CN106345397A - Novel adsorbing material for efficiently removing phosphorus out of water - Google Patents

Novel adsorbing material for efficiently removing phosphorus out of water Download PDF

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Publication number
CN106345397A
CN106345397A CN201611000708.2A CN201611000708A CN106345397A CN 106345397 A CN106345397 A CN 106345397A CN 201611000708 A CN201611000708 A CN 201611000708A CN 106345397 A CN106345397 A CN 106345397A
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phosphorus
lanthanum
water body
absorption material
efficient
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CN106345397B (en
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潘纲
徐睿
张美�
张美一
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Yantai Hubble algal bloom control and Ecological Restoration Technology Co., Ltd
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Research Center for Eco Environmental Sciences of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0248Compounds of B, Al, Ga, In, Tl
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents

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  • 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention relates to a novel absorbing material for efficiently removing phosphorus out of water and belongs to the technical field of environment protection. According to the invention, a lanthanum compound and an aluminium compound are selected as the raw materials, and a co-precipitation method is adopted to prepare the efficient phosphorus removing absorbent which can effectively remove different kinds of phosphorus out of the water under the action of electrostatic attraction, ligand exchange and absorbent surface oxygen vacancy. Compared with the existing phosphorus removing adsorbents, the novel adsorbing material is simple in preparation process, low in production cost, high in phosphorus removing efficiency, long-lasting in phosphorus fixing effect, low in ecological safety risk, wide in pH application scope, and convenient for storage, transportation and use.

