CN115318243A - Magnetic phosphorus removal particle adsorption material and preparation method and application thereof - Google Patents
Magnetic phosphorus removal particle adsorption material and preparation method and application thereof Download PDFInfo
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- CN115318243A CN115318243A CN202211015711.7A CN202211015711A CN115318243A CN 115318243 A CN115318243 A CN 115318243A CN 202211015711 A CN202211015711 A CN 202211015711A CN 115318243 A CN115318243 A CN 115318243A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/14—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic in rotating dishes or pans
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention provides a preparation method of a magnetic phosphorus removal particle adsorption material, wherein the raw materials of the material comprise natural clay, calcium hydroxide and ferroferric oxide, and the three materials are mixed according to a certain proportion and granulated by a disc granulator to obtain the magnetic phosphorus removal particle adsorption material. The material has strong phosphorus adsorption capacity and magnetism to water, has good magnetic separation effect, and is convenient for removing water ecosystem after phosphorus adsorption saturation. The material is slightly influenced by the pH value, and can be used for removing phosphorus from natural water bodies, black and odorous water bodies and urban sewage. The preparation method is simple, and the prepared magnetic phosphorus removal particle adsorbing material is wide in raw material source, low in cost, good in phosphorus removal effect, easy to recover, high in recovery rate, environment-friendly and free of secondary pollution.
Description
Technical Field
The invention belongs to the field of water pollution treatment, relates to a eutrophic water body treatment material, and a preparation method and application thereof, and particularly relates to a magnetic phosphorus removal particle adsorption material, and a preparation method and application thereof.
Background
Under the combined influence of human activities and climate change, lake eutrophication and algal bloom remain water ecological environmental problems for a long time in the future. Therefore, the research, development and application of water eutrophication treatment and algae bloom prevention and control technology are indispensable. Phosphorus is a main limiting factor in an aquatic ecosystem, is a key factor for driving algal bloom outbreak, and reducing the phosphorus load of a water body is an important method for treating water eutrophication and is also a conventional means for preventing and controlling algal bloom.
The adsorption method has the advantages of high efficiency, economy, simplicity, convenience, practicability and the like, and is widely applied to the phosphorus treatment of the eutrophic water body. The traditional phosphorus removal adsorption material is mainly metal salts such as aluminum, iron, calcium and the like, and metal cations can be combined with phosphate radicals in a water body to form a precipitate, so that active phosphorus in the water body or sediment is converted into insoluble inert phosphorus. In addition, the iron salt and the aluminum salt have strong flocculation, and the organic phosphorus or granular phosphorus in the water body is flocculated and settled to the bottom of the lake through the flocculation, so that the total phosphorus content of the water body is reduced. Although the adsorption or flocculation material prepared based on metal salts such as aluminum, iron, calcium and the like can effectively reduce the phosphorus content in the water body, the phosphorus is only temporarily sealed in the sediment in a more stable form, the phosphorus is not completely removed from a water ecosystem, and the phosphorus in the stable form has the risk of being released under the appropriate conditions; and the adsorbing material loses the adsorption effect after the phosphorus adsorption is saturated, and the long-term retention in the sediment has the possibility of secondary pollution. Therefore, the efficient phosphorus removal material which is low in cost, high in ecological safety, capable of being removed from a water ecosystem after being saturated in adsorption and capable of thoroughly reducing phosphorus load of water and sediment is urgently required to be prepared.
At present, relatively well-known phosphorus removal adsorption materials at home and abroad are based on rare element lanthanum modified clay minerals, such as widely-applied phosphorus locking agents
The university of science and technology in China invented a lanthanum modified magnetic bentonite phosphorus removal material (CN 110548490B), although the material has a good effect of removing phosphorus in a water body under a proper condition and is easy to recover. But the material is greatly influenced by the pH value, and the phosphorus removal effect is obviously reduced under the acidic condition. In addition, as a rare metal element, the ecological risk is high, and the price of lanthanum is increasing year by year and the like, which are key factors limiting the large-scale use of lanthanum. The calcium hydroxide is widely used for cleaning ponds of aquaculture water bodies, has small influence on water ecology, is low in price, can be combined with active phosphorus of the water bodies to form apatite sediment, and is widely applied to dephosphorization of various water bodies. Research shows that the calcium hydroxide modified zeolite is less influenced by pH value and can react with phosphorus under both acid-base and alkaline conditions. Therefore, the calcium-based magnetic flocculant has wider application prospect.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a magnetic phosphorus removal particle adsorption material which is low in cost, high in ecological safety and capable of removing the adsorption material after saturated adsorption out of a water ecosystem through a magnetic separation technology and a preparation method thereof.
The invention also aims to provide a calcium hydroxide modified clay-supported ferroferric oxide magnetic phosphorus removal adsorbing material.
The invention also provides a eutrophic water body dephosphorization treatment method.
In order to achieve the aim, the invention provides a magnetic phosphorus removal particle adsorption material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Grinding natural clay, ferroferric oxide and calcium hydroxide, and sieving with a 300-mesh sieve;
(2) Taking 6-8 parts of natural clay, 1-2 parts of ferroferric oxide and 1-2 parts of calcium hydroxide powder, and rapidly stirring the three materials in a disc granulator at the speed of 1200r/s for 2min to fully mix the materials;
(3) After fully mixing, adding a proper amount of water, regulating the speed of a disc granulator to 1200r/s, and granulating by utilizing a turbulent flow mixing principle to obtain a magnetic phosphorus removal adsorbing material; the granulation process is simple to operate, and the required granules can be prepared quickly and efficiently in a short time;
(4) And drying and sieving the magnetic phosphorus removal adsorbing material obtained by granulation to obtain the magnetic phosphorus removal granular adsorbing material with different grain sizes within the range of 1-5 mm.
Preferably, the natural clays include, but are not limited to: one or more of zeolite, attapulgite, bentonite, sepiolite and the like are mixed according to any proportion.
Preferably, the raw materials comprise the following components in parts by weight: 1 part of calcium hydroxide, 1 part of ferroferric oxide and 8 parts of zeolite; or the raw materials comprise the following components in parts by weight: 1 part of calcium hydroxide, 1 part of ferroferric oxide and 8 parts of attapulgite; or the raw materials comprise the following components in parts by weight: 1 part of calcium hydroxide, 1 part of ferroferric oxide and 8 parts of bentonite. Preferably, the prepared magnetic phosphorus removal particle adsorbing material has both magnetism and high-efficiency phosphorus adsorption capacity.
Preferably, the calcium hydroxide, the ferroferric oxide and the zeolite are mixed according to a specific ratio and granulated.
Preferably, the mixture is dried at 45 to 65 ℃ after granulation.
Preferably, the prepared magnetic phosphorus removal particle adsorbing material has both magnetism and high-efficiency phosphorus adsorption capacity.
Preferably, the prepared magnetic phosphorus removal particle adsorption material can be used for recovering the material through a magnetic separation technology after being adsorbed and saturated in the eutrophic water body so as to prevent secondary pollution of the material.
Preferably, the prepared magnetic phosphorus removal particle adsorption material has good phosphorus removal capability in a wide range of pH 3-11 of a water body.
Preferably, the prepared magnetic phosphorus removal particle adsorption material is applied to the field of water phosphorus removal.
The invention takes natural clay, hydrated lime (calcium hydroxide) and ferroferric oxide which are abundant in reserves and low in price in China as raw materials, has simple preparation process, does not relate to liquid phase precipitation/reduction, has low cost, and the prepared magnetic phosphorus removal adsorbing material has strong magnetism and is easy to recover, thereby effectively avoiding the problem of secondary pollution caused by the retention of the adsorbing material in sediments.
The magnetic phosphorus removal particle adsorption material and the preparation method thereof have the beneficial effects that the preparation method is simple in process, and the prepared magnetic phosphorus removal particle adsorption material is strong in magnetism, extremely strong in adsorption performance on eutrophic water phosphorus, easy to recover and environment-friendly.
Drawings
FIG. 1 is a diagram showing the magnetic phosphorus removal adsorption material and the magnetic effect prepared by the present invention;
FIG. 2 is a graph showing the relationship between the addition of the magnetic phosphorus removal adsorbent and the phosphorus removal rate;
FIG. 3 is a graph showing the relationship between the magnetic phosphorus removal adsorption material and the phosphorus removal rate under different pH conditions.
Detailed Description
The experimental methods used in the following examples are conventional unless otherwise specified.
The materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Embodiment 1 preparation of magnetic phosphorus removal adsorbing material
The zeolite, the calcium hydroxide and the ferroferric oxide are crushed and sieved by a 300-mesh sieve. Weighing 4kg of 300-mesh zeolite, 0.5kg of 300-mesh calcium hydroxide and 0.5kg of 300-mesh ferroferric oxide, adding the weighed materials into a disc granulator, and rapidly stirring for 2min at the speed of 1200rpm to fully mix the materials. After mixing, adding 1.5L of water, regulating the rotation speed of a rotor to 1200rpm, regulating the rotation speed of a granulating disc to 50rpm, operating for 2min to obtain the magnetic phosphorus removal adsorbing material, drying the prepared magnetic phosphorus removal adsorbing material in a constant-temperature air-blast drying oven at 65 ℃ for 48h, screening the magnetic phosphorus removal adsorbing material with the particle size of 2-3mm, and filling the magnetic phosphorus removal adsorbing material into a plastic bottle for sealing for later use.
Example 2 adsorption removal effect and recovery situation of magnetic phosphorus removal adsorption material on phosphorus in water body
The solution with the phosphorus concentration of 5mg/L is prepared by adopting monopotassium phosphate, and the pH value is adjusted to 7 by adopting 0.1mol/L HCl solution and 0.1mol/L NaOH solution. Then weighing the magnetic phosphorus removal adsorbing material prepared in the embodiment 1 according to 0.15, 0.3, 0.6, 1.2 and 2.4g/L, adding the magnetic phosphorus removal adsorbing material into 250mL of phosphorus solution, setting 3 times of repetition, and placing the magnetic phosphorus removal adsorbing material on a shaking table; the table was set at 200rpm,24h. And finally, filtering by adopting a 0.45-micron glass fiber filter membrane, measuring the phosphorus content of the stock solution and the phosphorus content after adsorption, and calculating the removal rate of the magnetic phosphorus removal adsorption material under different addition amounts. As a result, it was found that when the amount of addition was 0.6g/L, the removal rate of phosphorus reached 79%, at which time the amount of phosphorus adsorbed was 6mg/g at the highest; when the addition amounts were 1.2 and 2.4g/L, the removal rate of phosphorus reached 97% or more, and the amounts of phosphorus adsorbed were 4 and 2mg/g, respectively.
Example 3 influence of pH value on adsorption of water phosphorus by magnetic phosphorus removal adsorbing material
The solution with the phosphorus concentration of 5mg/L is prepared by adopting monopotassium phosphate, and the pH values of the solution are respectively adjusted to 3, 5, 7, 9 and 11 by adopting 0.1mol/L HCl solution and 0.1mol/L NaOH solution. Then weighing about 100mg of the magnetic phosphorus removal adsorbing material prepared in the example 1, adding the magnetic phosphorus removal adsorbing material into 250mL of phosphorus solution, setting for 3 times, and placing the mixture on a shaking table; the table was set at 200rpm,24h. And finally, filtering the reaction solution by adopting a 0.45-micrometer glass fiber filter membrane, measuring the phosphorus content of the stock solution and the phosphorus content after adsorption, and calculating the removal rate of the magnetic phosphorus removal adsorption material under different pH values. As a result, it was found that the pH value was less influenced by the magnetic adsorbent, and that the difference in the removal rate of the adsorbent was not so large and was maintained at 90% or more even when the pH value was in the range of 3 to 11.
Claims (9)
1. A preparation method of a magnetic phosphorus removal particle adsorption material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Grinding natural clay, ferroferric oxide and calcium hydroxide, and sieving with a 300-mesh sieve;
(2) Taking 6-8 parts of natural clay, 1-2 parts of ferroferric oxide and 1-2 parts of calcium hydroxide powder, and rapidly stirring the three materials in a disc granulator at the speed of 1200r/s for 2min to fully mix the materials;
(3) After fully mixing, adding a proper amount of water, regulating the speed of a disc granulator to 1200r/s, and granulating by utilizing a turbulent flow mixing principle to obtain a magnetic phosphorus removal adsorbing material; the granulation process is simple to operate, and the required granules can be prepared quickly and efficiently in a short time;
(4) And drying and sieving the magnetic phosphorus removal adsorbing material obtained by granulation to obtain the magnetic phosphorus removal granular adsorbing material with different grain sizes within the range of 1-5 mm.
2. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 1, wherein the preparation method comprises the following steps: the natural clay mainly comprises zeolite, attapulgite, bentonite and sepiolite.
3. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 2, characterized by comprising the following steps: the raw materials comprise the following components in parts by weight: 1 part of calcium hydroxide, 1 part of ferroferric oxide and 8 parts of zeolite; or the raw materials comprise the following components in parts by weight: 1 part of calcium hydroxide, 1 part of ferroferric oxide and 8 parts of attapulgite; or the raw materials comprise the following components in parts by weight: 1 part of calcium hydroxide, 1 part of ferroferric oxide and 8 parts of bentonite.
4. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 1, wherein the preparation method comprises the following steps: mixing calcium hydroxide, ferroferric oxide and zeolite according to a specific proportion and granulating.
5. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 1, wherein the preparation method comprises the following steps: mixing, granulating and drying at 45-65 ℃.
6. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 1, wherein the preparation method comprises the following steps: the prepared magnetic phosphorus removal particle adsorbing material has both magnetism and high-efficiency phosphorus adsorption capacity.
7. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 1, wherein the preparation method comprises the following steps: the prepared magnetic phosphorus removal particle adsorption material can be used for recovering the material through a magnetic separation technology after being adsorbed and saturated in eutrophic water so as to prevent secondary pollution of the material.
8. The preparation method of the magnetic phosphorus removal particle adsorbing material according to claim 1, wherein the preparation method comprises the following steps: the prepared magnetic phosphorus removal particle adsorption material has good phosphorus removal capability in a wide range of pH 3-11 of a water body.
9. The preparation method of the magnetic phosphorus removal particle adsorbing material as claimed in claim 1, wherein the prepared magnetic phosphorus removal particle adsorbing material is applied to the field of phosphorus removal in water.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1583881A (en) * | 1976-05-03 | 1981-02-04 | Commw Scient Ind Res Org | Water clarification |
| CN101306343A (en) * | 2007-11-14 | 2008-11-19 | 中国科学院南京土壤研究所 | Method for preparing water body dephosphorized granule adsorbent using attapulgite clay |
| CN104291420A (en) * | 2014-09-11 | 2015-01-21 | 陕西省石油化工研究设计院 | Phosphorus removing agent containing inorganic mineral and application method thereof |
| CN104815620A (en) * | 2015-05-05 | 2015-08-05 | 济南大学 | Preparation method of magnetic zeolite |
| CN106334518A (en) * | 2016-09-29 | 2017-01-18 | 环境保护部南京环境科学研究所 | Recyclable magnetic phosphorus adsorbent and preparation method thereof |
| CN107722991A (en) * | 2017-10-31 | 2018-02-23 | 中国环境科学研究院 | A kind of heavy metal-polluted soil pollution of chromium repair materials and preparation method and application |
| CN110508245A (en) * | 2019-08-29 | 2019-11-29 | 安徽禾美环保集团有限公司 | A kind of wastewater treatment adsorbent material and preparation method thereof |
-
2022
- 2022-08-23 CN CN202211015711.7A patent/CN115318243A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1583881A (en) * | 1976-05-03 | 1981-02-04 | Commw Scient Ind Res Org | Water clarification |
| CN101306343A (en) * | 2007-11-14 | 2008-11-19 | 中国科学院南京土壤研究所 | Method for preparing water body dephosphorized granule adsorbent using attapulgite clay |
| CN104291420A (en) * | 2014-09-11 | 2015-01-21 | 陕西省石油化工研究设计院 | Phosphorus removing agent containing inorganic mineral and application method thereof |
| CN104815620A (en) * | 2015-05-05 | 2015-08-05 | 济南大学 | Preparation method of magnetic zeolite |
| CN106334518A (en) * | 2016-09-29 | 2017-01-18 | 环境保护部南京环境科学研究所 | Recyclable magnetic phosphorus adsorbent and preparation method thereof |
| CN107722991A (en) * | 2017-10-31 | 2018-02-23 | 中国环境科学研究院 | A kind of heavy metal-polluted soil pollution of chromium repair materials and preparation method and application |
| CN110508245A (en) * | 2019-08-29 | 2019-11-29 | 安徽禾美环保集团有限公司 | A kind of wastewater treatment adsorbent material and preparation method thereof |
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