CN108325568A - A kind of preparation method of lignin-base storng-acid cation exchange resin - Google Patents
A kind of preparation method of lignin-base storng-acid cation exchange resin Download PDFInfo
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- CN108325568A CN108325568A CN201810174510.9A CN201810174510A CN108325568A CN 108325568 A CN108325568 A CN 108325568A CN 201810174510 A CN201810174510 A CN 201810174510A CN 108325568 A CN108325568 A CN 108325568A
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- lignin
- exchange resin
- base
- storng
- cation exchange
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- 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 73
- 239000002253 acid Substances 0.000 title claims abstract description 73
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920005610 lignin Polymers 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000000465 moulding Methods 0.000 claims abstract description 26
- 238000005342 ion exchange Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000010792 warming Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 239000002585 base Substances 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 229920001732 Lignosulfonate Polymers 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 239000003456 ion exchange resin Substances 0.000 abstract description 25
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 2
- 238000005341 cation exchange Methods 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 3
- 229940031826 phenolate Drugs 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004971 Cross linker Substances 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000004965 peroxy acids Chemical group 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of preparation methods of lignin-base storng-acid cation exchange resin.Include the following steps：(1) it dissolves：Lignin is added in alkaline solution, is stirred to dissolve；(2) reaction molding：Phenol, sulfonated reagent, formaldehyde are added in the alkaline lignin liquor that step (1) obtains, so that the mixture is warming up to reaction temperature, after reacted molding, obtains lignin-base storng-acid cation exchange resin precursor；(3) ion exchange：The lignin-base storng-acid cation exchange resin precursor that step (2) obtains is impregnated through acid solution, and washing obtains lignin-base storng-acid cation exchange resin.This method can single step reaction prepare the controllable lignin-base strong-acid ion exchange resin of ion-exchange capacity, simple process, yield is high, at low cost.
Description
Technical field
The present invention relates to a kind of preparation methods of lignin-base storng-acid cation exchange resin.
Background technology
Ion exchange resin is the netted insoluble functional high molecule material with ion-exchange group.Ion exchange resin
Matrix mainly have styrene and acrylic acid (ester) two major classes, they polymerize with cross-linker divinylbenzene, formed have network
The polymer of skeleton structure.According to ion exchange resin the property with active group, can be divided into strong-acid cation-exchange resin,
Weak-acid cation exchange resin, strong basic anion-exchange resin, weak basic anion exchange resin etc..Ion exchange resin, which has, to be handed over
The functions such as change, select, adsorb, be catalyzed and regenerate, in necks such as industrial high purity water preparation, medical and health, metallurgy industry, bioengineering
Domain, which is obtained for, to be widely applied.In terms of the condition of production of global ion exchange resin, highly acidic resin accounts for the 50%- of total output
60%, basic resin accounts for 25%-30%, and China's highly acidic resin occupies the proportion of bigger, accounts for about the 80% of total output.Due to
Ion exchange resin has certain service life, therefore has the petrochemical industry such as big weight phenylethylene and divinylbenzene base chemical every year
Product are expensive for producing ion exchange resin, and discarded ion exchange resin is difficult to biodegradation, need to pass through profession
Solid hazardous waste processing company is handled, and processing cost is high.
Lignin is unique a kind of natural resources of a large amount of existing renewable aromatic compounds in nature, is a kind of knot
The three-dimensional netted aromatics natural high polymer of structure complexity.The xylogen by-product that annual pulping and paper-making industry generates is up to 50,000,000
Ton, in addition to 2% or so is used effectively, most of lignin is directly burnt as a kind of low price fuel, to cause wood
The serious waste of quality resource.A large amount of reactivity site in lignin structure, such as phenolic hydroxyl group, alcoholic extract hydroxyl group, make it not only
With many potential reactivities, and industrial chemicals is also acted as, is used for the lignin-base material of synthetic environment close friend.Cause
This, the tridimensional network of lignin and its potential reactivity site prepare ion exchange resin for it and provide naturally
Advantage.But the structure due to lignin complexity and lower reactivity, it is limited in terms of ion exchange resin
Using only a small amount of researcher has carried out Primary Study to the preparation and application of lignin-base ion exchange resin.
In recent years, domestic and international scientific research personnel is prepared for wood using lignosulfonates, acidolysis lignin and alkali lignin
Quality base strong-acid ion exchange resin.Zhu Jianhua et al. is using lignosulfonates as raw material, using formaldehyde as crosslinking agent, by anti-
Phase emulsion polymerization means are prepared for spherical lignin-base cation exchange resin.This method using lignosulfonates per se with
Sulfonic acid group be ion exchange functional groups, the amberlite Ester exchange crosslink density and exchange capacity being prepared are relatively
Low (Zhu Jianhua, yellow slight snow, yellow such as cane, Song Qing, Chinese papermaking .1992,8+46.).CN103285942B is with lignosulfonates
For raw material, the lignin-base highly acidic cation with cation exchange capacity (CEC) has been obtained by high temperature cabonization lignosulfonates
Exchanger resin.However lignin quality loss is big in carbonisation, lignin-base storng-acid cation exchange resin yield is relatively low,
Cost is higher.Yasuda et al. is prepared for storng-acid cation exchange resin using acidolysis lignin as raw material by four-step reaction.
Acidolysis lignin prepares phenolate lignin by phenolate first；Secondly, obtained phenolate lignin cures using formaldehyde crosslinking
Make lignin tree esterification reaction；Again, the lignin of resinification is dissolved in tetrachloroethanes, is tried by sulfonation of chlorosulfonic acid
Agent makes Sulphonation of Lignin, obtains lignin-base ion exchange resin precursor；Finally, lignin-base ion exchange resin precursor passes through
It is peracid to have obtained storng-acid cation exchange resin.This method step is more, and sulfonation process needs to carry out in organic solvent,
Cost is higher, it is difficult to realization large-scale production (Yasuda, S., Asano, K., Journal of Wood Science.2000,
46,477-479.).Based on this, the present invention is prepared by the way that one-step method is simple and quick with compared with high cation exchange capacity
Lignin-base storng-acid cation exchange resin, to promote the utility value of lignin.
Invention content
The present invention prepares lignin-base storng-acid cation exchange resin using lignin as raw material, by one-step method.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of lignin-base storng-acid cation exchange resin, includes the following steps：
(1) it dissolves：Lignin is added in alkaline solution, is stirred to dissolve；
(2) reaction molding：Phenol, sulfonated reagent, formaldehyde are added in the alkaline lignin liquor that step (1) obtains, made
The mixture is warming up to reaction temperature, after reacted molding, obtains lignin-base storng-acid cation exchange resin precursor；
(3) ion exchange：The lignin-base storng-acid cation exchange resin precursor that step (2) obtains is soaked through acid solution
Stain, washing, obtains lignin-base storng-acid cation exchange resin.
The lignin includes alkali lignin, sulfate-reducing conditions, lignosulfonates, organic solvent lignin, enzymolysis
Any one or a few in lignin.
Step (1) the neutral and alkali solution includes any one in sodium hydroxide solution and potassium hydroxide solution；Alkalinity
Solution concentration is 2~40g/L.
Sulfonated reagent includes any one in sodium sulfite and sodium hydroxymethane sulfonate in the step (2).
Mass ratio in the step (2) in phenol addition and the step (1) between lignin addition is 4:1
~1:4.
Molar ratio in the step (2) in sulfonated reagent addition and the step (2) between phenol addition is
2:1~1:8.
Molar ratio in the step (2) in formaldehyde addition and the step (2) between phenol addition is 2:1~
6:1。
The solid content of mixture is 10%~80% in the step (2).
Reaction temperature is 80~200 degrees Celsius in the step (2), and the reaction time is 0~12 hour.
The reaction molding mode of lignin-base storng-acid cation exchange resin precursor includes reverse phase breast in the step (2)
Liquid polymerize and polymerisation in solution.
Acid solution includes any one in the inorganic acid solutions such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid in the step (3)
Or it is several.Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) it is that highly acidic cation prepared by functional group is exchanged with the sulfonic group carried using lignosulfonates itself
Resin is compared, and this method can introduce more sulfonic acid groups by the way that sulfonated reagent is added, and can be made by changing sulfonated reagent dosage
The controllable lignin-base strong-acid ion exchange resin of standby ion-exchange capacity.
(2) compared with multi-step preparation, the exchange of lignin-base highly acidic cation can be prepared by this method by a step
Resin, and need not react in organic solvent, manufacturing cost is low.
Specific implementation mode
With reference to embodiment, invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
(1) it dissolves：9.4g sulfate-reducing conditions are added to the reaction kettle of the sodium hydroxide solution for the 20g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：Step is added in the formaldehyde of the phenol of 0.1mol, the sodium hydroxymethane sulfonate of 0.025mol and 0.5mol
Suddenly in the alkaline lignin liquor that (1) obtains, said mixture is made to be warming up to 100 degrees Celsius, reacts 2 hours, after reaction,
It is cooling, it is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute salt
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 1.6mmol/g.
Embodiment 2
(1) it dissolves：9.4g sulfate-reducing conditions are added to the reaction kettle of the sodium hydroxide solution for the 20g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：Step is added in the formaldehyde of the phenol of 0.1mol, the sodium hydroxymethane sulfonate of 0.05mol and 0.5mol
Suddenly in the alkaline lignin liquor that (1) obtains, said mixture is made to be warming up to 100 degrees Celsius, reacts 2 hours, after reaction,
It is cooling, it is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute salt
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 1.7mmol/g.
Embodiment 3
(1) it dissolves：9.4g sulfate-reducing conditions are added to the reaction kettle of the sodium hydroxide solution for the 20g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：Step is added in the formaldehyde of the phenol of 0.1mol, the sodium hydroxymethane sulfonate of 0.1mol and 0.5mol
(1) in the alkaline lignin liquor obtained, said mixture is made to be warming up to 100 degrees Celsius, reacted 2 hours, it is after reaction, cold
But, it is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute salt
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 2.0mmol/g.
Embodiment 4
(1) it dissolves：18.8g alkali lignins are added in the reaction kettle of the potassium hydroxide solution for the 40g/L for filling 100mL,
It stirs to dissolve；
(2) reaction molding：Step (1) is added in the formaldehyde of the phenol of 0.2mol, the sodium sulfite of 0.2mol and 0.8mol
In obtained alkaline lignin liquor, said mixture is made to be warming up to 100 degrees Celsius, reacted 8 hours, it is after reaction, cooling,
It is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute sulphur
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 2.4mmol/g.
Embodiment 5
(1) it dissolves：18.8g alkali lignins are added in the reaction kettle of the potassium hydroxide solution for the 20g/L for filling 100mL,
It stirs to dissolve；
(2) reaction molding：Step (1) is added in the formaldehyde of the phenol of 0.2mol, the sodium sulfite of 0.1mol and 0.8mol
In obtained alkaline lignin liquor, said mixture is made to be warming up to 80 degrees Celsius, reacted 12 hours, it is after reaction, cooling,
It is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute sulphur
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 1.5mmol/g.
Embodiment 6
(1) it dissolves：4.7g sodium lignin sulfonates are added to the reaction kettle of the sodium hydroxide solution for the 2g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：The formaldehyde of the phenol of 0.05mol, the sodium hydroxymethane sulfonate of 0.025mol and 0.1mol is added
In the alkaline lignin liquor that step (1) obtains, said mixture is made to be warming up to 200 degrees Celsius, reacted 10 minutes, reaction terminates
Afterwards, cooling, it is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute nitre
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 2.5mmol/g.
Embodiment 7
(1) it dissolves：18.8g sodium lignin sulfonates are added to the reaction kettle of the sodium hydroxide solution for the 10g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：Step (1) is added in the formaldehyde of the phenol of 0.1mol, the sodium sulfite of 0.05mol and 0.4mol
In obtained alkaline lignin liquor, said mixture is made to be warming up to 120 degrees Celsius, reacted 2 hours, it is after reaction, cooling,
It is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute sulphur
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 2.8mmol/g.
Embodiment 8
(1) it dissolves：4.7g sodium lignin sulfonates are added to the reaction kettle of the sodium hydroxide solution for the 4g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：Step (1) is added in the formaldehyde of the phenol of 0.2mol, the sodium sulfite of 0.05mol and 0.4mol
In obtained alkaline lignin liquor, said mixture is made to be warming up to 120 degrees Celsius, reacted 2 hours, it is after reaction, cooling,
It is cut into the cake of 2mm thickness；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute sulphur
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 2.2mmol/g.
Embodiment 9
(1) it dissolves：9.4g sodium lignin sulfonates are added to the reaction kettle of the sodium hydroxide solution for the 8g/L for filling 100mL
In, it stirs to dissolve；
(2) reaction molding：Step (1) is added in the formaldehyde of the phenol of 0.1mol, the sodium sulfite of 0.05mol and 0.4mol
In obtained alkaline lignin liquor, 200mL paraffin oils are added and make reverse phase solvent, 10g sorbester p17s are added as dispersant, acutely
Stirring makes said mixture be warming up to 140 degrees Celsius, reacts 2 hours, after reaction, cooling, obtains spherical lignin-base strong acid
Property cation exchange resin precursor；
(3) ion exchange：The molding lignin-base storng-acid cation exchange resin precursor that step (2) obtains is through dilute salt
Acid solution impregnates, and washing obtains lignin-base storng-acid cation exchange resin.According to GB/T8144-2008 (cation exchange trees
Ester exchange solid measure method), measure the total ion exchange of lignin-base strong-acid ion exchange resin of the method for the present invention preparation
Capacity is 3.2mmol/g.
Claims (5)
1. a kind of preparation method of lignin-base storng-acid cation exchange resin, which is characterized in that include the following steps：
(1) it dissolves：Lignin is added in alkaline solution, is stirred to dissolve；
(2) reaction molding：Phenol, sulfonated reagent, formaldehyde are added in the alkaline lignin liquor that step (1) obtains, made described
Mixture is warming up to reaction temperature, after reacted molding, obtains lignin-base storng-acid cation exchange resin precursor；
(3) ion exchange：The lignin-base storng-acid cation exchange resin precursor that step (2) obtains is impregnated through acid solution,
Washing, obtains lignin-base storng-acid cation exchange resin.
2. a kind of preparation method of lignin-base storng-acid cation exchange resin according to claim 1, feature exist
Include that alkali lignin, sulfate-reducing conditions, lignosulfonates, organic solvent lignin, enzymolysis are wooden in, the lignin
Any one or a few in element.
3. a kind of preparation method of lignin-base storng-acid cation exchange resin according to claim 1, feature exist
In the alkaline solution described in step (1) includes any one in sodium hydroxide solution and potassium hydroxide solution；Alkaline solution
A concentration of 2~40g/L.
4. a kind of preparation method of lignin-base storng-acid cation exchange resin according to claim 1, feature exist
In the sulfonated reagent described in step (2) includes any one in sodium sulfite and sodium hydroxymethane sulfonate；
Mass ratio in the step (2) in phenol addition and the step (1) between lignin addition is 4:1~
1:4；
Molar ratio in the step (2) in sulfonated reagent addition and the step (2) between phenol addition is 2:1
~1:8；
Molar ratio in the step (2) in formaldehyde addition and the step (2) between phenol addition is 2:1~6:
1；
The solid content of mixture is 10%~80% in the step (2)；
Reaction temperature is 80~200 degrees Celsius in the step (2), and the reaction time is 0~12 hour；
The reaction molding mode of lignin-base storng-acid cation exchange resin precursor includes reversed-phase emulsion in the step (2)
Polymerization and polymerisation in solution.
5. a kind of preparation method of lignin-base storng-acid cation exchange resin according to claim 1, feature exist
In acid solution includes any one or a few in the inorganic acid solutions such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid in step (3).
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