Use of a sulfonated phthalocyanine material in chromium ion contamination

Abstract

The application discloses application of a sulfonated phthalocyanine material in chromium ion pollution and relates to the technical field of wastewater treatment. The sulfonated copper phthalocyanine is put into chromium ion wastewater to react with chromium ions in the wastewater to remove the chromium ions in the wastewater. The application of the sulfonated phthalocyanine material in chromium ion pollution can remove the chromium ions in the wastewater by putting the sulfonated copper phthalocyanine into the chromium ion wastewater. Compared with the existing method for removing chromium ion pollution from chromium-containing wastewater, the application has the advantages of simple operation and low cost. The sulfonated phthalocyanine material can be used to simply, efficiently and at low cost remove the chromium ions in the wastewater.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, specifically to the application of a sulfonated phthalocyanine material in chromium ion pollution. Background Technology

[0002] Chromium-containing wastewater is one of the research hotspots in the field of wastewater treatment.

[0003] Currently, commonly used methods for removing chromium-containing wastewater include chemical, physical, and biological methods. While these methods can remove chromium ions from wastewater to some extent, they all suffer from problems such as complex operation and high cost. Methods for removing chromium ions from wastewater include physical methods (such as adsorption, ion exchange, and electrodialysis), chemical methods (such as chemical reduction precipitation, electrolysis, and complexation), and biological methods. Although these methods can remove chromium ions from wastewater to some extent, each has its own advantages and disadvantages.

[0004] Phthalocyanine is a compound with a large conjugated system of 18 electrons. The phthalocyanine ring has a two-dimensional structure, and there is a cavity with a diameter of about 2.70 × 10⁻¹⁰ m at the center of its large conjugated ring structure. Metal elements such as copper, nickel, zinc, cobalt, and iron can chelate with phthalocyanine in the cavity through two covalent bonds and two coordinate bonds to form highly stable metal phthalocyanines, which have good stability against strong acids, strong bases, and high temperatures.

[0005] Due to the stability of phthalocyanine compounds, copper phthalocyanine almost never forms a complex with Cr(VI). Therefore, copper phthalocyanine cannot directly treat chromium-containing wastewater. Furthermore, while ordinary porous adsorbents have large surface areas and good adsorption effects, larger surface areas result in smaller pores, leading to poorer mass transfer during the reaction process, which is detrimental to the reaction. Larger pores improve mass transfer but reduce the stability of the loaded active component. Therefore, an application of sulfonated phthalocyanine materials in chromium ion pollution is proposed. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides an application of sulfonated phthalocyanine materials in chromium ion contamination, thus solving the problems mentioned in the background section.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solution: an application of sulfonated phthalocyanine material in chromium ion pollution, wherein sulfonated copper phthalocyanine is added to chromium ion wastewater to react with chromium ions in the wastewater and remove chromium ions from the wastewater.

[0008] Optionally, the preparation method of the sulfonated copper phthalocyanine includes the following steps:

[0009] S1: Take a certain amount of concentrated sulfuric acid with a mass fraction of 98% and pour it into a 250mL conical flask;

[0010] S2: Weigh a certain amount of copper phthalocyanine powder and add it to a conical flask containing concentrated sulfuric acid, stir and control the temperature.

[0011] S3: After reacting for a certain period of time, the solution is cooled, filtered, washed and dried, and then ground into powder in a mortar to obtain copper phthalocyanine sulfonate.

[0012] S4: Verify the effect of copper sulfonate phthalocyanine on the removal of chromium ions from wastewater under different conditions.

[0013] Optionally, step S4: verifying the effect of copper phthalocyanine sulfonate on the removal of chromium ions from wastewater under different conditions includes:

[0014] S41: Take 100 mL of 50 mg / L potassium dichromate solution into a 250 mL beaker;

[0015] S42: Take a certain amount of copper sulfonate phthalocyanine powder and add it to potassium dichromate solution, and stir and react at a certain temperature;

[0016] S43: After a certain reaction time, take a sample, centrifuge it, and determine it using the diphenylaminourea complexation colorimetric reaction.

[0017]

[0018] S4: Verify the effect of copper sulfonate phthalocyanine on the removal of chromium ions from wastewater under different conditions.

