CN115232232B - Preparation method of phosphonic acid type cation exchange resin - Google Patents
Preparation method of phosphonic acid type cation exchange resin Download PDFInfo
- Publication number
- CN115232232B CN115232232B CN202211103896.7A CN202211103896A CN115232232B CN 115232232 B CN115232232 B CN 115232232B CN 202211103896 A CN202211103896 A CN 202211103896A CN 115232232 B CN115232232 B CN 115232232B
- Authority
- CN
- China
- Prior art keywords
- polystyrene resin
- cation exchange
- parts
- phosphonic acid
- type cation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 50
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 35
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 229940102001 zinc bromide Drugs 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000007865 diluting Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000000413 hydrolysate Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 9
- 238000005954 phosphonylation reaction Methods 0.000 claims description 8
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 abstract description 12
- 230000008929 regeneration Effects 0.000 abstract description 11
- 238000009296 electrodeionization Methods 0.000 abstract description 4
- 238000005341 cation exchange Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000003795 desorption Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 229940023913 cation exchange resins Drugs 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012607 strong cation exchange resin Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012608 weak cation exchange resin Substances 0.000 description 1
Classifications
-
- 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
- C08F8/12—Hydrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of phosphonic acid type cation exchange resin. The phosphonic acid type cation exchange resin is mainly prepared from chloromethylation crosslinked polystyrene resin, triethyl phosphite, zinc bromide, 1, 2-dichloroethane, 98% sulfuric acid, acetone and deionized water; the method comprises the steps of cleaning, separating and drying chloromethylation crosslinked polystyrene resin by using acetone and deionized water, adding the obtained chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane, triethyl phosphite and zinc bromide into a reactor, filtering, washing and drying reaction liquid obtained by the reaction to obtain a phosphonated product, mixing and hydrolyzing the phosphonated product and 98% sulfuric acid, and diluting, filtering, washing and drying to obtain the phosphonic acid type cation exchange resin. The phosphonic acid type cation exchange resin synthesized by the invention has good cation exchange capacity and electrical regeneration performance, and can be used for realizing high purification treatment of inlet water by a membraneless electrodeionization technology.
Description
Technical Field
The invention relates to a preparation method of ion exchange resin in the field of ion exchange resin preparation, in particular to a preparation method of phosphonic acid type cation exchange resin capable of being used for electric regeneration.
Background
The electrochemical method is adopted to carry out the electric regeneration of the ion resin, so that the use of chemical agents in the deep desalting treatment technology can be effectively reduced. A great deal of researches and practices show that the electric regeneration characteristic of the ion exchange resin is closely related to the resin exchange characteristic, the sulfonic acid group of the strong cation exchange resin has higher capability of capturing counter ions, the adsorption exchange rate is high, but the electric desorption effect caused by the electric regeneration characteristic is poor; the carboxylic acid group of the weak cation exchange resin has higher hydrogen bonding energy, is beneficial to the electric desorption process of the resin, but has the defect of slower exchange rate, and is extremely easy to cause leakage of counter ions. The combination energy of the phosphonic acid group and the counter ion of the phosphonic acid type cation exchange resin is positioned between the two types of resins, has good counter ion adsorption and electric desorption characteristics, has good practicability as electric regeneration type resin, and has wide application prospect in desalting treatment by an ion exchange method.
At present, the synthesis method and route of phosphonic acid type cation exchange resin at home and abroad are still relatively lacking, and in most preparation methods, HBr, TMS bromine or HCl is used as a hydrolysis catalyst to hydrolyze trialkyl phosphate so as to obtain the phosphonic acid type cation exchange resin. However, the method uses halide with lower boiling point as a catalyst, so that the control on the reaction process is very strict, the hydrolysis degree is often lower, and the exchange capacity of the prepared phosphonic acid type cation exchange resin is lower, so that the popularization and the application of the phosphonic acid type cation exchange resin are severely limited.
Therefore, the prior art lacks a phosphonic acid type cation exchange resin preparation method which can obtain higher exchange capacity, greatly improve the cation exchange rate in the ion exchange reaction and reduce the electric energy loss in the electric regeneration process.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a preparation method of phosphonic acid type cation exchange resin, which takes concentrated sulfuric acid as a reaction catalyst to realize trialkyl phosphate hydrolysis, and the prepared phosphonic acid type cation exchange resin has good cation exchange capacity and electric regeneration performance, and can be used for realizing high purification treatment of inlet water by a membraneless electrodeionization technology.
