Water treatment agent contributing to improving descaling and deoxygenization and production process of water treatment agent

Abstract

The invention discloses a water treatment agent helpful for improving descaling and deoxygenization and a production process thereof, and belongs to the technical field of water treatment agents, and the production process comprises the following steps: synthesis of a metal organic framework material: uniformly mixing zinc sulfate heptahydrate, 2-methylimidazole and a methanol solution, adding into a reaction kettle, strongly stirring, centrifuging, washing with the methanol solution, and drying to obtain the metal organic framework material; drying in a drying oven; hydrogel is prepared, specifically, hemicellulose and PAM are cross-linked, then borax is introduced, and freeze-drying treatment is conducted; adding a metal organic framework material into a DMSO solvent, fully dispersing, and then adding the hydrogel to prepare slurry; and sucking the slurry with a dropper, dropwise adding the slurry into a container filled with deionized water to form spherical particles, standing the spherical particles, and drying the spherical particles in a drying oven to obtain the water treatment agent. According to the invention, the metal organic framework material and the hydrogel are combined to prepare the water treatment agent helpful for improving descaling and deoxidization, and performance test results show that the descaling rate, the deoxidization rate and the reusability all have better levels.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment agents, and in particular to a water treatment agent that helps to improve descaling and deoxygenation, and a production process thereof. Background Art

[0002] Metal-organic frameworks (MOFs) are porous materials composed of metal ion clusters linked by multi-site organic ligands through coordination bonds. They possess high surface area, tunable pore structure, and excellent chemical stability. They are widely used in catalysis, sensing, separation, gas storage, and other fields.

[0003] Metal-organic frameworks (MOFs) are typically prepared via solvothermal or hydrothermal methods. Metal salts and organic ligands are dissolved in a suitable solvent, added to a reactor, and reacted at a specific temperature and time. The resulting product is then filtered, washed, and dried. While MOFs hold great potential for removing various trace pollutants in wastewater treatment, they still have significant limitations in terms of scale removal and deoxygenation.

[0004] Based on this, the present invention designs a water treatment agent and a production process thereof that helps to improve descaling and deoxygenation to solve the above problems. Summary of the Invention

[0005] In view of the above-mentioned shortcomings of the prior art, the present invention provides a water treatment agent and a production process thereof that helps to improve descaling and deoxygenation.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A process for producing a water treatment agent that helps improve descaling and deoxygenation comprises the following steps: (1) Synthesis of metal-organic framework materials: Mix zinc sulfate heptahydrate, 2-methylimidazole and methanol solution, add them to the reactor, stir vigorously for 12-15 hours, centrifuge, wash with methanol solution, and dry in an oven at 50-55°C for 8-10 hours; (2) Preparation of hydrogel: Hemicellulose was cross-linked with PAM, and then borax was introduced and freeze-dried to obtain the hydrogel; (3) Add the metal organic framework material into DMSO solvent and fully disperse it, then add hydrogel with a mass of 0.8 to 1.1 times that of the metal organic framework material, heat it in a water bath at 38 to 42 ° C and stir it vigorously for 15 to 20 minutes to obtain a uniformly dispersed slurry; use a dropper to draw the slurry and drip it drop by drop into a container filled with deionized water to form spherical particles, let the spherical particles stand for 25 to 30 minutes, and then place them in a 50 to 55 ° C oven to dry for 8 to 10 hours to obtain a water treatment agent that helps improve scale removal and deoxygenation.

[0007] Furthermore, in step (1), the stirring speed is 800-1500 rpm.

[0008] Furthermore, in step (1), the mass ratio of zinc sulfate heptahydrate to 2-methylimidazole is 3.5-4.8:7.2-8.1.

[0009] Furthermore, step (2) is specifically as follows: adding hemicellulose to water to prepare a hemicellulose solution of 0.01~0.03 g / mL; adding PAM to water to prepare a PAM solution of 0.01~0.03 g / mL; adding borax to water to prepare a borax solution of 0.01~0.02 g / mL; then mixing the hemicellulose solution and the PAM solution in a mass ratio of 1:1~3, adding 1~2.2% of the mass of the mixed solution initiator and stirring evenly, placing it at 55~62°C to react for 1~1.5h; adding 8~12% of the mass of the mixed solution borax solution dropwise, stirring while dropping until the solution becomes viscous; finally placing it in a vacuum freeze dryer for freeze-drying to obtain a hydrogel.

[0010] Furthermore, in step (2), the freeze-drying treatment conditions are: vacuum degree <10Pa, -20°C, and freeze-drying for 12 to 15 hours.

