CN104707562A - Method for preparing magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent - Google Patents
Method for preparing magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent Download PDFInfo
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- CN104707562A CN104707562A CN201510164433.5A CN201510164433A CN104707562A CN 104707562 A CN104707562 A CN 104707562A CN 201510164433 A CN201510164433 A CN 201510164433A CN 104707562 A CN104707562 A CN 104707562A
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Abstract
The invention provides a method for preparing a magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent. The method is characterized by preparing the magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent with complete water hyacinth plant tissue as a template by using a one-pot method. The method comprises the following steps: soaking water hyacinth into a Ti precursor liquid for a certain time, adding magnesium and aluminum salts, continuously soaking at certain temperature, performing one-pot method reaction, filtering to obtain a primary solid product, and performing high-temperature calcinations, thereby obtaining the magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent. The method provided by the invention is simple in step and gentle in condition, the obtained magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent can be used for removing fluorine ions in fluorine-containing wastewater of different concentrations (300-1000mg/L), especially high-concentration fluorine-containing wastewater, the removal rate is as high as 85%-98%, and processed water can be clear. After the fluorine removal agent is used, no analysis phenomenon can be caused, the environment can be prevented from secondary pollution, and the fluorine removal agent can be repeatedly used after being calcined at high temperature, is small in use amount and low in cost, and is simple, safe and efficient.
Description
Technical field
The present invention relates to a kind of magnesium and the doped meso-porous TiO of aluminium double ion that remove high-concentration fluorine-containing waste water
2method, be particularly that template one kettle way prepares the doped meso-porous TiO of double ion with plant tissue
2for the preparation method of fluoride waste adsorbent, belong to environmental protection sewage treating material preparation field.
Background technology
Fluorine is one of trace element of needed by human, and appropriate fluorine is useful to human body, but for a long time excessive take the photograph people then can health risk.Along with the development of modern industry, the normal fluoride containing high concentration in the waste water of the industry such as coke, glass, electronics, plating, chemical fertilizer, agricultural chemicals discharge, the generation of waste water containing fluorine, causes great threat to environment and health.Industry fluoride waste is one of difficult problem of facing of every profession and trade always.Especially in traditional non-ferrous metal wet method lead-zinc smelting enterprise, when producing with fluorine-containing crude zinc oxide materials, arrange design outward for the open circuit of fluorine element specially because lacking in traditional handicraft, the fluorine element in raw material can pass through leaching process, enters solution system with the form of fluorine ion with zinc.And along with the closed cycle of production process, fluorine ion can continuous enrichment in the middle of solution, exceedes rapidly the design standard of electrolysis system.Once fluorine ion exceeds standard, the cathode zinc that electrolysis can be made to produce and cathode aluminum plate stick together, and produce cathode zinc and are difficult to the fault in productions such as stripping, cause the production capacity of enterprise to reduce, production even can be caused time serious to be absorbed in pause.And content of fluoride ion too high in solution also can heavy corrosion cathode aluminum plate, minus plate is damaged and accelerates, thus cause enterprise's production cost to rise.Dirt that Lead-zinc Smelting Enterprises produces acid, the contour fluoride waste of absorbing liquid are acid heavy metal industrial wastewater, have complicated component, toxicity large, be difficult to the features such as process.Current zinc hydrometallurgy industry is difficult to process containing the higher raw material of the Oil repellent such as zinc discarded object, and non-renewable mineral resources can only be selected to be that primary raw material is produced.For these fluoride wastes, current most domestic factory there is no perfect process and does not execute, and the fluorine in wastewater content's index of discharging not yet reaches discharging standards, and severe contamination the environment that the mankind depend on for existence.Therefore, research and development defluorinating agent product and operation thereof, have important social effect and economic worth for environmental improvement and resource recycling recycling.