The invention obtains the phosphonic acid type cation exchange resin with higher exchange capacity, greatly improves the exchange rate of cations in the ion exchange reaction, reduces the electric energy loss in the electric regeneration process, and has important practical value.
In order to achieve the above object, the specific technical scheme is as follows:
1. the phosphonic acid type cation exchange resin is mainly prepared from the following raw materials in parts by weight:
20-25 parts of chloromethylation crosslinked polystyrene resin
34-42 parts of triethyl phosphite
5-7 parts of zinc bromide
42-60 parts of 1, 2-dichloroethane
132-150 parts of 98% sulfuric acid
80-120 parts of acetone
5000-9000 parts of deionized water.
98% sulfuric acid represents 98% by mass of concentrated sulfuric acid.
The chloromethylation crosslinked polystyrene resin has a crosslinking degree of 7% and a chlorine content of 10 to 25%.
The phosphonylation product synthesized by triethyl phosphite, chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane and zinc bromide is directly hydrolyzed by 98% sulfuric acid.
2. A preparation method of phosphonic acid type cation exchange resin comprises the following steps:
step 1, phosphonylation of chloromethylated crosslinked polystyrene resin
Step 11, weighing triethyl phosphite, chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane and zinc bromide according to parts by weight, and then sequentially cleaning, separating and vacuum drying the chloromethylation crosslinked polystyrene resin by using acetone and deionized water to obtain clean chloromethylation crosslinked polystyrene resin for later use;
the chloromethylated crosslinked polystyrene resin was vacuum dried with acetone and deionized water at 60 c in step 11.
Step 12, adding chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane, triethyl phosphite and zinc bromide obtained in the step 11 into a reactor, and filtering, washing and drying reaction liquid obtained after the reaction to obtain phosphonated polystyrene resin;
the step 12 is specifically as follows:
adding chloromethylation crosslinked polystyrene resin and 1, 2-dichloroethane obtained in the step 11 into a reaction vessel, stirring for a period of time, specifically implementing for 10-15min, sequentially adding triethyl phosphite and zinc bromide powder into the reactor after stirring, raising the reaction temperature to 30-40 ℃ under stirring, reacting in the vessel for a period of time, specifically implementing for 3-4h, filtering the reaction solution after the reaction is finished, filtering to obtain filter balls, washing the obtained filter balls with acetone and deionized water respectively, and then drying at 30 ℃ to obtain the phosphonylated polystyrene resin.
Step 2, concentrated sulfuric acid hydrolysis of phosphonated resin
And (3) hydrolyzing the phosphonated polystyrene resin obtained in the step (12) by adopting 98% sulfuric acid in two steps to obtain the phosphonic acid type cation exchange resin.
The step 2 is specifically as follows:
weighing 98% sulfuric acid according to parts by weight, and hydrolyzing the phosphonated polystyrene resin obtained in the step 12 by adopting the 98% sulfuric acid in two steps; and (3) the first step of hydrolysis, namely adding the phosphonated polystyrene resin obtained in the step (12) and 98% sulfuric acid into a reaction container, stirring and reacting for a period of time in the container, wherein the specific implementation period of time is 2-3 hours, the reaction temperature is 60-80 ℃, the second step of hydrolysis, heating the hydrolysate of the first step to 90-125 ℃, reacting for a period of time in the container, wherein the specific implementation period of time is 2-6 hours, cooling the hydrolysate to normal temperature after the reaction is finished, diluting and filtering the reaction solution, washing the reaction solution with deionized water for multiple times, drying the reaction solution at the vacuum temperature of 40-60 ℃, and obtaining the phosphonic acid type cation exchange resin after drying the reaction solution.
The synthetic process of the phosphonic acid type cation exchange resin is schematically shown in figure 1.
The beneficial effects and advantages of the invention are as follows:
1) The preparation process is simple and easy to implement, and has wide applicability;
2) The invention takes concentrated sulfuric acid as a reaction catalyst, has higher boiling point, and can effectively improve the hydrolysis degree of the phosphonated resin;
3) The invention effectively improves the exchange rate of cations, reduces the electric energy loss in the electric regeneration process, and has important practical value.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of the phosphonic acid type cation exchange resin of the present invention.
Fig. 2 is a graph showing the effect of electro-desorption for a membraneless electro-deionization device according to the present invention.
