Solid rust remover composition, preparation method, protection method and application
By using a solid rust remover composition to capture and remove metal ions in the pipeline during the electroreduction of carbon dioxide to carbon monoxide, the problem of catalyst blockage is solved, catalyst life is extended, and conversion efficiency is improved.
Patent Information
- Application Number
- CN202512030956.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-05-01
AI Technical Summary
In the existing technology, during the electroreduction of carbon dioxide to carbon monoxide, the catalyst is deactivated due to the blockage of the catalyst by metal ions in the rust, which affects the conversion efficiency. It also suffers from problems such as low current efficiency, high energy consumption and expensive electrode materials.
A solid rust remover composition consisting of natural starch, alginate, acid-soluble chitosan, and wheat protein forms a network structure through a chemical reaction, capturing and removing metal ions from the pipeline and preventing them from contaminating the downstream catalyst.
It extends catalyst life, improves carbon dioxide conversion efficiency, reduces metal ion removal costs, and achieves efficient capture of rust ions with a capture rate of up to 99.7%.
Smart Images
Figure CN121945002A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of carbon dioxide electrochemical conversion technology, specifically to a solid rust remover composition, its preparation method, its protection method, and its application. Background Technology
[0002] Catalyst clogging is a common problem in the electroreduction of carbon dioxide to carbon monoxide. This is mainly because rust often forms in the pipelines as the electrolyte flows through the equipment. Rust easily clogs the catalyst and deactivates it, thus failing to achieve the required carbon dioxide conversion efficiency and causing unnecessary losses. Existing methods use electrode plates to electroadsorb iron ions to prevent rusting. However, metal ions remain after electroadsorption, and the method suffers from low overall current efficiency, high energy consumption, and expensive electrode materials. Therefore, it is urgent to solve the problem of catalyst clogging caused by metal ions in the rust on the equipment pipelines. Summary of the Invention
[0003] Therefore, the technical problem to be solved by the present invention is to overcome the defect of metal ions in rust clogging the catalyst in the prior art, thereby providing a solid rust remover composition, preparation method, protection method and application. The solid rust remover composition of the present invention can capture metal ions in water that will deactivate the catalyst, prevent rust from contaminating the downstream catalyst, extend the catalyst life and ultimately improve the carbon dioxide conversion efficiency.
[0004] To address the aforementioned technical problems, the present invention proposes the following technical solution: This invention provides a solid rust remover composition comprising the following raw materials in parts by weight: 28-32 parts natural starch, 3-5 parts alginate, 4-6 parts acid-soluble chitosan, 7-9 parts wheat protein, 2-3 parts acid and 32-38 parts water.
[0005] The solid rust remover composition of the present invention comprises 28-32 parts of natural starch, more preferably 30 parts. Preferably, the natural starch comprises at least one selected from tapioca starch, potato starch, corn starch, sweet potato starch, and taro starch.
[0006] The solid rust remover composition of the present invention comprises 3-5 parts of alginate, more preferably 4 parts. Preferably, the alginate comprises at least one selected from sodium alginate, potassium alginate, and ammonium alginate.
[0007] The solid rust remover composition of the present invention comprises 4-6 parts of acid-soluble chitosan, more preferably 5 parts.
[0008] The solid rust remover composition of the present invention comprises 7-9 parts of wheat protein, more preferably 8 parts.
[0009] The solid rust remover composition of the present invention comprises 2-3 parts of acid, more preferably 3 parts; preferably, the acid comprises at least one of phosphoric acid, citric acid and acetic acid.
[0010] The present invention does not have any special limitation on the source of the components in the solid rust remover composition; conventional commercially available products can be used.