[0019] Optionally, step S4: verifying the effect of sulfonated copper phthalocyanine on the removal of chromium ions in wastewater under different conditions includes verifying the effect of different sulfonation temperatures on the removal of chromium ions in wastewater, verifying the effect of different sulfonation times on the removal of chromium ions in wastewater, verifying the effect of different solution pH on the removal of chromium ions in wastewater, verifying the effect of different treatment temperatures on the removal of chromium ions in wastewater, and verifying the effect of different dosages of sulfonated copper phthalocyanine on the removal of chromium ions in wastewater.

[0020] Optionally, the verification of the effect of different sulfonation temperatures on the removal of chromium ions in wastewater was carried out by sulfonating copper phthalocyanine at different sulfonation temperatures: 50℃, 60℃, 70℃, 80℃, 90℃, 110℃, and 120℃, according to steps S1-S3. The sulfonation reaction time was four hours for each reaction, and the amount of sulfonated copper phthalocyanine used during the reaction was 1g. The displacement reaction was carried out at room temperature of about 25℃.

[0021] Optionally, the verification of the effect of different solution pH on the removal of chromium ions in wastewater is carried out by reacting copper phthalocyanine obtained under the conditions of sulfonation temperature of 80℃ and sulfonation time of 4h with a solution containing Cr(VI). The amount of copper phthalocyanine used in the reaction is 1g. The displacement reaction is carried out at room temperature of about 25℃. The pH of the reaction solution is adjusted with sodium hydroxide solution, pH = 4, 5, 6, 7, 8.

[0022] Optionally, the verification of the effect of different treatment temperatures on the removal of chromium ions in wastewater involves reacting sulfonated copper phthalocyanine obtained under the conditions of sulfonation temperature of 90℃ and sulfonation time of 4h with a solution containing Cr(VI). The amount of sulfonated copper phthalocyanine used in the reaction is 1g. Different reaction temperatures are achieved at room temperature of 25℃, 35℃, 45℃, 55℃, and 65℃.

[0023] Optionally, the verification of the effect of different amounts of sulfonated copper phthalocyanine on the removal of chromium ions in wastewater is carried out by reacting sulfonated copper phthalocyanine obtained under the conditions of sulfonation temperature of 90℃ and sulfonation time of 4h with a solution containing Cr(VI). The amount of sulfonated copper phthalocyanine used in the reaction is 1g, and the displacement reaction is carried out at room temperature of about 25℃.

[0024] This invention provides an application of sulfonated phthalocyanine materials in chromium ion contamination, which has the following beneficial effects:

[0025] The application of this sulfonated phthalocyanine material in chromium ion pollution can remove chromium ions from wastewater by adding sulfonated copper phthalocyanine to the wastewater. Compared with existing methods for removing chromium ion pollution from chromium-containing wastewater, it has the advantages of simple operation and low cost. Using sulfonated phthalocyanine material can remove chromium ions from wastewater simply, efficiently and at low cost. Attached Figure Description

[0026] Figure 1 This is a graph showing the effect of copper phthalocyanine sulfonation on the removal rate of Cr(VI) in solution at different sulfonation temperatures according to the present invention;

[0027] Figure 2 The graph shows the effect of different sulfonation times of copper phthalocyanine on the removal rate of Cr(VI) in the solution.

[0028] Figure 3 The graph shows the effect of copper sulfonate phthalocyanine on the removal rate of Cr(VI) in solution under different pH conditions according to the present invention.

[0029] Figure 4 This is a graph showing the effect of different complexation temperatures of copper phthalocyanine sulfonate on the removal rate of Cr(VI) in solution according to the present invention;

[0030] Figure 5 The graph shows the effect of different amounts of copper sulfonate phthalocyanine on the removal rate of Cr(VI) in the solution. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0032] Please see Figures 1 to 5 The present invention provides a technical solution: the application of sulfonated phthalocyanine material in chromium ion pollution, which involves adding sulfonated copper phthalocyanine to chromium ion wastewater to react with chromium ions in the wastewater and remove chromium ions from the wastewater.

[0033] The preparation method of copper phthalocyanine sulfonate includes the following steps:

[0034] S1: Take a certain amount of concentrated sulfuric acid with a mass fraction of 98% and pour it into a 250mL conical flask;

[0035] S2: Weigh a certain amount of copper phthalocyanine powder and add it to a conical flask containing concentrated sulfuric acid, stir and control the temperature.

[0036] S3: After reacting for a certain period of time, the solution is cooled, filtered, washed and dried, and then ground into powder in a mortar to obtain copper phthalocyanine sulfonate.

[0037] S4: Verify the effect of copper phthalocyanine sulfonate on the removal of chromium ions from wastewater under different conditions;

[0038] S4: The step of verifying the effect of copper phthalocyanine sulfonate on the removal of chromium ions from wastewater under different conditions includes:

[0039] S41: Take 100 mL of 50 mg / L potassium dichromate solution into a 250 mL beaker;

[0040] S42: Take a certain amount of copper sulfonate phthalocyanine powder and add it to potassium dichromate solution, and stir and react at a certain temperature;

[0041] S43: After a certain reaction time, take a sample, centrifuge it, and determine it using the diphenylaminourea complexation colorimetric reaction.

[0042]

[0043] The effect of different sulfonation temperatures on the removal of chromium ions from wastewater was verified: Following steps S1-S3, copper phthalocyanine was sulfonated at different temperatures: 50℃, 60℃, 70℃, 80℃, 90℃, 110℃, and 120℃ to prepare sulfonated copper phthalocyanine. The sulfonation reaction time was four hours for each reaction, and the amount of sulfonated copper phthalocyanine used was 1g. The displacement reaction was carried out at room temperature (approximately 25℃). The effect of sulfonated copper phthalocyanine obtained under different sulfonation temperatures on the removal rate of Cr(VI) in the solution was investigated. Figure 1 As shown,

[0044] Depend on Figure 1 It can be seen that when the reaction time is 80 minutes, the removal rates at different sulfonation temperatures are as follows: 15.70% at 50℃, 36.37% at 60℃, 52.61% at 70℃, 57.04% at 80℃, 73.54% at 90℃, 57.84% at 110℃, and 55.56% at 120℃.

[0045] When the sulfonation temperature is below 90℃, the removal rate of chromium ions by sulfonated copper phthalocyanine increases with increasing temperature, and the longer the reaction proceeds, the higher the removal rate. However, once the sulfonation temperature reaches 90℃, such as 110℃ or even 120℃, the removal rate not only does not increase but actually decreases.

[0046] Therefore, it was found that at different sulfonation temperatures, the sulfonated copper phthalocyanine exhibited the highest removal rate of chromium ions at a sulfonation temperature of 90℃, with a removal rate of 73.54%.

[0047] Verify the effect of different sulfonation times on the removal of chromium ions from wastewater:

[0048] Following steps S1-S3, copper phthalocyanine was sulfonated at different sulfonation times: 4h, 5h, 6h, 7h, 8h, and 9h to prepare sulfonated copper phthalocyanine. The sulfonation temperature was 90℃, and the amount of sulfonated copper phthalocyanine used in the reaction was 1g. The displacement reaction was carried out at room temperature of about 25℃.

[0049] Depend on Figure 2 It can be seen that when the reaction time is 80 minutes, the removal rate of chromium ions by sulfonated copper phthalocyanine at different sulfonation times is 68.90% for sulfonation time of 3h, 73.54% for 4h, 70.46% for 5h, 71.93% for 6h, 72.47% for 7h, 71.13% for 8h, and 70.99% for 9h.

[0050] When the sulfonation time is less than 4 hours, the removal rate of chromium ions by sulfonated copper phthalocyanine increases with the extension of sulfonation time; the longer the reaction proceeds, the higher the removal rate. However, after sulfonation time reaches 4 hours, further extending the sulfonation time has very little effect on the sulfonation effect; the removal rate not only does not increase but actually decreases.

[0051] Therefore, it can be concluded that among the sulfonated copper phthalocyanines obtained at different sulfonation times, the sulfonated copper phthalocyanines have the highest removal rate of chromium ions, which is 73.54%, when the sulfonation time is 4 hours.

[0052] Verify the effect of different solution pH on the removal of chromium ions from wastewater:

[0053] Following steps S1-S3, copper phthalocyanine was sulfonated at different sulfonation times: 4h, 5h, 6h, 7h, 8h, and 9h to prepare sulfonated copper phthalocyanine. The sulfonation temperature was 90℃, and the amount of sulfonated copper phthalocyanine used in the reaction was 1g. The displacement reaction was carried out at room temperature of about 25℃.

[0054] The effect of copper sulfonate phthalocyanine on the removal rate of Cr(VI) in solution under different pH conditions was investigated. Figure 3 It can be seen that when the reaction time is 80 minutes, the removal rate of chromium ions by copper phthalocyanine sulfonate under different pH conditions is 57.04% at pH=4, 58.38% at pH=5, 71.93% at pH=6, 69.79% at pH=7, and 51.13% at pH=8.

[0055] Because acidic or alkaline conditions can affect the structure of sulfonated phthalocyanine compounds, leading to a decrease in their adsorption capacity, sulfonated copper phthalocyanine showed the highest removal rate of chromium ions at pH=6, with a removal rate of 71.93%. Extending the reaction time helps to remove Cr(VI).

[0056] Verify the effect of different treatment temperatures on the removal of chromium ions from wastewater:

[0057] The sulfonated copper phthalocyanine obtained under the conditions of sulfonation temperature of 90℃ and sulfonation time of 4h was reacted with a Cr(VI) solution. The amount of sulfonated copper phthalocyanine used in the reaction was 1g. Different reaction temperatures were set at room temperature (25℃, 35℃, 45℃, 55℃, and 65℃).

[0058] The effect of copper sulfonate phthalocyanine dosage on the removal rate of Cr(VI) in solution, such as Figure 4 As shown;

[0059] Depend on Figure 4 It can be seen that the removal rates of chromium ions by sulfonated copper phthalocyanine at different complexation temperatures are 73.54% at room temperature (25℃), 57.31% at 35℃, 53.15% at 45℃, 47.51% at 55℃, and 39.19% at 65℃.

[0060] Therefore, it can be concluded that sulfonated copper phthalocyanine exhibits the best removal effect for chromium ions at room temperature. This is because the structure of the compound molecules changes at high temperatures, leading to a decrease in adsorption capacity; higher temperatures favor desorption, while lower temperatures favor adsorption. At room temperature (25℃), sulfonated copper phthalocyanine achieves a chromium ion removal rate of 73.54%.

[0061] Verify the effect of different dosages of copper phthalocyanine sulfonate on the removal of chromium ions from wastewater:

[0062] The sulfonated copper phthalocyanine obtained under the conditions of sulfonation temperature of 90℃ and sulfonation time of 4h was reacted with a Cr(VI)-containing solution. The amount of sulfonated copper phthalocyanine used in the reaction was 1g, and the displacement reaction was carried out at room temperature of about 25℃.

[0063] The effect of different amounts of copper sulfonate phthalocyanine on the removal rate of Cr(VI) in solution, such as Figure 5 As shown;

[0064] Depend on Figure 5 It can be seen that the removal rates of chromium ions by different dosages of copper phthalocyanine sulfonate are 40.66% at 1 g / L, 57.04% at 5 g / L, 73.54% at 10 g / L, 82.94% at 15 g / L, and 95.15% at 20 g / L.

[0065] Therefore, the more copper sulfonate phthalocyanine is used, the greater the removal rate. When the amount of copper sulfonate phthalocyanine is 2.0g, the removal rate of hexavalent chromium reaches 95.15%.

[0066] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. An application of a sulfonated phthalocyanine material in chromium ion contamination, characterized in that: Sulfonated copper phthalocyanine is added to chromium ion wastewater to react with chromium ions in the wastewater and remove chromium ions from the wastewater. The method for preparing the sulfonated copper phthalocyanine includes the following steps: S1: Take a certain amount of concentrated sulfuric acid with a mass fraction of 98% and pour it into a 250mL conical flask; S2: Weigh a certain amount of copper phthalocyanine powder and add it to a conical flask containing concentrated sulfuric acid, stir and control the temperature. S3: After reacting for a certain period of time, the solution is cooled, filtered, washed and dried, and then ground into powder in a mortar to obtain copper phthalocyanine sulfonate. S4: Verify the effect of copper sulfonate phthalocyanine on the removal of chromium ions from wastewater under different conditions.

2. The application of a sulfonated phthalocyanine material according to claim 1 in chromium ion contamination, characterized in that: Step S4: Verifying the effect of copper phthalocyanine sulfonate on the removal of chromium ions from wastewater under different conditions includes: S41: Take 100 mL of 50 mg / L potassium dichromate solution into a 250 mL beaker; S42: Take a certain amount of copper sulfonate phthalocyanine powder and add it to potassium dichromate solution, and stir and react at a certain temperature; S43: After a certain reaction time, take a sample, centrifuge it, and determine it using the diphenylaminourea complexation colorimetric reaction; Cr(VI) removal rate S4: Verify the effect of copper sulfonate phthalocyanine on the removal of chromium ions from wastewater under different conditions.

3. The application of a sulfonated phthalocyanine material according to claim 2 in chromium ion contamination, characterized in that: S4: Verifying the effect of sulfonated copper phthalocyanine on the removal of chromium ions from wastewater under different conditions includes verifying the effect of different sulfonation temperatures on the removal of chromium ions from wastewater, verifying the effect of different sulfonation times on the removal of chromium ions from wastewater, verifying the effect of different solution pH on the removal of chromium ions from wastewater, verifying the effect of different treatment temperatures on the removal of chromium ions from wastewater, and verifying the effect of different dosages of sulfonated copper phthalocyanine on the removal of chromium ions from wastewater.

4. The application of a sulfonated phthalocyanine material according to claim 3 in chromium ion contamination, characterized in that: The effect of different sulfonation temperatures on the removal of chromium ions from wastewater was verified as follows: sulfonated copper phthalocyanine was prepared by sulfonating copper phthalocyanine at different sulfonation temperatures: 50℃, 60℃, 70℃, 80℃, 90℃, 110℃, and 120℃, following steps S1-S3. The sulfonation reaction time was four hours for each reaction, and the amount of sulfonated copper phthalocyanine used was 1g. The displacement reaction was carried out at room temperature (25℃).

5. The application of a sulfonated phthalocyanine material according to claim 3 in chromium ion contamination, characterized in that: To verify the effect of different sulfonation times on the removal of chromium ions from wastewater, copper phthalocyanine was sulfonated at different sulfonation times (4h, 5h, 6h, 7h, 8h, and 9h) according to steps S1-S3 to prepare sulfonated copper phthalocyanine. The sulfonation temperature was 90℃, and the amount of sulfonated copper phthalocyanine used in the reaction was 1g. The displacement reaction was carried out at room temperature (25℃).

6. The application of a sulfonated phthalocyanine material according to claim 3 in chromium ion contamination, characterized in that: The effect of different solution pH on the removal of chromium ions in wastewater was verified by reacting copper phthalocyanine obtained under the conditions of sulfonation temperature of 80℃ and sulfonation time of 4h with a solution containing Cr(VI). The amount of copper phthalocyanine used in the reaction was 1g. The displacement reaction was carried out at room temperature of 25℃. The pH of the reaction solution was adjusted with sodium hydroxide solution, pH=4, 5, 6, 7, 8.

7. The application of a sulfonated phthalocyanine material according to claim 3 in chromium ion contamination, characterized in that: The effect of different treatment temperatures on the removal of chromium ions from wastewater was verified by reacting copper phthalocyanine obtained under the conditions of sulfonation temperature of 90℃ and sulfonation time of 4h with a solution containing Cr(VI). The amount of copper phthalocyanine used in the reaction was 1g. Different reaction temperatures were set at room temperature of 25℃, 35℃, 45℃, 55℃ and 65℃.

8. The application of a sulfonated phthalocyanine material according to claim 3 in chromium ion contamination, characterized in that: The effect of different amounts of sulfonated copper phthalocyanine on the removal of chromium ions from wastewater was verified by reacting sulfonated copper phthalocyanine obtained under the conditions of sulfonation temperature of 90℃ and sulfonation time of 4h with a solution containing Cr(VI). The displacement reaction was carried out at room temperature of 25℃.

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