The processing method of fluoride waste has multiple, bibliographical information has ion exchange resin, electrochemistry, membrane process, ultrafiltration, osmosis etc. can process fluoride waste, but there is the problems such as operating cost is high, complex process, be seldom applied to defluorinating process so far.Method conventional is both at home and abroad roughly divided into two classes, i.e. the precipitation method and absorption method.Wherein chemical precipitation method, employing adds a large amount of CaO and removes fluorine ion in system, and the method CaO dosage is excessive, the CaF of generation
2precipitation is wrapped in Ca(OH)
2particle surface, can not be fully utilized and cause waste.And flocculent precipitation can only be used for low concentration fluoride waste.Absorbing process is that China removes the more a kind of technique of fluorine area research.Mainly contain activated alumina, zeolite, magnesia for the adsorbent except fluorine at present, there was reported the higher hydroxyapatite of adsorption capacity of fluoride ion, zirconia etc. in recent years, but adsorbent is used for the removal of drinking water or low dose fluoride ion mostly.In the patent of high-concentration fluorine-containing waste water process, the patent of invention (publication number 102464394A) that Lei Chunsheng, Lei Siyu, Fan Lulu disclose " a kind of compound defluorinating agent and application process thereof removing high-concentration fluorine-containing waste water ", compound defluorinating agent by polyhydroxy, multi-carboxy compound and inorganic matter (in calcium salt, magnesium salts, phosphate, molysite two or more) are composite by a certain percentage forms, in pH value 9.0-11.0, high-concentration fluorine-containing waste water one step-down of 100mg/L ~ 1000mg/L is to below 0.5mg/L, and clearance reaches more than 99.9%.In the patent of invention (publication number: 101773816A) of Huang Limei etc. disclosed " a kind of preparation method of the zeolite for the load zirconium except fluorine " and the patent of invention (publication number: 101780397A) of Chen Honghong disclosed " a kind of preparation method of the zeolite for the lanthanum oxide-carrying except fluorine ", adsorbent relate to rare earth element doping or only for the fluoride waste of <50 mg/L.The patent of invention (publication number: 102267768A) that Meng Zhaofu etc. disclose " method of a kind of lime-flyash Combined Treatment high-concentration fluorine-containing waste water ", all discharging standards is met to the fluoride wastewater treatment effect of initial concentration 500 ~ 2000mg/L, but need be used in conjunction with the precipitation method.The problem such as be difficult to remove and existing adsorbent applicable pH range is narrow for high concentration fluorine ion, need development of new high performance agent for removing fluorin.
Titanic oxide material with its characteristic such as stable, nontoxic, inexpensive at catalyst with catalyst carrier, absorption, be separated, etc. field be widely used, receive more and more scientist and pay close attention to widely.As (" novel fluorine ion absorber active titanic dioxide is except the research of fluorine ", Tianjin Normal University's journal, 2001,21(4) such as Yu Guisheng, 41):, adopt the TiO after sulfuric acid acidation
2be mixed for Removal of Fluorine From Underground Water with gravel, clearance is more than 90%.(the mesoporous TiO such as Zhou Gexin
2preparation and Fluoride-Absorption Capacity research, functional material, 2010,41,76) adopt hydro-thermal method prepare the mesoporous TiO of moral
2in 10-15min, fluoride removing rate reaches 90%, reaches the water quality requirement of drinking water.(" the nano-TiO such as Yang Lijun
2remove the performance of fluorine ion ", applied chemistry, 29(11 in 2012), 1278) and use commercial nano-TiO
2can 97% be reached to the clearance of the fluorine-containing solution of 10-50ppm.
