CN1830544A - Rare earth loaded modified plant gum fluorine ion absorber and its preparation method - Google Patents
Rare earth loaded modified plant gum fluorine ion absorber and its preparation method Download PDFInfo
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- CN1830544A CN1830544A CN 200610038281 CN200610038281A CN1830544A CN 1830544 A CN1830544 A CN 1830544A CN 200610038281 CN200610038281 CN 200610038281 CN 200610038281 A CN200610038281 A CN 200610038281A CN 1830544 A CN1830544 A CN 1830544A
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- plant gum
- rare earth
- modified plant
- fluorine ion
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Abstract
An F ion adsorbent is a Mannich reaction modified vegetative gum carrying RE compound. Its preparing process includes preparing the modified vegetative gum and carrying RE compound. It has high adsorbing capacity and speed, easy regeneration and high strength and stability.
Description
Technical field
The present invention relates to a kind of fluorine ion absorber and preparation method thereof, especially a kind of rare earth loaded modified plant gum fluorine ion absorber and preparation method thereof, the preparing technical field that belongs to natural polymer/inorganic composite materials is used for the treatment technology of fluoride waste and high-fluorine water thereof.
Background technology
China's fluorine aboundresources in industrial processes such as chemical industry, printing and dyeing, plating, electronics, metallurgy and semiconductor, is often discharged a large amount of fluorine-containing industrial wastewaters, and content of fluoride ion does not wait from 50～3000mg/L in the waste water, the harm ecological environment; Endemia fluorosis is pandemic in the world endemic disease, and it is more that China relates to lesion population.The endemia fluorosis main cause is long-term drinking high-fluorine water (F
-＞1.0mg/L), causing the human body chronic fluorine poisoning, the fluorine dental plaque appears in the lighter, and weight person causes fluorosis of bone, the serious harm health.The defluorination method of the fluoride waste of high concentration mainly is a calcium precipitation at present, but the water outlet of this method is difficult to reach the industrial discharge standard (F of national regulation
-＜10mg/L), and water quality is degenerated, the dehydration and the processing of a large amount of mud of existence have secondary pollution problem.For further reducing fluorinion concentration and Treatment of High Fluoride Drinking Water in the industrial wastewater, must use aluminium salt or activated alumina adsorbents, but the efficient of this absorbent is still lower, and the residual of aluminium salt will further influence health.Therefore study that new and effective, low toxicity, adsorption capacity are big, long service life, reproducible fluorine ion absorber be necessary, finally can become the substitute products of activated alumina.China has abundant rare earth resources, and rare earth compound has higher adsorption capacity and good selectivity to fluorine ion, can be used as the advanced treating that defluorinating agent is used for fluorinated water.For making its regeneration convenient, can these are compound loaded on macroporous absorbent resin, be used for the processing of fluorinated water, but the macroporous absorbent resin price is more expensive, can not apply on a large scale.The inexpensive amount of natural plant gum is big, prepares new adsorbent with the alternative macroporous absorbent resin of natural plant gum and has better economy, society and resource environment benefit.
Summary of the invention
Technical problem: the invention provides a kind ofly have that adsorption capacity is big, fluorine removing rate is high, adsorption rate is fast, regeneration is easy and convenient, can be recycled, use cost is lower, preparation technology is simple, adsorbent good stability, adsorbent soak not deliquescing in water, rare earth loaded modified plant gum fluorine ion absorber of characteristics and preparation method thereof such as do not expand, do not break.
Technical scheme: fluorine ion absorber of the present invention is for to carry out modification back loading rare earth compound with hydramine to natural plant gum by Mannich reaction, and the amount of the rare earth ion of every gram modified plant gum load is 0.5～1.5mmol.Wherein, natural plant gum is larch extract or myrica extract or surplus mandarin orange tannin extract or Ternstroemia gymnanthera tannin extract.
