CN1772386A - 8-hydroxy quinoline type chelated resin and its synthesis - Google Patents
8-hydroxy quinoline type chelated resin and its synthesis Download PDFInfo
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Abstract
The 8-hydroxy quinoline type chelated resin has 8-hydroxy quinoline fixed onto macroporous silica gel through silanizing reagent and paraformaldehyde as spacer arm and bonding amount of 120-542 umol/g. Its synthesis process includes the steps of: pre-treating macroporous silica gel; introducing spacer arm; fixing ligand and acid washing to set via drying intermediate product II, washing with alcohol and drying for several times, washing with hydrochloric acid, and washing with deionized water to neutral so as to obtain yellow chelated resin. The resin has simple synthesis process, mild reaction condition, short synthesis time, easy control, high synthesis efficiency, low cost, high rigidity and high metal ion complexing capacity, and may be used in on-line enriching analysis of trace metal, enriching recovery of noble metals, purifying industrial waste water, etc.
Description
Technical field
The present invention relates to the improvement of chelating resin, especially a kind of oxine type chelating resin and synthetic method thereof.This chelating resin can be applied to remove the analysis of metal ion pollution and trace metal enrichment in the water body.
Background technology
At present, known metal ion-chelant resin all has matrix, spacerarm, ligand three parts, and wherein ligand is of paramount importance part, because the character of ligand has directly determined the absorption situation of resin to each metal ion species.Comparatively commonly used is that ligand is the chelating resin of iminodiacetic acid (salt) acid type or aminomethyl phosphonic acids type now.Method as the disclosed method for preparing the aminomethyl phosphonic acid resin of Chinese patent CN 1031581C number and CN 1143876C number disclosed iminodiacetic acid (salt) acid resin and aminomethyl phosphonic acid resin.But the kind of their adsorbing metal ions is few.Existing U.S. Pat A-3886080 discloses a kind of synthetic method that can be used for the ion chelating resin of the oxine type of contents of many kinds of heavy metal ion and enriched with trace metal ion in the waste water of place to go.This resin rigidity is better, and can be by selecting the eluent of different pH values for use, and with chelating different metal ion stepwise elution thereon.But this resin synthetic route is complicated, oxine is lower at the bonded amount of matrix surface, and the resin adsorption dynamic performance is relatively poor, and adsorption capacity is little, and agents useful for same toxicity is bigger in the building-up process, has seriously influenced the result of use of this resin reality.This American process is that silica gel is placed through the toluene that heavily steams, calcium chloride dewaters, add gamma-aminopropyl-triethoxy-silane, stirring and refluxing 15-24h, use toluene, the excessive silylating reagent of acetone flush away respectively, oven dry is placed in the 40-70ml chloroform, stirs to add 0.8-1.2g paranitrobenzoyl chloride and 0.8-1.2ml triethylamine, 40-60 ℃ of constant temperature oscillating reactions 40-60h down, with chloroform, methyl alcohol, acetone washing, this moment, product showed orange-yellow to product successively; Again this product is placed 40-60ml4-6% (w/v) hydrosulfurous acid sodium solution, 40-50 ℃ of constant temperature oscillating reactions 12-18h.Product fully washs the back with deionized water and adds the 2MHCl solution that contains the 0.8-1.2g natrium nitrosum, stirring reaction 20-40min under 0-4 ℃ of condition, with the washing of ice deionized water, at last product is added and contain in the 40-60ml ethanol solution of 0.8-1.2g8-oxyquinoline stirring reaction 2-4h under the normal temperature.Products therefrom with the salt acid elution of 1M, fully washs with deionized water earlier again, 50-70 ℃ dry product.The synthetic method of the ion chelating resin of this oxine type is one five step reaction, about 4 days of reaction time supply and demand, and employed nitrobenzoyl chloride in its reaction, the diazonium intermediate product that natrium nitrosum and reaction (IV) generate all are the chemicals that severe toxicity is arranged.
Summary of the invention
The objective of the invention is in order to overcome the ion chelating resin synthetic method complexity of existing oxine type, oxine is in the low deficiency of the bonded amount of carrier surface, so a kind of stable performance is provided, good rigidly, absorption heavy metal kind is many, the adsorption dynamics adsorption kinetics performance is good, and adsorption capacity is big, chelating resin that regenerative elution is easy and synthetic method thereof.
