CN112221461B - Phosphorus adsorption material and preparation method thereof - Google Patents
Phosphorus adsorption material and preparation method thereof Download PDFInfo
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- CN112221461B CN112221461B CN202011108477.3A CN202011108477A CN112221461B CN 112221461 B CN112221461 B CN 112221461B CN 202011108477 A CN202011108477 A CN 202011108477A CN 112221461 B CN112221461 B CN 112221461B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 69
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000011574 phosphorus Substances 0.000 title claims abstract description 61
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- -1 rare earth salt Chemical class 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 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
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000003463 adsorbent Substances 0.000 claims description 18
- 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 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 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
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 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
- 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
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group 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
- 238000011010 flushing procedure Methods 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
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 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
- 239000007864 aqueous solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 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
- 229910000420 cerium oxide Inorganic materials 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
- 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 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 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
- 150000002505 iron Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000004064 recycling Methods 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
- 238000003786 synthesis reaction Methods 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 20-70% of iron oxide and 30-80% of rare earth oxide by mass percent. The preparation method comprises the following steps: the method comprises the steps of taking a mixed solution of ferric salt and rare earth salt as a raw material, adding an alkali solution for reaction, and carrying out aging, cleaning, separation, drying to constant weight, calcining, crushing and screening on a generated precipitate. 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 method for removing phosphorus from sewage includes chemical precipitation method, electrolytic method, microorganism method, aquatic animal method, physical adsorption method, soil treatment method, membrane technology treatment method, etc. The adsorption method has the advantages of large capacity, low energy consumption, little pollution, quick removal, recycling and the like, and is widely applied to dephosphorization.
The phosphorus adsorption materials in the sewage commonly used at present mainly comprise: activated carbon-loaded transition metal, rare earth metal oxide, biomass metal (hydro) oxide, natural mineral adsorbent, in addition to the above-mentioned several kinds of adsorbents, iron ore, graphene, gel and the like can also be used as the adsorbent for removing phosphorus. In recent years, research has been conducted on the synthesis of adsorption materials by using rare earth elements as raw materials, and the adsorption materials have been attracting more and more attention because of the advantages of large adsorption capacity, wide pH suitability and the like.
However, the above adsorbents have defects which cannot be overcome at present: wherein the influence of the ions in the water on the dephosphorization of the modified activated carbon is remarkable; the adsorption capacity of natural minerals, activated carbon modified materials and biomass is smaller by 10-20mg/g; the change of the pH greatly affects the adsorption capacity of the metal oxide, the optimal pH of the adsorption is 2-6, the adsorption capacity is rapidly 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 low-valence rare earth elements such as trivalent cerium is easy to dissolve out in the application process, so that the material is lost. When rare earth elements with high valence state such as tetravalent cerium are used for preparation, oxidation-reduction reaction is easy to occur with valence-variable metals such as ferrous iron to generate trivalent cerium, so that the stability of the material is poor. Therefore, the development of the phosphorus adsorption material with good adsorption stability, high adsorption quantity and easy production and application has remarkable economic benefit and wide social benefit.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the phosphorus adsorption material which has the advantages of strong stability, wide applicable pH range, large adsorption capacity, good regeneration effect and the like;
the invention further aims to provide a preparation method of the phosphorus adsorption material, which has the advantages of short preparation period and easiness in production and application, and adsorption materials with different particle sizes can be prepared according to the use requirements.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a phosphorus adsorption material consists of 20-70% of iron oxide and 30-80% of rare earth oxide by mass.
Preferably, the iron oxide is ferroferric oxide; the rare earth oxide is cerium oxide, high cerium oxide or lanthanum oxide.
The preparation method of the phosphorus adsorption material comprises the following steps: the method comprises the steps of taking a mixed solution of ferric salt and rare earth salt as a raw material, adding an alkali solution for reaction, and carrying out aging, cleaning, separation, drying to constant weight, calcining, crushing and screening on a generated precipitate.
Preferably, the iron salt is ferrous nitrate, ferrous chloride, ferrous sulfate, ferric chloride, ferric sulfate, or ferric nitrate; the rare earth salt is 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 mol 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; an oxidant is added 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 hours; the drying temperature is 60-95 ℃; calcining for 3-24h at 300-650 ℃. More preferably, the specific operation steps of the preparation method are as follows:
1) Adding ferric salt and rare earth element salt compound into water to prepare solution, and stirring uniformly at room temperature; wherein the molar ratio of the iron to the rare earth element is 1:0.5-2;
2) Adding alkali liquor into the solution under the stirring condition 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 flushing the solid material with clear water until the washing solution is neutral;
5) Drying the washed solid material to constant weight at the temperature of 60-95 ℃;
6) Crushing and screening the dried block material to obtain granular or powdery material;
7) Roasting the crushed and sieved material at 300-650 deg.c for 3-24 hr to obtain the phosphorus adsorbing material.
The phosphorus adsorption 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, high production and application difficulty and the like of the existing adsorbent prepared based on divalent, trivalent ferric salts and rare earth element salts, and the prepared adsorption material has the advantages of high phosphorus adsorption capacity, high adsorption speed, high material stability, good regeneration effect and the like.
(2) The phosphorus adsorption material of the invention is based on the specific adsorption performance of iron oxide and rare earth oxide to phosphorus, adsorbs and fixes phosphate in water through hydroxyl exchange, and can be applied to phosphorus-containing sewage treatment, river treatment or lake treatment. Under neutral condition, the saturated adsorption quantity of phosphorus in water can reach 150mg/g, which is far higher than other adsorption materials.
Detailed Description
Example 1
Ferrous chloride and lanthanum chloride are mixed according to the mole ratio of Fe: dissolving La=1:2 to form an aqueous solution, wherein the concentration of iron ions is 0.5M, and stirring uniformly at room temperature; dropwise adding 4mol/L sodium hydroxide solution into the solution under the stirring condition, and stopping adding alkali when the pH value of the solution is 9.5; 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 the effluent is neutral; drying the washed product to constant weight at 95 ℃, crushing and sieving with a 200-mesh sieve; the obtained powdery product is roasted for 24 hours at 300 ℃ to obtain yellow brown powder, namely the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, when the initial total phosphorus is 13mg/L at the temperature of 25 ℃ and the pH=7, the adsorption equilibrium concentration is 1.2mg/L, and the adsorption quantity of phosphorus is 118 mg/g when the adding quantity of the adsorbent is 0.1 g/L.
Example 2
Ferrous sulfate and lanthanum nitrate are mixed according to the mole ratio of Fe: la=1:1.5, wherein the concentration of iron ions is 0.7M, and stirring is carried out uniformly at room temperature; under the stirring condition, dropwise adding 6mol/L ammonia water into the solution until the pH value of the solution is 7.0, stopping dropwise adding ammonia water, adding hydrogen peroxide into the mixed solution, keeping stirring and aging for 4 hours at the temperature of 55 ℃ under the hydrogen peroxide concentration of 0.35M; centrifugally separating and washing until the pH value of the effluent is neutral; drying the washed product to constant weight at 75 ℃, and roasting the crushed powdery product for 4 hours at 550 ℃ to obtain yellow brown powder, namely the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adsorbent dosage is 0.1g/L, the adsorption equilibrium concentration is 0.8mg/L, and the adsorption quantity of phosphorus is 122mg/g.
Example 3
Ferrous sulfate and ceric sulfate are mixed according to the mole ratio of Fe: dissolving in a ratio of ce=1:1 to form an aqueous solution, wherein the concentration of iron ions is 1M, and stirring uniformly at room temperature; dropwise adding 3mol/L potassium hydroxide solution into the solution under the stirring condition 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 the effluent is neutral; drying the washed product to constant weight at 60 ℃, and roasting the crushed powdery product at 600 ℃ for 3 hours to obtain yellow brown particles which are the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adsorbent dosage is 0.1g/L, the adsorption equilibrium concentration is 4.1mg/L, and the adsorption quantity of phosphorus is 89mg/g.
Example 4
Iron nitrate and cerium nitrate are mixed according to the mole ratio of Fe: dissolving in a ratio of ce=2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring uniformly at room temperature; dropwise adding 4mol/L sodium hydroxide solution into the solution under the stirring condition until the pH value of the solution is 8.5, and stopping adding alkali; ozone is introduced into the mixed solution, the ozone concentration is 1M, and the mixed solution is continuously stirred and aged for 7 hours at the temperature of 50 ℃; centrifugally separating and washing until the pH value of the effluent is neutral; drying the washed product to constant weight at 85 ℃, and roasting the crushed powdery product at 600 ℃ for 12 hours to obtain yellow brown particles which are the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adsorbent dosage is 0.1g/L, the adsorption equilibrium concentration is 3.2mg/L, and the adsorption quantity of phosphorus is 98mg/g.
Comparative example 1
Ferrous nitrate and cerium nitrate are mixed according to the mole ratio of Fe: ce=1: 0.1, wherein the concentration of iron ions is 1M, and stirring uniformly at room temperature; dropwise adding 3mol/L sodium hydroxide solution into the solution under the stirring condition 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 the effluent is neutral; drying the washed product to constant weight at 80 ℃, and roasting the crushed powdery product at 600 ℃ for 3 hours to obtain the yellow brown granular material.
The material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adding amount of the adsorbent is 0.1g/L, the adsorption equilibrium concentration is 10.4mg/L, and the adsorption amount of the adsorbent to phosphorus is 26mg/g.
Comparative example 2
Iron nitrate and cerium nitrate are mixed according to the mole ratio of Fe: dissolving in a ratio of ce=1:3 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring uniformly at room temperature; dropwise adding 4mol/L sodium hydroxide solution into the solution under the stirring condition until the pH value of the solution is 8.5, and stopping adding alkali; ozone is introduced into the mixed solution, the ozone concentration is 1M, and the mixed solution is continuously stirred and aged for 8 hours; centrifugally separating and washing until the pH value of the effluent is neutral; drying the washed product to constant weight at 85 ℃, and roasting the crushed powdery product at 600 ℃ for 3 hours to obtain the yellow brown granular material.
The material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adding amount of the adsorbent is 0.1g/L, the adsorption equilibrium concentration is 9.5mg/L, and the adsorption amount of the adsorbent to phosphorus is 35mg/g.
Comparative example 3
Iron nitrate and cerium nitrate are mixed according to the mole ratio of Fe: dissolving in a ratio of ce=2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring uniformly at room temperature; dropwise adding 4mol/L sodium hydroxide solution into the solution under the stirring condition until the pH value of the solution is 8.5, and stopping adding alkali; ozone is introduced into the mixed solution, the concentration of the ozone is 0.1M, and the mixed solution is continuously stirred and aged for 7 hours at the temperature of 50 ℃; centrifugally separating and washing until the pH value of the effluent is neutral; drying the washed product to constant weight at 85 ℃, and roasting the crushed powdery product at 600 ℃ for 12 hours to obtain yellow brown particles which are the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adsorbent dosage is 0.1g/L, the adsorption equilibrium concentration is 10.2mg/L, and the adsorption quantity of phosphorus is 28mg/g.
Comparative example 4
Iron nitrate and cerium nitrate are mixed according to the mole ratio of Fe: dissolving in a ratio of ce=2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring uniformly at room temperature; dropwise adding 4mol/L sodium hydroxide solution into the solution under the stirring condition until the pH value of the solution is 6, and stopping adding alkali; ozone is introduced into the mixed solution, the ozone concentration is 1M, and the mixed solution is continuously stirred and aged for 7 hours at the temperature of 50 ℃; centrifugally separating and washing until the pH value of the effluent is neutral; drying the washed product to constant weight at 85 ℃, and roasting the crushed powdery product at 600 ℃ for 12 hours to obtain yellow brown particles which are the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adsorbent dosage is 0.1g/L, the adsorption equilibrium concentration is 9.3mg/L, and the adsorption quantity of phosphorus is 37mg/g.
