on the carrier. The sludge is used as a carrier, so that the sludge can be recycled, the loaded ferroferric oxide has good magnetism, the rapid separation of the dephosphorizing agent can be realized in the recovery process of the dephosphorizing agent, the calcium oxide is used as a main dephosphorizing component, the phosphorus-containing component can be efficiently adsorbed, in addition, the ferrous salt and the 2-methylimidazole react to obtain the ZIF, on one hand, the ZIF can regulate and control the pore structure of the material, and on the other hand, the ferrous ion can further adsorb phosphate in water based on the chemical charge adsorption effect through the physical adsorption of phosphate in sewage, so that the ZIF has the functions of physical and chemical adsorption of phosphate. In summary, the dephosphorizing agent of the invention has the following advantages: (1) The phosphorus removal agent prepared by sludge recycling has high adsorption capacity to phosphorus-containing components in sewage, the highest adsorption capacity can reach 89.25mg P/g, and the sewage discharge standard requirement that the total phosphorus content is less than 0.5mg/L can be met; (2) The water-based magnetic particle has paramagnetism, can be rapidly separated from water under the magnetic field condition, and is easy to recycle.
It should be noted that the features and advantages described above for the method for preparing the dephosphorizing agent are equally applicable to the dephosphorizing agent, and are not described here again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
The term "molar concentration" as used herein refers to the ratio of the mass of the substance to be administered to the molecular weight of the substance.
Example 1
(1) Dissolving 1.5moL of FeCl3 in 50mL of deionized water, adding 0.1moL of CaCl2 after complete dissolution, continuously stirring the solution, adding 1.0moL of FeSO4 again, fully dissolving, adding 10g of dried sludge powder, and continuously stirring for 1.0h;
(2) Regulating the pH value of the solution to 10.0 by using 10mol/L NaOH solution, continuously stirring for 4 hours, pouring the mixed solution into a 100mL hydrothermal reaction kettle, reacting for 24 hours at 180 ℃, filtering out solid substances after the reaction is finished, washing the solid substances with deionized water to be neutral, and drying to obtain a dephosphorization agent precursor;
(3) Dissolving 0.01mol of FeSO4 in 20mL of deionized water, adding 1.0g of a dephosphorizing agent precursor after complete dissolution, stirring for 10min, adding 20mL of 2-methylimidazole aqueous solution dissolved with 0.01mol, continuing stirring for 10min, performing ultrasonic dispersion for 120min under 4000Hz, continuing stirring for 24h, centrifuging under 4000r/min to obtain a solid substance, washing with deionized water, centrifuging for three times, and drying to obtain the dephosphorizing agent.
The VSM characterization result of the phosphorus removal agent obtained in example 1 is shown in fig. 1, and the XPS characterization result is shown in fig. 2, wherein fig. 2A shows the existence form of Ca element in the phosphorus removal agent, fig. 2B shows the existence form of Fe element in the phosphorus removal agent, and fig. 2C shows the change before and after the adsorption of P element in the phosphorus removal agent. According to fig. 1 and 2, it can be seen that the phosphorus removal agent prepared in example 1 has good magnetism, and meanwhile, fe and Ca elements are successfully loaded on the surface of the phosphorus removal agent, and the increase of the peak intensity of P element before and after adsorption shows that the phosphorus removal agent has an obvious adsorption effect on phosphate.
Example 2
0.02mol of CaCl2 was added, with the other conditions being as in example 1.
Example 3
0.04mol of CaCl2 was added, with the other conditions being as in example 1.
Example 4
0.06mol of CaCl2 was added, with the other conditions as in example 1.
Example 5
0.08mol of CaCl2 was added, with the other conditions being as in example 1.
XRD characterization results of the dephosphorizing agents obtained in examples 1-5 are shown in FIG. 3, and the results show that Ca element is successfully loaded on the surface of the dephosphorizing agent in the form of CaO, and meanwhile, the peak intensity of CaO in the dephosphorizing agent gradually increases along with the increase of Ca concentration, which shows that the increase of Ca element concentration changes the crystal state of CaO compound on the surface of the dephosphorizing agent.
Example 6
20mL of an aqueous solution of 2-methylimidazole dissolved in 0.02mol was added thereto, and the conditions were the same as in example 1.
Example 7
20mL of an aqueous solution of 2-methylimidazole dissolved in 0.03mol was added thereto, and the conditions were the same as in example 1.
The characterization results obtained in example 1 and examples 6-7 are shown as a 4-phosphorus removal agent Ca0.1, and relatively obvious ZIF absorption peaks appear at 7 degrees, 12 degrees and 18 degrees, so that the ZIF material is proved to exist, and the intensity of the absorption peak is enhanced to a certain extent along with the increase of the concentration of the 2-methylimidazole solution.
Experimental example 1
And (3) preparing a phosphorus removal agent application test by sludge recycling of a sewage treatment facility in a village in the Panjin city. The test is applied to the industrial application of preparing the dephosphorization agent by utilizing sludge resources developed by sewage treatment facilities in villages and towns in the Panjin city, and in the application process, the dephosphorization agent is added to an inlet pipeline of the sewage treatment facilities, wherein the adding amount of the dephosphorization agent is 0.1g/L. The total phosphorus content of the sewage before the application of the phosphorus removing agent is 3.0-4.0 mg/L. One year of field application proves that the treatment index of the phosphate in the sewage by the dephosphorizing agent is better than the technical index before the dephosphorizing agent is not added, and fig. 5-6 show the performance test results of the dephosphorizing agent obtained in examples 1-7.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (9)