Task of the present invention is finished by following technical scheme, has developed a kind of Mannich reaction, synthetic oxine type chelating resin of passing through.Described chelating resin is with the ligand oxine,, is fixed on the macro porous silica gel matrix as spacerarm by silylating reagent and paraformaldehyde; The structural formula of described chelating resin is:
≡ SiO represents silica gel matrix I type in the formula)
The II type)
The oxine of this chelating resin at the bonded amount on silica gel surface at 120-542umol/g.
A kind of synthetic method of described oxine type chelating resin.Described synthetic method step is as follows:
1) preliminary treatment of macro porous silica gel: the macropore chromatographic silica gel is placed 0.05-0.15mol/L HCl solution, leave standstill 18-30h under 90 ℃, be washed till no chlorion with deionized water, dry good, standby in vacuum drying chamber;
2) introduce spacerarm: it places through the toluene that heavily steams and calcium chloride dewaters with the macropore chromatographic silica gel of above-mentioned processing, add silylating reagent, stirring and refluxing 12-24h uses toluene and the excessive silylating reagent of acetone flush away respectively, 100-120 ℃ of oven dry gets intermediate product I;
3) ligand is fixing; Oxine is dissolved in the ethanol of 50-70 ℃ of following low-grade fever, and then progressively adds the 10mmol paraformaldehyde successively, intermediate product I; At 50-70 ℃ of following stirring reaction 5-8 hour, get intermediate product II again;
4) pickling typing: with intermediate product II, at 80-100 ℃ of dry 1h down, again with ethanol several times after the washed product, at 100-120 ℃ of dry 2h down; Use the salt acid elution one time of first 1M at last, be washed till neutrality with deionized water again, obtain having yellow oxine type chelating resin.
Described macropore chromatographic silica gel, its specification is: the 50-100 order, its physical and chemical performance is: average pore size is at 10-60nm, average specific surface area 250-350m
2/ g, average pore volume 1.00-2.00ml/g.
Described silylating reagent, it is gamma-aminopropyl-triethoxy-silane (APTS), or is γ-An Bingjisanjiayangjiguiwan.When using γ-An Bingjisanjiayangjiguiwan, the I type of this chelating resin), few " CH in molecular formula II type) as the spacerarm of silylating reagent
2".
The beneficial effect of oxine type chelating resin of the present invention and synthetic method thereof is as follows: (1) is because raw material is conventional macropore chromatographic silica gel, silylating reagent and paraformaldehyde, it is cheap, the source is abundant, so chelating resin rigidity of the present invention is much better than polymeric matrix, can carry out the on-line preconcentration analysis to trace metal with the microtrabeculae of this kind chelating resin filling; (2) synthesis technique is simple, and building-up process is controlled easily, the combined coefficient height; (3) reaction time weak point, mild condition, basic nonhazardous, ligand has all improved nearly 5 times than traditional method at the bonded amount of matrix surface and to the chelating amount of metal ion.(4) chelating resin of the present invention has very high ligand complex ability, by changing the pH value of eluent, can realize enriching and recovering or the trace metal in the various water bodys is carried out the enrichment analysis multiple noble metal, also can purify the industrial wastewater that contains heavy metal element or radioactive element, have a wide range of applications.
Chelating resin counterweight metals like gold of the present invention, copper, lead, nickel etc. have excellent absorption and select performance, be used in the pH value scope of broad above-mentioned heavy metal ion in the water body is reclaimed purification with industrial wastewater, fields such as the enriching and recovering of heavy metal or online content analysis in the seawater.
Chemical reaction main among the present invention is as follows, and ≡ SiOI represents the silica gel matrix
(2) introduce spacerarm:
(3) ligand is fixing:
The accompanying drawing and the specific embodiment thereof
Embodiments of the invention further specify as follows in conjunction with the accompanying drawings:
Fig. 1 is the infrared spectrogram of oxine type chelating resin.
Among Fig. 1,1380cm
-1The spike at place is the in-plane bending vibration peak that 8-HQ goes up phenolic hydroxyl group, illustrates that 8-HQ has the amount of big bonding on the macro porous silica gel surface.1615cm
-1And 1510cm
-1The peak at place is respectively the vibration peak of aromatic ring frame and the vibration peak of aromatic ring.1420cm
-1The very weak peak at place is-CH
2Cut the peak.These characteristic peaks all are consistent with oxine type chelating resin structure.