[0011] Furthermore, ammonium persulfate is used as the initiator.

[0012] In order to better achieve the purpose of the present invention, the present invention also provides a water treatment agent prepared according to the production process, which helps to improve scale removal and deoxygenation.

[0013] In order to better achieve the purpose of the present invention, the present invention also provides the use of the water treatment agent in wastewater treatment.

[0014] Compared to existing technologies, this invention offers the following advantages: It combines metal-organic frameworks with hydrogels to create a water treatment agent that enhances both scale and oxygen removal. Performance testing demonstrates superior scale removal, oxygen removal, and reusability. This approach is widely applicable to wastewater treatment applications, enhancing both scale and oxygen removal. DETAILED DESCRIPTION

[0015] To make the purpose, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0016] Example 1: A process for producing a water treatment agent that helps improve descaling and deoxygenation, comprising the following steps: (1) Synthesis of metal-organic framework materials: 3.5 g zinc sulfate heptahydrate, 7.2 g 2-methylimidazole and 150 ml methanol solution were mixed evenly, added to the reactor, vigorously stirred (800 rpm) for 15 h, centrifuged, washed with methanol solution, and dried in a 50 °C oven for 10 h; (2) Preparation of hydrogel: Hemicellulose is cross-linked with PAM (polyacrylamide), and then borax is introduced and freeze-dried to obtain a hydrogel; specifically, hemicellulose is added to water to prepare a 0.01 g / mL hemicellulose solution; PAM is added to water to prepare a 0.01 g / mL PAM solution; borax is added to water to prepare a 0.01 g / mL borax solution; then the hemicellulose solution and the PAM solution are mixed in a mass ratio of 1:1, and an initiator (ammonium persulfate) of 1% by mass of the mixed solution is added and stirred evenly, and placed at 55°C for reaction for 1.5 hours; 8% by mass of the mixed solution is added dropwise with stirring until the solution becomes viscous; finally, the solution is placed in a vacuum freeze dryer for freeze-drying (vacuum degree <10 Pa, -20°C, freeze-dried for 12 hours) to obtain a hydrogel.

[0017] (3) The metal organic framework material is added to DMSO (dimethyl sulfoxide) solvent and fully dispersed, and then a hydrogel with a mass 0.8 times that of the metal organic framework material is added, and the mixture is heated in a water bath at 38°C and vigorously stirred for 20 minutes to obtain a uniformly dispersed slurry. The slurry is drawn with a dropper and dripped dropwise into a container filled with deionized water to form spherical particles. The spherical particles are allowed to stand for 25 minutes and then placed in a 50°C oven to dry for 10 hours to obtain a water treatment agent that helps improve scale removal and deoxygenation.

[0018] Example 2: A process for producing a water treatment agent that helps improve descaling and deoxygenation, comprising the following steps: (1) Synthesis of metal-organic framework materials: 4.8 g zinc sulfate heptahydrate, 8.1 g 2-methylimidazole and 180 ml methanol solution were mixed evenly, added to a reactor, and vigorously stirred (1500 rpm) for 12 h. After centrifugation and washing with methanol solution, the mixture was placed in a 55 °C oven to dry for 8 h. (2) Preparation of hydrogel: Hemicellulose is cross-linked with PAM (polyacrylamide), and then borax is introduced and freeze-dried to obtain the hydrogel; Specifically, hemicellulose is added to water to prepare a 0.03 g / mL hemicellulose solution; PAM is added to water to prepare a 0.03 g / mL PAM solution; borax is added to water to prepare a 0.02 g / mL borax solution; then the hemicellulose solution and the PAM solution are mixed in a mass ratio of 1:3, and an initiator (ammonium persulfate) of 2.2% by mass of the mixed solution is added and stirred evenly, and placed at 62°C for reaction for 1 hour; a borax solution of 12% by mass of the mixed solution is added dropwise while stirring until the solution becomes viscous; finally, the solution is placed in a vacuum freeze dryer for freeze-drying (vacuum degree <10 Pa, -20°C, freeze-drying for 15 hours) to obtain a hydrogel.

[0019] (3) The metal organic framework material was added to DMSO (dimethyl sulfoxide) solvent and fully dispersed, and then a hydrogel with a mass 1.1 times that of the metal organic framework material was added, and the mixture was heated in a water bath at 42°C and vigorously stirred for 15 minutes to obtain a uniformly dispersed slurry. The slurry was drawn with a dropper and dripped dropwise into a container filled with deionized water to form spherical particles. The spherical particles were allowed to stand for 30 minutes and then dried in an oven at 55°C for 8 hours to obtain a water treatment agent that helps to improve descaling and deoxygenation.

[0020] Example 3: A process for producing a water treatment agent that helps improve descaling and deoxygenation, comprising the following steps: (1) Synthesis of metal-organic framework materials: 4.0 g zinc sulfate heptahydrate, 7.5 g 2-methylimidazole and 165 ml methanol solution were mixed evenly, added to a reactor, and vigorously stirred (1000 rpm) for 13 h. After centrifugation and washing with methanol solution, the mixture was placed in a 53 °C oven to dry for 9 h. (2) Preparation of hydrogel: Hemicellulose is cross-linked with PAM (polyacrylamide), and then borax is introduced and freeze-dried to obtain the hydrogel; Specifically, hemicellulose was added to water to prepare a 0.02 g / mL hemicellulose solution; PAM was added to water to prepare a 0.02 g / mL PAM solution; borax was added to water to prepare a 0.015 g / mL borax solution; then the hemicellulose solution and the PAM solution were mixed in a mass ratio of 1:2, and an initiator (ammonium persulfate) of 1.6% by mass of the mixed solution was added and stirred evenly, and placed at 58°C for reaction for 1.2 hours; a borax solution of 10% by mass of the mixed solution was added dropwise while stirring until the solution became viscous; finally, the solution was placed in a vacuum freeze dryer for freeze-drying (vacuum degree <10 Pa, -20°C, freeze-drying for 13 hours) to obtain a hydrogel.

[0021] (3) The metal organic framework material is added to DMSO (dimethyl sulfoxide) solvent and fully dispersed, and then a hydrogel with a mass that is 1 times that of the metal organic framework material is added, and the mixture is heated in a water bath at 40°C and vigorously stirred for 18 minutes to obtain a uniformly dispersed slurry; the slurry is drawn with a dropper and dripped dropwise into a container filled with deionized water to form spherical particles, which are allowed to stand for 28 minutes and then placed in a 52°C oven to dry for 9 hours to obtain a water treatment agent that helps improve scale removal and deoxygenation.

[0022] Example 4: A process for producing a water treatment agent that helps improve descaling and deoxygenation, comprising the following steps: (1) Synthesis of metal-organic framework materials: 3.8 g zinc sulfate heptahydrate, 7.6 g 2-methylimidazole and 165 ml methanol solution were mixed evenly, added to a reactor, and vigorously stirred (1200 rpm) for 14 h. After centrifugation and washing with methanol solution, the mixture was placed in a 52 °C oven to dry for 8.5 h. (2) Preparation of hydrogel: Hemicellulose is cross-linked with PAM (polyacrylamide), and then borax is introduced and freeze-dried to obtain the hydrogel; Specifically, hemicellulose was added to water to prepare a 0.015 g / mL hemicellulose solution; PAM was added to water to prepare a 0.25 g / mL PAM solution; borax was added to water to prepare a 0.013 g / mL borax solution; the hemicellulose solution and the PAM solution were then mixed in a mass ratio of 1:1.2, and an initiator (ammonium persulfate) accounting for 2% of the mass of the mixed solution was added and stirred evenly, and the mixture was placed at 60°C for reaction for 1.3 hours; a borax solution accounting for 11% of the mass of the mixed solution was added dropwise while stirring until the solution became viscous; and finally, the mixture was placed in a vacuum freeze dryer for freeze-drying (vacuum degree <10 Pa, -20°C, freeze-drying for 13.5 hours) to obtain a hydrogel.

[0023] (3) The metal organic framework material was added to DMSO (dimethyl sulfoxide) solvent and fully dispersed, and then a hydrogel with a mass 0.9 times that of the metal organic framework material was added, and the mixture was heated in a water bath at 39°C and vigorously stirred for 17 minutes to obtain a uniformly dispersed slurry. The slurry was drawn with a dropper and dripped dropwise into a container filled with deionized water to form spherical particles. The spherical particles were allowed to stand for 27 minutes and then dried in an oven at 54°C for 9.5 hours to obtain a water treatment agent that helps improve descaling and deoxygenation.

[0024] Comparative Example 1: Different from Example 3, in step (3), the metal organic framework material is mixed with a hydrogel having a mass that is 1 times that of the metal organic framework material, and the mixture is placed in an oven at 52° C. and dried for 9 hours to obtain a treating agent.

[0025] Comparative Example 2: The difference from Example 3 is that in step (3), the metal organic framework material is added to a DMSO (dimethyl sulfoxide) solvent and fully dispersed, and then a hydrogel with a mass twice that of the metal organic framework material is added, and the mixture is heated in a water bath at 40°C and vigorously stirred for 18 minutes to obtain a uniformly dispersed slurry; the slurry is drawn up with a dropper and dripped dropwise into a container filled with deionized water to form spherical particles, and the spherical particles are allowed to stand for 28 minutes and then placed in a 52°C oven to dry for 9 hours to obtain a water treatment agent that helps improve scale removal and deoxygenation.

[0026] Performance test results of water treatment agents of Examples 1 to 4: Descaling rate: Take 50ml of CaCl2 solution (1000 mg / L), add water treatment agent (addition amount 1g / L), shake at 25℃ for 2 hours, Ca 2+ Removal rate is greater than 92.5%; Deoxygenation rate: Take 100 mL of dissolved oxygen water (DO concentration 5 mg / L), add water treatment agent (addition amount 1g / L), react at 30℃ for 1 hour, and the dissolved oxygen (DO) concentration is reduced to less than 0.45 mg / L; Reusability: Performance retention rate is greater than 87% after 5 cycles.

[0027] Comparative Example 1 Water treatment agent performance test results: Descaling rate: Ca 2+ Removal rate: 89.4%; oxygen removal rate: dissolved oxygen (DO) concentration dropped to 0.67 mg / L; reusability: performance retention rate after 5 cycles: 81%.

[0028] Comparative Example 2 Water treatment agent performance test results: Descaling rate: Ca 2+ Removal rate: 92.5%; oxygen removal rate: dissolved oxygen (DO) concentration dropped to 0.85 mg / L; reusability: performance retention rate after 5 cycles: 72%.

[0029] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A production process for a water treatment agent that helps improve descaling and deoxygenation, characterized in that: The following steps are involved: (1) Synthesis of metal-organic framework materials: Mix zinc sulfate heptahydrate, 2-methylimidazole and methanol solution, add them to the reactor, stir vigorously for 12-15 hours, centrifuge, wash with methanol solution, and dry in an oven at 50-55°C for 8-10 hours; (2) Preparation of hydrogel: Hemicellulose was cross-linked with PAM, and then borax was introduced and freeze-dried to obtain the hydrogel; (3) Add the metal organic framework material into DMSO solvent and fully disperse it, then add hydrogel with a mass of 0.8 to 1.1 times that of the metal organic framework material, heat it in a water bath at 38 to 42 ° C and stir it vigorously for 15 to 20 minutes to obtain a uniformly dispersed slurry; use a dropper to draw the slurry and drip it drop by drop into a container filled with deionized water to form spherical particles, let the spherical particles stand for 25 to 30 minutes, and then place them in a 50 to 55 ° C oven to dry for 8 to 10 hours to obtain a water treatment agent that helps improve scale removal and deoxygenation.

2. The production process of a water treatment agent that helps improve descaling and deoxygenation according to claim 1, characterized in that: In step (1), the stirring speed is 800~1500 rpm.

3. The production process of a water treatment agent that helps improve descaling and deoxygenation according to claim 1, characterized in that: In step (1), the mass ratio of zinc sulfate heptahydrate to 2-methylimidazole is 3.5-4.8:7.2-8.

1.

4. The production process of a water treatment agent that helps improve descaling and deoxygenation according to claim 1, characterized in that: Step (2) is specifically as follows: adding hemicellulose to water to prepare a hemicellulose solution of 0.01-0.03 g / mL; adding PAM to water to prepare a PAM solution of 0.01-0.03 g / mL; adding borax to water to prepare a borax solution of 0.01-0.02 g / mL; then mixing the hemicellulose solution and the PAM solution in a mass ratio of 1:1-3, adding 1-2.2% of the mass of the mixed solution initiator and stirring evenly, placing it at 55-62°C to react for 1-1.5 hours; adding 8-12% of the mass of the mixed solution borax solution dropwise, stirring while dropping until the solution becomes viscous; finally placing it in a vacuum freeze dryer for freeze-drying to obtain a hydrogel.

5. The production process of a water treatment agent that helps improve descaling and deoxygenation according to claim 4, characterized in that: In step (2), the freeze-drying treatment conditions are: vacuum degree <10Pa, -20°C, freeze-drying for 12 to 15 hours.

6. The production process of a water treatment agent that helps improve descaling and deoxygenation according to claim 4, characterized in that: Ammonium persulfate was used as the initiator.

7. A water treatment agent that helps improve scale removal and deoxygenation, prepared according to the production process of any one of claims 1 to 6.

8. Use of the water treatment agent according to claim 7 in wastewater treatment.