CN102407099B - Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal - Google Patents
Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal Download PDFInfo
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Abstract
The invention relates to a preparation method of chelating resin for highly effective boron absorption, especially a preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal. The method comprises reacting meglumine and silane coupling agent in inert organic solvent, generating meglumine modified silane coupling agent, making the meglumine modified silane coupling agent react with activated silica gel, and finally generating a silica gel loaded polyhydroxyl chelating resin for highly effective boron removal. Compared with the conventional macromolecule-based boron-removing chelating resin, the invention has simple and economical method, overcomes the detects in the present synthesis flow that the silica gel is dissolved for alkalinity of the reaction system is too high (pH more than 11) when surface modified halogen or silica gel of epoxide group reacts with meglumine to synthesize the silica gel loaded polyhydroxyl boron-removing chelating resin, or that the silica gel loaded polyhydroxyl boron-removing chelating resin cannot be synthesized for the nucleophilic substitution of halogen or epoxide group with meglumine cannot be carried out effectively when alkalinity of the reaction system is too low (pH less than 10).
Description
Technical field:
The present invention relates to a kind of preparation method who boron is had the chelating resin of high efficiency of additive capability, particularly a kind of silica gel load polyhydroxy efficiently removes the preparation method of boron chelating resin.
Background technology:
China's boron aboundresources, boron reserves occupy the 5th, the world, but lean ore is many, rich ore is few, along with exploitation in decades, high-grade solid boron resource approaches exhausted, therefore carries boron the salt lake bittern that enriches the boron resource and becomes the main path that obtains in recent years the boron resource from containing to have.The method of carrying boron from salt lake bittern mainly contains: acid precipitation method, floatation, chelating absorption method, solvent extraction etc., wherein the chelating absorption method is applicable to process the lower bittern of boron concentration, and it has the characteristics of selective strong, easy and simple to handle, environmentally safe and has broad application prospects.Vicinal hydroxyl groups in meglumine is to B (OH)
4 -Ion has efficient sequestering power, therefore be widely used in removing with the enrichment water body in boron element.Existing polyhydroxy except the boron chelating resin mostly adopt Macroporous styrene-divinybenzene copolymers (as
IRA743, D564), the high molecular polymer matrix such as shitosan, cellulose, they have higher adsorbance, but bad mechanical strength, easy aging swelling, production cost higher (Y T.Wei, Y M.Zheng, J.Paul Chen.Design and fabrication of an innovative and environmental friendly adsorbent for boron removal, Water research, 2011,45:2297～2305; Y.Inukai, Y Tanaka, T.Matsuda, N.Mihara, K.Yamada, N.Nambu, O.Itoh, T.Doi, Y Kaida, S.Yasuda, Removal of boron (III) by N-methylglucamine-type cellulose derivatives with higher adsorption rate.Anal.Chim.Acta 2004,511:261～265.), therefore be difficult to promote in large-scale salt lake bittern is proposed boron industry.