Embodiment 1:
(1) takes by weighing the common commercially available 50-100 order chromatographic silica gel of 10g and place in the 100ml round-bottomed flask, to wherein adding the pure HCl solution of 0.1mol/L top grade, leave standstill 24h under 90 ℃, be washed till neutrality with deionized water, 150 ℃ of oven dry in vacuum drying chamber;
(2) will place in the 100ml round-bottomed flask through the silica gel that step (1) is handled, adding is through the 50mL toluene, the 5mL gamma-aminopropyl-triethoxy-silane that heavily steam, calcium chloride dewaters, stirring and refluxing 18h uses toluene, acetone, the excessive silylating reagent of ethanol flush away respectively, 120 ℃ of dry for standby;
(3) 8-HQ that takes by weighing 0.73g places in the 100ml round-bottomed flask and is dissolved in 25ml ethanol under the low-grade fever, progressively adds the product that 0.3g paraformaldehyde and step (2) are handled again then successively, 50 ℃ of following stirring reactions of constant temperature 7 hours;
(4) 100 ℃ of products that step (3) is handled dry 1h down divide after 7 washed product dry 2h under 120 ℃ with 140ml ethanol again.Use the pure HCl solution salt acid elution of first 15ml1M top grade one time at last, be washed till neutrality with deionized water again.Promptly make oxine type chelating resin.
Because reaction time, temperature, various reactant feed are than all exerting an influence to final bonding effect.Therefore choose 4 factors of ratio of reaction time, reaction temperature, APTS consumption and APTS and 8HQ, with Cu
2+For investigating index, use L in the fixing adsorbance that goes up mutually
9(3
4) orthogonal test table, see Table 1.Orthogonal experiments sees Table 2.
Table 1 bonding method orthogonal test
| Horizontal level | Factor f action | |||
| APTS consumption Vol.of APTS V (ml) | Reaction time Time T (h) | Reaction temperature Temperaturet (C °) | APTS∶8HQ V∶V | |
| 1 | 0.3 | 4 | 50 | 1∶0.75 |
| 2 | 0.5 | 5 | 60 | 1∶1.00 |
| 3 | 0.7 | 6 | 70 | 1∶1.25 |
Table 2 bonding method orthogonal experiments
| Experiment Number | Row Column number | Cu 2+Adsorbance Adsorption of Cu 2+ ions (umol/g) | |||
| A | B | C | D | ||
| 1 | 0.3 | 4 | 50 | 1∶0.75 | 277.12 |
| 2 | 0.3 | 5 | 60 | 1∶1.00 | 254.71 |
| 3 | 0.3 | 6 | 70 | 1∶1.25 | 264.77 |
| 4 | 0.5 | 4 | 60 | 1∶1.25 | 276.15 |
| 5 | 0.5 | 5 | 70 | 1∶0.75 | 283.35 |
| 6 | 0.5 | 6 | 50 | 1∶1.00 | 297.29 |
| 7 | 0.7 | 4 | 70 | 1∶1.00 | 287.75 |
| 8 | 0.7 | 5 | 50 | 1∶1.25 | 338.66 |
| 9 | 0.7 | 6 | 60 | 1∶0.75 | 327.36 |
| Average 1 | 265.53 | 280.34 | 304.36 | 295.94 | |
| Average 2 | 285.60 | 292.24 | 286.07 | 279.92 | |
| Average 3 | 317.92 | 296.47 | 278.62 | 293.19 | |
| Extreme difference | .52.39 | 16.13 | 25.73 | 16.02 | |
As shown in Table 2, these four factors to the influence of product are in proper order: A＞C＞B=D.Optimum synthesis condition is A
3B
3C
1D
1The SHQ performance comparison of synthesizing according to the synthetic SHQ of this condition and conventional method sees Table 3.Take by weighing two kinds of each 5mg of SHQ in the 5ml volumetric flask, after adding 1M KOH solution constant volume respectively, vibration 30min, after treating that SHQ dissolves fully, survey UV spectrum, dissolve the 8-HQ of variable concentrations again with 1M KOH solution, survey UV spectrum, utilize the characteristic absorption peak at 223nm place, make calibration curve, can converse the fixing bonded amount of going up 8-HQ mutually of SHQ.The results are shown in Table 3.