Description

A kind of efficient novel absorption material removing phosphorus in water body
(1) technical field
The present invention relates to a kind of efficient novel absorption material removing phosphorus in water body, belong to environmental protection technical field.
(2) background technology
Body eutrophication has become one of important water resources problem of facing mankind.At present, in world wide about There is different degrees of eutrophication in 30%~40% lake, reservoir.The eutrophication problem in China lake is then more Sternness, is more than 1km in area2More than 2300 lake in the lake more than 56% be in eutrophic state or just be subject to richness The threat of nutrient laden.And the eutrophic lake more than 80% belongs to phosphorus restricted type in the world, the rich battalion in the most of lake of China Fosterization process is also controlled by phosphorus recycling.Therefore, in water body, the control of phosphorus and removal become improvement body eutrophication Key link.
Body eutrophication control measures mainly include external source Environmental capacity and endogenous pollution controls two aspects.Absorption method Have been obtained for widely studied as a kind of efficient method removing phosphorus in water body.Conventional phosphorus ligands material includes clay pit Thing, zeolite, industrial residue, charcoal etc..But, traditional adsorbent has the following disadvantages: although its suction of natural material Attached function admirable but it is relatively costly, regeneration difficult;Although and its raw material of industrial or agricultural waste residue be easy to get, cheap, its absorption Effect is poor.Therefore, the cost-effective new adsorbent of synthetic receives the close attention of countries in the world research worker.
Because rare-earth elements of lanthanum has stronger phosphorus crystallized ability, extensive ph range of application, price compared with other rare earth units The advantages of element is cheap, lanthanum modification dephosphorization adsorbent has become the focus and emphasis of this area research.At present multiple lanthanums occur to change Property adsorbent, such as lanthanum modified alta-mudLanthanum PERFORMANCE OF MODIFIED VERMICULITE, lanthanum modification mcm-41, lanthanum aluminum are modified montmorillonite used, lanthanum aluminum Modified zeolite etc., for the research of phosphorus ligands in eutrophication water.WhereinIn Europe, the U.S., Xin Xi The eutrophication water large scale application such as blue, Australian.AlthoughCertain part is occupied abroad on market Volume, but because the market price at home is higher, and phosphorus adsorbance is relatively low, limits it in China's eutrophication water Popularization and application.And the lanthanum modification dephosphorization adsorbent of other reports is also limited only to the laboratory experiment stage, in the domestic market simultaneously Do not carry out throwing in and use.At present, domestic market do not occur can permanently effective administer body eutrophication lanthanum modified adsorbent, Greatly hinder the development of China's eutrophication water correlation control.
(2) content of the invention
The purpose of the present invention is: chooses cheap, widely used phosphorus ligands raw material, is produced by coprecipitation method Prepare a kind of efficient dephosphorization adsorbent.This dephosphorization adsorbent low production cost, simple production process, phosphorus ligands efficiency high, Ecological safety risk is low, can efficiently remove different types of phosphorus in water body, effectively slow down body eutrophication process.
A kind of efficient novel absorption material removing phosphorus in water body it is characterised in that: in terms of the butt of powder product, each become The content divided is by weight for lanthanum hydroxide 4%-30%, aluminium hydroxide 65%-95%, lanthanum aluminate 1%-5%, its molecular structure In the first coordination sphere lanthanum oxygen ligancy be 6.0-8.0, for a kind of unsaturated structure of coordination, containing Lacking oxygen.
A kind of efficient novel absorption material removing phosphorus in water body is it is characterised in that preparation process is as follows:
(1) mol ratio pressing lanthanum with aluminum dissolves a certain amount of lanthanum compound and aluminium compound for 1:5-40;
(2) precipitant is added in step (1), keep system temperature to be 50~90 DEG C, and be stirred continuously;
(3) stop stirring after solution ph is for 8-11, keep system temperature to be 50~90 DEG C and continue heating 2-10 hour, will Solid sediment washing, lyophilization or drying, grinding, the solid, powdery product obtaining is new phosphorus adsorbent.
A kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: described lanthanum compound be lanthanum chloride or One of Lanthanum (III) nitrate or two kinds.
A kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: described aluminium compound be aluminum chloride, nitre One or more of sour aluminum, aluminum sulfate or Alumen.
A kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: described precipitant be sodium hydroxide, hydrogen One or more of potassium oxide, ammonium hydroxide or carbamide.
Currently preferred technical scheme is: in terms of the butt of powder product, the content of each composition is by weight for hydrogen-oxygen Change lanthanum 18%, aluminium hydroxide 77%, lanthanum aluminate 5%.
The effect of the present invention:
The present invention adopts simple preparation method, produces the preferable dephosphorization adsorbent of cheap effect.This dephosphorization is inhaled Attached dose is passed through electrostatic attraction, ligand exchange and the effect of adsorbent surface Lacking oxygen, to phosphorus compound different types of in water body It is respectively provided with higher removal effect.Ph is applied widely, and ecological security is high, storage, transport, easy to use, phosphorus fixed effect Persistently, remarkable in economical benefits.
