CN112221461A - Phosphorus adsorption material and preparation method thereof - Google Patents
Phosphorus adsorption material and preparation method thereof Download PDFInfo
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- CN112221461A CN112221461A CN202011108477.3A CN202011108477A CN112221461A CN 112221461 A CN112221461 A CN 112221461A CN 202011108477 A CN202011108477 A CN 202011108477A CN 112221461 A CN112221461 A CN 112221461A
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- phosphorus
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011574 phosphorus Substances 0.000 title claims abstract description 60
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 title abstract description 47
- 230000032683 aging Effects 0.000 claims abstract description 21
- -1 rare earth salt Chemical class 0.000 claims abstract description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 150000002505 iron Chemical class 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000010865 sewage Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000003463 adsorbent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 3
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
- B01J20/02—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
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the field of environment-friendly materials, and particularly relates to a phosphorus adsorption material and a preparation method thereof. The phosphorus adsorption material consists of iron oxide and rare earth oxide, wherein the mass percentage of the iron oxide is 20-70%, and the mass percentage of the rare earth oxide is 30-80%. The preparation method comprises the following steps: the mixed solution of iron salt and rare earth salt is used as a raw material, alkaline solution is added for reaction, and the generated precipitate is prepared by aging, cleaning, separating, drying to constant weight, calcining, crushing and screening. The phosphorus adsorption material has the advantages of strong stability, wide applicable pH range, large adsorption capacity, good regeneration effect and the like; can be applied to phosphorus-containing sewage treatment, river treatment or lake treatment.
Description
Technical Field
The invention belongs to the field of environment-friendly materials, and particularly relates to a phosphorus adsorption material and a preparation method thereof.
Background
The sewage dephosphorization method comprises a chemical precipitation method, an electrolysis method, a microbiological method, a hydrobiological method, a physical adsorption method, a soil treatment method, a membrane technology treatment method and the like. The adsorption method has the advantages of large capacity, low energy consumption, low pollution, quick removal, recyclability and the like, and is widely applied to the aspect of dephosphorization.
The phosphorus adsorption material in the sewage commonly used at present mainly comprises: the activated carbon loaded transition metal, rare earth metal oxide, biomass metal (hydrogen) oxide and natural mineral adsorbent, except the above adsorbents, iron ore, graphene, gel and the like can also be used as the phosphorus removal adsorbent. In recent years, research on synthesizing the adsorbing material by using rare earth elements as raw materials has attracted more and more attention due to the advantages of large adsorption capacity, wide suitable pH range and the like.
However, the above adsorbents have the defects which cannot be overcome at present: wherein ions in water have obvious influence on the phosphorus removal of the modified activated carbon; the adsorption capacity of natural minerals, active carbon modified materials and biomass is smaller by 10-20 mg/g; the change of pH has great influence on the adsorption capacity of the metal oxide, the optimum pH of the adsorption is 2-6, the adsorption capacity is sharply reduced when the pH exceeds 7, and the regeneration effect is poor, so that the metal oxide is difficult to recycle; the composite material prepared by using the rare earth element with a low valence state such as trivalent cerium is easy to dissolve out in the application process, so that the material loss is caused. When the high-valence rare earth element such as tetravalent cerium is used for preparation, the rare earth element is easy to generate oxidation reduction reaction with valence-variable metal such as ferrous to generate trivalent cerium, so that the stability of the material is poor. Therefore, the development of the phosphorus adsorption material which has good adsorption stability, high adsorption quantity and easy production and application has obvious economic benefit and wide social benefit.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the phosphorus adsorbing material which has the advantages of strong stability, wide applicable pH range, large adsorption capacity, good regeneration effect and the like;
the invention also aims to provide a preparation method of the phosphorus adsorbing material, which has the advantages of short preparation period and easy production and application, and can prepare adsorbing materials with different particle sizes according to use requirements.
In order to realize the purpose, the invention adopts the following technical scheme:
the phosphorus adsorbing material consists of iron oxide and RE oxide, and the iron oxide accounts for 20-70 wt% and the RE oxide accounts for 30-80 wt%.
Preferably, the iron oxide is ferroferric oxide; the rare earth oxide is cerium oxide, cerium oxide or lanthanum oxide.
The preparation method of the phosphorus adsorption material comprises the following steps: the mixed solution of iron salt and rare earth salt is used as a raw material, alkaline solution is added for reaction, and the generated precipitate is prepared by aging, cleaning, separating, drying to constant weight, calcining, crushing and screening.
