CN101642700B - Preparation method of boron adsorbent - Google Patents
Preparation method of boron adsorbent Download PDFInfo
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- CN101642700B CN101642700B CN2009101920274A CN200910192027A CN101642700B CN 101642700 B CN101642700 B CN 101642700B CN 2009101920274 A CN2009101920274 A CN 2009101920274A CN 200910192027 A CN200910192027 A CN 200910192027A CN 101642700 B CN101642700 B CN 101642700B
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Abstract
The invention relates to a preparation method of a boron adsorbent. The boron adsorbent with high selectivity and high adsorption capacity is prepared from a function group compound loaded on the carrier surface of silicone-polyamine composite material through functional grafting reaction, which takes silicone-polyamine composite material as backbone. The boron adsorbent of the invention has the advantages of high adsorption capacity, fast adsorption speed, easy regeneration, capability of recyclable use and low transformation expansion rate in the process of adsorption-desorption and the like to boric acid in water body, and is mainly applied to removal, separation or concentration recycling of boric acid in agriculture and industry, social life, or the process of sea water desalinization.
Description
Technical field
The present invention relates to the preparation method of a kind of ion-exchange and adsorbing domain, particularly a kind of boron adsorbent.
Background technology
Often face the technical problem of removing boron in industrial and agricultural production and the social life.When preparing as nuclear fuel, the uranium compound that lixiviate is come out from the uranium ore leachate contains boron compound toward contact.Because boron has the ability of very strong intercept neutrons, be typical high neutron absorption cross-section element or neutron poison, even trace B exists chain reaction of nuclear fission can not be kept down in nuclear fuel, therefore when the pure uranium compound of preparation nuclear level, need remove boron.And for example when preparation highly-purity magnesite and magnesium metal, also need boron is wherein removed, otherwise can influence the quality of highly-purity magnesite and magnesium metal.On the agricultural, boron is the necessary a kind of basic nutrition element of plant growth, but its activity is very low, when its concentration is high slightly, will the borism phenomenon occur, show as the yellow point of appearance on the leaf doing deposits yields harm, claim chlorosis, fruit quickens to rot, even causes species to be withered away.Boron is except the direct influence to crop, and enrichment also can work the mischief to soil in soil because it can with complexings such as heavy metal Pb, Cd, Cu, Ni, the material toxicity after the complexing is greater than the material before the complexing, and is bigger to crop harm.In addition, development of industry and agriculture has caused the scarcity of freshwater resources, desalinization becomes the new way that solves water resources shortage, and the about 5mg/L of boron average content in the seawater, far above drinking water standard, must remove, cause human reproductive system's disease and neural slow poisoning easily otherwise take in boron compound for a long time.
The main method of removing boron at present has: flocculation-sedimentation, oxide absorption, extraction, hyperfiltration, electroosmose process, boron adsorbent absorption method.Flocculation-sedimentation and oxide absorption method can only be handled the water body of high boron concentration, and be powerless to the processing of low boron concentration water body.The extraction ratio juris be with contain o-dihydroxy and with the immiscible organic matter of water as extractant, make extractant and acid reaction form complex compound and be extracted to organic facies, thereby reach the purpose of separation and concentration, extraction equipment complexity, the organic extractant price is higher and be partially soluble in water, cause environmental pollution and toxigenicity easily, so be not used widely.Hyperfiltration removes boron, and influenced by pH bigger, along with the rising of pH value of solution value, utilize hyperfiltration to remove boron efficient and also improve thereupon, when pH value 10 when above, hyperfiltration removes the boron rate near 100%, but the meeting of pH value height cause remarkable infringement to reverse osmosis membrane.Electroosmose process is a kind of physicochemical boron removal method, under the function of current, anion is moved by the anion-exchange membrane anode, and cation can not pass through amberplex.Boric acid in the aqueous solution with B (OH)
4 -Form enter the anode region by anion-exchange membrane.Electroosmose process can be handled the low solution of boron content, ion remaval rate height, and shortcoming is the expense costliness, removing boron, influenced by salinity very big.