For making TiO
2there is good absorption property, preparing the mesoporous TiO of bigger serface
2time, usually use chemical template, biological template etc.Wherein the especially each Plants of biological template due to aboundresources, pattern various and easily the feature such as acquisition more and more used.As Xu Qin etc. discloses in the patent of invention (publication number 103288128A) of " method of biological template synthesizing flaky anatase titania ", flake porous nanocrystalline by being used as Template preparation after petal acid bubble, processed.Paying grand just etc. having disclosed in the patent of invention (publication number 102513076A) of " utilizing biological template to prepare the method for porous nanocrystalline titanium deoxide catalyst " adopts stem or leaf of cattail leaf or cornstalk to be that template has prepared porous nano crystal titanium dioxide through the process such as ultrasonic disperse, back flow reaction.Adopt ultrasonic method to react in acid condition in the patent of invention (publication number 101491756) that Zhu Shenmin etc. disclose " preparation method of titanium dioxide photocatalyst of plant graded structure ", high-temperature roasting obtains the titanium dioxide of plant graded structure.Master's thesis of Yunnan University Master degree candidate Yu Fei " take leaves of hyacinth as the mesoporous TiO of template
2preparation and the research of catalytic performance ", when relating to associated biomolecule templated synthesis metal oxide, template have passed through come unstuck, dewater, pretreatment that demetalization impurity etc. is expensive, and mesoporous TiO prepared by this paper
2as photocatalyst applications.
This patent combines except the good aluminium oxide of fluorine, magnesium oxide material and mesoporous TiO
2, in preparation process, select water hyacinth global tissue to be template, template, without the need to the loaded down with trivial details processing procedure such as acid bubble, dehydration, prepares the mesoporous TiO of magnesium ion and Al-doping through one kettle way with water hyacinth template, solion and titanium precursor liquid
2defluorinating agent, this method institute prepared material Fluoride-Absorption Capacity is good, and has no relevant report.
Summary of the invention
The present invention is directed to high concentration fluorine ion to be difficult to remove, existing adsorbent can only, in effective problem in neutral or alkaline water quality, provide a kind of one kettle way to prepare magnesium and the mesoporous TiO of Al-doping
2the method of material, the method for template with the global tissue of water hyacinth, does not need complicated pretreatment, has more actual application value.Made defluorinating agent can be used for the removal of fluorine ion in variable concentrations fluoride waste, has wide market application foreground.
The object of this invention is to provide a kind of preparations and applicatio method of mesoporous adsorbent that efficiently can process fluoride waste, with low cost, non-secondary pollution, recoverable, preparation condition is gentle, and technique simple and stable, reliably, cost is low, and product defluorination effect is good.
Technical scheme of the present invention first water hyacinth tissue templates is slightly dealt with, and is then immersed in Ti precursor liquid; After a period of time, add magnesium ion and aluminium ion salting liquid continuation immersion, finally filter and obtain initial solid product, through high-temperature calcination, obtain the mesoporous TiO of magnesium, the doping of aluminium double ion
2.
Now describe technical scheme of the present invention in detail.
Water hyacinth tissue templates slightly deals with by the first step, is then immersed in Ti precursor liquid.
Water hyacinth global tissue containing root, stem, leaf, flower is soaked in Ti precursor liquid after airing, fragmentation, Ti precursor liquid is the mixed liquor of titanium source, ethanol and acetylacetone,2,4-pentanedione, and titanium source: ethanol: the ratio of acetylacetone,2,4-pentanedione is 1:15:0.1 ~ 9:35:1.5, titanium source is titanium sulfate or titanium tetrachloride or titanium tetraisopropylate or butyl titanate.
Described water hyacinth tissue and the mass ratio of Ti precursor liquid are 1:5 ~ 1:30, and soak time is 1 ~ 24h.
Second step adds magnesium ion and aluminium ion salting liquid forms water hyacinth, Ti precursor liquid and metal ion mixed liquor continuation immersion.
Described magnesium and aluminium ion are nitrate or sulfate or chlorate, and magnesium and aluminum ions ratio are 1:1 ~ 1:20, and magnesium and aluminium ion solution addition are 0.01% ~ 20% of solution gross mass.
Described water hyacinth, Ti precursor liquid, magnesium ion and aluminium ion salt mixed liquor are 40 ~ 95
0immersion 1 ~ 48h is continued under C.