The preparation method of fluorine ion absorber of the present invention comprises following steps:
The preparation of A, modified plant gum: under the mechanical agitation, natural plant gum is added in the deionized water, making mass percent is the brown natural plant gum aqueous solution of 10%-30%, adds hydramine by every gram natural plant gum 1-3mL hydramine then, with inorganic acid pH is transferred to 2.0～3.5, join in the above-mentioned solution by every gram natural plant gum 0.5-1.5mL formaldehyde then, react 0.5～1.5h under the room temperature, filter, it is colourless spending deionised water to filtrate, vacuum drying gets modified plant gum to doing;
B, rare earth loaded modified plant gum: above-mentioned modified plant gum is joined in the alcoholic solution or the aqueous solution of rare earth nitrades of 0.5～10.0mmol/L, transferring pH with inorganic acid or ammoniacal liquor is 5.0～10.0, stirring at normal temperature 24～48h, filter, and to doing, obtain the ion type rareearth loaded modified plant gum fluorine ion absorber with deionized water repeated washing, vacuum drying; Described inorganic acid is nitric acid or sulfuric acid or hydrochloric acid.Alcoholic solution is methyl alcohol or ethanol, and this adsorbent can be reused with the NaOH regeneration back of 0.1～1.0mol/L.
Beneficial effect: characteristics of the present invention are that the cost of adsorbent is low, and defluorination effect is good, do adsorbing agent carrier with natural modified natural plant gum first, and utilize the high selectivity of rare earth to fluorine ion absorption, have solved some shortcomings of other adsorbents.Natural plant gum has raw material sources wide (output is only second to secondary products of forestry such as cellulose, lignin), and cost is lower, and is nontoxic, unique advantages such as easily biological-degradable, non-secondary pollution.
Natural plant gum is a natural macromolecular material less expensive in the forestry waste material, that contain tannin polyatomic phenol derivative, its aromatic rings contains the great amount of hydroxy group active group, natural polymer itself has certain flocculation, and product is nontoxic, price is relatively cheap, and it all has adsorption capacity to protein, nucleic acid, heavy metal ion.The present invention overcomes the weak point of existing adsorbent, and a kind of rare earth loaded modified plant gum fluorine ion absorber efficiently is provided, and integrates absorption and flocculation function, can be used for handling high-concentration fluorine-contained waste water (F
-≤ 50mg/L), make it reach discharge standard (F
-＜10mg/L); And the advanced treating of handling high-fluorine water and fluoride waste, make it reach drinking water standard (F
-＜1mg/L).
The saturated adsorption capacity of the rare earth loaded modified plant gum fluorine ion absorber that the present invention obtains is 18～22mg/g, can be used for handling the fluorine-containing factory effluent (F of industry dischargings such as chemistry, chemical industry, printing and dyeing, plating, electronics, metallurgy, agricultural chemicals
-≤ 50mg/L) and high fluorine groundwater, fluoride removing rate height (fluoride removing rate 〉=98%) can be with the F in the fluoride waste
-Concentration is reduced to below the 1mg/L.This adsorbent has that the scope of application is wide, adsorption capacity is big, adsorption rate is fast, easily regeneration cycle is used, use cost is lower, preparation technology is simple and practical, the adsorbent good stability, in water, soak not deliquescing, characteristics such as do not expand, do not break.
The specific embodiment
The preparation method of rare-earth adsorbent provided by the invention has adopted cheap natural material-natural plant gum (larch extract or myrica extract or surplus mandarin orange tannin extract or Ternstroemia gymnanthera tannin extract etc.), with hydramine natural plant gum is carried out modification by Mannich reaction; Make new and effective fluorine ion absorber behind the modified support supported rare earth compound.
Natural plant gum is carried out modification with hydramine to natural plant gum by Mannich reaction, prepare novel fluorine ion absorber with rare earth nitrate aqueous solution or rare earth nitrades alcoholic solution dipping respectively then.
Take by weighing natural plant gum, be dissolved in the deionized water, make 10%～35% brown natural plant gum aqueous solution.Stir down, drip hydramine, with inorganic acid (HNO
3, H
2SO
4Or hydrochloric acid) pH is transferred to 2.0～3.5, add formaldehyde 1～4mL then in above-mentioned solution.10 ℃～35 ℃ are reacted 0.5～1.5h down.Above-mentioned product is filtered, and it is colourless repeatedly washing to filtrate with deionized water, and 45 ℃～60 ℃ vacuum drying obtain the alkamine modified natural plant gum of product to doing.Get nitrate aqueous solution or alcoholic solution that the alkamine modified natural plant gum of 2～10g joins 0.5～10.0mmol/L rare earth, 10 ℃～35 ℃ are stirred 24～48h down, filter and with after the deionized water repeated washing, 45 ℃～65 ℃ vacuum drying obtain rare earth loaded modified plant gum fluorine ion absorber to doing.
PH influences the load capacity of rare earth ion on modified plant gum, and the pH of preparation rare earth loaded modified plant gum fluorine ion absorber is 5.0～10.0 (regulating with inorganic acid or ammoniacal liquor).The pH that rare earth loaded modified plant gum fluorine ion absorber is used to handle fluoride waste is 3.0～7.0.Ion type rareearth loaded modified plant gum fluorine ion absorber defluorination temperature is 10～30 ℃, can handle the fluorinated water of fluorinion concentration≤50mg/L, under best pH and temperature, handling every liter of sorbent used amount of fluorinated water is 3.0～4.0g, but adsorption time is different: for ionic (the water as solvent preparation) rare earth loaded modified plant gum fluorine ion absorber, adsorption time 150～180min, for ionic (alcohol is done the solvent preparation) rare earth loaded modified plant gum fluorine ion absorber, adsorption time 30～60min, fluoride removing rate all can reach more than 98%.
The used hydramine reagent of Mannich reaction is: monoethanolamine, diethanol amine, carbinolamine;
Rare earth compound is: lanthanum nitrate, cerous nitrate, mixed rare earth nitrates.
Embodiment 1: take by weighing natural plant gum (larch extract or myrica extract or surplus mandarin orange tannin extract or Ternstroemia gymnanthera tannin extract) 25g, be dissolved in the deionized water, make the 25% brown natural plant gum aqueous solution.
Under the mechanical agitation, drip monoethanolamine, use HNO
3With 3.0 of pH accent, add formaldehyde 2mL then in above-mentioned solution.React 1h under the room temperature.Above-mentioned product is filtered, repeatedly washed to filtrate with deionized water is colourless, and 50 ℃ of vacuum drying obtain product monoethanolamine modified plant gum to doing.Get the La (NO that 5g monoethanolamine modified plant gum joins 5mmol/L
3)
3In the aqueous solution, transferring pH with ammoniacal liquor is 8.0 stirring at normal temperature 24h, filters and with after the deionized water repeated washing, 50 ℃ of vacuum drying obtain ionic load adsorbent to dried.The fluoride waste of this sorbent treatment fluorinion concentration 8mg/L, pH is 5.0, and adsorption temp is 15 ℃, and the consumption of the adsorbent of every liter of fluorinated water is 3.3g, and adsorption time is 160min, fluoride removing rate reaches 98.5%.
Embodiment 2:5g monoethanolamine (the modified plant gum method of modifying is with example 1) joins the La (NO of 0.8mmol/L
3)
3In the ethanolic solution, transferring pH with ammoniacal liquor is 7.5, and stirring at normal temperature 24h filters, and 50 ℃ of vacuum drying obtain ion load type adsorbent to doing.The fluorinated water of this sorbent treatment fluorinion concentration 20mg/L, pH is 5.5, and temperature is 25 ℃, and the consumption of the adsorbent of every liter of fluorinated water is 3.2g, and adsorption time is 40min, fluoride removing rate reaches 98%.
The new adsorbent that makes not only has simple, the high fluoride removing rate of preparation method and high-adsorption-capacity, high treating effect, and the preparation raw material is cheap and easy to get, power of regeneration is strong, non-secondary pollution, fluorinion concentration can reach " integrated wastewater discharge standard " (GB8978-88) (F≤10mg/L) in the waste water of handling, further advanced treating can reach " drinking water sanitary standard " (GB 5749-85) (F≤1mg/L), have better economic, environment and resource social benefit of country.
Claims (5)
1, a kind of rare earth loaded modified plant gum fluorine ion absorber, it is characterized in that this fluorine ion absorber for by the natural plant gum load after the Mannich reaction modification rare earth compound, the amount of the rare earth ion of every gram modified plant gum load is 0.5～1.5mmol.
2, rare earth loaded modified plant gum fluorine ion absorber according to claim 1 is characterized in that in Mannich reaction, with hydramine natural plant gum is carried out modification.
3, rare earth loaded modified plant gum fluorine ion absorber according to claim 1 is characterized in that described natural plant gum is larch extract or myrica extract or surplus mandarin orange tannin extract or Ternstroemia gymnanthera tannin extract.
4, a kind of preparation method of rare earth loaded modified plant gum fluorine ion absorber according to claim 1 is characterized in that the method includes the steps of:
The preparation of A, modified plant gum: under the mechanical agitation, natural plant gum is added in the deionized water, making mass percent is the brown natural plant gum aqueous solution of 5%-30%, adds hydramine by every gram natural plant gum 1-3mL hydramine then, with inorganic acid pH is transferred to 2.0～3.5, join in the above-mentioned solution by every gram natural plant gum 0.5-1.5mL formaldehyde then, react 0.5～1.5h under the room temperature, filter, it is colourless spending deionised water to filtrate, vacuum drying gets modified plant gum to doing;
The preparation of B, rare earth loaded modified plant gum: above-mentioned modified plant gum is joined in the alcoholic solution or the aqueous solution of rare earth nitrades of 0.5～10.0mmol/L, transferring pH with inorganic acid or ammoniacal liquor is 5.0～10.0, stirring at normal temperature 24～48h, filter, and use the deionized water repeated washing, vacuum drying obtains the ion type rareearth loaded modified plant gum fluorine ion absorber to doing.
5, the preparation method of a kind of rare earth loaded modified plant gum fluorine ion absorber according to claim 4 is characterized in that described inorganic acid is nitric acid or sulfuric acid or hydrochloric acid; Used alcoholic solution is methyl alcohol or ethanolic solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984738A (en) * | 2015-06-16 | 2015-10-21 | 西南科技大学 | Method for preparing granular modified abandoned leather fluorinion adsorbing material |
| CN113769702A (en) * | 2021-08-16 | 2021-12-10 | 中化学朗正环保科技有限公司 | Modified titanium-based adsorbent for removing fluoride ions in wastewater and preparation method thereof |
| CN115301209A (en) * | 2022-08-26 | 2022-11-08 | 华中科技大学 | Efficient fluorine reducing agent and preparation and application thereof |
-
2006
- 2006-02-14 CN CN 200610038281 patent/CN1830544A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984738A (en) * | 2015-06-16 | 2015-10-21 | 西南科技大学 | Method for preparing granular modified abandoned leather fluorinion adsorbing material |
| CN113769702A (en) * | 2021-08-16 | 2021-12-10 | 中化学朗正环保科技有限公司 | Modified titanium-based adsorbent for removing fluoride ions in wastewater and preparation method thereof |
| CN115301209A (en) * | 2022-08-26 | 2022-11-08 | 华中科技大学 | Efficient fluorine reducing agent and preparation and application thereof |
| CN115301209B (en) * | 2022-08-26 | 2024-05-24 | 华中科技大学 | High-efficiency fluorine-reducing agent and preparation and application thereof |
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Open date: 20060913 |