Detailed Description
The following examples prepared phosphonic acid type cation exchange resins were measured according to GB/T8144-2008 "cation exchange resin exchange Capacity measurement method". To analyze the effect of the phosphonic acid type cation exchange resin in the following examples in the electro-deionization process without membrane, the phosphonic acid type cation exchange resins of example 1, example 2 and example 3 were subjected to NaCl saturation treatment, and electro-desorption analysis was performed in a non-membrane electro-regeneration test apparatus (diameter 3cm, height 50cm, anion resin PFA400OH, anion resin ratio 1:1, rinse water flow rate 20m/h, electro-desorption current density 80A/m 2), and a commercial sulfonic acid group 001×7 cation resin was generated by a certain factory for comparison.
Example 1:
step 1, phosphonylation of chloromethylated crosslinked polystyrene resin
Weighing 38 parts of triethyl phosphite, 22 parts of chloromethylation crosslinked polystyrene resin, 55 parts of 1, 2-dichloroethane and 6 parts of zinc bromide according to parts by weight, cleaning and separating the 22 parts of chloromethylation crosslinked polystyrene resin by using 50 parts of acetone and 2220 parts of deionized water in sequence, and vacuum drying at 60 ℃ to obtain the cleaned chloromethylation crosslinked polystyrene resin; adding the clean chloromethylation crosslinked polystyrene resin and 55 parts of 1, 2-dichloroethane into a reaction vessel, stirring for 15min, sequentially adding 38 parts of triethyl phosphite and 6 parts of zinc bromide powder into the reactor after stirring, raising the reaction temperature to 40 ℃ under stirring, reacting for 4h in the vessel, filtering the reaction solution after the reaction is finished, filtering to obtain filter balls, washing the obtained filter balls by 55 parts of acetone and 2220 parts of deionized water respectively, drying at 30 ℃, and drying to obtain the phosphonylated polystyrene resin.
Step 2, concentrated sulfuric acid hydrolysis of phosphonated resin
145 parts of 98% sulfuric acid is weighed according to parts by weight, and the phosphonated polystyrene resin obtained in the step 1 is hydrolyzed by adopting the 98% sulfuric acid in two steps. The first step of hydrolysis, namely adding the phosphonated polystyrene resin obtained in the step 1 and 145 parts of 98% sulfuric acid into a reaction container, stirring and reacting for 2 hours in the container, wherein the reaction temperature is 60 ℃; and step two, hydrolyzing, namely heating the hydrolysate in the step one to 120 ℃, reacting in a container for 6 hours, cooling the hydrolysate to normal temperature after the reaction is finished, diluting and filtering the reaction liquid, washing the reaction liquid with 2220 parts of deionized water for multiple times, drying the reaction liquid at the temperature of 60 ℃ in vacuum, and obtaining the phosphonic acid type cation exchange resin after drying.
The exchange capacity of the phosphonic acid type cation exchange resin obtained above was 6.22mmol/g.
The effect of the above-obtained phosphonic acid type cation exchange resin in electric desorption is shown in fig. 2.
Example 2:
step 1, phosphonylation of chloromethylated crosslinked polystyrene resin
Weighing 38 parts of triethyl phosphite, 22 parts of chloromethylation crosslinked polystyrene resin, 55 parts of 1, 2-dichloroethane and 6 parts of zinc bromide according to parts by weight, cleaning and separating the 22 parts of chloromethylation crosslinked polystyrene resin by using 50 parts of acetone and 2220 parts of deionized water in sequence, and vacuum drying at 60 ℃ to obtain the cleaned chloromethylation crosslinked polystyrene resin; adding the clean chloromethylation crosslinked polystyrene resin and 55 parts of 1, 2-dichloroethane into a reaction vessel, stirring for 15min, sequentially adding 38 parts of triethyl phosphite and 6 parts of zinc bromide powder into the reactor after stirring, raising the reaction temperature to 40 ℃ under stirring, reacting for 4h in the vessel, filtering the reaction solution after the reaction is finished, filtering to obtain filter balls, washing the obtained filter balls by 55 parts of acetone and 2220 parts of deionized water respectively, drying at 30 ℃, and drying to obtain the phosphonylated polystyrene resin.
Step 2, concentrated sulfuric acid hydrolysis of phosphonated resin
145 parts of 98% sulfuric acid is weighed according to parts by weight, and the phosphonated polystyrene resin obtained in the step 1 is hydrolyzed by adopting the 98% sulfuric acid in two steps. The first step of hydrolysis, namely adding the phosphonated polystyrene resin obtained in the step 1 and 145 parts of 98% sulfuric acid into a reaction container, stirring and reacting for 2 hours in the container, wherein the reaction temperature is 80 ℃; and (2) hydrolyzing, namely heating the hydrolysate in the first step to 105 ℃, reacting for 6 hours in a container, cooling the hydrolysate to normal temperature after the reaction is finished, diluting and filtering the reaction liquid, washing the reaction liquid with 2220 parts of deionized water for multiple times, and drying the reaction liquid at the vacuum temperature of 60 ℃ to obtain the phosphonic acid type cation exchange resin.