Mixed liquor filters and obtains initial solid product by the 3rd step, through high-temperature calcination, obtains the mesoporous TiO of magnesium, the doping of aluminium double ion
2.
Described solid calcining heat is 500 ~ 1000 DEG C, and the time is 1-10 hour.
Compare with existing defluorinating agent patent, the maximum feature of this patent is as follows.
1., using this natural plants of water hyacinth as biological template, prepare the TiO of magnesium, the doping of aluminium double ion innovatively through one kettle way
2defluorinating agent.
2. obtain through one kettle way, take full advantage of raw material, no coupling product; Preparation condition is gentle, and technique simple and stable, reliably, cost is low.
Made defluorinating agent can be used for the removal that concentration is fluorine ion in 100 ~ 1000mg/L fluoride waste, especially shows excellent effect to the removal of fluorine ion in the lead-zinc smelting wastewater being representative with dirty acid and absorbing liquid.
The mesoporous TiO of made magnesium, aluminium double ion doping
2for fluoride waste except fluorine process and effect as follows: be drop into the mesoporous TiO of 1g in the waste water of 405mg/L at fluoro-containing concentration
2defluorinating agent, the clearance of reaction 3 hours fluorine reaches more than 85%, and about 6 h reach adsorption equilibrium.
Magnesium of the present invention, the doped meso-porous TiO of aluminium double ion
2defluorinating agent has the following advantages.
Can not be there is parsing phenomenon in the defluorinating agent after 1, using, can not cause secondary pollution to environment.High temperature is again calcined and can be reused, and this defluorinating agent consumption is little, simple, safe, efficient.
2, the mesoporous TiO of gained
2defluorinating agent is a kind of green non-pollution, recyclablely recycles, and stable performance under high temperature, has good economic benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is the mesoporous TiO of modification
2the X-ray diffractogram of material;
Fig. 2 is the mesoporous TiO of modification
2the SEM figure of material.
Detailed description of the invention
Embodiment 1.
Template water hyacinth 5g after dehydration is joined (Titanium Nitrate: ethanol: acetylacetone,2,4-pentanedione=1:19:0.1) and 1% magnesium and aluminium nitrate in Ti precursor liquid 30g, magnesium ion and aluminium ion ratio are 1:2, and mixed solution supersonic oscillations are carried out ultrasonic immersion 20 hours.Solution after immersion is evaporated whole moisture one kettle way at 100 DEG C and obtains initial product, within 4 hours, obtain white powder with calcining in 460 DEG C again after afterwards product temperature programming being calcined 2 hours in 280 DEG C, be mesoporous TiO
2defluorinating agent.
Embodiment 2.
Template water hyacinth 1g after dehydration is joined (titanium sulfate: ethanol: acetylacetone,2,4-pentanedione=5:28:0.8) and 5% magnesium and aluminium sulfate in Ti precursor liquid 10g, magnesium ion and aluminium ion ratio are 1:5, and mixed solution supersonic oscillations are carried out ultrasonic immersion 10 hours.Solution after immersion is evaporated whole moisture one kettle way at 100 DEG C and obtains initial product, product Muffle furnace is calcined in 400 DEG C obtain white powder in 5 hours afterwards, be the mesoporous TiO of modification
2defluorinating agent.
Embodiment 3.
Template water hyacinth 10g after dehydration is joined (titanium chloride: ethanol: acetylacetone,2,4-pentanedione=9:25:1) and 10% magnesium and aluminium chlorate in Ti precursor liquid 30g, magnesium ion and aluminium ion ratio are 1:10, and mixed solution supersonic oscillations are carried out ultrasonic immersion 15 hours.Solution after immersion is evaporated whole moisture one kettle way at 100 DEG C and obtains initial product, product Muffle furnace is calcined in 1000 DEG C obtain white powder in 3 hours afterwards, be the mesoporous TiO of modification
2defluorinating agent.
