CN101775089A - Boron adsorption resin containing difunctional groups - Google Patents
Boron adsorption resin containing difunctional groups Download PDFInfo
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- CN101775089A CN101775089A CN201010017965A CN201010017965A CN101775089A CN 101775089 A CN101775089 A CN 101775089A CN 201010017965 A CN201010017965 A CN 201010017965A CN 201010017965 A CN201010017965 A CN 201010017965A CN 101775089 A CN101775089 A CN 101775089A
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- Prior art keywords
- resin
- boron
- bifunctional
- acyl
- synthetic method
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- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 title abstract description 10
- 150000002337 glycosamines Chemical class 0.000 claims abstract description 8
- 230000010933 acylation Effects 0.000 claims abstract description 3
- 238000005917 acylation reaction Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000001588 bifunctional effect Effects 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 4
- 229960002442 glucosamine Drugs 0.000 claims description 4
- MSWZFWKMSRAUBD-GASJEMHNSA-N 2-amino-2-deoxy-D-galactopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@H](O)[C@@H]1O MSWZFWKMSRAUBD-GASJEMHNSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- 229920005990 polystyrene resin Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000009920 chelation Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 101150050387 Galns gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- MXCPYJZDGPQDRA-UHFFFAOYSA-N dialuminum;2-acetyloxybenzoic acid;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].CC(=O)OC1=CC=CC=C1C(O)=O MXCPYJZDGPQDRA-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- -1 iminodipropylene Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention discloses boron adsorption resin containing difunctional groups and a preparation method thereof. The boron adsorption resin containing the difunctional groups is characterized in that the boron adsorption resin containing the difunctional groups is prepared by the reaction of halogenated acylation resin and amino sugar. The carrying quantity of the difunctional groups of the boron adsorption resin prepared by the method is 0.1 to 2.8mmol/g, and the preparation process of the resin is safe and simple. The difunctional groups of alpha-glycyl and orthohydroxy group in the resin generate a synergistic action, the functions of adsorption and chelation of the resin to boron are enhanced, and the resin can replace the traditional boron-specific resin.
Description
Technical field
The invention belongs to filed of functional.Be specifically related to a kind of suction boron resin that contains bifunctional.
Background technology
Boron is as a kind of important industrial raw material, the general a plurality of fields such as metallurgy, nuclear technique, military project, space flight, the energy, agricultural, medicine and automobile that are applied to of factory.The discharging of large amount of sewage has not only caused a large amount of boron resource losses in the boron compound production process, also environment is caused serious pollution.Run off, the below standard discharging of waste water containing boron of contaminate environment, make boron too high levels in the people drinking water source, thereby cause numerous disease.(World Health Organization WHO) requires the boron concentration in the tap water to be lower than 0.3mg/L, and therefore, studying the boron waste water treatment and utilizing becomes the important topic that the mankind face in the World Health Organization.
At present, existing many to the bibliographical information that the boron in the waste water is removed, method commonly used has the precipitator method, extraction process, reverse osmosis method, electrocoagulation, resin adsorption method (Simonnot, M.-O, Castel, C., NicolaI M., et al.Boron removalfrom drinking water with a boron selective resin:Is the treatment really selective? WaterResearch, 2000,34 (1): 109-116.Senkal, B.F., Bicak, N.Polymer supported iminodipropylene glycolfunctions for removal of boron.Reactive ﹠amp; Functional Polymers, 2003,55:27-33.Liu, H., Ye, X., Li, Q., et al.Boron adsorption using a new boron-selective hybrid gel and the commercial resinD564.Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2009,341:118-126.) etc.It is controlled thorough that wherein resin adsorption method has the boron of removal, and the boron resource can be recycled through desorption, and polymeric adsorbent then can repeat advantages such as recycling utilization, is one of enrichment or removal boron the best way.
Nineteen fifty-seven, Lyman and Preuss (Lyman, W.R., Abington, Preuss, A.F.Boron-adsorbing resin andprocess for removing boron compounds from fluids, USA 1957:Vol.2813838.) at first makes a kind of effects of boron resin with chloromethylated polystyrene and the reaction of N-methyl glucoside amine.This resin has higher selectivity to boron in the solution, but this resin is subjected to the influence of multiple ambient conditions in application, afterwards through constantly development, people have synthesized many novel polymeric adsorbents, but there is certain problem in these resins, as adsorption rate and less stable, the resin building-up process is more loaded down with trivial details.Comparatively speaking, the suction boron resin that contains α-amine ethanoyl and adjacent hydroxyl bifunctional simultaneously is not only safer in preparation process, has reduced the harm to environment, and the α on the resin-amine ethanoyl and adjacent hydroxyl synergy has increased the adsorptive capacity of resin.The resin absorption amount can reach 28mg/g-and do agent.But therefore waste water qualified discharge after the plastic resin treatment can replace traditional effects of boron resin.
Summary of the invention
The present invention relates to a kind of suction boron resin that contains bifunctional and preparation method thereof.
The suction boron resin of bifunctional of the present invention has following structure:
R and R '=H or CH in the formula
3R ": be the residue of aminosugar such as N-methyl glucoside amine or GalN or glucosamine or chitosan.
The preparation of the wetting ability polymeric adsorbent of bifunctional of the present invention can be synthesized by the following method: with the PS-Acyl-X resin after solvent-swollen 0-24 hour; with a certain proportion of aminosugar under 25-100 ℃; reacted 3-24 hour, and obtained containing the wetting ability suction boron resin of α-amine ethanoyl and adjacent hydroxyl bifunctional.
The described PS-Acyl-X resin of present method can be linear or crosslinked, macropore or gel; Particle diameter is 5-1300 μ m; In the reaction in aminosugar and the PS-Acyl-X resin-mol ratio of X is 1-5; Wherein solvent can be water, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol or water and N, dinethylformamide or tetrahydrofuran (THF) or methyl alcohol or alcoholic acid mixture.
Advantage of the present invention: the suction boron resin that contains bifunctional of the present invention is reacted by halo acylations resin and aminosugar and makes.The poly-hydroxy of the suction boron resin that present method makes has very strong huge legendary turtle cooperation usefulness to boron, and the α on the resin-amine ethanoyl and adjacent hydroxyl synergy have increased the adsorptive capacity of resin.
Specific embodiments
Embodiment 1
0% (V/V) DVB), 1.790 GalNs, 20ml N (degree of crosslinking:, dinethylformamide adds to be furnished with in the reactor of stirring, 90 ℃ of reactions 7 hours to take by weighing 1g PS-Acyl-Br.Promptly obtaining loading is 2.12mmol/g.
Embodiment 2
Take by weighing 1g PS-Acyl-Br resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 5 μ m), 3.580g N-methyl glucoside amine, 20ml water adds and is furnished with in the reactor of stirring, 80 ℃ of reactions 5 hours.Promptly obtaining loading is 2.51mmol/g.
Embodiment 3
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 200 μ m), 0.3804g N-methyl glucoside amine, 25ml tetrahydrofuran (THF) adds and is furnished with in the reactor of stirring, 60 ℃ of reactions 3.5 hours.Promptly obtaining loading is 0.50mmol/g.
Embodiment 4
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 1% (V/V) DVB; Particle diameter 1300 μ m), 5ml ethanol adds and to be furnished with in the reactor of stirring, normal temperature swelling 12 hours adds 5ml water, 70 ℃ of reactions of 1.5659g N-methyl glucoside amine 4 hours again.Promptly obtaining loading is 1.65mmol/g.
Embodiment 5
Take by weighing 1g PS-Acyl-Br resin (degree of crosslinking: 1% (V/V) DVB; Particle diameter 500 μ m), 1.3425g glucosamine, 10ml water, 5ml methyl alcohol add and be furnished with in the reactor of stirring, 40 ℃ of reactions 10 hours.Promptly obtaining loading is 0.69mmol/g.
Embodiment 6
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 30% (V/V) DVB; Particle diameter 800 μ m), 0.8482g N-methyl glucoside amine, 25ml methyl alcohol adds and is furnished with in the reactor of stirring, 50 ℃ of reactions 6 hours.Promptly obtaining loading is 1.01mmol/g.
Embodiment 7
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 50 μ m), 0.5007g chitosan, 10ml dilute hydrochloric acid add and be furnished with in the reactor of stirring, 60 ℃ of reactions 24 hours.Promptly obtaining loading is 1.02mmol/g.
Embodiment 8
Take by weighing 1g PS-Acyl-Br (degree of crosslinking: 1% (V/V) DVB; Particle diameter 500 μ m), 4.4750g; Glucosamine, 30ml ethanol add to be furnished with in the reactor of stirring, and 70 ℃ were reacted 16 hours.Promptly obtaining loading is 1.38mmol/g.
Embodiment 9
Take by weighing 1g PS-Acyl-Cl resin (degree of crosslinking: 7% (V/V) DVB; Particle diameter 1000 μ m), 1.3425g GalN, 10ml water, 5ml tetrahydrofuran (THF) add and be furnished with in the reactor of stirring, 40 ℃ of reactions 10 hours.Promptly obtaining loading is 1.69mmol/g.
Embodiment 10
Take by weighing 1g PS-Acyl-Br resin (degree of crosslinking: 80% (V/V) DVB; Particle diameter 1000 μ m), 0.8201g chitosan, the rare nitric acid of 10ml, 5ml N, dinethylformamide adds to be furnished with in the reactor of stirring, 70 ℃ of reactions 20 hours.Promptly obtaining loading is 1.53mmol/g.
Claims (7)
1. suction boron resin that contains bifunctional is characterized in that the suction boron resin of described bifunctional contains following structure:
R and R '=H or CH in the formula
3R ": be the residue of aminosugar such as N-methyl glucoside amine or GalN or glucosamine or chitosan.
2. a kind of suction boron resin that contains bifunctional according to claim 1; it is characterized in that this resin can prepare by following synthetic method: with a certain proportion of macromole halo acylations polystyrene resin; or be called for short PS-Acyl-X, aminosugar and solvent adding and be furnished with in the reactor of stirring; in the certain temperature oil bath, react certain hour, obtain above-mentioned hydrophilic, the suction boron resin that contains α-amine ethanoyl and adjacent hydroxyl bifunctional.
3. a kind of suction boron resin that contains bifunctional according to claim 1, the content that it is characterized in that α-amine ethanoyl in the described bifunctional resin and adjacent hydroxyl bifunctional are that 0.1-2.8mmol/g-does agent.
4. synthetic method according to claim 2 is characterized in that described PS-Acyl-X resin for linear or crosslinked, macropore or gel, particle diameter is 5-1300 μ m.
5. synthetic method according to claim 2, it is characterized in that in the described PS-Acyl-X resin-X is Cl or Br.
6. synthetic method according to claim 2, it is characterized in that in described aminosugar and the PS-Acyl-X resin-mol ratio of X is 1-5.
7. synthetic method according to claim 2 is characterized in that described solvent can be water, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol or water and N, dinethylformamide or tetrahydrofuran (THF) or methyl alcohol or alcoholic acid mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100179653A CN101775089B (en) | 2010-01-19 | 2010-01-19 | Boron adsorption resin containing difunctional groups |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100179653A CN101775089B (en) | 2010-01-19 | 2010-01-19 | Boron adsorption resin containing difunctional groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101775089A true CN101775089A (en) | 2010-07-14 |
| CN101775089B CN101775089B (en) | 2011-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010100179653A Expired - Fee Related CN101775089B (en) | 2010-01-19 | 2010-01-19 | Boron adsorption resin containing difunctional groups |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421132A (en) * | 2013-06-04 | 2013-12-04 | 南京工业大学 | Method for recycling of recovery solution during synthesis of PS-acyl-MG |
| CN115023407A (en) * | 2020-11-05 | 2022-09-06 | 瓦克化学股份公司 | Process for removing impurities from chlorosilane mixtures |
| CN115945179A (en) * | 2023-02-20 | 2023-04-11 | 江苏苏青水处理工程集团有限公司 | Low-solution-loss high-adsorption-capacity salt lake lithium extraction and boron extraction adsorption material and preparation method thereof |
-
2010
- 2010-01-19 CN CN2010100179653A patent/CN101775089B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421132A (en) * | 2013-06-04 | 2013-12-04 | 南京工业大学 | Method for recycling of recovery solution during synthesis of PS-acyl-MG |
| CN115023407A (en) * | 2020-11-05 | 2022-09-06 | 瓦克化学股份公司 | Process for removing impurities from chlorosilane mixtures |
| CN115945179A (en) * | 2023-02-20 | 2023-04-11 | 江苏苏青水处理工程集团有限公司 | Low-solution-loss high-adsorption-capacity salt lake lithium extraction and boron extraction adsorption material and preparation method thereof |
| CN115945179B (en) * | 2023-02-20 | 2023-08-29 | 江苏苏青水处理工程集团有限公司 | Low-solution-loss high-adsorption capacity salt lake lithium-extracting boron-extracting adsorption material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101775089B (en) | 2011-12-28 |
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Granted publication date: 20111228 Termination date: 20180119 |