Comparative example 5
Iron nitrate and cerium nitrate are mixed according to the mole ratio of Fe: dissolving in a ratio of ce=2:1 to form an aqueous solution, wherein the concentration of iron ions is 2M, and stirring uniformly at room temperature; dropwise adding 4mol/L sodium hydroxide solution into the solution under the stirring condition until the pH value of the solution is 8.5, and stopping adding alkali; ozone is introduced into the mixed solution, the ozone concentration is 1M, and the mixed solution is continuously stirred and aged for 3 hours at the temperature of 35 ℃; centrifugally separating and washing until the pH value of the effluent is neutral; drying the washed product to constant weight at 85 ℃, and roasting the crushed powdery product at 600 ℃ for 12 hours to obtain yellow brown particles which are the phosphorus adsorption material.
The phosphorus adsorption material is used for removing phosphate in water, and when the temperature is 25 ℃, the pH=7, the initial total phosphorus is 13mg/L, the adsorbent dosage is 0.1g/L, the adsorption equilibrium concentration is 8.9mg/L, and the adsorption quantity of phosphorus is 41mg/g.
Claims (7)
1. The preparation method of the phosphorus adsorption material is characterized by comprising 20-70% of iron oxide and 30-80% of rare earth oxide by mass percent; the iron oxide is ferroferric oxide; the phosphorus adsorption material comprises the following steps: taking a mixed solution of ferric salt and rare earth salt as a raw material, adding an alkali solution for reaction, and generating a precipitate, aging, cleaning, separating, drying to constant weight, calcining, crushing and screening to obtain the rare earth alkaline compound; an oxidant is added in the aging process; wherein: the mol ratio of the ferric salt to the rare earth salt is 1:0.5-2, and an alkali solution is added until the pH value is 7-10, wherein the mol ratio of the ferric salt to the oxidant is 2-5:1, the aging time is 4 h-8h, and the aging temperature is 20-55 ℃; the ferric salt at least contains ferrous salt.
2. The method of claim 1, wherein the rare earth oxide is ceria, or lanthana.
3. The method of claim 1, wherein the ferrous salt is ferrous nitrate, ferrous chloride, or ferrous sulfate; the rare earth salt is 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.
4. The method of claim 1, wherein the oxidizing agent is sodium chlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide, or ozone.
5. The method of claim 1, wherein the drying temperature is 60 ℃ to 95 ℃; calcination is carried out at 300-650 ℃ for 3-h-24 h.
6. The preparation method according to any one of claims 1 to 5, characterized by the specific operation steps of:
1) Adding ferric salt and rare earth element salt compound into water to prepare solution, and stirring uniformly at room temperature; wherein the molar ratio of the iron to the rare earth element is 1:0.5-2;
2) Adding alkali liquor into the solution under the stirring condition 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 flushing the solid material with clear water until the washing solution is neutral;
5) Drying the washed solid material to constant weight at the temperature of 60-95 ℃;
6) Crushing and screening the dried material to obtain granular or powdery material;
7) Roasting the crushed and sieved material at 300-650 deg.c for 3-24 hr to obtain the phosphorus adsorbing material.
7. The use of the phosphorus adsorbent material prepared by the preparation method of any one of claims 1 to 5, characterized in that the phosphorus adsorbent material can be applied to phosphorus-containing sewage treatment, river management or lake management.
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| CN115155542B (en) * | 2022-02-22 | 2023-09-12 | 武汉轻工大学 | Preparation method of dephosphorizing agent and packing column |
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