Take silica gel as matrix inorganic/organic material is one of focus of current research, this be due to silica gel except having good mechanical strength, higher chemical stability and heat endurance, also having outstanding characteristics is that its contained abundant silicon hydroxyl in surface can show good hydrophily, thereby greatly improves the absorption property of resin.In bibliographical information, the silica gel load polyhydroxy mainly contains two kinds except the preparation method of boron chelating resin, and the first is first grafting, rear functionalization, that is: at first by ethyl orthosilicate contain template (as CTMAB, P
123) the aqueous solution in be hydrolyzed, remove template by high-temperature roasting or extraction and obtain the mesoporous silica gel matrix, again by Silanization reaction at Silica Surface load halogen or epoxide group, under alkali condition, make the silica gel matrix of area load halogen or epoxy radicals and meglumine reaction generate mesoporous type silica gel load polyhydroxy except the boron chelating resin at last.Our research is found, adopt this synthetic route to the pH value of reaction system, strict requirement to be arranged, this is because meglumine contains a large amount of amino, very easily make the local alkalescence very high (pH＞11) of reaction solution, cause the dissolving of silica gel matrix, can guarantee that the silica gel matrix is insoluble if adopt the lower single solvent (as dioxane) of polarity or mixed solvent (as dioxane+water) to regulate alkalescence (pH＜10), but this moment, reaction solution alkalescence was low, made the nucleophilic substitution of halogen or epoxide group and meglumine be difficult to effectively carry out.In addition, this method complex procedures, the matrix granularity is less and cost is higher, and the adsorption capacity of institute's synthetic resin is not high, is difficult to be applied in the middle of actual production.The second synthetic route is first functionalization, rear grafting, that is: first make the reaction of meglumine and halogen or epoxy silane coupling generate modified silane coupler, be hydrolyzed in the aqueous solution by ethyl orthosilicate again modified silane coupler is carried out generating gel after physically encapsulation, at last the gel after oven dry is carried out mechanical disintegration, obtain gel-type silica gel load polyhydroxy except the boron chelating resin.in this synthetic method, the generation of modified silane coupler can effectively reduce the alkalescence of meglumine in reaction system, avoid silica gel to dissolve in modifying process, thereby effectively improve the combined coefficient of resin, but the synthetic resin size of this method distributes wide, adsorption capacity is lower, involve great expense and the synthesis procedure complexity, be difficult to effectively promote in actual applications (O.Kaftan, M.Acikel, A.E.Eroglu, T.Shahwan, L.Artok, C.Ni, Synthesis, characterization and application of a novel sorbent, glucamine-modified MCM-41, for the removal/preconcentration of boron from waters, Anal.Chim.Acta 2005, 547:31～41, B.Tural, Separation and preconcentration of boron with a glucamine modified novel magnetic sorbent.Clean-Soil, Air, Water 2010,38:321～327, H.N.Liu, X.S.Ye, Q.Li, T.Kim, B.J.Qing, M.Guo, F Ge, Z.J.Wu, K.Lee, Boron adsorption using a new boron-selective hybrid gel and the commercial resin D564.Colloids and Surfaces A:Physicochemical and Engineering Aspects 2009,341:118～126.).
Summary of the invention:
The purpose of this invention is to provide a kind of silica gel load polyhydroxy and efficiently remove the preparation method of boron chelating resin, can effectively improve the polyhydroxy chelating resin to the adsorption capacity of boron, also overcome to a certain extent situation too harsh to the requirement of pH value in existing process.
Technical scheme of the present invention is:
A kind of silica gel load polyhydroxy efficiently removes the preparation method of boron chelating resin: at first silane coupler and meglumine are generated the meglumine modified silane coupler under inert organic solvents, then the meglumine modified silane coupler that generates is grafted to the surface of silica silica gel.
Described silane coupler and meglumine by etc. mole react.
50～100 ℃ of described silane coupler and meglumine temperature of reaction system react under nitrogen atmosphere, reaction time 6～24h.
Described inert organic solvents is a kind of in cyclohexane, heptane, DMF, toluene.
Described silane coupler comprises a kind of in 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, 3-chloropropyl triethoxysilane, 3-bromopropyl triethoxysilane.
The concrete steps of silane coupler and meglumine reaction are as follows:
Get meglumine, inert organic solvents is added to three-necked bottle, mechanical agitation, the heating make reaction system be warming up to 50～100 ℃; Dropwise splash into three-necked bottle after separately inert organic solvents and silane coupler being mixed, keep 50～100 ℃ of system temperatures, the nitrogen atmosphere 6～24h that refluxes in whole course of reaction; After reaction is completed, suction filtration obtains solid product, it is extracted with the methyl alcohol Soxhlet, and the suction filtration solid product, vacuum drying obtains the meglumine modified silane coupler.