The bonding concentration on table 3 silica gel surface
| Surface bond concentration (umol/g) | |||
| 8-HQ is in silica gel surface bond amount | Cu 2+Adsorbance | Ni 2+Adsorbance | |
| Conventional method is synthesized the SHQ filler | 117 | 76 | 64 |
| New method is synthesized the SHQ filler | 542 | 347 | 290 |
Embodiment 2:
Institute only changes used silylating reagent into γ-An Bingjisanjiayangjiguiwan in steps with embodiment 1.Promptly make oxine type chelating resin.
Embodiment 3:
Institute only changes used silylating reagent into γ-An Bingjisanjiayangjiguiwan in steps with embodiment 1; Oxine-5-sulfonic acid of getting 1g again carries out synthetic reaction.Promptly make oxine type chelating resin.
Embodiment 4:
(1) take by weighing synthetic oxine type chelating (SHQ) resin of 5g said method, put into conical flask, in the CuSO4/NiSO4/Fe that wherein adds 50mM (NO3) 3 solution, resin is taken out in normal temperature vibration 2 hours.
(2) the sour eluent of usefulness pH=1, the Cu2+/Ni2+/Fe3+ that adsorbs on the desorb resin.
This chelating resin is under 5 the condition, to Cu at pH
2+Saturated quiet adsorption capacity be 0.65mmol (Cu)/g (doing), to Ni
2+Saturated quiet adsorption capacity be 0.53mmol (Ni)/g (doing), Fe
3+Saturated quiet adsorption capacity be 0.27mmol (Fe)/g (doing).
Embodiment 5:
(1) (Φ 1cm * 10cm) places deionized water with the SHQ bonded stationary phase of 1g, becomes homogenate through sonic oscillation, fills the dress post with wet method to use an end that the glass column of core is housed.After the column filling, with peristaltic pump, gradient mixer and automatically the component gatherer form tomographic system with it, after the redistilled water flushing, go into the Cu2+/Ni2+ salting liquid (pH=5.0) of 50mM in order to the 0.5ml/min flow velocity with infusion again, until saturated.
(2) the abundant unconjugated Cu2+ ion of flush away of water and 0.03mol/L2-(N-morphine quinoline) ethyl sulfonic acid (MES) cushioning liquid (PH=5.0) that contains 0.005% (v/v) polyethylene glycol oxide bay ether (Brij-35) then.
With the HCl solution washing Cu2+ pillar that ion/the Ni2+ ion is saturated of 10ml 1M, measure the wherein concentration of metal ion with ICP-MS with after 1000 times of the eluent dilutions.Conversion can get the adsorbance of Cu2+/Ni2+ ion on the SHQ post.Data see Table 3.
Embodiment 6:
Get the oxine type chelating resin 0.1g for preparing, the dry method internal diameter 3mm that packs into, in polytetrafluoroethylene (PTFE) (Teflon) microtrabeculae of long 50mm two ends filling mineral wool, with Teflon pipe ( 0.5mm) microtrabeculae is linked to each other with flow injection system and inductivity coupled plasma mass spectrometry (ICP-MS) again.Get 50ml ocean Copenhagen waters (CASS-4), wherein the dense standard value of Pb is 9.8 ± 3.6ng/L, through 0.45 μ m membrane filtration and after having added the processing of Pb standard liquid, make it carry out preenrichment by microtrabeculae, remove base matter with ultra-pure water flushing again, use the pure nitric acid of the top grade of 1M with its wash-out at last, eluent directly enters ICP-MS and detects, measure for continuous 4 times, the result who obtains is in known standard value scope.Its detectability can reach 10ng/L.
Those of ordinary skill in the art can understand, and in protection scope of the present invention, makes amendment for the foregoing description, and it all is possible adding and replacing, and it does not all exceed protection scope of the present invention.
Claims (4)
1, a kind of oxine type chelating resin, it is characterized in that: described chelating resin is with the ligand oxine,, is fixed on the macro porous silica gel matrix as spacerarm by silylating reagent and paraformaldehyde; The structural formula of described chelating resin is:
≡ SiO represents silica gel matrix I type in the formula)
The II type)
The oxine of this chelating resin at the bonded amount on silica gel surface at 120-542umol/g.