The exchange capacity of the phosphonic acid type cation exchange resin obtained above was 4.55mmol/g.
The effect of the above-obtained phosphonic acid type cation exchange resin in electric desorption is shown in fig. 2.
Example 3:
step 1, phosphonylation of chloromethylated crosslinked polystyrene resin
Weighing 38 parts of triethyl phosphite, 22 parts of chloromethylation crosslinked polystyrene resin, 55 parts of 1, 2-dichloroethane and 6 parts of zinc bromide according to parts by weight, cleaning and separating the 22 parts of chloromethylation crosslinked polystyrene resin by using 50 parts of acetone and 2220 parts of deionized water in sequence, and vacuum drying at 60 ℃ to obtain the cleaned chloromethylation crosslinked polystyrene resin; adding the clean chloromethylation crosslinked polystyrene resin and 55 parts of 1, 2-dichloroethane into a reaction vessel, stirring for 15min, sequentially adding 38 parts of triethyl phosphite and 6 parts of zinc bromide powder into the reactor after stirring, raising the reaction temperature to 40 ℃ under stirring, reacting for 4h in the vessel, filtering the reaction solution after the reaction is finished, filtering to obtain filter balls, washing the obtained filter balls by 55 parts of acetone and 2220 parts of deionized water respectively, drying at 30 ℃, and drying to obtain the phosphonylated polystyrene resin.
Step 2, concentrated sulfuric acid hydrolysis of phosphonated resin
145 parts of 98% sulfuric acid is weighed according to parts by weight, and the phosphonated polystyrene resin obtained in the step 1 is hydrolyzed by adopting the 98% sulfuric acid in two steps. The first step of hydrolysis, namely adding the phosphonated polystyrene resin obtained in the step 1 and 145 parts of 98% sulfuric acid into a reaction container, stirring and reacting for 2 hours in the container, wherein the reaction temperature is 80 ℃; and step two, hydrolyzing, namely heating the hydrolysate in the step one to 120 ℃, reacting in a container for 6 hours, cooling the hydrolysate to normal temperature after the reaction is finished, diluting and filtering the reaction liquid, washing the reaction liquid with 2220 parts of deionized water for multiple times, drying the reaction liquid at the temperature of 60 ℃ in vacuum, and obtaining the phosphonic acid type cation exchange resin after drying.
The exchange capacity of the phosphonic acid type cation exchange resin obtained above was 4.89mmol/g.
The effect of the above-obtained phosphonic acid type cation exchange resin in electric desorption is shown in fig. 2.
The phosphonic acid type cation exchange resins obtained in the examples 1,2 and 3 are basically equivalent to the commercial sulfonic acid type cation exchange resins in exchange capacity (the exchange capacity provided by manufacturers is more than or equal to 4.5 mmol/g), but the electric desorption concentrated water conductivity of the phosphonic acid type cation exchange resins is obviously improved (as shown in figure 2), the highest concentrated water conductivity is improved from 29.3us/cm to 176.2us/cm (example 2), and the electric regeneration of saturated resins is basically realized by 100min electric desorption treatment.