Preferably, the iron salt is ferrous nitrate, ferrous chloride, ferrous sulfate, ferric chloride, ferric sulfate or ferric nitrate; the rare earth salts are cerium chloride, cerium sulfate, ceric sulfate, cerium nitrate, lanthanum chloride, lanthanum nitrate or lanthanum sulfate; the alkali solution is sodium hydroxide solution, potassium hydroxide solution or ammonia water.
Preferably, the molar ratio of the ferric salt to the rare earth salt is 1: 0.5-2; adding an alkali solution to a pH of 7-10; adding an oxidant in the aging process; wherein the molar ratio of the ferric salt to the oxidant is 2-5: 1.
Preferably, the oxidizing agent is sodium chlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide, or ozone.
Preferably, the aging time is 4 h-8 h; the drying temperature is 60-95 ℃; the calcination is carried out for 3 to 24 hours at the lower stage of 300 to 650 ℃. More preferably, the preparation method comprises the following specific operation steps:
1) adding iron salt and rare earth element salt compounds into water to prepare a solution, and uniformly stirring at room temperature; wherein the molar ratio of the iron to the rare earth elements is 1: 0.5-2;
2) adding alkali liquor into the solution under the condition of stirring until the pH value of the solution is 8.5-10;
3) adding an oxidant into the mixed solution prepared in the step 2), and stirring and aging for 4-8 h at the temperature of 20-55 ℃;
4) after the aging is finished, separating the obtained solid material from the mixed solution, and washing the solid material with clear water until the washing solution is neutral;
5) drying the washed solid material at 60-95 ℃ to constant weight;
6) crushing and screening the dried blocky material to obtain a granular or powdery material;
7) and roasting the crushed and sieved material at 300-650 ℃ for 3-24h to obtain the phosphorus adsorbing material.
The phosphorus adsorbing material can be applied to phosphorus-containing sewage treatment, river treatment or lake treatment.
Advantageous effects
(1) The invention solves the problems of poor stability, lower adsorption capacity, large production and application difficulty and the like of the traditional adsorbent prepared based on ferrous and ferric salts and rare earth element salts, and the prepared adsorption material has the advantages of large phosphorus adsorption capacity, high adsorption speed, strong material stability, good regeneration effect and the like.
(2) The phosphorus adsorption material is based on the specific adsorption performance of iron oxide and rare earth oxide on phosphorus, adsorbs and fixes phosphate in water through hydroxyl exchange effect, and can be applied to phosphorus-containing sewage treatment, river treatment or lake treatment. Under the neutral condition, the saturated adsorption capacity of the adsorbent to phosphorus in water can reach 150mg/g, which is far higher than that of other adsorbent materials.
Detailed Description
Example 1
Ferrous chloride and lanthanum chloride are mixed according to the mol ratio of Fe: dissolving La =1:2 to form an aqueous solution, wherein the concentration of iron ions is 0.5M, and stirring the solution uniformly at room temperature; under the condition of stirring, dropwise adding 4mol/L sodium hydroxide solution into the solution until the pH value of the solution is 9.5, and stopping adding alkali; adding sodium chlorate with the concentration of 0.15M into the mixed solution, and continuously stirring and aging for 8 hours at the temperature of 20 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 95 ℃ to constant weight, crushing and sieving with a 200-mesh sieve; the obtained powdery product is roasted for 24 hours at the temperature of 300 ℃, and then the tawny powder which is the phosphorus adsorption material is obtained.
The phosphorus adsorbing material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 1.2mg/L and an adsorption amount of 118 mg/g when the initial total phosphorus is 13mg/L and the addition amount of an adsorbent is 0.1g/L under the conditions that the temperature is 25 ℃ and the pH = 7.
Example 2
Ferrous sulfate and lanthanum nitrate are mixed according to the mol ratio of Fe: dissolving La =1:1.5 to form an aqueous solution, wherein the concentration of iron ions is 0.7M, and uniformly stirring at room temperature; under the condition of stirring, dropwise adding 6mol/L ammonia water into the solution until the pH value of the solution is 7.0, stopping dropwise adding the ammonia water, adding hydrogen peroxide into the mixed solution, wherein the concentration of the hydrogen peroxide is 0.35M, and continuously stirring and aging for 4 hours at the temperature of 55 ℃; centrifugally separating and washing until the pH value of effluent is neutral; and drying the washed product at 75 ℃ to constant weight, and roasting the crushed powder product at 550 ℃ for 4 hours to obtain brown powder, namely the phosphorus adsorbing material.