2, a kind of synthetic method of the type of oxine according to claim 1 chelating resin, it is characterized in that: described synthetic method step is as follows:
1) preliminary treatment of macro porous silica gel: the macropore chromatographic silica gel is placed 0.05-0.15mol/L HCl solution, leave standstill 18-30h under 90 ℃, be washed till no chlorion with deionized water, dry good, standby in vacuum drying chamber;
2) introduce spacerarm: it places through the toluene that heavily steams and calcium chloride dewaters with the macropore chromatographic silica gel of above-mentioned processing, add silylating reagent, stirring and refluxing 12-24h uses toluene and the excessive silylating reagent of acetone flush away respectively, 100-120 ℃ of oven dry gets intermediate product I;
3) ligand is fixing; Oxine is dissolved in the ethanol of 50-70 ℃ of following low-grade fever, and then progressively adds the 10mmol paraformaldehyde successively, intermediate product I; At 50-70 ℃ of following stirring reaction 5-8 hour, get intermediate product II again;
4) pickling typing: with intermediate product II, at 80-100 ℃ of dry 1h down, again with ethanol several times after the washed product, at 100-120 ℃ of dry 2h down; Use the salt acid elution one time of first 1M at last, be washed till neutrality with deionized water again, obtain having yellow oxine type chelating resin.
3, according to the synthetic method of the described oxine type of claim 2 chelating resin, it is characterized in that: described macropore chromatographic silica gel, its specification is: the 50-100 order, its physical and chemical performance is: average pore size is at 10-60nm, average specific surface area 250-350m
2/ g, average pore volume 1.00-2.00ml/g.
4, according to the synthetic method of the described oxine type of claim 2 chelating resin, it is characterized in that: described silylating reagent, it is a gamma-aminopropyl-triethoxy-silane, or is γ-An Bingjisanjiayangjiguiwan.
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| CN101869232A (en) * | 2010-06-13 | 2010-10-27 | 北京欧凯纳斯科技有限公司 | Silica gel compound chelated with heavy metal elements as well as preparation method and application thereof |
| CN101353436B (en) * | 2008-09-17 | 2011-05-04 | 淮海工学院 | Polystyrene functional high polymer material and preparation thereof |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
| CN102671644A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Silica gel loaded polymeric amine and 8-hydroxyquinoline dual-function base compound adsorption material and preparation method |
| CN102773082A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Novel immobilized 8-hydroxyquinoline type chelate adsorption material and preparation method thereof |
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| CN101353436B (en) * | 2008-09-17 | 2011-05-04 | 淮海工学院 | Polystyrene functional high polymer material and preparation thereof |
| CN101869232A (en) * | 2010-06-13 | 2010-10-27 | 北京欧凯纳斯科技有限公司 | Silica gel compound chelated with heavy metal elements as well as preparation method and application thereof |
| CN101869232B (en) * | 2010-06-13 | 2013-04-24 | 北京欧凯纳斯科技有限公司 | Silica gel compound chelated with heavy metal elements as well as preparation method and application thereof |
| CN102391399A (en) * | 2011-10-10 | 2012-03-28 | 中国地质大学（武汉） | Preparation method for chelating ion exchange resin using inorganic substance as matrix |
| CN102671644A (en) * | 2012-05-28 | 2012-09-19 | 陕西安圣美贸易发展有限公司 | Silica gel loaded polymeric amine and 8-hydroxyquinoline dual-function base compound adsorption material and preparation method |
| CN102671644B (en) * | 2012-05-28 | 2014-12-31 | 陕西厚亿节能环保新材料科技有限公司 | Silica gel loaded polymeric amine and 8-hydroxyquinoline dual-function base compound adsorption material and preparation method |
| CN102773082A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Novel immobilized 8-hydroxyquinoline type chelate adsorption material and preparation method thereof |
| CN102773082B (en) * | 2012-07-17 | 2014-12-03 | 中北大学 | Novel immobilized 8-hydroxyquinoline type chelate adsorption material and preparation method thereof |
| CN108212225A (en) * | 2018-03-15 | 2018-06-29 | 李宾 | A kind of inorganic type silica gel chelating ion exchange resin and preparation method thereof |
| CN113952921A (en) * | 2021-08-24 | 2022-01-21 | 厦门稀土材料研究所 | Preparation method of functionalized silicon material and application of functionalized silicon material in impurity removal and enrichment of ionic rare earth ammonia-free leaching solution |
| CN116393101A (en) * | 2023-05-31 | 2023-07-07 | 矿冶科技集团有限公司 | Silica gel-based adsorbent and molybdenum-rhenium combined separation method |
| CN116393101B (en) * | 2023-05-31 | 2023-09-05 | 矿冶科技集团有限公司 | Silica gel-based adsorbent and molybdenum-rhenium combined separation method |
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