Embodiment 4.
Template water hyacinth 10g after dehydration is joined (titanium tetraisopropylate: ethanol: acetylacetone,2,4-pentanedione=8:30:1.2) and 2% magnesium and aluminium nitrate in Ti precursor liquid 30g, magnesium ion and aluminium ion ratio are 1:15, and mixed solution supersonic oscillations are carried out ultrasonic immersion 8 hours.Solution after immersion is evaporated whole moisture one kettle way at 100 DEG C and obtains initial product, product Muffle furnace is calcined in 1200 DEG C obtain white powder in 1 hour afterwards, be the mesoporous TiO of modification
2defluorinating agent.
Embodiment 5.
Template water hyacinth 15g after dehydration is joined (butyl titanate: ethanol: acetylacetone,2,4-pentanedione=2:15:0.1) and 20% magnesium and aluminium nitrate in Ti precursor liquid 25g, magnesium ion and aluminium ion ratio are 1:8, and mixed solution supersonic oscillations are carried out ultrasonic immersion 6 hours.Solution after immersion is evaporated whole moisture one kettle way at 100 DEG C and obtains initial product, product Muffle furnace is calcined in 1200 DEG C obtain white powder in 2 hours afterwards, be the mesoporous TiO of modification
2defluorinating agent.
Embodiment 6.
Template water hyacinth 2g after dehydration is joined (tetraisopropyl titanate: ethanol: acetylacetone,2,4-pentanedione=2:20:0.2) and 20% magnesium and aluminium nitrate in Ti precursor liquid 30g, magnesium ion and aluminium ion ratio are 1:17, and mixed solution supersonic oscillations are carried out ultrasonic immersion 6 hours.Solution after immersion is evaporated whole moisture one kettle way at 100 DEG C and obtains initial product, product Muffle furnace is calcined in 300 DEG C obtain white powder in 5 hours afterwards, be the mesoporous TiO of modification
2defluorinating agent.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, the present invention can have various change; All done within the spirit and principles in the present invention any amendment, improvement etc., equivalent replacement; Use needs as long as meet, all should be included within protection scope of the present invention.
embody rule example
Application example 1.
Get the waste water 500mL that certain factory's fluoro-containing concentration is 405mg/L, add mesoporous TiO
2defluorinating agent 7.5g, under normal temperature stirring reaction after 6 hours Funing tablet be 13mg/L, clearance is 96.8%.
Application example 2.
Get the waste water 500mL that certain factory's fluoro-containing concentration is 925mg/L, add mesoporous TiO
2defluorinating agent 15g, under normal temperature stirring reaction after 6 hours Funing tablet be 117mg/L, clearance is 87%.
Application example 3.
Get the waste water 500mL that certain factory's fluoro-containing concentration is 367mg/L, add mesoporous TiO
2defluorinating agent 8g, under normal temperature stirring reaction after 3 hours Funing tablet be 34mg/ L, clearance is 91%.
Application example 4.
Get the waste water 500mL that certain factory's fluoro-containing concentration is 822mg/L, add mesoporous TiO
2defluorinating agent 10g, under normal temperature stirring reaction after 1 hour Funing tablet be 160mg/L, clearance is 93%.
Claims (6)
1. a magnesium, the doped meso-porous TiO of aluminium double ion
2the preparation method of defluorinating agent, is characterized in that concrete steps are as follows:
(1) water hyacinth tissue templates is slightly dealt with, be then immersed in Ti precursor liquid;
(2), after a period of time, add magnesium ion and aluminium ion salting liquid and continue at a certain temperature to soak,
(3) filtration obtains initial solid product, through high-temperature calcination, obtains the mesoporous TiO of magnesium, the doping of aluminium double ion
2.