Claims (7)
1. A phosphonic acid type cation exchange resin characterized in that:
the material is mainly prepared from the following raw materials in parts by weight:
20-25 parts of chloromethylation crosslinked polystyrene resin
34-42 parts of triethyl phosphite
5-7 parts of zinc bromide
42-60 parts of 1, 2-dichloroethane
132-150 parts of 98% sulfuric acid
80-120 parts of acetone
5000-9000 parts of deionized water;
the phosphonic acid type cation exchange resin is prepared and obtained according to the following preparation method:
step 1, phosphonylation of chloromethylated crosslinked polystyrene resin
Step 11, weighing triethyl phosphite, chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane and zinc bromide according to parts by weight, and then sequentially cleaning, separating and vacuum drying the chloromethylation crosslinked polystyrene resin by using acetone and deionized water to obtain clean chloromethylation crosslinked polystyrene resin for later use;
step 12, adding chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane, triethyl phosphite and zinc bromide obtained in the step 11 into a reactor, and filtering, washing and drying reaction liquid obtained after the reaction to obtain phosphonated polystyrene resin;
step 2, concentrated sulfuric acid hydrolysis of phosphonated resin
Hydrolyzing the phosphonated polystyrene resin obtained in the step 12 by adopting 98% sulfuric acid in two steps to obtain phosphonic acid type cation exchange resin;
the step 2 specifically comprises the following steps:
weighing 98% sulfuric acid according to parts by weight, and hydrolyzing the phosphonated polystyrene resin obtained in the step 12 by adopting the 98% sulfuric acid in two steps; and (3) the first step of hydrolysis, namely adding the phosphonated polystyrene resin obtained in the step (12) and 98% sulfuric acid into a reaction container, stirring and reacting for a period of time in the container, wherein the reaction temperature is 60-80 ℃, the second step of hydrolysis, heating the hydrolysate of the first step to 90-125 ℃, reacting for a period of time in the container, cooling the hydrolysate to normal temperature after the reaction is finished, diluting and filtering the reaction solution, washing with deionized water for multiple times, and drying at the vacuum temperature of 40-60 ℃ to obtain the phosphonic acid type cation exchange resin.
2. A phosphonic acid type cation exchange resin of claim 1 wherein:
the chloromethylation crosslinked polystyrene resin has a crosslinking degree of 7% and a chlorine content of 10-25%.
3. A phosphonic acid type cation exchange resin of claim 1 wherein:
the phosphonylation product synthesized by triethyl phosphite, chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane and zinc bromide is directly hydrolyzed by 98% sulfuric acid.
4. The method for preparing a phosphonic acid type cation exchange resin according to claim 1, characterized in that the method comprises the steps of:
step 1, phosphonylation of chloromethylated crosslinked polystyrene resin
Step 11, weighing triethyl phosphite, chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane and zinc bromide according to parts by weight, and then sequentially cleaning, separating and vacuum drying the chloromethylation crosslinked polystyrene resin by using acetone and deionized water to obtain clean chloromethylation crosslinked polystyrene resin for later use;
step 12, adding chloromethylation crosslinked polystyrene resin, 1, 2-dichloroethane, triethyl phosphite and zinc bromide obtained in the step 11 into a reactor, and filtering, washing and drying reaction liquid obtained after the reaction to obtain phosphonated polystyrene resin;
step 2, concentrated sulfuric acid hydrolysis of phosphonated resin
And (3) hydrolyzing the phosphonated polystyrene resin obtained in the step (12) by adopting 98% sulfuric acid in two steps to obtain the phosphonic acid type cation exchange resin.
5. The method for preparing a phosphonic acid type cation exchange resin according to claim 4, wherein: the step 12 specifically includes:
adding chloromethylation crosslinked polystyrene resin and 1, 2-dichloroethane obtained in the step 11 into a reaction vessel, stirring for a period of time, sequentially adding triethyl phosphite and zinc bromide powder into the reactor after stirring, raising the reaction temperature to 30-40 ℃ under stirring, reacting in the vessel for a period of time, filtering the reaction solution after the reaction is finished, filtering to obtain filter balls, washing the obtained filter balls with acetone and deionized water respectively, drying at 30 ℃, and obtaining the phosphonated polystyrene resin after drying.
6. The method for preparing a phosphonic acid type cation exchange resin according to claim 4, wherein:
the step 2 specifically comprises the following steps:
weighing 98% sulfuric acid according to parts by weight, and hydrolyzing the phosphonated polystyrene resin obtained in the step 12 by adopting the 98% sulfuric acid in two steps; and (3) the first step of hydrolysis, namely adding the phosphonated polystyrene resin obtained in the step (12) and 98% sulfuric acid into a reaction container, stirring and reacting for a period of time in the container, wherein the reaction temperature is 60-80 ℃, the second step of hydrolysis, heating the hydrolysate of the first step to 90-125 ℃, reacting for a period of time in the container, cooling the hydrolysate to normal temperature after the reaction is finished, diluting and filtering the reaction solution, washing with deionized water for multiple times, and drying at the vacuum temperature of 40-60 ℃ to obtain the phosphonic acid type cation exchange resin.
7. The method for preparing a phosphonic acid type cation exchange resin according to claim 4, wherein: the chloromethylated crosslinked polystyrene resin was vacuum dried with acetone and deionized water at 60 c in step 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211103896.7A CN115232232B (en) | 2022-09-09 | 2022-09-09 | Preparation method of phosphonic acid type cation exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211103896.7A CN115232232B (en) | 2022-09-09 | 2022-09-09 | Preparation method of phosphonic acid type cation exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115232232A CN115232232A (en) | 2022-10-25 |
| CN115232232B true CN115232232B (en) | 2024-01-26 |
Family
ID=83681036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211103896.7A Active CN115232232B (en) | 2022-09-09 | 2022-09-09 | Preparation method of phosphonic acid type cation exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115232232B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120561A (en) * | 2022-12-26 | 2023-05-16 | 宁波争光树脂有限公司 | Phosphoric acid resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1539768A (en) * | 1966-07-20 | 1968-09-20 | Diamond Alkali Co | Process for the haloalkylation of crosslinked polymers |
| CN111607024A (en) * | 2020-05-25 | 2020-09-01 | 浙江大学 | Grafted quaternary ammonium group positive resin and preparation method thereof |
| CN112876587A (en) * | 2021-01-27 | 2021-06-01 | 浙江大学 | Medium-strength alkaline styrene amphoteric ion exchange resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000001458A1 (en) * | 1998-07-02 | 2000-01-13 | Arch Development Corporation | Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same |
-
2022
- 2022-09-09 CN CN202211103896.7A patent/CN115232232B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1539768A (en) * | 1966-07-20 | 1968-09-20 | Diamond Alkali Co | Process for the haloalkylation of crosslinked polymers |
| CN111607024A (en) * | 2020-05-25 | 2020-09-01 | 浙江大学 | Grafted quaternary ammonium group positive resin and preparation method thereof |
| CN112876587A (en) * | 2021-01-27 | 2021-06-01 | 浙江大学 | Medium-strength alkaline styrene amphoteric ion exchange resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115232232A (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115232232B (en) | Preparation method of phosphonic acid type cation exchange resin | |
| CN109546163B (en) | Modification method of graphite felt electrode for organic flow battery | |
| WO2021238315A1 (en) | Grafted quaternary ammonium group cation resin and preparation method therefor | |
| CN108114599A (en) | It is a kind of based on salt error the electrodialysis reversal of production soda acid to be driven to couple bipolar membranous system and its production method | |
| CN107200690A (en) | A kind of application membrane technology produces the environmental protection method of TPAOH | |
| CN110644014A (en) | Preparation method of tetraethyl ammonium hydroxide | |
| CN114210374B (en) | Ion exchange resin suitable for petrochemical wastewater treatment and preparation method thereof | |
| CN103724644B (en) | A kind of based on polymine with the preparation method of polyvinyl alcohol fuel cell composite proton conductive membranes | |
| CN109574151B (en) | Method for continuous low-energy-consumption desalting by using material electrochemistry and application thereof | |
| CN205856062U (en) | A kind of condensate polishing treatment resin regeneration the wash water online recycling water mixed-bed system | |
| CN109161927B (en) | It is a kind of using porous anode membrane as Bipolar Membrane of substrate and preparation method thereof | |
| JP3339961B2 (en) | Method for producing amphoteric membrane and aqueous alkali metal hydroxide solution | |
| CN104716343B (en) | A kind of high-performance is combined carbon felt | |
| CN103626357B (en) | The preparation method of Al-ZnO-AC electrode and a kind of nanometer electro-adsorption remove slightly salty salt separating device | |
| Sata | Properties of a cation-exchange membrane adsorbed or ion-exchanged with hexadecylpyridinium chloride | |
| CN109004253A (en) | A kind of hydroxide ion exchange membrane being used to prepare fuel cell hydrogen and preparation method | |
| Davidov et al. | Using a microheterogeneous model to assess the applicability of ion-exchange membranes in the process of reverse electrodialysis | |
| CN105140498B (en) | A kind of liquid phase reactor preparation method of zinc load material | |
| Moresi et al. | Effect of some operating variables on citrate recovery from model solutions by electrodialysis | |
| CN110813387B (en) | Preparation method of monovalent anion exchange membrane | |
| CN106268984A (en) | A kind of renovation process of the cation exchange membrane of the polyethyleneimine-modified of inefficacy | |
| CN102276439B (en) | Method for preparing fatty acid radical ionic liquid | |
| CN109437311A (en) | A kind of dumbbell shaped MnO@C complex microsphere and preparation method | |
| CN109019512A (en) | A kind of reaction unit being used to prepare no deuterium-oxide | |
| CN205061638U (en) | Electric desalination device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |