CN109749031B - Cross-linked sulfonated aldehyde ketone cation exchange resin and preparation method and application thereof - Google Patents
Cross-linked sulfonated aldehyde ketone cation exchange resin and preparation method and application thereof Download PDFInfo
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- CN109749031B CN109749031B CN201910014165.7A CN201910014165A CN109749031B CN 109749031 B CN109749031 B CN 109749031B CN 201910014165 A CN201910014165 A CN 201910014165A CN 109749031 B CN109749031 B CN 109749031B
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- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 88
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 150000002576 ketones Chemical class 0.000 title claims abstract description 49
- 150000001299 aldehydes Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004132 cross linking Methods 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 13
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008233 hard water Substances 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000004321 preservation Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 5
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 5
- 235000019252 potassium sulphite Nutrition 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 4
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 4
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 3
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 3
- 229940099427 potassium bisulfite Drugs 0.000 claims description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940001482 sodium sulfite Drugs 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 51
- 229920005989 resin Polymers 0.000 abstract description 51
- 238000006277 sulfonation reaction Methods 0.000 abstract description 22
- 239000004793 Polystyrene Substances 0.000 abstract description 13
- 229920002223 polystyrene Polymers 0.000 abstract description 13
- 235000013305 food Nutrition 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 15
- 125000000542 sulfonic acid group Chemical group 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000012263 liquid product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 229940023913 cation exchange resins Drugs 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- 239000012224 working solution Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229940118019 malondialdehyde Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention belongs to the technical field of cation exchange resin, and discloses a cross-linked sulfonated aldehyde ketone cation exchange resin as well as a preparation method and application thereof. Firstly, carrying out aldol condensation reaction on sulfite, ketone and aldehyde to obtain an oligomer, and then adding phenol to carry out thermal insulation polycondensation reaction to prepare a reactive polycondensate; and (4) preserving heat, curing and crosslinking reaction to obtain the crosslinking sulfonated aldehyde ketone cation exchange resin. The invention also provides the cross-linking sulfonated aldehyde ketone cation exchange resin obtained by the method and application in removing calcium and magnesium ions in hard water. The method firstly performs sulfonation and then performs crosslinking, thereby subverting the traditional production process of firstly performing crosslinking and then performing sulfonation, and having mild sulfonation reaction and simple, convenient and controllable process; the ketone unit in the obtained exchange resin is fully sulfonated, the actual exchange equivalent is higher than that of the #732 polystyrene type cation exchange resin, the exchange resin can be directly used for exchanging calcium and magnesium ions in hard water, can be widely applied to the fields of water treatment, food, metallurgy and the like, and has wide application value.
Description
Technical Field
The invention belongs to the technical field of cation exchange resin, and particularly relates to a cross-linked sulfonated aldehyde ketone cation exchange resin as well as a preparation method and application thereof.
Background
The ion exchange resin as a cross-linked high polymer loaded with active groups has the functions of exchange, absorption, catalysis and the like, and is mainly used in the fields of water treatment, food, electric power, medicine and health, metallurgy and the like. In China, the dosage of the strong acid type cation exchange resin is large, and occupies 80 percent of the total yield of the ion exchange resin. Most of the currently commercially available cation exchange resins are prepared by using styrene and acrylic acid (ester) as raw materials, performing crosslinking polymerization reaction with a crosslinking agent of divinylbenzene to prepare a three-dimensional polymer with a network skeleton structure, and sulfonating with fuming sulfuric acid to prepare the sulfonated polystyrene cation exchange resin. Sulfonated polystyrene cation exchange resin is sulfonated by fuming sulfuric acid, so that the danger of sulfonation reaction is high, the sulfonation reaction is insufficient, and the actual exchange equivalent of the resin is low.