(4) brief description
Fig. 1 is a kind of efficient stereoscan photograph removing the novel absorption material of phosphorus in water body
Fig. 2 is a kind of efficient xrd diffraction pattern removing the novel absorption material of phosphorus in water body
Fig. 3 is a kind of efficient la l removing the novel absorption material of phosphorus in water bodyiii- edge exafs collection of illustrative plates
(5) specific embodiment
Embodiment 1:
Weigh 4g lanthanum chloride and 13g aluminum chloride to (1) in 1l conical flask;Add 200ml deionized water, 60 DEG C of water bath condition Lower stirring 10min is so as to be completely dissolved (2);Add 2mol l-1Sodium hydroxide solution to ph be 9 when stop add (3);Protect Holding system temperature is 10 hours (4) of 60 DEG C of continuation heating;With about 1l deionized water wash product 3 to 4 times, centrifugation removes supernatant Liquid, lyophilization (5);Grinding obtains dephosphorization adsorbent powder product (6).Wherein, lanthanum hydroxide content accounts for product dry basis 18%, aluminium hydroxide content accounts for product dry basis 77%;Lanthanum aluminate accounts for product dry basis 5%;The ph scope of application is 4-10.
In gained powder: containing la%=13%;Containing al%=27%.
Embodiment 2:
Weigh 4g lanthanum chloride and 20g aluminum chloride to (1) in 1l conical flask;Remaining preparation process repeats step in embodiment 1 (2)~(6).Wherein, lanthanum hydroxide content accounts for product dry basis 14%, and aluminium hydroxide content accounts for product dry basis 85%;Aluminic acid Lanthanum accounts for product dry basis 1%;The ph scope of application is 4-10.
In gained powder: containing la%=10%;Containing al%=29%.
Embodiment 3:
Weigh 4g lanthanum chloride and 27g aluminum chloride to (1) in 1l conical flask;Remaining preparation process repeats step in embodiment 1 (2)~(6).Wherein, lanthanum hydroxide content accounts for product dry basis 11%, and aluminium hydroxide content accounts for product dry basis 86%;Aluminic acid Lanthanum accounts for product dry basis 3%;The ph scope of application is 4-10.
In gained powder: containing la%=8%;Containing al%=30%.
Embodiment 4:
Weigh 4g lanthanum chloride and 33g aluminum chloride to (1) in 1l conical flask;Remaining preparation process repeats step in embodiment 1 (2)~(6).Wherein, lanthanum hydroxide content accounts for product dry basis 8%, and aluminium hydroxide content accounts for product dry basis 91%;Lanthanum aluminate Account for product dry basis 1%;The ph scope of application is 4-10.
In gained powder: containing la%=6%;Containing al%=31%.
Embodiment 5:
Weigh 4g lanthanum chloride and 40g aluminum chloride to (1) in 1l conical flask;Remaining preparation process repeats step in embodiment 1 (2)~(6).Wherein, lanthanum hydroxide content accounts for product dry basis 7%, and aluminium hydroxide content accounts for product dry basis 92%;Lanthanum aluminate Account for product dry basis 1%;The ph scope of application is 4-10.
In gained powder: containing la%=5%;Containing al%=32%.
Application Example 1:
Configure a series of phosphorus initial concentrations be 10,20,30,40,50,60mg p l-1Potassium dihydrogen phosphate 40ml, and (solid concentration is 1.0g l to be separately added into dephosphorization adsorbent in 0.04g above-described embodiment 1-1).170rpm vibration 24h at 25 DEG C After filter, measure solution in phosphatic clearance.
Phosphorus initial concentration is 10,20,30,40,50,60mg p l-1Under, dephosphorization adsorbent is to phosphatic clearance respectively For 97%, 98%, 96%, 98%, 95%, 95%.
Application Example 2:
Configure a series of phosphorus initial concentrations be 10,20,30,40,50,60mg p l-1Sodium pyrophosphate solution 40ml, and point Not Jia Ru in 0.04g above-described embodiment 1 dephosphorization adsorbent (solid concentration is 1.0g l-1).After 170rpm vibration 24h at 25 DEG C Filter, measure the clearance of pyrophosphate in solution.
Phosphorus initial concentration is 10,20,30,40,50,60mg p l-1Under, dephosphorization adsorbent divides to the clearance of pyrophosphate Wei 100%, 92%, 69%, 55%, 43%, 36%.
Application Example 3:
Configure a series of phosphorus initial concentrations be 10,20,30,40,50,60mg p l-1Sodium phytate solution 40ml, and respectively (solid concentration is 1.0g l to add dephosphorization adsorbent in 0.04g above-described embodiment 1-1).Mistake after 170rpm vibration 24h at 25 DEG C Filter, measures the clearance of phytic acid in solution.
Phosphorus initial concentration is 10,20,30,40,50,60mg p l-1Under, dephosphorization adsorbent is respectively to the clearance of phytic acid 99%th, 99%, 99%, 98%, 91%, 77%.
Application Example 4:
Configure a series of phosphorus initial concentrations be 10,20,30,40,50,60mg p l-1Potassium dihydrogen phosphate 40ml, and (solid concentration is 1.0g l to be separately added into dephosphorization adsorbent in 0.04g above-described embodiment 3-1).170rpm vibration 24h at 25 DEG C After filter, measure solution in phosphatic clearance.
Phosphorus initial concentration is 10,20,30,40,50,60mg p l-1Under, dephosphorization adsorbent is to phosphatic clearance respectively For 90%, 92%, 92%, 92%, 90%, 91%.
Application Example 5:
Configure a series of phosphorus initial concentrations be 10,20,30,40,50,60mg p l-1Potassium dihydrogen phosphate 40ml, and (solid concentration is 1.0g l to be separately added into dephosphorization adsorbent in 0.04g above-described embodiment 5-1).170rpm vibration 24h at 25 DEG C After filter, measure solution in phosphatic clearance.
Phosphorus initial concentration is 10,20,30,40,50,60mg p l-1Under, dephosphorization adsorbent is to phosphatic clearance respectively For 92%, 90%, 89%, 86%, 81%, 77%.