2. magnesium according to claim 1, the doped meso-porous TiO of aluminium double ion
2the preparation method of defluorinating agent, it is characterized in that: the water hyacinth global tissue containing root, stem, leaf, flower is soaked in Ti precursor liquid after airing, fragmentation, Ti precursor liquid is the mixed liquor of titanium source, ethanol and acetylacetone,2,4-pentanedione, and titanium source: ethanol: the ratio of acetylacetone,2,4-pentanedione is 1:15:0.1 ~ 9:35:1.5, titanium source is that titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, butyl titanate are wherein a kind of.
3. magnesium according to claim 1, the doped meso-porous TiO of aluminium double ion
2the preparation method of defluorinating agent, is characterized in that: water hyacinth tissue and Ti precursor liquid take mass ratio as 1:5 ~ 1:30 mixing immersion 1 ~ 24h.
4. magnesium according to claim 1, the doped meso-porous TiO of aluminium double ion
2the preparation method of defluorinating agent, is characterized in that: described magnesium and aluminium ion are that nitrate, sulfate, chlorate are wherein a kind of, and magnesium and aluminum ions ratio are 1:1 ~ 1:20, and magnesium and aluminium ion solution addition are 0.01% ~ 20% of solution gross mass.
5. magnesium according to claim 1, the doped meso-porous TiO of aluminium double ion
2the preparation method of defluorinating agent, is characterized in that: water hyacinth, Ti precursor liquid, magnesium ion and aluminium ion salt mixed liquor are 40 ~ 95
0c continues immersion 1 ~ 48h.
6. magnesium according to claim 1, the doped meso-porous TiO of aluminium double ion
2the preparation method of defluorinating agent, is characterized in that: gained solid calcining heat is 500 ~ 1000 DEG C, and the time is 1-10 hour.
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| CN201510164433.5A CN104707562A (en) | 2015-04-09 | 2015-04-09 | Method for preparing magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512936A (en) * | 2016-11-11 | 2017-03-22 | 镇江市高等专科学校 | Hydrothermal method for preparing fluoride removal adsorbent and application thereof |
| CN108911007A (en) * | 2018-07-12 | 2018-11-30 | 齐鲁工业大学 | A kind of preparation method of the Al-Mg oxide de-fluoridation material based on biological template |
| CN112547014A (en) * | 2020-12-07 | 2021-03-26 | 神美科技有限公司 | Preparation method of carbon-doped magnesium hydroxide whisker-loaded rare earth metal defluorination material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192902A (en) * | 2014-08-28 | 2014-12-10 | 云南大学 | Preparation method of modified mesoporous TiO2 for removing fluorinion in lead and zinc smelting waste water |
-
2015
- 2015-04-09 CN CN201510164433.5A patent/CN104707562A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192902A (en) * | 2014-08-28 | 2014-12-10 | 云南大学 | Preparation method of modified mesoporous TiO2 for removing fluorinion in lead and zinc smelting waste water |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106512936A (en) * | 2016-11-11 | 2017-03-22 | 镇江市高等专科学校 | Hydrothermal method for preparing fluoride removal adsorbent and application thereof |
| CN106512936B (en) * | 2016-11-11 | 2018-10-02 | 镇江市高等专科学校 | A kind of hydro-thermal method prepares de-fluoridation adsorbent and its application |
| CN108911007A (en) * | 2018-07-12 | 2018-11-30 | 齐鲁工业大学 | A kind of preparation method of the Al-Mg oxide de-fluoridation material based on biological template |
| CN108911007B (en) * | 2018-07-12 | 2021-03-16 | 齐鲁工业大学 | Preparation method of Al-Mg oxide defluorination material based on biological template |
| CN112547014A (en) * | 2020-12-07 | 2021-03-26 | 神美科技有限公司 | Preparation method of carbon-doped magnesium hydroxide whisker-loaded rare earth metal defluorination material |
| CN112547014B (en) * | 2020-12-07 | 2022-06-28 | 神美科技有限公司 | Preparation method of carbon-doped magnesium hydroxide whisker-loaded rare earth metal defluorination material |
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