There are two main directions for the current development of new cation exchange resins: a composite polystyrene cation exchange resin is prepared from fossil raw material and biomass raw material through cross-linking reaction. Patent CN107519947A (a preparation method of polystyrene cation exchange resin for sewage treatment) discloses a method for preparing composite polystyrene cation exchange resin by reacting calcined cotton stalk, zeolite powder, ethyl styrene, methylene bisacrylamide and the like, which has low raw material cost, good adsorption effect and low exchange equivalent when applied to sewage treatment; patent CN107652406A (a preparation method of strong acid polystyrene cation exchange resin) discloses a strong acid polystyrene cation exchange resin prepared by reacting methyl styrene, methylene bisacrylamide, pretreated rice hull, gelatin and the like, which solves the problems of compact structure and low degree of crosslinking of the traditional polystyrene cation exchange resin.
The other method is to prepare the bio-based cation exchange resin by taking biomass resources as raw materials. Patent CN108325568A (a preparation method of lignin-based strong acid cation exchange resin) synthesizes lignin-based strong acid cation exchange resin with high cation exchange capacity by using lignin, phenol, a sulfonation reagent, formaldehyde and the like as raw materials through a one-step method. Yasuda et al (JWood Sci (2000)46:477-479) synthesize strongly acidic cation exchange resin by using acid hydrolysis lignin as raw material through phenolization, sulfonation, acidification and other steps. However, the degree of activity of the prepared resin is low and the exchange equivalent is small.
In summary, most of the existing strong acid cation exchange resins are sulfonated crosslinked polystyrene cation exchange resins, or copolymers or composites of styrene with other monomers and fillers. Although the application of the sulfonated crosslinked polystyrene type cation exchange resin is common, such as #732 type cation exchange resin, the danger of fuming sulfuric acid sulfonation reaction is large; and the sulfonation is carried out after the polymerization, so that the sulfonation efficiency is low, and the actual exchange equivalent of the resin is far lower than the theoretical exchange equivalent. The actual exchange equivalent of both the composite polystyrene type cation exchange resin and the bio-based cation exchange resin is not ideal. How to synthesize the strong acid type cation exchange resin under mild conditions and effectively improve the actual exchange equivalent is a difficult problem to be solved in the field of the strong acid type cation exchange resin at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method for preparing the crosslinking sulfonated aldehyde ketone cation exchange resin with mild sulfonation reaction.
The preparation method comprises the steps of firstly carrying out aldol condensation reaction on sulfite, ketone and aldehyde to obtain an oligomer, then adding phenol to carry out polycondensation reaction to prepare a reactive polycondensate, and carrying out heat preservation curing crosslinking reaction under alkaline conditions to obtain the crosslinking sulfonated aldehyde ketone cation exchange resin. The preparation method of the invention firstly carries out sulfonation and then carries out crosslinking, and the reaction is mild and controllable.
The invention also aims to provide the cross-linking sulfonated aldehyde ketone cation exchange resin prepared by the method. The cation exchange resin of the invention is a strong acid type cation exchange resin with a novel structure, and has high exchange equivalent, particularly high exchange equivalent of calcium and magnesium ions in hard water.
The invention also aims to provide the application of the cross-linked sulfonated aldehyde ketone cation exchange resin in removing calcium and magnesium ions in hard water.
The purpose of the invention is realized by the following scheme:
a method for preparing cross-linking sulfonated aldehyde ketone cation exchange resin with mild sulfonation reaction comprises the steps of firstly carrying out aldol condensation reaction on sulfite, ketone and aldehyde to obtain oligomer, and then adding phenol to carry out thermal insulation polycondensation reaction to prepare active polycondensate; and (4) preserving heat, curing and crosslinking reaction to obtain the crosslinking sulfonated aldehyde ketone cation exchange resin.
In the preparation method, the dosage of each component is calculated by mass parts as follows: 8-12 parts of sulfite, 6-12 parts of ketone, 7-14 parts of aldehyde and 1-5 parts of phenol.
In the present invention, the sulfite may be, but is not limited to, at least one of potassium sulfite, sodium sulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, and ammonium sulfite.
In the present invention, the ketone may be, but is not limited to, at least one of acetone, butanone, 2-pentanone, and cyclohexanone.
In the present invention, the aldehyde may be, but is not limited to, at least one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, and furfural.
According to the invention, the oligomer is obtained by firstly carrying out aldol condensation reaction on sulfite, ketone and aldehyde, and the oligomer can be obtained by firstly adding the sulfite and the ketone into water for mixing reaction and then adding the aldehyde for heating reaction.
The mixing reaction temperature is preferably 50-57 ℃, and the reaction time is preferably 10-20 min.
The temperature of the temperature rise reaction is preferably 80-90 ℃, and the reaction time is preferably 1-3 h.
The addition amount of the water is preferably 40 to 50 parts by mass.
The aldehyde is preferably added dropwise, and more preferably is added dropwise within 0.5-1 h.
In the invention, the temperature of the heat-preservation polycondensation reaction is preferably 85-95 ℃, and the reaction time is preferably 10-15 min.
In the present invention, the thermal curing and crosslinking reaction is preferably carried out in a closed vessel. The temperature of the heat preservation is preferably 90-95 ℃; the reaction time is preferably 12-24 h.
More specifically, the preparation method comprises the following steps:
dissolving 8-12 parts by mass of sulfite and 6-12 parts by mass of ketone in 40-50 parts by mass of water, and heating to 50-57 ℃ for reaction; dropwise adding 7-14 parts of aldehyde, heating to 80-90 ℃, and carrying out heat preservation reaction; then adding 1-5 parts of phenol, and carrying out heat preservation reaction at 85-95 ℃ to obtain a reactive condensation polymer; placing the mixture into a closed container, and preserving the heat for 12-24 hours at the temperature of 90-95 ℃ to obtain the cross-linked sulfonated aldehyde ketone cation exchange resin.
The invention also provides the cross-linking sulfonated aldehyde ketone cation exchange resin prepared by the method. The cation exchange resin is a strong acid type cation exchange resin with a novel structure, has high exchange equivalent, particularly has high exchange equivalent for calcium and magnesium ions in hard water, is far higher than that of the traditional sulfonated polyethylene cation exchange resin, and can be applied to removal of the calcium and magnesium ions in hard water.
The cross-linked sulfonated aldehyde ketone cation exchange resin of the invention has high exchange equivalent weight and is mainly based on:
(1) the traditional production process of sulfonated polystyrene cation exchange resin is that a polystyrene framework is prepared firstly, then the framework resin is sulfonated, and much styrene in the polystyrene framework is not fully sulfonated, so that the sulfonation efficiency is low, and the actual exchange equivalent is far lower than the theoretical exchange equivalent;
(2) the method firstly carries out sulfonation grafting reaction on the ketone unit, and then carries out polycondensation crosslinking reaction, so that the ketone unit in the obtained exchange resin is fully sulfonated, the sulfonation efficiency is high, and the actual exchange equivalent is high.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method has the advantages of mild sulfonation reaction, simple and controllable synthesis process and low raw material cost.
2. The cation exchange resin is sulfonated and then crosslinked, the traditional production process of first crosslinking and then sulfonation is overturned, ketone units in the prepared exchange resin are fully sulfonated, the sulfonation efficiency is high, the sulfonated group content is high, and the actual exchange equivalent is high.
3. The ketosulfonic acid cation exchange resin enriches the types of strong acid type cation exchange resins and widens the research scope of the strong acid type cation exchange resins.
Drawings
FIG. 1 is an infrared spectrum of the crosslinked sulfonated aldehyde ketone cation exchange resin obtained in examples 1 to 4.
FIG. 2 is a graph showing the regeneration exchange performance of the crosslinked sulfonated aldehyde ketone cation exchange resin obtained in examples 1 to 4 and a commercial resin # 732.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available. The amount of each material is calculated by mass portion.
Example 1
Dissolving 10 parts of sodium sulfite and 9 parts of acetone in 45 parts of water, heating to 55 ℃, reacting for 10 minutes, and then dropwise adding 10.6 parts of formaldehyde within 0.5 hour; after the dropwise addition, heating to 90 ℃, preserving heat and reacting for 1 hour, then adding 1.5 parts of phenol, and preserving heat and reacting for 10 minutes at 90 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction for 12 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain 2mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.619 mmol/g.
Example 2
Dissolving 10 parts of potassium sulfite and 7.5 parts of acetone in 40 parts of water, heating to 50 ℃ for reaction for 15 minutes, and then dropwise adding 9 parts of formaldehyde within 0.5 hour; after the dropwise addition, heating to 85 ℃, preserving heat and reacting for 1 hour, then adding 1 part of phenol, and preserving heat and reacting for 15 minutes at 95 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction at 95 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 3 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.988 mmol/g.
Example 3
Dissolving 10 parts of sodium bisulfite and 7.5 parts of acetone in 42 parts of water, heating to 57 ℃, reacting for 20 minutes, and then dropwise adding 9.6 parts of formaldehyde within 0.5 hour; after the dropwise addition, heating to 80 ℃, preserving heat and reacting for 1 hour, then adding 1.2 parts of phenol, and preserving heat and reacting for 10 minutes at 95 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction for 24 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 1 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 3.030 mmol/g.
Example 4
Dissolving 10 parts of sodium sulfite and 6.4 parts of acetone in 45 parts of water, heating to 53 ℃ for reaction for 10 minutes, and then dropwise adding 7.6 parts of formaldehyde within 0.5 hour; after the dropwise addition, heating to 85 ℃, preserving heat and reacting for 1 hour, then adding 1 part of phenol, and preserving heat and reacting for 10 minutes at 95 ℃ to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, carrying out heat preservation reaction for 18 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 1.5 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 3.176 mmol/g.
Example 5
Dissolving 10 parts of sodium sulfite and 6 parts of acetone in 45 parts of water, heating to 55 ℃, reacting for 10 minutes, and then dropwise adding 7 parts of formaldehyde within 0.5 hour; after the dropwise addition, heating to 90 ℃, preserving heat and reacting for 2 hours, then adding 1.2 parts of phenol, and preserving heat and reacting for 15 minutes at 95 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction for 24 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain 2mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 3.252 mmol/g.
Example 6
Dissolving 8 parts of potassium sulfite and 8 parts of butanone in 40 parts of water, heating to 52 ℃, reacting for 20 minutes, and dripping 9 parts of acetaldehyde in 45 minutes; after the dropwise addition, heating to 84 ℃, preserving heat and reacting for 2 hours, then adding 2 parts of phenol, and preserving heat and reacting for 10 minutes at 90 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction for 12 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 3 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.668 mmol/g.
Example 7
Dissolving 8 parts of potassium bisulfite, 2 parts of ammonium sulfite and 10 parts of butanone in 48 parts of water, heating to 54 ℃, reacting for 15 minutes, and then dropwise adding 9.5 parts of propionaldehyde in 45 minutes; after the dropwise addition, heating to 85 ℃, preserving heat and reacting for 3 hours, then adding 2.5 parts of phenol, preserving heat and reacting for 15 minutes at 85 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction for 15 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 1.8 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.473 mmol/g.
Example 8
Dissolving 11 parts of sodium metabisulfite and 12 parts of 2-pentanone in 50 parts of water, heating to 56 ℃ for reacting for 15 minutes, and then dropwise adding 11 parts of malondialdehyde within 1 hour; after the dropwise addition, heating to 90 ℃, preserving heat and reacting for 2 hours, then adding 3 parts of phenol, and preserving heat and reacting for 10 minutes at 93 ℃ to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, carrying out heat preservation reaction for 20 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain 2.4mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.214 mmol/g.
Example 9
Dissolving 10 parts of potassium metabisulfite and 10 parts of acetone in 47 parts of water, heating to 50 ℃ for reacting for 20 minutes, and then dropwise adding 14 parts of succinaldehyde within 1 hour; after the dropwise addition, heating to 87 ℃, preserving heat and reacting for 3 hours, then adding 3.5 parts of phenol, and preserving heat and reacting for 10 minutes at 87 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction for 15 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 1.4 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.618 mmol/g.
Example 10
Dissolving 12 parts of ammonium sulfite and 12 parts of cyclohexanone in 45 parts of water, heating to 55 ℃, reacting for 15 minutes, and then dropwise adding 13 parts of glutaraldehyde within 1 hour; after the dropwise addition, heating to 90 ℃, preserving heat and reacting for 1 hour, then adding 5 parts of phenol, and preserving heat and reacting for 15 minutes at 95 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction at 95 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 1.6 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.707 mmol/g.
Example 11
Dissolving 8 parts of potassium sulfite, 3 parts of potassium metabisulfite and 10 parts of 2-pentanone in 50 parts of water, heating to 57 ℃, reacting for 10 minutes, and dripping 10 parts of formaldehyde in 45 minutes; after the dropwise addition, heating to 88 ℃, preserving heat and reacting for 2 hours, then adding 4 parts of phenol, and preserving heat and reacting for 10 minutes at 88 ℃ to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, carrying out heat preservation reaction for 20 hours at 95 ℃ to obtain crosslinked solid resin, and crushing the product to obtain 2.3mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.553 mmol/g.
Example 12
Dissolving 6 parts of sodium sulfite, 2 parts of ammonium sulfite and 9 parts of acetone in 40 parts of water, heating to 50 ℃ for reaction for 15 minutes, and then dropwise adding 14 parts of furfural within 1 hour; after the dropwise addition, heating to 90 ℃, preserving heat and reacting for 3 hours, then adding 5 parts of phenol, and preserving heat and reacting for 15 minutes at 93 ℃ to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, carrying out heat preservation reaction at 95 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 3 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 3.029 mmol/g.
Description of the effects of the embodiments
Table 1 is a table of data of elemental analyses of examples 1 to 5, and the results of the elemental analyses were calculated to obtain theoretical sulfonate capacity (mmol/g) of the sample.
TABLE 1 elemental analysis of samples of examples 1 to 5
As can be seen from the elemental analysis data in Table 1, as the proportion of sulfite increases, the sulfur content in the product increases, and the sulfonic acid group content of the product, calculated from the sulfur content, increases, so that the theoretical exchange equivalent of the product also increases. The above five examples were used to perform a uniformly mixed ion exchange experiment using calcium and magnesium ion solutions of 25mmol/L, 50mmol/L and 100mmol/L, respectively (molar ratio of calcium ion to magnesium ion is 1:1) in a mass ratio of 1:5, respectively, and after exchanging in a shaking table at 25 ℃ and 200r/min for 24 hours, the dry-based exchange equivalent of the samples of examples 1 to 5 was measured and compared with the exchange performance of a commercial cation exchange resin of type #732 (crosslinked polystyrene sulfonic acid type cation exchange resin), and the results are shown in Table 2:
TABLE 2 examples 1-5 Dry base exchange equivalents (units: mmol/g) of resin samples with #732 resin
As can be seen from the results of the exchange experiments in Table 2, the cation exchange resins synthesized in examples 1 to 5 all had a dry basis exchange equivalent larger than that of the commercial strong-acid cation exchange resin #732 in three different concentrations of 25mmol/L, 50mmol/L and 100mmol/L of Ca and Mg ions. And the dry-based exchange equivalent of the five resins in 100mmol/L working solution is very close to the theoretical exchange equivalent calculated in the table 1, which shows that the ion exchange resin synthesized by the method not only shows the dry-based exchange equivalent better than the commercial resin, but also has high utilization rate of effective groups in the resin and better performance of the resin.
The cation exchange resins synthesized in examples 1 to 4 were subjected to a regeneration experiment in a working solution of 50mmol/L calcium and magnesium ions, and the regeneration performance of the resins of examples 1 to 4 was compared with that of the resin # 732. The regeneration test method is as follows: and washing and filtering the resin after the first exchange with water, mixing and regenerating the filtered wet-based resin and a sodium chloride solution with the mass fraction of 10% according to the mass ratio of 1:1, working in a vibration table at 25 ℃ and 200r/min for 24 hours, washing the regenerated resin, and filtering to obtain the wet-based resin. And mixing and exchanging the obtained regenerated resin with 50mmol/L calcium-magnesium ion working solution according to the mass ratio of 1:5, and then measuring the dry-base exchange equivalent of the resin to finish the first regeneration experiment. The above procedure was repeated seven times, and the regeneration ability of the resin synthesized in example and the commercial resin was measured seven times, and the experimental results are shown in FIG. 2. As can be seen from FIG. 2, the synthetic resins of examples 1 to 4 after seven regenerations all had higher dry-based exchange equivalent weights than the strong-acid cation exchange resin #732, and the ion exchange capacity after regeneration was 1mmol/L or more. FIG. 1 is an infrared spectrum of the crosslinked sulfonated aldehyde ketone cation exchange resin obtained in examples 1 to 4.
The sulfonated aldehyde ketone resin cation exchange resin prepared in the embodiment of the invention takes sulfite, ketone, aldehyde and phenol as raw materials, and is synthesized into sulfonated aldehyde ketone polycondensate through aldehyde ketone condensation reaction, and then is subjected to high-temperature crosslinking resinification to obtain the sulfonic acid type cation exchange resin. The cation exchange resin is sulfonated and then crosslinked, the traditional production process of first crosslinking and then sulfonation is overturned, ketone units in the prepared exchange resin are fully sulfonated, the sulfonation efficiency is high, the sulfonated group content is high, and the actual exchange equivalent is high. The sulfonation reaction is mild, the synthesis process is simple and controllable, and the cost of raw materials is low. The dry-base exchange equivalent of the cation exchange resin is higher than that of the #732 polystyrene cation exchange resin, can be directly used for exchanging calcium and magnesium ions in hard water, can be widely applied to the fields of water treatment, food, metallurgy and the like, and has wide application value.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of cross-linking sulfonated aldehyde ketone cation exchange resin is characterized in that firstly sulfite, ketone and aldehyde are subjected to aldol condensation reaction to obtain oligomer, and then phenol is added to carry out thermal insulation polycondensation reaction to prepare active polycondensate; carrying out heat preservation, curing and crosslinking reaction to obtain a crosslinking sulfonated aldehyde ketone cation exchange resin;
the dosage of each component is calculated by mass portion: 8-12 parts of sulfite, 6-12 parts of ketone, 7-14 parts of aldehyde and 1-5 parts of phenol.
2. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: the sulfite comprises at least one of potassium sulfite, sodium sulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite and ammonium sulfite;
the ketone comprises at least one of acetone, butanone, 2-pentanone and cyclohexanone; the aldehyde comprises at least one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and furfural.
3. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: firstly, carrying out aldol condensation reaction on sulfite, ketone and aldehyde to obtain an oligomer, firstly adding the sulfite and the ketone into water for mixing reaction, then adding the aldehyde for heating reaction to obtain the oligomer.
4. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 3, comprising: the temperature of the mixing reaction is 50-57 ℃, and the reaction time is 10-20 min; the temperature of the heating reaction is 80-90 ℃, and the reaction time is 1-3 h.
5. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: the temperature of the heat preservation polycondensation reaction is 85-95 ℃, and the reaction time is 10-15 min.
6. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: the heat preservation temperature of the heat preservation curing crosslinking reaction is 90-95 ℃; the reaction time is 12-24 h.
7. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising the steps of: dissolving 8-12 parts by mass of sulfite and 6-12 parts by mass of ketone in 40-50 parts by mass of water, and heating to 50-57 ℃ for reaction; dropwise adding 7-14 parts of aldehyde, heating to 80-90 ℃, and carrying out heat preservation reaction; then adding 1-5 parts of phenol, and carrying out heat preservation reaction at 85-95 ℃ to obtain a reactive condensation polymer; placing the mixture into a closed container, and preserving the heat for 12-24 hours at the temperature of 90-95 ℃ to obtain the cross-linked sulfonated aldehyde ketone cation exchange resin.
8. A crosslinked sulfonated aldehyde ketone cation exchange resin characterized by being obtained by the production method according to any one of claims 1 to 7.
9. Use of the cross-linked sulfonated aldehyde ketone cation exchange resin of claim 8 for removing calcium and magnesium ions from hard water.
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