Graft reaction be will the activation silica silica gel and the meglumine modified silane coupler in inert organic solvents, 50～100 ℃ of system temperatures, react 12～36h under nitrogen atmosphere, described inert organic solvents is a kind of in cyclohexane, heptane, DMF, toluene.The silica silica gel of activation and the reaction usage ratio of meglumine modified silane coupler are 4g: 2～20g.
During graft reaction, drip the mixed solution of the hydrochloric acid of absolute ethyl alcohol and 2%～20%; The volume ratio of absolute ethyl alcohol and hydrochloric acid solution is 4: 1.
The concrete steps of graft reaction are as follows:
Getting meglumine modified silane coupler and inert organic solvents joins in three-necked bottle, 50～100 ℃ of lower mechanical agitation, then getting activation silica silica gel adds, the hydrochloric acid mixed solution of getting at last absolute ethyl alcohol and 2%～20% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 12～36h; After reaction is completed, suction filtration obtains solid shape product, and this product is rear in vacuum drying with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
of the present invention with the silica gel load polyhydroxy efficiently except the preparation synthetic route of boron chelating resin, redesign through the inventor, not only effectively improved the adsorption capacity of silica gel load polyhydroxy except the boron chelating resin, when having avoided simultaneously the silica gel of finishing halogen in existing synthetic route or epoxy radicals and meglumine reaction preparation silica gel load polyhydroxy except the boron chelating resin, because reaction system alkalescence too high (pH＞11) causes the silica gel dissolving, or alkalescence too low (pH＜10) makes the nucleophilic substitution of halogen or epoxy radicals and meglumine be difficult to effectively carry out, can not generate the silica gel load polyhydroxy except the boron chelating resin.
Efficiently except the preparation method of boron chelating resin, concrete steps are a kind of silica gel load polyhydroxy of the present invention:
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, uses successively deionized water and methanol wash to neutral it, and drying at room temperature 12h obtains activated silica gel.
(2) get the 20g meglumine, the 200ml inert organic solvents is added to the 500ml three-necked bottle, mechanical agitation, oil bath heating makes reaction system be warming up to 50～100 ℃; Dropwise splash into three-necked bottle after 40ml inert organic solvents and 30ml silane coupler mix, keep 50～100 ℃ of system temperatures in whole course of reaction, nitrogen atmosphere backflow 6～24h.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains the meglumine modified silane coupler.
(3) getting the middle meglumine modified silane coupler of 2～20g step (2) and 200ml inert organic solvents joins in the 500ml three-necked bottle, 50～100 ℃ of lower mechanical agitation of oil bath, then getting the middle 4g activated silica gel of step (1) adds, the hydrochloric acid mixed solution of getting at last 16ml absolute ethyl alcohol and 4ml 2%～20% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 12～36h.After reaction is completed, suction filtration obtains solid shape product, and this product is rear in 50 ℃ of vacuum drying 12h with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
The described inert organic solvents of step (2) comprises a kind of in cyclohexane, heptane, DMF, toluene.
The described inert organic solvents of step (3) comprises a kind of in cyclohexane, heptane, DMF, toluene.
The described silane coupler of step (3) comprises a kind of in 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, 3-chloropropyl triethoxysilane, 3-bromopropyl triethoxysilane.
Advantage of the present invention and good effect are: provide a kind of adsorption capacity large (pH value of solution=9 o'clock, the boron adsorbance can reach 1.6mmol/g, improved 40% than existing silica gel load polyhydroxy except the adsorbance of boron chelating resin, suitable with the absorption property of the boron special efficacy commercial resin D564 of domestic macroporous styrene-divinylbenzene copolymer matrix), synthetic method is simple, the rate of adsorption is fast, mechanical strength is good silica gel load polyhydroxy is efficiently except boron chelating resin and preparation method thereof.By method of the present invention, not only effectively improved the adsorption capacity of silica gel load polyhydroxy except the boron chelating resin, when having avoided in existing synthetic route area load halogen or epoxy radicals silica gel and meglumine reaction preparation polyhydroxy except the boron chelating resin, because reaction system alkalescence too high (pH＞11) causes the silica gel dissolving, or alkalescence too low (pH＜10) makes the nucleophilic substitution of halogen or epoxy radicals and meglumine be difficult to effectively carry out, and can not generate the silica gel load polyhydroxy and remove the boron chelating resin.