Boron adsorbent is generally the sorbing material that contains the o-dihydroxy functional group, and its clearance and selectivity to boric acid is better.Rohm﹠amp; USP2813838 of Haas house journal and relevant patent GB816510 thereof and CA645758 disclose the boron resin that removes of polystyrene microsphere graft N-methyl D-aminoglucose functional group preparation, product trade mark Amberlite IRA-743, and should remove boron resin takes off boron in the boracic water body application.Chinese patent publication number CN101444756 discloses a kind of ion-exchange fibre with boron adsorptive selectivity, and adopting the composite fibre of polypropylene fibre graft phenylethene during preparation is skeleton, and by chloromethylation, graft N-methyl glucoside amine forms then.Prepare boron adsorbent after people such as Bahire FilizSenkal and Niyazi Bicak disclose a kind of cross-linked polystyrene resin grafting glycidol, see Reactive﹠amp; Functional Polymers 2003,55,27-33.Above-mentioned several all is to be carrier with the organic polymer, alternative attracts boron behind the certain functional group of load, but polymer support heat endurance, mechanical stability, anti-solvent and radiation resistance are relatively poor, and preparing carriers need consume a large amount of petrochemical industry resources.
Chinese patent publication number CN1666813 discloses boron sorbing material of a kind of inorganic skeleton and preparation method thereof, prepares the boron sorbing material by inorganic porous carrier surface load polyhydroxy functional group.People such as M.Dolores Marcos and Ramon Martinez-Manez disclose mesopore silica gel surface with after containing the silane coupler coupling of amine propyl group, utilize the coupling amido at NaBH again
3Following and the sweet mellow wine grafting of CN effect, thus the preparation boron adsorbent is seen Chem.Commun, 2004,2198-2199.These two documents have overcome the inherent defect of organic backbone boron adsorbent, adopted physics and chemical stability silica gel good and cheap and easy to get as main framework material, but the selection on synthetic route has limited the grafting amount of boron adsorption function group greatly, finally causes the adsorption capacity of boron sorbing material lower.
Summary of the invention
It is skeleton with silica gel-polyamine composite that purpose of the present invention just provides a kind of, be reflected at silica gel-polyamine composite material carrier area load o-dihydroxy compound functional group by functional graft, thereby preparation have high selectivity and high-adsorption-capacity, the stable boron adsorbent of physical and chemical performance.
The preparation method of boron adsorbent: (1) adds 10 weight portion silica-gel carriers in 20～200 parts by volume organic solvents, add 3～30 parts by volume organo silane coupling agents again, reaction temperature is that normal temperature is between the organic solvent boiling point, confined reaction 10～50 hours, use organic solvent washing then, 20～50 ℃ of vacuum drying obtain alkylated silica gel to constant weight; (2) with 3～30 weight portion polyamine mixings, 50～80 ℃ were reacted 10～50 hours down, used solvent wash then, obtained silica gel-polyamine composite in alkylated silica gel adding 50～500 parts by volume solvents that step (1) obtained; (3) silica gel that step (2) is obtained-polyamine composite and 5～50 weight portion o-dihydroxy compounds reacted 10～50 hours down at 50～80 ℃, obtained boron adsorbent.
Silica-gel carrier in the described step (1) is macro porous silica gel or mesopore silica gel, amorphous silica gel, SBA series ordered mesoporous molecular sieve, MCM series ordered mesoporous molecular sieve.
The specific area of the silica-gel carrier in the described step (1) is 200～1500m
2/ g, aperture 1～100nm, pore volume 0.4～2ml/g.
Organic solvent in the described step (1) is methyl alcohol or ethanol, toluene, ether, acetone, hexane, perhaps the mixed solvent of choosing 2～6 kinds of compositions wherein.
Organo silane coupling agent in the described step (1) is γ-halogen propyl trimethoxy silicane or γ-halogen propyl-triethoxysilicane, γ-halogen propyltrichlorosilan, and halogen wherein is chlorine or bromine, iodine.
Polyamine in the described step (2) is polymine or polyvinylamine, PAH, polyethylene polyamine.
Solvent in the described step (2) is water or methyl alcohol, ethanol, ether, acetone, perhaps the mixed solvent of choosing 2～5 kinds of compositions wherein.
O-dihydroxy compound in the described step (3) is glycerine and derivative or carbohydrate and derivative thereof.
