Application of amino acid as antichlor

By using amino acid compounds such as D-tryptophan to react with the available chlorine in water to change its state, the problem of difficulty in reducing the concentration of available chlorine in wastewater and domestic water in the existing technology is solved, and a high-efficiency and low-cost dechlorination effect is achieved.

CN120736656APending Publication Date: 2025-10-03ZHEJIANG GONGSHANG UNIVERSITY
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Patent Information

Application Number
CN202510848946.1
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-06-24
Publication Date
2025-10-03

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Abstract

The invention provides an application of amino acid as a chlorine removal agent. The amino acid is D-tryptophan, L-tryptophan, D-histidine, D-glutamine, L-histidine, L-leucine, L-phenylalanine, L-methionine or L-tyrosine. The amino acid, especially D-tryptophan, can react with available chlorine in water to reduce the concentration of available chlorine in water, and the amino acid can be used as a dechlorinating agent for treating chlorine-containing industrial wastewater, biological treatment wastewater and domestic wastewater or reducing the content of available chlorine in daily domestic water or drinking water. The invention also provides a method for reducing the available chlorine concentration in the chlorine-containing water sample by using the amino acid. The invention provides a novel dechlorinating agent which is high in efficiency and low in cost and has a wide application prospect.
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Description

Technical Field

[0001] The invention belongs to the technical field of water treatment, and particularly relates to the use of amino acid compounds as dechlorinating agents to reduce the effective chlorine concentration in water. Background Art

[0002] With the continuous development of the economy and technology, and the increasing level of industrialization, the discharge of domestic and industrial wastewater has also increased significantly, and wastewater treatment has gradually attracted widespread attention. While existing water treatment technologies such as precipitation, reduction, and electrochemical methods can remove pollutants to a certain extent, they still have drawbacks such as high treatment costs, complex operations, and the potential for reduced dissolved oxygen in the water.

[0003] Many industry regulations and environmental protection standards set clear limits on the effective chlorine concentration of domestic and industrial wastewater before discharge. For example, the Shanghai Integrated Wastewater Discharge Standard (DB31 / 199-2018) specifies that the chloride limit for saponin-based industrial wastewater is 200-300 mg / L. According to the "Medical Institution Water Pollutant Discharge Standard" (GB18466-2005), medical institutions using chlorine-containing disinfectants must dechlorinate wastewater discharged into surface waters or the sea to a total residual chlorine level of <0.5 mg / L.

[0004] If wastewater contains high concentrations of available chlorine and is discharged directly into natural water bodies without treatment, it will not only disrupt the ecological balance and cause toxic damage to aquatic life, but may also pose a threat to human health. This is especially true in drinking water, where chlorine concentrations above 90 ppm can irritate the throat and oral mucosa. Therefore, effectively reducing the concentration of available chlorine in wastewater and domestic water is crucial for safeguarding ecological and environmental safety and public health.

[0005] Common amino acid compounds are commonly used as food additives, cosmetic ingredients, biosynthetic raw materials, and pharmaceutical ingredients, but their association with wastewater treatment is less frequently reported. D-tryptophan is a common amino acid, typically found at low levels in organisms. Containing an indole ring and pendant amino and carboxyl groups, D-tryptophan exhibits chemical activity and can participate in redox reactions. It also possesses chelating properties, forming complexes with metal ions and other chemical substances. In materials science, it can be used in the preparation of biosensors and as a drug carrier.

[0006] There are no reports on the interaction between D-tryptophan and chloride ions in water. Summary of the Invention

[0007] The present invention aims to provide an application of amino acids, especially D-tryptophan, as a chlorine removal agent, wherein the amino acids can reduce the effective chlorine concentration in water.

[0008] To achieve the above object, the present invention provides the following technical solutions: Application of amino acids as chlorine removal agents.

[0009] Furthermore, the amino acid is D-tryptophan, L-tryptophan, D-histidine, D-glutamine, L-histidine, L-leucine, L-phenylalanine, L-methionine or L-tyrosine, preferably D-tryptophan, L-tryptophan, L-tyrosine or L-methionine, more preferably D-tryptophan.