The specific embodiment
Following embodiment is intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1 adopts the different inert organic solvent to prepare the meglumine modified silane coupler
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, uses successively deionized water and methanol wash to neutral it, and drying at room temperature 12h obtains activated silica gel.
(2) get the 20g meglumine, the 200ml inert organic solvents is added to the 500ml three-necked bottle, mechanical agitation, oil bath heating makes reaction system be warming up to 50～100 ℃; 40ml inert organic solvents and 30ml 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane dropwise splashes into three-necked bottle after mixing, and keeps 80 ℃ of system temperatures, nitrogen atmosphere backflow 24h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains the meglumine modified silane coupler.
(3) getting the middle meglumine modified silane coupler of 8g step (2) and 200ml toluene joins in the 500ml three-necked bottle, 80 ℃ of lower mechanical agitation of oil bath, then getting the middle 4g activated silica gel of step (1) adds, the hydrochloric acid mixed solution of getting at last 16ml absolute ethyl alcohol and 4ml 5% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 36h.After reaction is completed, suction filtration obtains solid shape product, and this product is rear in 50 ℃ of vacuum drying 12h with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
Table 1 adopts different inert organic solvent synthetic meglumine modified silane coupler and its nitrogen content relation
Embodiment 2 adopts the different inert organic solvent to prepare the silica gel load polyhydroxy efficiently except the boron chelating resin
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, uses successively deionized water and methanol wash to neutral it, and drying at room temperature 12h obtains activated silica gel.
(2) get 20g meglumine, 200mlN, dinethylformamide is added to the 500ml three-necked bottle, mechanical agitation, and the oil bath heating makes reaction system be warming up to 80 ℃; 40ml DMF and 30ml 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane dropwise splashes into three-necked bottle after mixing, and keeps 80 ℃ of system temperatures, nitrogen atmosphere backflow 24h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains the meglumine modified silane coupler.
(3) get the middle meglumine modified silane coupler of 8g step (2) and 200ml cyclohexane, heptane, N, dinethylformamide, toluene join in the 500ml three-necked bottle, 50～100 ℃ of lower mechanical agitation of oil bath, then getting the middle 4g activated silica gel of step (1) adds, the hydrochloric acid mixed solution of getting at last 16ml absolute ethyl alcohol and 4ml 5% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 12～36h.After reaction is completed, suction filtration obtains solid shape product, and this product is rear in 50 ℃ of vacuum drying 12h with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
Table 2 adopts the different inert organic solvent to prepare the silica gel load polyhydroxy efficiently except boron chelating resin and boron absorption the relationship between quantities
Embodiment 3 adopts different silane couplers to prepare the silica gel load polyhydroxy efficiently except the boron chelating resin
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, uses successively deionized water and methanol wash to neutral it, and drying at room temperature 12h obtains activated silica gel.
(2) get 20g meglumine, 200mlN, dinethylformamide is added to the 500ml three-necked bottle, mechanical agitation, and the oil bath heating makes reaction system be warming up to 80 ℃; Dropwise splash into three-necked bottle after 40ml DMF and 30ml silane coupler mix, keep 80 ℃ of system temperatures, nitrogen atmosphere backflow 24h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains the meglumine modified silane coupler.
