CN101812138A - Preparation method of modified chitosan copper coordination compound and application thereof - Google Patents

Abstract

A preparation method and application of a modified chitosan copper complex relates to a preparation method and application of the complex. The invention solves the problem that the existing treatment process has poor ammonia nitrogen removal ability in polluted water source water. Its preparation method is as follows: 1. prepare chitosan acetate sol; 2. prepare copper acetate solution; Then add dilute alkali solution to adjust the pH value, then wash with deionized water until the lotion is neutral, ultrafilter, dry, and then pulverize to obtain the modified chitosan copper complex. Modified chitosan copper complex is used to remove ammonia nitrogen in water. The modified chitosan copper complex obtained in the invention has a removal rate of 60% to 93% for ammonia nitrogen in water.

Description

Preparation method and application of modified chitosan copper complex

technical field

The invention relates to a preparation method and application of a complex.

Background technique

According to statistics, the environmental pollution of surface water in my country is worrying. Among the seven major water systems, only the Yangtze River and the Pearl River are in good condition, and the water quality is declining year by year. Ammonia nitrogen appears frequently in the surface water body exceeding the standard pollutants. Studies have shown that the "coagulation-sedimentation-filtration-disinfection" and other treatment processes used in conventional treatment are mainly to remove suspended solids and colloidal particles in water, but their ability to remove ammonia nitrogen, a dissolved substance in polluted water source water, is inferior poor.

Contents of the invention

The technical problem to be solved by the present invention is to solve the problem of the existing treatment process in polluted water source water.

The problem of poor removal ability of ammonia nitrogen provides a preparation method and application of modified chitosan copper complex.

The preparation method of the modified chitosan copper complex of the present invention is as follows: one, chitosan and acetic acid are mixed according to the mass ratio of 1:50～100, are formulated into chitosan acetate sol; two, copper acetate is added to the Dissolve copper acetate completely in deionized water to obtain a copper acetate solution, wherein the ratio of copper acetate to chitosan is 4-8:1; 3. Drop chitosan acetate sol into the copper acetate solution, stir and mix well, Carry out the complexation reaction at room temperature for 8h-24h to obtain the complexed complex; 4. Add dilute alkali solution to the complexed complex at room temperature at a speed of 100r/min-180r/min to adjust the pH value 8 to 11, and then washed with deionized water until the lotion is neutral, ultrafiltered, dried under vacuum at 50°C to 70°C, and then pulverized to obtain the modified chitosan copper complex; The chitosan mentioned above is chitosan with dehydration acetylation degree ≥ 95%. The application of the modified chitosan copper complex in water treatment is used for removing ammonia nitrogen in water.

The modified chitosan copper complex obtained in the invention has a removal rate of 60% to 93% for ammonia nitrogen in water.

Description of drawings

表示氨氮浓度为3mg/L的原水经具体实施方式十一中改性壳聚糖铜配合物处理后出水的氨氮浓度曲线，

表示氨氮浓度为5mg/L的原水经具体实施方式十一中改性壳聚糖铜配合物处理后出水的氨氮浓度曲线，

表示氨氮浓度为7mg/L的原水经具体实施方式十一中改性壳聚糖铜配合物处理后出水的氨氮浓度曲线，

表示氨氮浓度为10mg/L的原水经具体实施方式十一中改性壳聚糖铜配合物处理后出水的氨氮浓度曲线。Fig. 1 is the raw water of different ammonia nitrogen concentration after the modified chitosan copper complex treatment in specific embodiment 11, the ammonia nitrogen concentration curve contrast figure of effluent, among the figure

Represent ammonia nitrogen concentration is the ammonia nitrogen concentration curve of effluent after the raw water of 3mg/L is treated with the modified chitosan copper complex in the specific embodiment 11,

Represent ammonia nitrogen concentration is the ammonia nitrogen concentration curve of effluent after the raw water of 5mg/L is treated with the modified chitosan copper complex in the specific embodiment 11,

Representing that the ammonia nitrogen concentration is the ammonia nitrogen concentration curve of the effluent after the raw water of 7mg/L is treated with the modified chitosan copper complex in the eleventh specific embodiment,

It represents the ammonia nitrogen concentration curve of the effluent after the raw water with an ammonia nitrogen concentration of 10 mg/L is treated with the modified chitosan copper complex in Embodiment 11.

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific embodiment one: the preparation method of modified chitosan copper complex in the present embodiment is as follows: one, chitosan and acetic acid are mixed according to the mass ratio of 1:50～100, are mixed into chitosan acetate sol; 1. Add copper acetate to deionized water until the copper acetate is completely dissolved to obtain a copper acetate solution, wherein the ratio of copper acetate to chitosan is 4-8:1; 3. Add chitosan acetate sol to copper acetate In the solution, stir and mix well, carry out the complexation reaction at room temperature for 8h-24h, and obtain the complexed complex; 4. Add Dilute alkaline solution to adjust the pH value to 8-11, then wash with deionized water until the lotion is neutral, ultrafilter, then dry at 50°C-70°C under vacuum, and then pulverize to obtain modified chitosan copper Complexes.

The modified chitosan copper complex obtained in this embodiment has a removal rate of ammonia nitrogen in water of 60% to 93%.

Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the chitosan described in step 1 is chitosan with dehydration acetylation degree ≥ 95%. Others are the same as in the first embodiment.

Embodiment 3: This embodiment is different from Embodiment 1 or Embodiment 2. In step one, the mass ratio of chitosan to acetic acid is 1:60-90, and the others are the same as in one of the specific embodiments one or two.

Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that the mass ratio of chitosan to acetic acid in step 1 is 1:75. Others are the same as those in the first to third specific embodiments.

Embodiment 5: The difference between this embodiment and one of Embodiments 1 to 4 is that the ratio of copper acetate to chitosan in step 2 is 5-7:1. Others are the same as one of the specific embodiments 1 to 4.

Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the ratio of copper acetate to chitosan in step 2 is 6:1. Others are the same as one of the specific embodiments 1 to 5.

Embodiment 7: This embodiment is different from Embodiment 1 to Embodiment 6 in that the complexation reaction time in step 3 is 10h-22h. Others are the same as one of the specific embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that the complexation reaction time in step 3 is 12 hours. Others are the same as one of the specific embodiments 1 to 7.

Embodiment 9: The difference between this embodiment and Embodiment 1 to Embodiment 8 is that in Step 4, dilute alkaline solution is added to adjust the pH value to 10.3. Others are the same as one of the specific embodiments 1 to 8.

Embodiment 10: The application of the modified chitosan copper complex described in this embodiment in water treatment is used to remove ammonia nitrogen in water.

Embodiment 11: The preparation method of modified chitosan copper complex in this embodiment is as follows: 1. Chitosan and acetic acid are mixed according to the mass ratio of 1:75 to prepare chitosan acetate sol; 2. Add copper acetate to deionized water until the copper acetate is completely dissolved to obtain a copper acetate solution, wherein the ratio of copper acetate to chitosan is 4:1; three, chitosan acetate sol is dropped into the copper acetate solution, Stir and mix well, carry out the complexation reaction at room temperature for 12 hours, and obtain the complexed complex; 4. Add dilute alkali solution to the complexed complex at room temperature at a speed of 170r/min to adjust the pH value to 10.3, Then wash with deionized water until the washing solution is neutral, ultrafilter, dry at 70° C. under vacuum, and then pulverize to obtain the modified chitosan copper complex.

Specific embodiment twelve: the preparation method of modified chitosan copper complex in the present embodiment is as follows: one, 0.5g chitosan is mixed with 50ml acetic acid, is mixed with chitosan acetate sol; Two, copper acetate is added In deionized water until the copper acetate is completely dissolved to obtain a copper acetate solution, wherein the ratio of copper acetate to chitosan is 4:1; three, drop the chitosan acetate sol into the copper acetate solution, stir and mix, Carry out the complexation reaction at room temperature for 16 hours to obtain the complexed complex; 4. Add dilute alkali solution to the complexed complex at room temperature at a speed of 160r/min to adjust the pH value to 10.5, and then use deionized Washing with water until the lotion is neutral, ultrafiltering, drying under vacuum at 60°C, and then pulverizing to obtain the modified chitosan copper complex.

Under the condition of room temperature, configuration pH=6.8, the ammonia nitrogen aqueous solution that concentration is 10mg/L, then the modified chitosan copper complex that 0.5g present embodiment obtains is joined in the aqueous solution that 100ml ammonia nitrogen concentration is 10mg/L, React for 18 hours, then filter, and use Nash reagent spectrophotometry to measure the ammonia nitrogen content in the filtrate to be 4 mg/L. The removal rate of ammonia nitrogen by modified chitosan copper complex is 60%.

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Claims (10)

1. the preparation method of modified chitosan copper coordination compound is characterized in that the preparation method of modified chitosan copper coordination compound is as follows: one, chitosan is mixed with the mass ratio of acetic acid according to 1 ﹕ 50～100, be mixed with chitosan acetic acid colloidal sol; Two, neutralized verdigris is joined in the deionized water to neutralized verdigris and dissolve fully, obtain neutralized verdigris solution, wherein neutralized verdigris is 4～8 ﹕ 1 with the primitive ratio of chitosan; Three, chitosan acetic acid colloidal sol is splashed in the neutralized verdigris solution, stirring and evenly mixing at room temperature carries out complex reaction 8h～24h, the title complex after the complexing; Four, be 8～11 at room temperature to add dilute alkaline soln adjusting pH value in the title complex of speed after complexing of 100r/min～180r/min, it is neutral being washed till washing lotion with deionized water then, ultrafiltration, dry under the condition of 50 ℃～70 ℃ of vacuum again, pulverize then, promptly get modified chitosan copper coordination compound.

2. the preparation method of modified chitosan copper coordination compound according to claim 1 is characterized in that the chitosan described in the step 1 is the chitosan of dehydration acetyl degree 〉=95%.

3. the preparation method of modified chitosan copper coordination compound according to claim 1 and 2 is characterized in that the mass ratio of chitosan and acetic acid is 1 ﹕ 60～90 in the step 1.

4. the preparation method of modified chitosan copper coordination compound according to claim 3 is characterized in that the mass ratio of chitosan and acetic acid is 1 ﹕ 75 in the step 1.

5. according to the preparation method of claim 1,2 or 4 described modified chitosan copper coordination compounds, it is characterized in that the primitive ratio of neutralized verdigris and chitosan is 5～7 ﹕ 1 in the step 2.

6. according to the preparation method of claim 1,2 or 4 described modified chitosan copper coordination compounds, it is characterized in that the primitive ratio of neutralized verdigris and chitosan is 6 ﹕ 1 in the step 2.

7. the preparation method of modified chitosan copper coordination compound according to claim 5, the time that it is characterized in that complex reaction in the step 3 is 10h～22h.

8. the preparation method of modified chitosan copper coordination compound according to claim 5, the time that it is characterized in that complex reaction in the step 3 is 12h.

9. according to the preparation method of claim 1,2,4 or 7 described modified chitosan copper coordination compounds, it is characterized in that adding in the step 4 dilute alkaline soln adjusting pH value is 10.3.

10. the application of modified chitosan copper coordination compound is characterized in that the application of described modified chitosan copper coordination compound in water treatment, is used for removing the ammonia nitrogen of water.

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