The phosphorus adsorbing material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 0.8mg/L and an adsorption amount of 122mg/g for phosphorus when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the adding amount of an adsorbent is 0.1 g/L.
Example 3
Ferrous sulfate and ceric sulfate are mixed according to the mol ratio of Fe: dissolving Ce =1:1 to form an aqueous solution, wherein the concentration of iron ions is 1M, and stirring the aqueous solution uniformly at room temperature; under the condition of stirring, dropwise adding 3mol/L potassium hydroxide solution into the solution until the pH value of the solution is 10.0, and stopping dropwise adding potassium hydroxide; adding potassium permanganate into the mixed solution, wherein the concentration of the potassium permanganate is 0.2M, and continuously stirring and aging for 6 hours at the temperature of 45 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 60 ℃ to constant weight, and roasting the crushed powder product at 600 ℃ for 3 hours to obtain yellow brown particles, namely the phosphorus adsorbing material.
The phosphorus adsorbing material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 4.1mg/L and an adsorption amount of 89mg/g when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the adding amount of an adsorbent is 0.1 g/L.
Example 4
Mixing ferric nitrate and cerous nitrate according to a molar ratio of Fe: dissolving Ce =2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring the aqueous solution uniformly at room temperature; under the condition of stirring, 4mol/L sodium hydroxide solution is dripped into the solution until the pH value of the solution is 8.5, and then the alkali addition is stopped; introducing ozone into the mixed solution, wherein the concentration of the ozone is 1M, and continuously stirring and aging for 7 hours at the temperature of 50 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 85 ℃ to constant weight, and roasting the crushed powder product at 600 ℃ for 12 hours to obtain yellow brown particles, namely the phosphorus adsorbing material.
The phosphorus adsorption material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 3.2mg/L and an adsorption amount of 98mg/g for phosphorus when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the addition amount of an adsorbent is 0.1 g/L.
Comparative example 1
Ferrous nitrate and cerous nitrate are mixed according to the mol ratio of Fe: ce =1: dissolving at a ratio of 0.1 to form an aqueous solution, wherein the concentration of iron ions is 1M, and uniformly stirring at room temperature; under the condition of stirring, dropwise adding 3mol/L sodium hydroxide solution into the solution until the pH value of the solution is 10.0, and stopping dropwise adding sodium hydroxide; adding sodium chlorate with the concentration of 0.3M into the mixed solution, and continuously stirring and aging for 6 hours at the temperature of 45 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 80 ℃ to constant weight, crushing to obtain a powdery product, and roasting at 600 ℃ for 3 hours to obtain the tawny granular material.
The material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the adding amount of an adsorbent is 0.1g/L, the adsorption equilibrium concentration is 10.4mg/L and the adsorption amount to phosphorus is 26 mg/g.
Comparative example 2
Mixing ferric nitrate and cerous nitrate according to a molar ratio of Fe: dissolving Ce =1:3 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring the aqueous solution uniformly at room temperature; under the condition of stirring, 4mol/L sodium hydroxide solution is dripped into the solution until the pH value of the solution is 8.5, and then the alkali addition is stopped; introducing ozone into the mixed solution, wherein the concentration of the ozone is 1M, and continuously stirring and aging for 8 hours; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 85 ℃ to constant weight, crushing to obtain a powdery product, and roasting at 600 ℃ for 3 hours to obtain the tawny granular material.
The material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the adding amount of an adsorbent is 0.1g/L, the adsorption equilibrium concentration is 9.5mg/L and the adsorption amount to phosphorus is 35 mg/g.
Comparative example 3
Mixing ferric nitrate and cerous nitrate according to a molar ratio of Fe: dissolving Ce =2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring the aqueous solution uniformly at room temperature; under the condition of stirring, 4mol/L sodium hydroxide solution is dripped into the solution until the pH value of the solution is 8.5, and then the alkali addition is stopped; introducing ozone into the mixed solution, wherein the concentration of the ozone is 0.1M, and continuously stirring and aging for 7 hours at the temperature of 50 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 85 ℃ to constant weight, and roasting the crushed powder product at 600 ℃ for 12 hours to obtain yellow brown particles, namely the phosphorus adsorbing material.
The phosphorus adsorbing material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 10.2mg/L and an adsorption amount of 28mg/g for phosphorus when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the adding amount of an adsorbent is 0.1 g/L.