(3) getting the middle meglumine modified silane coupler of 8g step (2) and 200ml toluene joins in the 500ml three-necked bottle, 80 ℃ of lower mechanical agitation of oil bath, then getting the middle 4g activated silica gel of step (1) adds, the hydrochloric acid mixed solution of getting at last 16ml absolute ethyl alcohol and 4ml 5% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 36h.After reaction is completed, suction filtration obtains solid shape product, and this product is rear in 50 ℃ of vacuum drying 12h with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
Table 3 adopts different silane couplers to prepare the silica gel load polyhydroxy efficiently except boron chelating resin and boron absorption the relationship between quantities
| The experiment sequence number | Silane coupler | Boron adsorbance (mmol/g) |
| Run 1 | 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane | 1.6 |
| Run 2 | The 3-chloropropyl triethoxysilane | 1.1 |
| Run 3 | 3-bromopropyl triethoxysilane | 1.3 |
Embodiment 4 adopts the variable concentrations hydrochloric acid solution to prepare the silica gel load polyhydroxy efficiently except the boron chelating resin
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO3 solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, use successively deionized water and methanol wash to neutral it, drying at room temperature 12h obtains activated silica gel.
(2) get 20g meglumine, 200mlN, dinethylformamide is added to the 500ml three-necked bottle, mechanical agitation, and the oil bath heating makes reaction system be warming up to 80 ℃; 40ml DMF and 30ml 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane dropwise splashes into three-necked bottle after mixing, and keeps 80 ℃ of system temperatures, nitrogen atmosphere backflow 24h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains the meglumine modified silane coupler.
(3) getting the middle meglumine modified silane coupler of 8g step (2) and 200ml toluene joins in the 500ml three-necked bottle, 80 ℃ of lower mechanical agitation of oil bath, then getting the middle 4g activated silica gel of step (1) adds, the hydrochloric acid mixed solution of getting at last 16ml absolute ethyl alcohol and 4ml 2%～20% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 36h.After reaction is completed, suction filtration obtains solid shape product, and this product is rear in 50 ℃ of vacuum drying 12h with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
Table 4 adopts the variable concentrations hydrochloric acid solution to prepare the silica gel load polyhydroxy efficiently except boron chelating resin and boron absorption the relationship between quantities
| The experiment sequence number | Concentration of hydrochloric acid % | Boron adsorbance (mmol/g) |
| Run 1 | 2 | 0.4 |
| Run 2 | 5 | 1.6 |
| Run 3 | 10 | 1.3 |
| Run4 | 20 | 1.8 |
Embodiment 5 adopts the variable concentrations hydrochloric acid solution to prepare the silica gel load polyhydroxy efficiently except the boron chelating resin
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO3 solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, use successively deionized water and methanol wash to neutral it, drying at room temperature 12h obtains activated silica gel.
(2) get 20g meglumine, 200mlN, dinethylformamide is added to the 500ml three-necked bottle, mechanical agitation, and the oil bath heating makes reaction system be warming up to 80 ℃; 40ml DMF and 30ml 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane dropwise splashes into three-necked bottle after mixing, and keeps 80 ℃ of system temperatures, nitrogen atmosphere backflow 24h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains the meglumine modified silane coupler.
(3) getting the middle meglumine modified silane coupler of 2g-20g step (2) and 200ml toluene joins in the 500ml three-necked bottle, 80 ℃ of lower mechanical agitation of oil bath, then getting the middle 4g activated silica gel of step (1) adds, the hydrochloric acid mixed solution of getting at last 16ml absolute ethyl alcohol and 4ml 5% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 36h.After reaction is completed, suction filtration obtains solid shape product, and this product is rear in 50 ℃ of vacuum drying 12h with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
Table 5 adopts different quality meglumine modified silane coupler to prepare the silica gel load polyhydroxy efficiently except boron chelating resin and boron absorption the relationship between quantities
| The experiment sequence number | Meglumine modified silane coupler g | Boron adsorbance (mmol/g) |
| Run1 | 2 | 0.5 |
| Run2 | 4 | 0.8 |
| Run3 | 8 | 1.6 |
| Run4 | 12 | 1.6 |
| Run5 | 16 | 1.7 |
| Run6 | 20 | 1.7 |
Comparative Examples 1
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, uses successively deionized water and methanol wash to neutral it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical agitation, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and 20ml 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane dropwise splashes into three-necked bottle after mixing, and keeps 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains silanized silica gel.
