Patent ID: 12221503

DETAILED DESCRIPTION OF THE EMBODIMENTS

An exchange capacity of the following resin was determined according to GB/T8144-2008 “Determination Method of Exchange Capacity of Cation-Exchange Resin” and GB/T 11992-2008 “Determination Method of Exchange Capacity of Chlorine-type Strong-base Anion-exchange Resin”.

Example 1

1) Introduction of a quaternary ammonium group into a chloromethylated cross-linked PS resin;

1.1) 15 parts of a chloromethylated cross-linked PS resin and 18 parts of trimethylamine hydrochloride were successively added to a reaction vessel.

1.2) 72 parts of a 20% sodium hydroxide aqueous solution were added dropwise to the reaction vessel within 1 hour, a temperature was kept at 30° C. to 40° C., and a resulting mixture was continuously stirred to allow a reaction for 2 hours.

1.3) After the reaction was completed, a reaction solution was filtered to obtain a resin, and the resin was washed with 750 parts of a 5% sodium hydroxide aqueous solution, converted with 750 parts of a 5% hydrochloric acid aqueous solution, and washed with 4,500 parts of deionized water until an effluent had a pH of 7.

1.4) The resin was dried at 60° C. to obtain a quaternary ammonium group-grafted chloromethylated cross-linked PS resin.

2) Sulfonation of the quaternary ammonium group-grafted chloromethylated cross-linked PS resin;

2.1) 15 parts of the resin obtained in step 1.4), 60 parts of 1,2-dichloroethane, 0.75 part of silver sulfate, 15 parts of concentrated sulfuric acid, and 15 parts of fuming sulfuric acid were added successively to a reaction vessel.

2.2) A temperature was kept at 50° C. to 60° C., and a resulting mixture was continuously stirred to allow a reaction for 1 hour.

2.3) The temperature was raised to 70° C. to 80° C., and the mixture was continuously stirred to allow a reaction for 1 hour.

2.4) The temperature was raised to 115° C. to 125° C., and the mixture was continuously stirred to allow a reaction for 5 hours.

2.5) After the reaction was completed, a resulting reaction solution was cooled to room temperature, diluted, and filtered to obtain a resin; and the resin was washed with 4,500 parts of deionized water, then converted with 750 parts of a 5% hydrochloric acid aqueous solution, and washed with 4,500 parts of deionized water until an effluent had a pH of 7.

2.6) The resin was dried at 60° C. to obtain the quaternary ammonium group-grafted cation resin.

The chloromethylated cross-linked PS resin had a crosslinking degree of 7% and a chlorine content of 10%.

The fuming sulfuric acid had a mass fraction of 600%.

The cation resin obtained above had an exchange capacity of 0.90 mol/L, and the quaternary ammonium group had an exchange capacity of 0.09 mol/L.

Example 2

1) Introduction of a quaternary ammonium group into a chloromethylated cross-linked PS resin;

1.1) 20 parts of a chloromethylated cross-linked PS resin and 20 parts of trimethylamine hydrochloride were successively added to a reaction vessel.

1.2) 80 parts of a 20% sodium hydroxide aqueous solution were added dropwise to the reaction vessel within 1 hour, a temperature was kept at 30° C. to 40° C., and a resulting mixture was continuously stirred to allow a reaction for 2 hours.

1.3) After the reaction was completed, a reaction solution was filtered to obtain a resin, and the resin was washed with 1000 parts of a 5% sodium hydroxide aqueous solution, converted with 1000 parts of a 5% hydrochloric acid aqueous solution, and washed with 6000 parts of deionized water until an effluent had a pH of 7.

1.4) The resin was dried at 60° C. to obtain a quaternary ammonium group-grafted chloromethylated cross-linked PS resin.

2) Sulfonation of the quaternary ammonium group-grafted chloromethylated cross-linked PS resin;

2.1) 20 parts of the resin obtained in step 1.4), 80 parts of 1,2-dichloroethane, 1 part of silver sulfate, 30 parts of concentrated sulfuric acid, and 30 parts of fuming sulfuric acid were added successively to a reaction vessel.

2.2) A temperature was kept at 50° C. to 60° C., and a resulting mixture was continuously stirred to allow a reaction for 1 hour.

2.3) The temperature was raised to 70° C. to 80° C., and the mixture was continuously stirred to allow a reaction for 1 hour.