Comparative example 4
Mixing ferric nitrate and cerous nitrate according to a molar ratio of Fe: dissolving Ce =2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring the aqueous solution uniformly at room temperature; under the condition of stirring, dropwise adding 4mol/L sodium hydroxide solution into the solution until the pH value of the solution is 6, and stopping adding alkali; introducing ozone into the mixed solution, wherein the concentration of the ozone is 1M, and continuously stirring and aging for 7 hours at the temperature of 50 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 85 ℃ to constant weight, and roasting the crushed powder product at 600 ℃ for 12 hours to obtain yellow brown particles, namely the phosphorus adsorbing material.
The phosphorus adsorbing material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 9.3mg/L and an adsorption amount of 37mg/g for phosphorus when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the adding amount of an adsorbent is 0.1 g/L.
Comparative example 5
Mixing ferric nitrate and cerous nitrate according to a molar ratio of Fe: dissolving Ce =2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring the aqueous solution uniformly at room temperature; under the condition of stirring, 4mol/L sodium hydroxide solution is dripped into the solution until the pH value of the solution is 8.5, and then the alkali addition is stopped; introducing ozone into the mixed solution, wherein the concentration of the ozone is 1M, and continuously stirring and aging for 3 hours at the temperature of 35 ℃; centrifugally separating and washing until the pH value of effluent is neutral; drying the washed product at 85 ℃ to constant weight, and roasting the crushed powder product at 600 ℃ for 12 hours to obtain yellow brown particles, namely the phosphorus adsorbing material.
The phosphorus adsorbing material is used for removing phosphate in water, and has an adsorption equilibrium concentration of 8.9mg/L and an adsorption amount of 41mg/g for phosphorus when the temperature is 25 ℃, the pH =7 and the initial total phosphorus is 13mg/L and the addition amount of an adsorbent is 0.1 g/L.
Claims (9)
1. The phosphorus adsorbing material is characterized by comprising 20-70% of iron oxide and 30-80% of rare earth oxide by mass.
2. The phosphorus sorbent of claim 1, wherein the iron oxide is ferroferric oxide; the rare earth oxide is cerium oxide, cerium oxide or lanthanum oxide.
3. A method for preparing a phosphorus adsorbent material according to claim 1 or 2, characterized in that the following steps are used: the mixed solution of iron salt and rare earth salt is used as a raw material, alkaline solution is added for reaction, and the generated precipitate is prepared by aging, cleaning, separating, drying to constant weight, calcining, crushing and screening.
4. The method according to claim 3, wherein the iron salt is ferrous nitrate, ferrous chloride, ferrous sulfate, ferric chloride, ferric sulfate, or ferric nitrate; the rare earth salts are cerium chloride, cerium sulfate, ceric sulfate, cerium nitrate, lanthanum chloride, lanthanum nitrate or lanthanum sulfate; the alkali solution is sodium hydroxide solution, potassium hydroxide solution or ammonia water.
5. The preparation method according to claim 3, wherein the molar ratio of the iron salt to the rare earth salt is 1: 0.5-2; adding an alkali solution to a pH of 7-10; adding an oxidant in the aging process; wherein the molar ratio of the ferric salt to the oxidant is 2-5: 1.
6. The method of claim 5, wherein the oxidizing agent is sodium chlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide, or ozone.
7. The method according to claim 3, wherein the aging time is 4 to 8 hours, and the aging temperature is 20 to 55 ℃; the drying temperature is 60-95 ℃; the calcination is carried out for 3 to 24 hours at the lower stage of 300 to 650 ℃.
8. The preparation method according to any one of claims 3 to 7, characterized by comprising the following specific steps:
1) adding iron salt and rare earth element salt compounds into water to prepare a solution, and uniformly stirring at room temperature; wherein the molar ratio of the iron to the rare earth elements is 1: 0.5-2;
2) adding alkali liquor into the solution under the condition of stirring until the pH value of the solution is 7-10;
3) adding an oxidant into the mixed solution prepared in the step 2), keeping the temperature at 20-55 ℃, and stirring and aging for 4-8 h;
4) after the aging is finished, separating the obtained solid material from the mixed solution, and washing the solid material with clear water until the washing solution is neutral;
5) drying the washed solid material at 60-95 ℃ to constant weight;
6) crushing and screening the dried material to obtain a granular or powdery material;
7) and roasting the crushed and sieved material at 300-650 ℃ for 3-24h to obtain the phosphorus adsorbing material.
9. Use of the phosphorus adsorbent material according to claim 1 or 2, wherein the phosphorus adsorbent material is used in phosphorus-containing sewage treatment, river treatment or lake treatment.
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