(3) get silanized silica gel that 10g step (2) obtains respectively with the 100ml absolute methanol, or absolute ethyl alcohol or dioxane, deionized water joins in the 250ml three-necked bottle, is heated to 60 ℃.Add the 20g meglumine, react 24h under mechanical agitation.Suction filtration obtains solid product, and this product is used deionized water, 1mol/L sulfuric acid, 1mol/L ammoniacal liquor, methanol wash successively, in 50 ℃ of vacuum drying 12h, obtains the silica gel load polyhydroxy except the boron chelating resin.
Table 5 the first silanization of silica gel again in the synthesis flow of grafting meglumine different solvents adsorb the relationship between quantities with prepared silica gel load polyhydroxy except boron chelating resin boron
| The experiment sequence number | Organic solvent | Boron adsorbance (mmol/g) |
| Run 1 | Absolute methanol | The silica gel dissolving |
| Run 2 | Absolute ethyl alcohol | 0.3 |
| Run 3 | Dioxane | 0.4 |
| Run 4 | Deionized water | The silica gel dissolving |
| Run5 | Methyl alcohol+deionized water | The silica gel dissolving |
| Run6 | Dioxane+deionized water | 0.6 |
Comparative Examples 2
(1) get the 30g chromatogram and fill out post silica silica gel in the 500ml three-necked bottle, add 1mol/L HNO
3Solution 200ml, at 50 ℃ of lower mechanical agitation 6h, after reaction, suction filtration gets solid product, uses successively deionized water and methanol wash to neutral it, and drying at room temperature 12h obtains activated silica gel.
(2) get activated silica gel, the 150ml toluene that 20g step (1) obtains and be added to the 500ml three-necked bottle, mechanical agitation, the oil bath heating makes reaction system be warming up to 110 ℃; 80ml toluene and 20ml 3-(2,3-epoxy the third oxygen) dropwise splash into three-necked bottle after propyl trimethoxy silicane or 3-chloropropyl triethoxysilane or 3-bromopropyl triethoxysilane mix, keep 110 ℃ of system temperatures, nitrogen atmosphere backflow 48h in whole course of reaction.After reaction is completed, suction filtration obtains solid product, and it is extracted 6h with the methyl alcohol Soxhlet, and the suction filtration solid product in 50 ℃ of vacuum drying 12h, obtains silanized silica gel.
(3) get silanized silica gel and the 100ml dioxane that 10g step (2) obtains and join in the 250ml three-necked bottle, be heated to 60 ℃.Add the 20g meglumine, react 24h under mechanical agitation.Suction filtration obtains solid product, and this product is used deionized water, 1mol/L sulfuric acid, 1mol/L ammoniacal liquor, methanol wash successively, in 50 ℃ of vacuum drying 12h, obtains the silica gel load polyhydroxy except the boron chelating resin.
Table 6 is used in the synthesis flow of grafting meglumine by different silane couplers and prepared silica gel load polyhydroxy at the first silanization of silica gel again and is adsorbed the relationship between quantities except boron chelating resin boron
| The experiment sequence number | Silane coupler | Boron adsorbance (mmol/g) |
| Run 1 | 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane | 0.5 |
| Run 2 | The 3-chloropropyl triethoxysilane | 0.3 |
| Run 3 | 3-bromopropyl triethoxysilane | 0.7 |
Claims (8)
1. a silica gel load polyhydroxy efficiently removes the preparation method of boron chelating resin, it is characterized in that, at first silane coupler and meglumine are generated the meglumine modified silane coupler in inert organic solvents, then the meglumine modified silane coupler that generates is grafted to the surface of silica silica gel;
Graft reaction be will the activation silica silica gel and the meglumine modified silane coupler in inert organic solvents, 50 ~ 100 ℃ of system temperatures, react 12 ~ 36h under nitrogen atmosphere, described inert organic solvents is a kind of in cyclohexane, heptane, DMF, toluene.
2. preparation method according to claim 1, is characterized in that, 50 ~ 100 ℃ of described silane coupler and meglumine temperature of reaction system react under nitrogen atmosphere, reaction time 6 ~ 24h.
3. preparation method according to claim 1, is characterized in that, described inert organic solvents is a kind of in cyclohexane, heptane, DMF, toluene.
4. preparation method according to claim 1, is characterized in that, described silane coupler comprises 3-(2,3-epoxy the third oxygen) a kind of in propyl trimethoxy silicane, 3-chloropropyl triethoxysilane, 3-bromopropyl triethoxysilane.
5. according to claim 1-4 described preparation methods of any one, is characterized in that, the concrete steps of silane coupler and meglumine reaction are as follows:
Get meglumine, inert organic solvents is added to three-necked bottle, mechanical agitation, the heating make reaction system be warming up to 50 ~ 100 ℃; Dropwise splash into three-necked bottle after separately inert organic solvents and silane coupler being mixed, keep 50 ~ 100 ℃ of system temperatures, the nitrogen atmosphere 6 ~ 24h that refluxes in whole course of reaction; After reaction is completed, suction filtration obtains solid product, it is extracted with the methyl alcohol Soxhlet, and the suction filtration solid product, vacuum drying obtains the meglumine modified silane coupler.
6. preparation method according to claim 1, is characterized in that, the silica silica gel of activation and the reaction usage ratio of meglumine modified silane coupler are 4g:2 ~ 20g.
7. preparation method according to claim 1, is characterized in that, during graft reaction, drips the mixed solution of the hydrochloric acid of absolute ethyl alcohol and 2% ~ 20%; The volume ratio of absolute ethyl alcohol and hydrochloric acid solution is 4:1.
8. according to claim 1 or 6 or 7 described preparation methods, is characterized in that, the concrete steps of graft reaction are as follows:
Getting meglumine modified silane coupler and inert organic solvents joins in three-necked bottle, 50 ~ 100 ℃ of lower mechanical agitation, then getting activation silica silica gel adds, the hydrochloric acid mixed solution of getting at last absolute ethyl alcohol and 2% ~ 20% dropwise joins in three-necked bottle, the dropping process continues to stir, and continues reaction 12 ~ 36h; After reaction is completed, suction filtration obtains solid shape product, and this product is rear in vacuum drying with the absolute methanol washing, obtains the silica gel load polyhydroxy efficiently except the boron chelating resin.
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| CN103043649B (en) * | 2012-12-30 | 2015-04-15 | 北京大学深圳研究生院 | Preparation method for porous carbon spheres |
| CN103521186B (en) * | 2013-09-27 | 2016-08-17 | 湖南中烟工业有限责任公司 | A kind of area load ionic liquid and the silica gel of mercaptan and preparation method and application |
| CN103877941B (en) * | 2014-03-20 | 2016-04-06 | 浙江大学 | A kind of spherical silica-based hybrid inorganic-organic boron adsorbent and preparation method thereof |
| US11014830B2 (en) * | 2016-12-15 | 2021-05-25 | Ada Carbon Solutions, Llc | Sorbent compositions for the removal of boron from aqueous mediums |
| CN110465275A (en) * | 2018-05-09 | 2019-11-19 | 天津工业大学 | A kind of preparation method for the nonwoven basalt fibre base boron chelate sorbent mentioning boron for salt lake |
| CN112919480B (en) * | 2021-02-01 | 2023-02-10 | 中国石油天然气股份有限公司 | Dihydroxy silica gel, preparation method thereof and detection system for concentration of functional polymer in produced liquid |
| 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 |
| CN113634234B (en) * | 2021-07-29 | 2023-08-22 | 山东省水利科学研究院 | Adsorbent for desalting seawater and removing boron as well as preparation method and application thereof |
| 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 |
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