Claims (5)

1. a kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: in terms of the butt of powder product, each composition Content by weight for lanthanum hydroxide 4%-30%, aluminium hydroxide 65%-95%, lanthanum aluminate 1%-5%, in its molecular structure First coordination sphere lanthanum oxygen ligancy is 6.0-8.0, is coordinated unsaturated structure for a kind of, containing Lacking oxygen.
2. a kind of efficient novel absorption material removing phosphorus in water body is it is characterised in that preparation process is as follows:
(1) mol ratio pressing lanthanum with aluminum dissolves a certain amount of lanthanum compound and aluminium compound for 1:5-40;
(2) precipitant is added in step (1), keep system temperature to be 50~90 DEG C, and be stirred continuously;
(3) stop stirring after solution ph is for 8-11, keep system temperature to be 50~90 DEG C and continue heating 2-10 hour, by solid Precipitate washing, lyophilization or drying, grinding, the solid, powdery product obtaining is new phosphorus adsorbent.
3. according to claim 2 a kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: described lanthanum Compound is one of lanthanum chloride or Lanthanum (III) nitrate or two kinds.
4. according to claim 2 a kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: described calorize Compound is one or more of aluminum chloride, aluminum nitrate, aluminum sulfate or Alumen.
5. according to claim 2 a kind of efficient remove water body in phosphorus novel absorption material it is characterised in that: described precipitation Agent is one or more of sodium hydroxide, potassium hydroxide, ammonium hydroxide or carbamide.
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN107010705A (en) * 2017-05-05 2017-08-04 中国科学院生态环境研究中心 A kind of preparation method of rare earth aluminium polychloride water treatment agent
CN110038511A (en) * 2018-01-17 2019-07-23 华中科技大学 A kind of preparation method and applications carrying lanthanum modified alta-mud dephosphorization material
CN110759451A (en) * 2019-10-18 2020-02-07 东北石油大学 Rare earth cationic-composite aluminum organic heteropolymeric flocculant
CN112044393A (en) * 2019-06-06 2020-12-08 中南大学 Two-dimensional clay-based composite phosphorus removal agent and preparation method and application thereof
CN113087028A (en) * 2021-02-25 2021-07-09 苏州威德姆生态科技有限公司 Endogenous phosphorus passivation material and method for repairing eutrophic water body by using same
CN113457618A (en) * 2021-07-27 2021-10-01 北京师范大学珠海校区 Lanthanum-doped ordered mesoporous molecular sieve for environmental remediation and preparation method and application thereof
CN114669270A (en) * 2022-04-19 2022-06-28 中南民族大学 Composite material for efficiently passivating deposit phosphorus and preparation method thereof
CN114749163A (en) * 2022-04-18 2022-07-15 南京大学 Preparation method of Ce-Al dephosphorization material

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107010705A (en) * 2017-05-05 2017-08-04 中国科学院生态环境研究中心 A kind of preparation method of rare earth aluminium polychloride water treatment agent
CN110038511A (en) * 2018-01-17 2019-07-23 华中科技大学 A kind of preparation method and applications carrying lanthanum modified alta-mud dephosphorization material
CN112044393A (en) * 2019-06-06 2020-12-08 中南大学 Two-dimensional clay-based composite phosphorus removal agent and preparation method and application thereof
CN112044393B (en) * 2019-06-06 2021-05-04 中南大学 Two-dimensional clay-based composite phosphorus removal agent and preparation method and application thereof
CN110759451A (en) * 2019-10-18 2020-02-07 东北石油大学 Rare earth cationic-composite aluminum organic heteropolymeric flocculant
CN113087028A (en) * 2021-02-25 2021-07-09 苏州威德姆生态科技有限公司 Endogenous phosphorus passivation material and method for repairing eutrophic water body by using same
CN113457618A (en) * 2021-07-27 2021-10-01 北京师范大学珠海校区 Lanthanum-doped ordered mesoporous molecular sieve for environmental remediation and preparation method and application thereof
CN114749163A (en) * 2022-04-18 2022-07-15 南京大学 Preparation method of Ce-Al dephosphorization material
CN114669270A (en) * 2022-04-19 2022-06-28 中南民族大学 Composite material for efficiently passivating deposit phosphorus and preparation method thereof
CN114669270B (en) * 2022-04-19 2024-04-02 中南民族大学 Composite material for efficiently passivating sediment phosphorus and preparation method thereof

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