1. A method of preparing a phosphorous removal agent, the method comprising:
(1) Dissolving ferric salt in deionized water, sequentially adding divalent calcium salt and first divalent ferrous salt, uniformly stirring, adding sludge powder, and uniformly mixing to obtain a precursor solution;
(2) After regulating the pH value of the precursor solution, reacting in a reaction kettle, and obtaining a dephosphorizing agent precursor after first treatment;
(3) Dissolving second ferrous ferrite in deionized water, mixing with the phosphorus removing agent precursor, adding a 2-methylimidazole solution, and performing second treatment to obtain a phosphorus removing agent;
in the step (3), the mixing ratio of the second ferrous ferrite, deionized water, the dephosphorizing agent precursor and the 2-methylimidazole is (0.01-0.04) mol:20mL: (0.1 to 1.0) g: (0.01 to 0.12) mol.
2. The method of claim 1, wherein in the step (1), the mixing ratio of the trivalent iron salt, deionized water, divalent calcium salt, first divalent ferrous salt, sludge powder is (1-2) mol:50mL: (0.2-1) mol: (0.5 to 1.5) mol:10g.
3. The method according to claim 2, characterized in that the molar ratio of the trivalent iron salt to the first divalent ferrous salt is 1.5 (0.5-1.0).
4. The method according to claim 1, wherein in step (2), the pH is adjusted to 9 to 12.
5. A method according to claim 1 or 3, wherein in step (2), the reaction conditions in the reaction vessel are 150 to 220 ℃ for 24 to 48 hours.
6. A method according to claim 1 or 3, wherein in step (2), the first treatment comprises: and filtering, washing and drying a reaction product obtained by the reaction in the reaction kettle to obtain a dephosphorization agent precursor.
7. The method according to claim 1, wherein the molar ratio of the second ferrous salt to the 2-methylimidazole is 1 (1-3).
8. The method of claim 1, wherein in step (3), the second processing comprises: and dissolving the second ferrous ferrite in deionized water, dispersing, cleaning, performing solid-liquid separation and drying a mixture of the second ferrous ferrite and the phosphorus removing agent precursor, and obtaining the phosphorus removing agent.
9. A dephosphorizing agent, characterized in that the dephosphorizing agent is prepared by the method of any one of claims 1-8.
CN202311764009.5A 2023-12-21 2023-12-21 Dephosphorization agent and preparation method thereof Active CN117427616B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311764009.5A CN117427616B (en) 2023-12-21 2023-12-21 Dephosphorization agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311764009.5A CN117427616B (en) 2023-12-21 2023-12-21 Dephosphorization agent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN117427616A CN117427616A (en) 2024-01-23
CN117427616B true CN117427616B (en) 2024-03-01

Family

ID=89558663

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311764009.5A Active CN117427616B (en) 2023-12-21 2023-12-21 Dephosphorization agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117427616B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797798A (en) * 2022-04-14 2022-07-29 中国科学院青岛生物能源与过程研究所 Preparation method and application of MOF/corn straw composite material and device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797798A (en) * 2022-04-14 2022-07-29 中国科学院青岛生物能源与过程研究所 Preparation method and application of MOF/corn straw composite material and device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Phosphate Removal by Ca-Modified Magnetic Sludge Biochar Prepared by a One-Step Hydrothermal Method;Xu Liu etal.;《catalysts》;20230524;第13卷;927(1-15) *
磁性 ZIF-67 复合吸附剂对阴离子污染物的吸附特性与作用机制;薛英浩;《中国优秀硕士学位论文全文数据库》;20220415;第1-81页 *

Also Published As

Publication number Publication date
CN117427616A (en) 2024-01-23

Similar Documents

Publication Publication Date Title
CN105417767A (en) Method for removing arsenic from sulfate acidic wastewater
KR101438713B1 (en) water treatment agent for separating hexavalent chromium from wastewater, and method for treating wastewater using the same
CN105567976B (en) A kind of vanadium extraction industrial acidic wastewater processing and the method for valuable metal synthetical recovery
CN103332810A (en) Treatment method of heavy metals in desulfurization waste water
CN111573806A (en) Deep fluorine removal agent and preparation method and application thereof
CN103950987A (en) Recycling method of pickling sludge
CN102115234A (en) Preparation method of flocculant capable of removing phosphate from red mud
CN111170400A (en) Water quality substrate modifying agent, preparation method thereof and water quality substrate modifying method
CN101503217A (en) Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater
CN101613149A (en) The method of a kind of dephosphorization agent and preparation method thereof and dephosphorization
US20220379283A1 (en) Phosphorus adsorbent
JP2005028281A (en) Composite adsorbent and method for wastewater treatment by using the adsorbent
Okano et al. A simple technology for phosphorus recovery using acid-treated concrete sludge
CN117427616B (en) Dephosphorization agent and preparation method thereof
CN102399047A (en) Dehydration method of calcium-based sludge
Yi et al. Phosphate removal of acid wastewater from high-phosphate hematite pickling process by in-situ self-formed dynamic membrane technology
CN104692787B (en) Solidifying comprehensive recovery method of electroplating sludge ferrite
CN104016567B (en) A kind of mud magnetic dewatering agent and dewatering thereof
KR20170003771A (en) Agent for reducing foul smell and moisture content of sewage or wastewater sludge and manufacturing method thereof
Cheng et al. Optimized Ca-Al-La modified biochar with rapid and efficient phosphate removal performance and excellent pH stability
CN111547777B (en) Method for removing arsenic in contaminated acid by ferroferric oxide/kaolin nanocomposite
CN101956069A (en) Method for reducing and leaching manganese from pyrolusite in sulfuric acid solution by using sludge
WO2013052326A1 (en) Methods for treating metals and metalloids
CN102992460B (en) Production process of composite water purifier polymeric aluminum ferric phosphate sulfate
CN113387525B (en) Curing agent for in-situ remediation of black and odorous water body sediment and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant