CN104177536A - Chelating resin adsorbing material and preparation method thereof - Google Patents
Chelating resin adsorbing material and preparation method thereof Download PDFInfo
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- CN104177536A CN104177536A CN201410360870.XA CN201410360870A CN104177536A CN 104177536 A CN104177536 A CN 104177536A CN 201410360870 A CN201410360870 A CN 201410360870A CN 104177536 A CN104177536 A CN 104177536A
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- sorbing material
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001429 chelating resin Polymers 0.000 title abstract 6
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 28
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 26
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 33
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 150000002314 glycerols Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 19
- 150000002500 ions Chemical class 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 4
- 229910052793 cadmium Inorganic materials 0.000 abstract 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 2
- 230000004048 modification Effects 0.000 abstract 2
- 229910052759 nickel Inorganic materials 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 0 C*(*CCC(N)=O)N Chemical compound C*(*CCC(N)=O)N 0.000 description 1
- 101100400452 Caenorhabditis elegans map-2 gene Proteins 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a chelating resin adsorbing material and a preparation method thereof, and belongs to the field of environmental functional material synthesis and application. The chelating resin adsorbing material is prepared through suspension copolymerization and nucleophilic substitution reaction by adopting an organic monomer as a raw material; the chelating resin adsorbing material comprises a skeleton and hydroxamic acid, wherein the skeleton is formed by copolymerizing methyl acrylate and divinylbenzene, and the hydroxamic acid is formed through surface modification. The synthetic method disclosed by the invention is simple. According to the chelating resin adsorbing material, the equilibrium adsorption time of heavy metal ions, namely cadmium, nickel, lead and the like which are contained in group chelating water formed through the modification of a functional group modified on the surface of the prepared chelating resin adsorbing material and the resin skeleton, is about only 20 minutes, and the saturation adsorption capacity on the heavy metal ions, namely the cadmium, the nickel, the lead and the like, is more than or equal to 2 mmol/g.
Description
Technical field:
The invention discloses a kind of sorbing material and preparation method thereof, say more specifically a kind of resin sorbing material and preparation method thereof, the vinylformic acid formicester of modifying based on hydroxamic acid base and resin of divinylbenzene copolymerization and preparation method thereof.
Background technology:
In recent years, along with national water quality standard progressively improves, more and more strict for the restriction of heavy metals ionic concn, efficiently removing heavy metal ion in water becomes the study hotspot in water pollution control field.Although existing traditional Coagulation Method and chemical precipitation method technical maturity are simple to operate, the plurality of heavy metal body refuse producing in treating processes is difficult to dispose, and easily brings secondary pollution.And electrolytic process, membrane separation process are subject to the factor restrictions such as processing cost and are difficult for being used by large-scale promotion; Although Zeo-karb has very high adsorption rate and capacity for heavy metal ion, its immunity from interference to calcium ions and magnesium ions and natural organic matter need to improve.Resin has very strong sequestering action by contained functional group to heavy metal ion, is subject to hardly the impact of calcium ions and magnesium ions and natural organic matter in adsorption process, becomes first-selected sorbing material in heavy metal wastewater thereby improvement.
But existing resin is mainly polystyrene series and polyacrylate based series, its synthetic method is mainly synthetic polystyrene-divinylbenzene polymer or polyacrylate polymers, then on polymkeric substance, modify the functional group such as carboxyl, amino, utilize the above-mentioned group chelating of modifying to remove heavy metal ion in water, but in adsorption process, polystyrene-divinylbenzene, polyacrylic ester in polymer backbone are not participated in sequestering action, and this causes the absorption property of such resin to be controlled by the functional group quantity of finishing completely.But the functional group limited amount of existing resin surface chemical modification, therefore resin is difficult to be greatly improved to the loading capacity of heavy metal ion.
Therefore, how in resin rhetorical function group, to make resin polystyrene-divinylbenzene skeleton, polyacrylic ester skeleton itself participate in heavy metal ion in sequestering action water, it is an effective approach that improves resin loading capacity, application for resin in heavy metal wastewater thereby is administered has important pushing effect, has great theory directive significance and actual application value.
Summary of the invention:
1, the technical problem that invention will solve
The technical barrier that cannot promote because being controlled by finishing group quantity completely the loading capacity of heavy metal ion for existing resin, the invention provides a kind of resin sorbing material and preparation method thereof: the multipolymer that makes methyl acrylate and divinylbenzene by suspension polymerization, then by azanol, interpolymer skeleton itself is directly carried out to chemically modified, make the resin that contains hydroxamic acid structure.Freshly prepd resin not only can be removed heavy metal ion in water by the azanol group chelating of modifying, and carbonyl intrinsic on resin matrix also can participate in sequestering action, even in the situation that concentration of heavy metal ion is very low, still there is good Adsorption effect, and loading capacity is large.
2, technical scheme
Resin sorbing material of the present invention is by after methyl acrylate and divinylbenzene copolymerization, carries out chemically modified preparation and obtains, be i.e. the hydroxamic acid formation that its skeleton forming with methyl acrylate and divinylbenzene copolymerization and finishing forms.On resin upper skeleton, intrinsic carbonyl participates in chelating heavy metal effect (wherein M represents heavy metal ion) jointly with the azanol group on modifying.
A kind of resin sorbing material, following (the wherein R of its synthesis flow and basic structure formula
1=NH-OH, R
2=OCH
3or NH-OH):
A kind of resin sorbing material preparation method, the steps include:
(1) preparation reaction emulsion
By polymerization reaction monomer, linking agent, dispersion agent, pore-creating agent and distilled water mixed preparing reaction emulsion, wherein the proportioning of polymerization reaction monomer, linking agent, dispersion agent, pore-creating agent and distilled water is 90mL:8～12mL:6g:30～40mL:400mL;
The monomer using in step (1) is methyl acrylate; The linking agent using is divinylbenzene; The dispersion agent using is the one in gelatin, polyvinyl alcohol or polyethylene wax; The pore-creating agent using is a kind of or its two kinds the mixture in normal heptane, ethyl acetate, toluene.
(2) copolyreaction
In emulsion, add initiator, the ratio of initiator and emulsion is 1～2g:500mL or 1～2mL:500mL, reacts 8～12 hours at 90～95 DEG C, obtains copolymerization ball WJNCC, 40～50 DEG C of vacuum-dryings after ethanol cleans.
The initiator using in step (2) is selected from the one in benzoyl peroxide, di-t-butyl peroxide or azo diethyl butyronitrile.
(3) copolymerization ball finishing
(a) alkali and azanol, emulsifying agent, distilled water are mixed with to reaction solution, its proportioning is 2～3g:2～3g:1mL:100mL;
(b) after copolymerization ball is mixed with above-mentioned reaction solution, the mass ratio of copolymerization ball and azanol is 1:1～1.5,45～60 DEG C of reactions 12～16 hours, obtains final product resin sorbing material MA-DVB, 40～50 DEG C of vacuum-dryings after distilled water cleans.
The alkali using in step (3-a) is sodium hydroxide or potassium hydroxide; The azanol using is elected oxammonium hydrochloride or oxammonium sulfate as; The emulsifying agent using is the one in polyethenoxy sorbitan oleic acid ester, polyoxyethylene oleic acid ester, Glycerol dimer polypropylene glycol ether.
3, beneficial effect
The invention provides a kind of preparation method of resin sorbing material: methyl acrylate and divinylbenzene copolymer, after chemically modified, form hydroxamic acid structure on resin matrix.This resin can be used in heavy metal wastewater thereby adsorption treatment field, and the heavy metal wastewater thereby of high density and lower concentration is all had to good treatment effect.The main raw material that the present invention simultaneously adopts is large Chemicals, and cheap and easy to get, synthesis technique step is simple.
Brief description of the drawings
Owing to preparing monomer and linking agent only has one, the group that chemically modified forms only has hydroxamic acid one, so the structure of the resin sorbing material preparing only has one.Common trait be due to chemically modified be difficult to carry out completely, cause certainly existing methoxyl group in resin sorbing material chemical structure.
Fig. 1 is the structure that the structure iron of the resin sorbing material for preparing of example 1-6 of the present invention contains hydroxamic acid.
Fig. 2 is copolymerization ball and resin sorbing material infrared spectrum, wherein the δ 1736.2cm that example 4 of the present invention prepares
-1for the ester group characteristic peak of copolymerization ball, 1737.8cm
-1for the ester group characteristic peak of resin, 1572.8cm
-1and 3432.5cm
-1for resin functional group characteristic peak, according to reference (Xing Qiyi, Pei Weiwei etc., basic organic chemistry, Higher Education Publishing House, the third edition in 2005, p184); Wherein WJNCC is the copolymerization ball that copolyreaction obtains, and MA-DVB is the resin after copolymerization Geochemistry is modified.
The solid-state nuclear magnetic resonance carbon spectrum of the resin sorbing material that Fig. 3 (a) prepares for embodiment 4; Fig. 3 (b) solid-state nuclear magnetic resonance
13structure iron corresponding to C NMR collection of illustrative plates characteristic peak, in Fig. 3 (a), its characteristic peak δ 185.79, δ 175.92, δ 144.74, δ 128.48, δ 51.78, the corresponding structure of δ 40.88 are listed in Fig. 3 (b).According to reference (Xing Qiyi, Pei Weiwei etc., basic organic chemistry, Higher Education Publishing House, the third edition in 2005, p216).
Fig. 4 is 500 times of Electronic Speculum figure of resin scanning that embodiment 4 makes.
Fig. 5 is the resin graph of pore diameter distribution that embodiment 4 makes, and X-coordinate is aperture (nm), and ordinate zou is pore volume (cm
3/ g) differential (the cm to aperture
3g
-1nm
-1).Fig. 5 shows that resin aperture prepared by embodiment 4 is mainly distributed in 4～6nm, is mainly mesopore (mesopore).
Embodiment
Embodiment 1
90mL methyl acrylate, 9mL divinylbenzene, gelatin 6g, 35mL normal heptane, 400mL distilled water are made into emulsion.The 500mL emulsion of preparation is poured in 1000mL three-necked flask, added benzoyl peroxide 1g, 95 DEG C of heating in water bath, and with the rotating speed stirring reaction of 60r/min 8 hours, reaction gained copolymerization ball is carried out to solid-liquid separation, and by washing with alcohol, 50 DEG C of vacuum-dryings.Get 10g potassium hydroxide, 15g oxammonium sulfate, 5mL polyoxyethylene oleic acid ester, 500mL distilled water wiring solution-forming, pour in 1000mL three-necked flask, after adding 10g copolymerization ball, mix, stir speed (S.S.) with 60r/min at 45 DEG C is reacted 16 hours, after filtering, product uses distilled water wash, vacuum-drying at 50 DEG C, obtains resin sorbing material finished product.
Its physicochemical property of resin sorbing material that the present embodiment prepares is as follows:
Resin structure as shown in Figure 1.
Embodiment 2
90mL methyl acrylate, 11mL divinylbenzene, polyvinyl alcohol 6g, 40mL ethyl acetate, 400mL distilled water are made into emulsion.500mL emulsion is poured in 1000mL three-necked flask, added di-t-butyl peroxide 2mL, 94 DEG C of heating in water bath, and with the rotating speed stirring reaction of 60r/min 9 hours, reaction gained copolymerization ball is carried out to solid-liquid separation, and by washing with alcohol, 45 DEG C of vacuum-dryings.Get 15g sodium hydroxide, 10g oxammonium hydrochloride, 5mL polyethenoxy sorbitan oleic acid ester, 500mL distilled water wiring solution-forming, pour in 1000mL three-necked flask, after adding 10g copolymerization ball, mix, stir speed (S.S.) with 60r/min at 48 DEG C is reacted 15 hours, after filtering, product uses distilled water wash, vacuum-drying at 45 DEG C, obtains resin sorbing material finished product.Its physicochemical property of resin sorbing material that the present embodiment prepares is as follows:
Resin structure as shown in Figure 1.
Embodiment 3
90mL methyl acrylate, 8mL divinylbenzene, polyethylene wax 6g, 30mL toluene, 400mL distilled water are made into emulsion.500mL emulsion is poured in 1000mL three-necked flask, added azo diethyl butyronitrile 2g, 93 DEG C of heating in water bath, and with the rotating speed stirring reaction of 60r/min 10 hours, reaction gained copolymerization ball is carried out to solid-liquid separation, and by washing with alcohol, 40 DEG C of vacuum-dryings.Get 12g sodium hydroxide, 12g oxammonium sulfate, 5mL Glycerol dimer polypropylene glycol ether, 500mL distilled water wiring solution-forming, pour in 1000mL three-necked flask, after adding 10g copolymerization ball, mix, stir speed (S.S.) with 60r/min at 52 DEG C is reacted 14 hours, after filtering, product uses distilled water wash, vacuum-drying at 40 DEG C, obtains resin sorbing material finished product.Its physicochemical property of resin sorbing material that the present embodiment prepares is as follows:
Resin structure as shown in Figure 1.
Embodiment 4
90mL methyl acrylate, 12mL divinylbenzene, gelatin 6g, 20mL ethyl acetate, 20mL normal heptane, 400mL distilled water are made into emulsion.500mL emulsion is poured in 1000mL three-necked flask, added benzoyl peroxide 1.5g, 92 DEG C of heating in water bath, and with the rotating speed stirring reaction of 60r/min 11 hours, reaction gained copolymerization ball is carried out to solid-liquid separation, and by washing with alcohol, 40 DEG C of vacuum-dryings.Get 14g potassium hydroxide, 11g oxammonium hydrochloride, 5mL polyoxyethylene oleic acid ester, 500mL distilled water wiring solution-forming, pour in 1000mL three-necked flask, after adding 10g copolymerization ball, mix, stir speed (S.S.) with 60r/min at 56 DEG C is reacted 13 hours, after filtering, product uses distilled water wash, vacuum-drying at 45 DEG C, obtains resin sorbing material finished product.
Be illustrated in figure 1 the structure iron of the resin sorbing material that the present embodiment prepares, be illustrated in figure 2 the FT-IR collection of illustrative plates of the resin sorbing material that the present embodiment prepares, after copolymerization, occur ester group characteristic peak at δ 1736.2 places; After chemically modified, occurring N-H flexural vibration absorption peak at δ 1572.8, occur N-H stretching vibration absorption peak at δ 3432.5, is also O-H stretching vibration absorption peak, prove the existence of hydroxamic acid structure, the resin sorbing material preparing for the present embodiment as Fig. 3 (a)
13c NMR collection of illustrative plates, its characteristic peak δ 185.79, δ 175.92, δ 144.74, δ 128.48, δ 51.78, the corresponding structure of δ 40.88 are listed in Fig. 3 (b).Synthesizing map 2 Infrared spectroscopy and Fig. 3 nuclear magnetic resonance spectroscopy, can confirm that resin sorbing material is as the structure of Fig. 1.Fig. 4 is the resin scanning electron microscope (SEM) photograph that the present embodiment makes.Fig. 5 is the resin graph of pore diameter distribution that the present embodiment makes.Its physicochemical property of resin sorbing material that the present embodiment prepares is as follows:
This embodiment is most preferred embodiment: pore-creating agent ethyl acetate boiling point lower (77 DEG C), and normal heptane boiling point higher (98.5 DEG C), the use that mixes pore-creating agent makes the pore effect of pore-creating agent just be embodied in preparation process, along with the rising of temperature, ethyl acetate can be evaporated in advance, the space staying makes normal heptane be more prone to penetrate into resin matrix, obtains better pore passage structure.
Embodiment 5
90mL methyl acrylate, 10mL divinylbenzene, polyvinyl alcohol 6g, 20mL toluene, 20mL ethyl acetate, 400mL distilled water are made into emulsion.500mL emulsion is poured in 1000mL three-necked flask, added di-t-butyl peroxide 1.5mL, 90 DEG C of heating in water bath, and with the rotating speed stirring reaction of 60r/min 12 hours, reaction gained copolymerization ball is carried out to solid-liquid separation, and by washing with alcohol, 50 DEG C of vacuum-dryings.Getting 12g sodium hydroxide, 13g oxammonium hydrochloride, 5mL polyethenoxy sorbitan oleic acid ester, 500mL distilled water wiring solution-forming pours in 1000mL three-necked flask, after adding 10g copolymerization ball, mix, stir speed (S.S.) with 60r/min at 60 DEG C is reacted 12 hours, after filtering, product uses distilled water wash, vacuum-drying at 50 DEG C, obtains resin sorbing material finished product.
Resin structure as shown in Figure 1.
Embodiment 6
Concrete steps and amount of substance are with embodiment 5, and difference is to add di-t-butyl peroxide 1.0mL.Prepare resin sorbing material finished product.
Resin structure as shown in Figure 1.
Claims (5)
1. a resin sorbing material, is characterized in that, the hydroxamic acid that the skeleton that it forms with methyl acrylate and divinylbenzene copolymerization and finishing form forms, and its basic structure formula is as follows:
wherein R
1=NH-OH, R
2=OCH
3or NH-OH.
2. a preparation method for resin sorbing material, the steps include:
(1) preparation reaction emulsion
By polymerization reaction monomer, linking agent, dispersion agent, pore-creating agent and distilled water mixed preparing reaction emulsion, wherein the proportioning of polymerization reaction monomer, linking agent, dispersion agent, pore-creating agent and distilled water is 90mL:8～12mL:6g:30～40mL:400mL;
(2) copolyreaction
In the emulsion making in step 1, add initiator, the ratio of initiator and emulsion is 1～2g:500mL or 1～2mL:500mL, reacts 8～12 hours at 90～95 DEG C, obtains copolymerization ball WJNCC, 40～50 DEG C of vacuum-dryings after ethanol cleans;
(3) chemically modified of copolymerization ball
A. alkali and azanol, emulsifying agent, distilled water are mixed with to reaction solution, its proportioning is: 2～3g:2～3g:1mL:100mL;
B. after copolymerization ball step (2) being made mixes with the reaction solution of preparing in above-mentioned steps 3-a, wherein the mass ratio of copolymerization ball and azanol is 1:1～1.5,45～60 DEG C of reactions 12～16 hours, obtain resin sorbing material MA-DVB, 40～50 DEG C of vacuum-dryings after distilled water cleans.
3. the preparation method of resin sorbing material according to claim 2, is characterized in that, the polymerization reaction monomer of described step (1) is methyl acrylate; Linking agent is divinylbenzene; Dispersion agent is the one in gelatin, polyvinyl alcohol or polyethylene wax; Pore-creating agent is a kind of or its two or more mixtures in normal heptane, ethyl acetate, toluene.
4. according to the preparation method of the resin sorbing material described in claim 2 or 3, it is characterized in that, the initiator of described step (2) is the one in benzoyl peroxide, di-t-butyl peroxide or Diisopropyl azodicarboxylate.
5. according to the preparation method of a kind of resin sorbing material described in claim 2 or 3, it is characterized in that, the alkali of described step (3) is elected potassium hydroxide or sodium hydroxide as; Azanol is elected oxammonium hydrochloride or oxammonium sulfate as; Emulsifying agent is the one in polyethenoxy sorbitan oleic acid ester, polyoxyethylene oleic acid ester or Glycerol dimer polypropylene glycol ether.
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| WO2016011900A1 (en) * | 2014-07-25 | 2016-01-28 | 南京大学 | Chelating resin adsorbing material and preparation method therefor |
| CN106807340A (en) * | 2017-02-06 | 2017-06-09 | 中南大学 | A kind of crosslinked resin hydroximic acid composite adsorbing material and preparation method and application |
| CN109183199A (en) * | 2018-11-22 | 2019-01-11 | 淮安天然丝纺织科技有限公司 | A kind of NMMO solvent recovery method for concentration |
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| CN106807340B (en) * | 2017-02-06 | 2019-07-12 | 中南大学 | A kind of crosslinked resin-hydroximic acid composite adsorbing material and the preparation method and application thereof |
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| CN113083256A (en) * | 2021-04-13 | 2021-07-09 | 北京赛科康仑环保科技有限公司 | Adsorbing material for deep oil removal of neutral phosphorus-containing extraction system and preparation and application methods thereof |
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