2.4) The temperature was raised to 115° C. to 125° C., and the mixture was continuously stirred to allow a reaction for 5 hours.

2.5) After the reaction was completed, a resulting reaction solution was cooled to room temperature, diluted, and filtered to obtain a resin; and the resin was washed with 6,000 parts of deionized water, then converted with 1,000 parts of a 5% hydrochloric acid aqueous solution, and washed with 6,000 parts of deionized water until an effluent had a pH of 7.

2.6) The resin was dried at 60° C. to obtain the quaternary ammonium group-grafted cation resin.

The chloromethylated cross-linked PS resin had a crosslinking degree of 7% and a chlorine content of 10%.

The fuming sulfuric acid had a mass fraction of 60%.

The cation resin obtained above had an exchange capacity of 1.10 mol/L, and the quaternary ammonium group had an exchange capacity of 0.07 mol/L.

Example 3

1) Introduction of a quaternary ammonium group into a chloromethylated cross-linked PS resin;

1.1) 10 parts of a chloromethylated cross-linked PS resin and 5 parts of trimethylamine hydrochloride were successively added to a reaction vessel.

1.2) 20 parts of a 20% sodium hydroxide aqueous solution were added dropwise to the reaction vessel within 1 hour, a temperature was kept at 30° C. to 40° C., and a resulting mixture was continuously stirred to allow a reaction for 2 hours.

1.3) After the reaction was completed, a reaction solution was filtered to obtain a resin, and the resin was washed with 500 parts of a 5% sodium hydroxide aqueous solution, converted with 500 parts of a 5% hydrochloric acid aqueous solution, and washed with 3,000 parts of deionized water until an effluent had a pH of 7.

1.4) The resin was dried at 60° C. to obtain a quaternary ammonium group-grafted chloromethylated cross-linked PS resin.

2) Sulfonation of the quaternary ammonium group-grafted chloromethylated cross-linked PS resin;

2.1) 10 parts of the resin obtained in step 1.4), 40 parts of 1,2-dichloroethane, 0.5 part of silver sulfate, 20 parts of concentrated sulfuric acid, and 20 parts of fuming sulfuric acid were added successively to a reaction vessel.

2.2) A temperature was kept at 50° C. to 60° C., and a resulting mixture was continuously stirred to allow a reaction for 1 hour.

2.3) The temperature was raised to 70° C. to 80° C., and the mixture was continuously stirred to allow a reaction for 1 hour.

2.4) The temperature was raised to 115° C. to 125° C., and the mixture was continuously stirred to allow a reaction for 5 hours.

2.5) After the reaction was completed, a resulting reaction solution was cooled to room temperature, diluted, and filtered to obtain a resin; and the resin was washed with 3,000 parts of deionized water, then converted with 500 parts of a 5% hydrochloric acid aqueous solution, and washed with 3,000 parts of deionized water until an effluent had a pH of 7.

2.6) The resin was dried at 60° C. to obtain the quaternary ammonium group-grafted cation resin.

The chloromethylated cross-linked PS resin had a crosslinking degree of 7% and a chlorine content of 10%.

The fuming sulfuric acid had a mass fraction of 600%.

The cation resin obtained above had an exchange capacity of 1.35 mol/L, and the quaternary ammonium group had an exchange capacity of 0.05 mol/L.

A Nicolet 370 Fourier transform infrared (FTIR) spectrometer was used to conduct FTIR analysis on the cation resin prepared in the above example, and a spectrum thereof was shown inFIG.1, wherein a characteristic peak at 1,180 cm−1indicated the successful grafting of the sulfonic acid group and a characteristic peak at 976 cm−1indicated the introduction of the quaternary ammonium group.

The cation resin prepared in the above example was mixed with a strong-base resin and converted into a Na—Cl type, and then used in an MFEDI device, and the electrical regeneration performance was tested, with a strong-acid and strong-base mixed resin as a contrast. When the MFEDI device was filled with different resins, a conductivity change of a regeneration solution was shown inFIG.2. A regeneration solution of a mixed resin of the cation resin prepared in the present disclosure and the strong-base resin had an average Na+concentration of 20.8 mg/L, while a regeneration solution of the strong-acid and strong-base mixed resin had an average Na+concentration only of 9.6 mg/L, indicating that, compared with the commercially available strong-acid resins, the prepared cation resin shows improved electrical regeneration performance due to the introduction of the quaternary ammonium group.