[0010] Preferably, the present invention provides use of D-tryptophan as a chlorine removal agent.

[0011] Furthermore, the application method is preferably: Add amino acids to the chlorine-containing water sample to be treated and mix to react.

[0012] The present invention also provides a method for reducing the effective chlorine concentration in a chlorine-containing water sample, the method comprising: Amino acids are added to the chlorine-containing water sample to be treated, mixed and reacted to obtain a water sample with a reduced effective chlorine concentration.

[0013] The reaction time is 10 to 20 minutes.

[0014] The volume ratio of the amino acid feed mass to the chlorine-containing water sample to be treated is 8-85 mg / L, preferably 16-85 mg / L.

[0015] Amino acids can be prepared into amino acid solutions and added to chlorine-containing water samples, with a concentration generally ranging from 10 to 50 mM.

[0016] The chlorine-containing water sample can be chlorine-containing wastewater discharged from a factory, or daily water or drinking water.

[0017] The amino acid of the present invention removes the available chlorine mainly through the reaction between the amino acid and the available chlorine in water, thereby changing the existing state of chlorine and reducing the available chlorine concentration in the water sample.

[0018] Increasing the amount of amino acids increases the removal rate of available chlorine concentration, but the water color will also change. For wastewater with high chloride ion concentration, it is preferable to increase the amount of amino acids to improve the removal rate. For daily water or drinking water, the available chlorine concentration is low. It is preferable to use a low-concentration amino acid solution or reduce the amount. This reduces the available chlorine concentration in the water sample and minimizes the color change of the water sample.

[0019] The present invention also provides the use of amino acids as dechlorinating agents in treating chlorine-containing industrial wastewater, biological treatment wastewater, and domestic wastewater.

[0020] The present invention also provides the use of amino acids as dechlorinating agents in reducing the effective chlorine content of daily water or drinking water.

[0021] The present invention also provides a chlorine removal agent, which comprises amino acids. The amino acids are D-tryptophan, L-tryptophan, D-histidine, D-glutamine, L-histidine, L-leucine, L-phenylalanine, L-methionine or L-tyrosine, preferably D-tryptophan.

[0022] The present invention has the following beneficial effects: (1) This invention proposes for the first time that amino acids can reduce the effective chlorine concentration in water samples, providing a new choice of dechlorination agent with high efficiency and low cost, and has broad application prospects.

[0023] (2) Different feed amounts can be used for different application scenarios, which not only ensures the effectiveness of the method but also reduces the impact of side effects. This method has the advantages of simple operation and obvious effect.

[0024] (3) The present invention can be used to treat wastewater discharged from industrial production such as printing and dyeing factories, chemical factories, and food factories, thereby reducing the impact of discharged wastewater on the environment. It can also be used to treat water used in people's daily lives. This helps protect the environment and maintain people's health. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a comparison diagram of the available chlorine concentration of Example 1 and Comparative Example 1.

[0026] Figure 2 The graph shows the effective chlorine removal rate results of different amino acids (volume ratio 1:99).

[0027] Figure 3 The graph shows the effective chlorine removal rate results of different amino acids (volume ratio 1:1).

[0028] Figure 4 This is a line graph showing the effect of different amounts of D-tryptophan added on reducing the available chlorine concentration in water.

[0029] Figure 5 This is a bar graph showing the effect of different amounts of D-tryptophan added on reducing the available chlorine concentration in water. DETAILED DESCRIPTION

[0030] The present invention will be further described below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below generally represent only a portion of the present invention, rather than all of the embodiments. Therefore, all other embodiments derived by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0031] Example 1 (1) Weigh 0.0204 g of D-tryptophan powder and dissolve it in 10 mL of pure water. Ultrasonicate for 3 min to fully dissolve it to obtain a 10 mM D-tryptophan solution.

[0032] (2) Mix 1 mL of D-tryptophan solution with 99 mL of slightly acidic electrolyzed water and allow to react for 10 min.

[0033] (3) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0034] Example 2 The D-tryptophan in Example 1 was replaced by L-tryptophan, L-tyrosine, and L-methionine, respectively. The other steps were the same as in Example 1. The effective chlorine concentration after 10 minutes of reaction was detected, and the effective chlorine clearance rate was calculated. The effective chlorine clearance rate results of different amino acids are shown in FIG. Figure 2 shown.

[0035] The results showed that after a 10mM amino acid solution was mixed with slightly acidic electrolyzed water at a volume ratio of 1:99 for 10 minutes, D-tryptophan had the highest effective chlorine removal rate, followed by L-tryptophan, L-tyrosine, and L-methionine. Subsequent studies on the effects of varying amino acid additions on reducing effective chlorine concentration in water focused on D-tryptophan, which had the highest removal rate.

[0036] Example 3 In preliminary experiments, 40mM D-tryptophan and slightly acidic electrolyzed water were mixed in a volume ratio of 1:1 and reacted for 10 minutes. The available chlorine concentration was measured by iodine titration and available chlorine test paper, but no result was detected.

[0037] Prepare 40mM D-histidine, D-glutamine, L-histidine, L-leucine, and L-phenylalanine. Mix 10mL of the amino acid solution with 10mL of slightly acidic electrolyzed water and react for 10 minutes. Determine the available chlorine concentration in the mixed solution by iodine titration, and calculate the available chlorine clearance rate. The available chlorine clearance rates of different amino acids are shown in the following table. Figure 3 shown.

[0038] The results showed that D-histidine, D-glutamine, L-histidine, L-leucine and L-phenylalanine all had certain chlorine removal capabilities, among which D-histidine had the best chlorine removal effect.

[0039] Example 4 (1) Weigh 0.0816 g of D-tryptophan powder and dissolve it in 10 mL of pure water. Ultrasonicate for 3 min to fully dissolve it to obtain a 40 mM D-tryptophan solution. (2) Mix 1 mL of D-tryptophan solution with 99 mL of slightly acidic electrolyzed water and allow to react for 10 minutes.

[0040] (3) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0041] Example 5 (1) Weigh 0.0816 g of D-tryptophan powder and dissolve it in 10 mL of pure water. Ultrasonicate for 3 min to fully dissolve it to obtain a 40 mM D-tryptophan solution. (2) Mix 1 mL of D-tryptophan solution with 100 mL of slightly acidic electrolyzed water and allow to react for 10 min.

[0042] (3) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0043] Example 6 (1) Weigh 0.0816 g of D-tryptophan powder and dissolve it in 10 mL of pure water. Ultrasonicate for 3 min to fully dissolve it to obtain a 40 mM D-tryptophan solution. (2) Mix 500 μL of D-tryptophan solution with 100 mL of slightly acidic electrolyzed water and allow to react for 10 min.

[0044] (3) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0045] Example 7 (1) Weigh 0.0816 g of D-tryptophan powder and dissolve it in 10 mL of pure water. Ultrasonicate for 3 min to fully dissolve it to obtain a 40 mM D-tryptophan solution. (2) Mix 200 μL of D-tryptophan solution with 100 mL of slightly acidic electrolyzed water and allow to react for 10 min.

[0046] (3) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0047] Example 8 (1) Weigh 0.0816 g of D-tryptophan powder and dissolve it in 10 mL of pure water. Ultrasonicate for 3 min to fully dissolve it to obtain a 40 mM D-tryptophan solution. (2) Mix 100 μL of D-tryptophan solution with 100 mL of slightly acidic electrolyzed water and allow to react for 10 min.

[0048] (3) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0049] Comparative Example 1 (1) Add 1 mL of pure water to 99 mL of slightly acidic electrolyzed water and mix.

[0050] (2) The effective chlorine concentration in the mixed solution is determined by iodine titration to obtain the final result.

[0051] Comparative Example 2 The effective chlorine concentration in the slightly acidic electrolyzed water was determined by iodine titration, and the final result was 104.93 mg / L.

[0052]

Performance test

[0053] Through Examples 5 to 8 and Comparative Example 2, the effect of different addition amounts of D-tryptophan on reducing the available chlorine concentration in slightly acidic electrolyzed water was studied. Figure 4 and Figure 5 As shown, the addition amount is 0, which is control example 2.

[0054] By comparison, it can be seen that as the amount of D-tryptophan added increases, the effective chlorine concentration in slightly acidic electrolyzed water decreases more and more. Through calculation, the following results can be obtained: when the amount of D-tryptophan added is 100μL, the effective chlorine concentration removal efficiency is 18.2%; when the amount of D-tryptophan added is 200μL, the effective chlorine concentration removal efficiency is 45.4%; when the amount of D-tryptophan added is 500μL, the effective chlorine concentration removal efficiency is 63.6%; when the amount of D-tryptophan added is 1mL, the effective chlorine concentration removal efficiency is 81.8%.

[0055] 2. Apply color testing In Examples 5-8 and Comparative Example 2, the color changes after adding different amounts of D-tryptophan solution to slightly acidic electrolyzed water and allowing the mixture to react for 10 minutes were observed. Slightly acidic electrolyzed water itself is transparent and colorless, as is a 40 mM D-tryptophan solution. When 1 mL of D-tryptophan was added (the D-tryptophan mass to wastewater volume ratio was 81.6 mg / L), the solution's final color turned purple. When 500 μL of D-tryptophan was added, the solution's final color turned light yellow. When 200 μL of D-tryptophan was added (the D-tryptophan mass to wastewater volume ratio was 16.32 mg / L), the solution's final color turned faintly pale yellow. When 100 μL of D-tryptophan was added (the D-tryptophan mass to wastewater volume ratio was 8.16 mg / L), the solution's final color turned colorless. The depth of the color change reflects the amount of D-tryptophan bound to available chlorine in the water. A greater amount of D-tryptophan added results in a darker color and, consequently, a higher efficiency in removing available chlorine.

Claims

1. The application of amino acid as dechlorination agent is characterized in that The amino acid is D-tryptophan, L-tryptophan, D-histidine, D-glutamine, L-histidine, L-leucine, L-phenylalanine, L-methionine or L-tyrosine.

2. The use according to claim 1, characterized in that The amino acid is D-tryptophan, L-tryptophan, L-tyrosine or L-methionine.

3. The use according to claim 2, characterized in that The amino acid is D-tryptophan.

4. The use according to claim 1, characterized in that Amino acids are used as dechlorinating agents in treating chlorine-containing industrial wastewater, biological treatment wastewater, domestic wastewater, or in reducing the effective chlorine content of daily water or drinking water.

5. A method for reducing the effective chlorine concentration in a chlorine-containing water sample, characterized in that The method is: Amino acids are added to the chlorine-containing water sample to be treated, mixed and reacted to obtain a water sample with a reduced effective chlorine concentration. The amino acids are D-tryptophan, L-tryptophan, D-histidine, D-glutamine, L-histidine, L-leucine, L-phenylalanine, L-methionine or L-tyrosine.

6. The method according to claim 5, wherein The reaction time is 10 to 20 minutes.

7. The method according to claim 5, wherein The ratio of the amino acid feed mass to the volume of the chlorine-containing water sample to be treated is 8~85mg / L.

8. The method according to claim 5, wherein The amino acid is D-tryptophan.

9. A chlorine removal agent, characterized in that The dechlorination agent comprises amino acids, and the amino acids are D-tryptophan, L-tryptophan, D-histidine, D-glutamine, L-histidine, L-leucine, L-phenylalanine, L-methionine or L-tyrosine.

10. The chlorine removal agent according to claim 9, wherein The amino acid is D-tryptophan.

Citation Information

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