Described glycerine and derivative thereof are glycerine or glycidol, 3-chloro-1, the 2-propane diols.
Described carbohydrate and derive and be N-methyl D-aminoglucose or gucosamine, glucose, sweet mellow wine, sorbierite.
Advantage that the present invention has and effect:
(1) the present invention comprises three steps, i.e. the area load of the synthetic and o-dihydroxy compound functional group of the preparation of alkylated silica gel, silica gel-polyamine composite.The entire synthesis process of boron adsorbent has the reaction condition gentleness, and raw material are cheap and easy to get, and boron adsorption function group grafts on carrier surface so that the mode of chemical bonding is stable, has the big characteristics of grafting amount.
(2) the present invention can adopt batch process, promptly adds adsorbent and adsorb in filling the container of BAS; Also can adopt the column continuous process, adsorbent is loaded on ion exchange column, make BAS pass through exchange column then and adsorb.
Advantages such as (3) the present invention has the adsorption capacity height, the rate of adsorption is fast, regeneration is easy, adsorption-desorption process expansion rate transition is low.
(4) the present invention's repeated use capable of circulation after regenerating.During adsorbent reactivation, earlier under acid condition, adsorbed boric acid is carried out wash-out with hydrochloric acid, and then with in the ammoniacal liquor with excessive hydrochloric acid.The boron adsorption capacity of adsorbent does not have obvious decline after 10 regeneration cycle.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described, but it is not represented as unique embodiment of the present invention.
Embodiment one
Get specific area 1500m
2The silica-gel carrier 20g of/g, average pore size 1nm, pore volume 0.4ml/g, add in 40ml methyl alcohol or the ethanol, add 6ml γ-r-chloropropyl trimethoxyl silane or γ-bromopropyl trimethoxy silane again, normal-temperature reaction is 10 hours in closed system, then with methyl alcohol and ethanol or toluene and the washing of hexane mixed solvent, to remove excessive unreacted γ-r-chloropropyl trimethoxyl silane or γ-bromopropyl trimethoxy silane, to constant weight, promptly obtain the alkylated silica gel that the surface contains chloropropyl or bromopropyl after 20 ℃ of vacuum drying.Silica-gel carrier is an amorphous silica gel.
Alkylated silica gel adds in 100ml water or the methyl alcohol, mixes with 6g polymine or polyvinylamine then, and 50 ℃ were reacted 50 hours, and water and methyl alcohol or ethanol and ether washing obtain silica gel-polyamine composite.
Silica gel-polyamine composite and 10g N-methyl D-aminoglucose or gucosamine, glucose, sweet mellow wine, sorbierite obtain flaxen boron adsorbent 50 ℃ of reactions 50 hours.
Get adsorbent 0.1g of the present invention, add the waste water 100ml contain boric acid 500ppm, intermittent oscillation absorption is after 4 hours, adopts the concentration of solution mesoboric acid before and after the titration measuring absorption, is the 2.0mmol/g adsorbent to the adsorption capacity of boric acid.
Boron adsorbent of the present invention regeneration is soaked 10h with mass concentration 3%HCl solution, with distilled water adsorbent is carried out drip washing then, and being neutralized to pH with the ammoniacal liquor of mass concentration 1% again is 6～7, regeneration ending.Adsorbent can enter the next circulation of using.
Embodiment two
Get specific area 200m
2The silica-gel carrier 20g of/g, average pore size 100nm, pore volume 2ml/g, add in 400ml toluene or the hexane, add 60ml γ-chloropropyl trichloro-silane or γ-bromopropyl trichlorosilane again, normal-temperature reaction is 50 hours in closed system, mixed solvent with toluene and hexane or acetone and ether washs then, to remove excessive unreacted γ-chloropropyl trichloro-silane or γ-bromopropyl trichlorosilane, to constant weight, promptly obtain the alkylated silica gel that the surface contains chloropropyl or bromopropyl after 50 ℃ of vacuum drying.Silica-gel carrier is macro porous silica gel or mesopore silica gel.
Alkylated silica gel adds in 1000ml ethanol or the ether, mixes with the 60g PAH then, and 80 ℃ were reacted 10 hours, and the mixed solvent washing that water, methyl alcohol, ethanol and ether are formed obtains silica gel-polyamine composite.
Silica gel-polyamine composite and 100g glycerine or glycidol, 3-chloro-1, the 2-propane diols obtains flaxen boron adsorbent 80 ℃ of reactions 10 hours.
Get adsorbent 0.1g of the present invention, add the waste water 100ml contain boric acid 500ppm, intermittent oscillation absorption is after 4 hours, adopts the concentration of solution mesoboric acid before and after the titration measuring absorption, is the 1.4mmol/g adsorbent to the adsorption capacity of boric acid.
The renovation process of boron adsorbent of the present invention is identical with embodiment one.
Embodiment three
Get specific area 250m
2The silica-gel carrier 20g of/g, average pore size 13nm, pore volume 1ml/g, add in 50ml acetone or the ether, add 12ml γ-chloropropyl trichloro-silane or γ-bromopropyl trichlorosilane again, normal-temperature reaction is 20 hours in closed system, mixed solvent with toluene and hexane or acetone and ether washs then, to remove excessive unreacted γ-chloropropyl trichloro-silane or γ-bromopropyl trichlorosilane, to constant weight, promptly obtain the alkylated silica gel that the surface contains chloropropyl or bromopropyl after 40 ℃ of vacuum drying.Silica-gel carrier is SBA series ordered mesoporous molecular sieve or MCM series ordered mesoporous molecular sieve.
Alkylated silica gel adds in 200ml ethanol or the ether, mixes with the 30g polyethylene polyamine then, and 70 ℃ were reacted 30 hours, and the mixed solvent washing that water, methyl alcohol, ethanol, ether and acetone are formed obtains silica gel-polyamine composite.
Silica gel-polyamine composite and 50g glycerine or glycidol, 3-chloro-1, the 2-propane diols obtains flaxen boron adsorbent 60 ℃ of reactions 25 hours.
Get adsorbent 0.1g of the present invention, add the waste water 100ml contain boric acid 500ppm, intermittent oscillation absorption is after 4 hours, adopts the concentration of solution mesoboric acid before and after the titration measuring absorption, is the 1.3mmol/g adsorbent to the adsorption capacity of boric acid.
The renovation process of boron adsorbent of the present invention is identical with embodiment one.
Claims (8)
1. the preparation method of a boron adsorbent is characterized in that:
(1) 10 weight portion silica-gel carriers is added in 20～200 parts by volume organic solvents, add 3～30 parts by volume organo silane coupling agents again, reaction temperature is that normal temperature is between the organic solvent boiling point, confined reaction 10～50 hours, use organic solvent washing then, 20～50 ℃ of vacuum drying obtain alkylated silica gel to constant weight;
(2) with 3～30 weight portion polyamine mixings, 50～80 ℃ were reacted 10～50 hours down, used solvent wash then, obtained silica gel-polyamine composite in alkylated silica gel adding 50～500 parts by volume solvents that step (1) obtained;
(3) silica gel that step (2) is obtained-polyamine composite and 5～50 weight portion o-dihydroxy compounds reacted 10～50 hours down at 50～80 ℃, obtained boron adsorbent.
2. the preparation method of boron adsorbent according to claim 1 is characterized in that silica-gel carrier in the described step (1) is macro porous silica gel or mesopore silica gel, amorphous silica gel, SBA series ordered mesoporous molecular sieve, MCM series ordered mesoporous molecular sieve.
3. the preparation method of boron adsorbent according to claim 1, the specific area that it is characterized in that the silica-gel carrier in the described step (1) is 200～1500m
2/ g, aperture 1～100nm, pore volume 0.4～2ml/g.
4. the preparation method of boron adsorbent according to claim 1 is characterized in that organic solvent in the described step (1) is methyl alcohol or ethanol, toluene, ether, acetone, hexane, the perhaps mixed solvent of choosing 2～6 kinds of compositions wherein.
5. the preparation method of boron adsorbent according to claim 1, it is characterized in that organo silane coupling agent in the described step (1) is γ-halogen propyl trimethoxy silicane or γ-halogen propyl-triethoxysilicane, γ-halogen propyltrichlorosilan, halogen wherein is chlorine or bromine, iodine.
6. the preparation method of boron adsorbent according to claim 1 is characterized in that polyamine in the described step (2) is polymine or polyvinylamine, PAH, polyethylene polyamine.
7. the preparation method of boron adsorbent according to claim 1 is characterized in that solvent in the described step (2) is water or methyl alcohol, ethanol, ether, acetone, the perhaps mixed solvent of choosing 2～5 kinds of compositions wherein.
8. the preparation method of boron adsorbent according to claim 1, it is characterized in that the o-dihydroxy compound in the described step (3) is glycerine and derivative or carbohydrate and derivative thereof, described glycerine and derivative thereof are glycerine or glycidol, 3-chloro-1, the 2-propane diols; Described carbohydrate and derivative thereof are N-methyl D-aminoglucose or gucosamine, glucose, sweet mellow wine, sorbierite.
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| CN101905146A (en) * | 2010-07-30 | 2010-12-08 | 陈东升 | Silica gel-polyethylene polyamine, preparation method and application thereof to absorbing heavy metal ions |
| CN102188957B (en) * | 2011-04-26 | 2013-02-06 | 湖南大学 | Polyethyleneimine modified magnetic porous adsorbent and preparation method and application thereof |
| CN102500345B (en) * | 2011-11-01 | 2013-06-05 | 河北工业大学 | Boron adsorption gel material and preparation method thereof |
| CN102671642B (en) * | 2012-05-28 | 2013-07-10 | 陕西水木油田技术服务有限公司 | Polyamine composite adsorbing material loaded on silica gel and preparation method thereof |
| CN103241742B (en) * | 2013-05-13 | 2015-02-18 | 杨恺 | High-purity SiCl4 purification method |
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| CN105457609A (en) * | 2015-12-11 | 2016-04-06 | 安徽省中日农业环保科技有限公司 | Heavy metal absorbent containing pectin and preparation method of absorbent |
| CN105585188B (en) * | 2016-02-23 | 2019-04-02 | 江苏达诺尔科技股份有限公司 | A kind of preparation method of no boron ultrapure water |
| EP3398677A1 (en) * | 2017-05-03 | 2018-11-07 | Basf Se | Glycidol modified silica for removing boron from water |
| CN109718740B (en) * | 2017-10-31 | 2022-04-22 | 万华化学集团股份有限公司 | Supported hydrogen chloride adsorbent and preparation method, regeneration method and application thereof |
| CN111039381A (en) * | 2018-10-15 | 2020-04-21 | 中国科学院过程工程研究所 | Method for improving quality of reverse osmosis seawater desalination produced water |
| CN115155529A (en) * | 2021-04-01 | 2022-10-11 | 南开大学 | Boron adsorption resin and preparation method thereof |
| CN113304724A (en) * | 2021-06-03 | 2021-08-27 | 徐州禹慧环境科技研究院有限公司 | Preparation method of functional inorganic silica-based adsorption material |
| CN115350685B (en) * | 2022-08-16 | 2024-01-23 | 青海师范大学 | Attapulgite composite material rich in ortho-hydroxyl and preparation method and application thereof |
| CN115382501B (en) * | 2022-08-16 | 2023-10-13 | 青海师范大学 | Efficient boron-removing adsorbent and preparation method and application thereof |
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| CN1666813A (en) * | 2004-03-12 | 2005-09-14 | 中国科学院过程工程研究所 | Boron absorptive material and its preparing method |
| CN101444541A (en) * | 2007-11-26 | 2009-06-03 | 中国中医科学院中药研究所 | Application of bonded silicagel composite material to removing heavy metals from tradition Chinese medicine extracting solution |
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Patent Citations (2)
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|---|---|---|---|---|
| CN1666813A (en) * | 2004-03-12 | 2005-09-14 | 中国科学院过程工程研究所 | Boron absorptive material and its preparing method |
| CN101444541A (en) * | 2007-11-26 | 2009-06-03 | 中国中医科学院中药研究所 | Application of bonded silicagel composite material to removing heavy metals from tradition Chinese medicine extracting solution |
Non-Patent Citations (1)
| Title |
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