[0011] Interaction mechanism of each component: The alginate in this invention has an extremely strong ability to adsorb metal ions, but it cannot be stably formed in liquid. Tapioca flour provides an attachment scaffold, preventing the alginate from completely dissolving in the liquid. Simultaneously, the addition of wheat protein enhances the overall wet strength, allowing the alginate to form in the liquid and preventing deformation from water flow. Furthermore, the acid-soluble chitosan is dissolved by acid, and phosphoric acid promotes the esterification reaction of carboxyl and hydroxyl groups. This causes the carboxyl and hydroxyl groups in the tapioca flour, alginate, and wheat protein to undergo esterification and dehydration to form ester groups. Phosphoric acid also makes it easier for the ester groups to subsequently combine with the amino groups of the acid-soluble chitosan through amidation, enhancing the overall toughness and preventing breakage. This allows the rust remover to exist as a solid, used to capture metal ions in the pipeline, preventing metal ions from contaminating the downstream catalyst. In specific embodiments of this invention, tapioca flour is rich in hydroxyl groups, alginate is rich in hydroxyl and carboxyl groups, wheat protein is rich in thiol, amino, and hydroxyl groups, and acid-soluble chitosan is rich in amino and hydroxyl groups. These functional groups all possess the ability to adsorb and chelate metal ions.
[0012] This invention provides a method for preparing the solid rust remover composition described in the above technical solution, wherein the natural starch, wheat protein and a first portion of water are mixed to obtain a first viscous substance; The first viscous substance and the alginate are mixed to obtain a second viscous substance; The acid-soluble chitosan, the second portion of water, and the acid are mixed to obtain a third viscous substance; The second viscous substance is mixed with the third viscous substance and then fumigated to obtain a solid rust remover.
[0013] Preferably, after mixing, the mixture is further subjected to cutting before fumigation. This invention does not impose any special limitations on the cutting method or shape; conventional methods are acceptable. In this invention, the solid rust remover is cut into spheres with a diameter of 0.5 cm.
[0014] Preferably, the volume ratio of the first portion of water to the second portion of water is (1-3):5, more preferably 2:5. Setting the volume ratio of the first portion of water to the second portion of water allows each substance to dissolve fully, resulting in the best morphology after molding, and sufficient strength and toughness to prevent breakage in water.
[0015] Preferably, the natural starch and the first portion of water are mixed to obtain a natural starch solution, and the mass-to-volume ratio of the natural starch to the first portion of water is (4-2):1, more preferably 3:1; the mass ratio of the natural starch solution to the wheat protein is (7-3):1, more preferably 5:1.
[0016] The mass ratio of the first viscous substance to the alginate is (8-16):1, more preferably 12:1; The mass-to-volume ratio of the acid-soluble chitosan to the second portion of water is 1:(3-7), more preferably 1:5; the acid-soluble chitosan and the second portion of water are mixed to obtain an acid-soluble chitosan system; the amount of phosphoric acid added is 5%-15% of the volume of the acid-soluble chitosan system, more preferably 10%.
[0017] Preferably, the fumigation includes steam fumigation, and the fumigant is deionized water. The fumigation temperature is 50-70℃, more preferably 60℃, and the time is 4-6 hours, more preferably 5 hours. The purpose of fumigation is to retain moisture during the heating process, ensuring sufficient humidity for the final formation of spheres.
[0018] The present invention provides the application of the solid rust remover composition described in the above technical solution or the solid rust remover composition obtained by the preparation method described in the above technical solution in protecting carbon dioxide electrochemical conversion catalyst.
[0019] This invention provides a method for protecting a carbon dioxide electrochemical conversion catalyst, wherein a solid rust remover composition is placed in the pipeline of a carbon dioxide electrochemical conversion device; the solid rust remover composition is either the solid rust remover composition prepared by the method described in the above technical solution.
[0020] Preferably, the catalyst includes catalysts involved in the electrochemical conversion of carbon dioxide, including but not limited to Ni-Fe LDH, Co-Al LDH, Co phthalocyanine, Fe porphyrin, and Ni porphyrin; carbon dioxide is converted into carbon monoxide under the action of the electrochemical conversion catalyst.
[0021] The technical solution of this invention has the following advantages: 1. The present invention provides a solid rust remover composition, wherein natural starch cassava flour, alginate, acid-soluble chitosan, wheat protein, and phosphoric acid are cross-linked through a chemical reaction to form a solid rust remover. In the prior art, rust removers are generally liquids. The solid rust remover of the present invention is more convenient and simple to use, and can directly adsorb and remove metal rust in solution.
[0022] 2. The preparation method of the solid rust remover composition provided by the present invention is simple and easy to operate.
[0023] 3. The application of the solid rust remover composition provided by the present invention in protecting the carbon dioxide electrochemical conversion catalyst: the solid rust remover only needs to be placed in the electrolyte pipeline before entering the catalyst to prevent rust from poisoning the catalyst.
[0024] 4. The method for protecting the catalyst of carbon dioxide electrochemical conversion provided by the present invention involves placing a solid rust remover composition in the pipeline of the carbon dioxide electrochemical conversion device; the solid rust remover only needs to be placed in the electrolyte pipeline before entering the catalyst to prevent rust from poisoning the catalyst. It is simple to apply and has good effect.
[0025] The key innovation of this invention lies in the fact that the effective raw materials of the main solid rust remover are all natural products, making it environmentally friendly. After the raw materials are combined, the overall wet strength and toughness increase, making it more suitable for capturing metal ions in aquatic environments. The capture of colored ions such as iron and copper results in a visible color change; rust turns red, while copper, less common, turns green. The captured iron ions turn red, and the captured copper ions turn green. The agent can be replaced or regenerated based on the color change. Rich in functional groups such as carboxyl, hydroxyl, and amino groups, it forms a network with an extremely high capture rate, capable of capturing over 99.7% of rust ions.
[0026] This invention utilizes cassava flour to enable alginate to form in water, wheat protein to increase wet strength, and acid-soluble chitosan to increase overall toughness. Simultaneously, the cassava flour is rich in hydroxyl groups, the alginate is rich in hydroxyl and carboxyl groups, the wheat protein is rich in thiol, amino, and hydroxyl groups, and the acid-soluble chitosan is rich in amino and hydroxyl groups. Through the formation of a network by hydroxyl, amino, and carboxyl groups, rust ions are captured. The solid rust remover composition (i.e., solid gel) of this invention captures metal ions in water that would deactivate the catalyst, extending catalyst life, improving carbon dioxide conversion efficiency, and simultaneously reducing the cost of removing metal ions while increasing their removal efficiency. Attached Figure Description
[0027] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0028] Figure 1 This is a schematic diagram of the fumigation process for producing the rust remover in Embodiment 1 of the present invention; Figure 2 This is a schematic diagram of the application of introducing rust ions in Embodiment 1 of the present invention. Detailed Implementation
[0029] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.
[0030] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.
[0031] Example 1 1. Raw materials for preparing solid rust remover compositions: 30g tapioca flour, 4g sodium alginate, 5g acid-soluble chitosan, 8g wheat protein, 3mL phosphoric acid, and 35mL deionized water.
[0032] 2. Preparation method: (1) Take 30g of cassava flour and 10ml of deionized water in a mass-volume ratio of 3:1, mix them to obtain a cassava flour solution, then add wheat protein to it, the mass ratio of wheat protein to cassava flour solution is 1:5, stir thoroughly until it becomes viscous, and after dissolving, obtain 48g of the first viscous substance.
[0033] (2) Pour 4g of sodium alginate into the first viscous substance and stir thoroughly to obtain the second viscous substance.
[0034] (3) Take 5g of acid-soluble chitosan and 25ml of deionized water and mix them at a mass-volume ratio of 1:5. Then add 3mL of phosphoric acid to the mixture to promote its dissolution and viscosity, and obtain the third viscous substance.
[0035] (4) After the second viscous substance and the third viscous substance are mixed evenly at high speed, they are cut into 0.5cm spheres to obtain small balls.
[0036] (5) The small balls were fumigated with deionized water at 60°C for 5 hours to obtain the rust remover. The fumigation diagram is shown below. Figure 1 . Figure 1 The small and medium-sized balls undergo a final fumigation step after being cut. The blue liquid is deionized water. This humid fumigation process does not remove moisture, allowing the small balls to finally take shape.
[0037] Example 2 1. Raw materials for preparing solid rust remover compositions: 28g tapioca flour, 3g alginate, 4g acid-soluble chitosan, 7g wheat protein, 2mL phosphate, and 38mL deionized water.
[0038] 2. Preparation method: (1) Mix 28g of cassava flour with 14mL of deionized water at a mass-volume ratio of 2:1 to obtain a cassava flour solution. Add 7g of wheat protein to the cassava flour solution. The mass ratio of 7g of wheat protein to the cassava flour solution is 1:6. Then stir thoroughly until it becomes viscous to obtain 49g of the first viscous substance.
[0039] (2) Pour 3g of alginate into the first viscous substance and stir thoroughly to obtain the second viscous substance.
[0040] (3) Take 4g of acid-soluble chitosan and 24mL of deionized water and mix them at a mass-volume ratio of 1:6. Then add 2mL of phosphoric acid to the mixture to promote its dissolution and viscosity, and obtain the third viscous substance.
[0041] (4) After the second and third viscous substances are mixed evenly at high speed, they are cut into 0.5cm spheres to obtain small balls.
[0042] (5) The rust remover is obtained by fumigating the small balls with deionized water at 70°C for 4 hours.
[0043] Comparative Example 1 1. Raw materials for preparing solid rust remover compositions: 30g tapioca flour, 4g sodium alginate, 5g acid-soluble chitosan, 8g wheat protein, and 40mL deionized water. The ingredients do not contain acid.
[0044] 2. The preparation method is as follows: (1) Take 30g of cassava flour and 15mL of deionized water and mix them in a mass-volume ratio of 3:1 to obtain a mixture. Add wheat protein to the mixture in a mass ratio of 1:5. Stir thoroughly until the mixture becomes viscous to obtain the first viscous substance.
[0045] (2) Pour 4g of sodium alginate into the first viscous substance and stir thoroughly to obtain the second viscous substance.
[0046] (3) Take 5g of acid-soluble chitosan and 25mL of deionized water and mix them at a mass-volume ratio of 1:5 to obtain the third suspension.
[0047] (4) After the second viscous substance and the third suspension are stirred evenly at high speed, they are cut into 0.5cm spheres to obtain small balls.
[0048] (5) The small balls are fumigated with deionized water at 60°C for 5 hours to obtain the rust remover.
[0049] Comparative Example 2 1. Raw materials for preparing solid rust remover compositions: The ingredients include 4g alginate, 5g acid-soluble chitosan, 8g wheat protein, 3mL phosphate, and 65mL deionized water. No natural starch is present in the raw materials.
[0050] 2. The preparation method is as follows: (1) Take 8g of wheat protein and 40mL of deionized water and stir thoroughly at a mass-volume ratio of 1:5 to obtain the first viscous substance.
[0051] (2) Pour 4g of alginate into the first viscous substance and stir thoroughly to obtain the second viscous substance.
[0052] (3) Take 5g of acid-soluble chitosan and 25mL of deionized water and mix them at a mass-volume ratio of 1:5. Then add 3mL of phosphoric acid to the mixture to promote its dissolution and viscosity, and obtain the third viscous substance.
[0053] (4) After the second viscous substance and the third viscous substance are mixed evenly at high speed, they are cut into 0.5cm spheres to obtain small balls.
[0054] (5) The small balls are fumigated with deionized water at 60°C for 5 hours to obtain the rust remover.
[0055] Comparative Example 3 1. Raw materials for preparing solid rust remover compositions: 30g tapioca flour, 4g sodium carboxymethyl cellulose, 5g acid-soluble chitosan, 8g wheat protein, 3mL phosphoric acid, and 35mL deionized water.
[0056] 2. Preparation method: (1) Take 30g of cassava flour and 10ml of deionized water in a mass-volume ratio of 3:1, mix them to obtain a cassava flour solution, then add wheat protein to it, with a mass ratio of wheat protein to cassava flour solution of 1:5, stir thoroughly until it becomes viscous, and after dissolving, obtain the first viscous substance.
[0057] (2) Pour 4g of sodium carboxymethyl cellulose into the first viscous substance and stir thoroughly to obtain the second viscous substance.
[0058] (3) Take 5g of acid-soluble chitosan and 25ml of deionized water and mix them at a mass-volume ratio of 1:5. Then add 3mL of phosphoric acid to the mixture to promote its dissolution and viscosity, and obtain the third viscous substance.
[0059] (4) After the second viscous substance and the third viscous substance are mixed evenly at high speed, they are cut into 0.5cm spheres to obtain small balls.
[0060] (5) The small balls were fumigated with deionized water at 60°C for 5 hours to obtain the rust remover. The fumigation diagram is shown below. Figure 1 . Figure 1 The small and medium-sized balls undergo a final fumigation step after being cut. The blue liquid is deionized water. This humid fumigation process does not remove moisture, allowing the small balls to finally take shape.
[0061] Comparative Example 4 1. Raw materials for preparing solid rust remover compositions: 30g tapioca flour, 4g sodium alginate, 5g acid-soluble chitosan, 8g soy protein, 3mL phosphoric acid, and 35mL water.
[0062] 2. Preparation method: (1) Take 30g of cassava flour and 10ml of deionized water in a mass-volume ratio of 3:1, mix them to obtain a cassava flour solution, then add soybean protein to it. The mass ratio of 8g of soybean protein to the cassava flour solution is 1:5. Stir thoroughly until it becomes viscous, and after dissolving, obtain the first viscous substance.
[0063] (2) Pour 4g of sodium alginate into the first viscous substance and stir thoroughly to obtain the second viscous substance.
[0064] (3) Take 5g of acid-soluble chitosan and 25ml of deionized water and mix them at a mass-volume ratio of 1:5. Then add 3mL of phosphoric acid to the mixture to promote its dissolution and viscosity, and obtain the third viscous substance.
[0065] (4) After the second viscous substance and the third viscous substance are mixed evenly at high speed, they are cut into 0.5cm spheres to obtain small balls.
[0066] (5) The small balls were fumigated with deionized water at 60°C for 5 hours to obtain the rust remover. The fumigation diagram is shown below. Figure 1 . Figure 1 The small and medium-sized balls undergo a final fumigation step after being cut. The blue liquid is deionized water. This humid fumigation process does not remove moisture, allowing the small balls to finally take shape.
[0067] Application examples The rust removers prepared in the examples and comparative examples were placed in an acrylic cylinder, and a 50 mg / L iron ion solution was passed through in a single pass. The iron ion concentration before and after rust removal was measured. This simulates actual application where the volume of the iron ion solution remains constant before and after the pass; the overall test involves a flowing liquid, and everything except the iron ions is unaffected.
[0068] Application diagrams are shown below. Figure 2 The test data is shown in Table 1.
[0069] Table 1. Test results of the rust removers prepared in the examples and comparative examples.
[0070] Rust removal rate (%) = (Iron ion concentration before removal - Iron ion concentration after removal) / Iron ion concentration before removal × 100%.
[0071] In summary, the solid rust remover of the present invention has a high rust removal rate and excellent application effect.
[0072] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A solid rust remover composition, characterized in that, The ingredients include the following parts by weight: 28-32 parts natural starch, 3-5 parts alginate, 4-6 parts acid-soluble chitosan, 7-9 parts wheat protein, 2-3 parts acid and 32-38 parts water.
2. The solid rust remover composition according to claim 1, characterized in that, The acid includes at least one of phosphoric acid, acetic acid, and citric acid.
3. The solid rust remover composition according to claim 1, characterized in that, The natural starch includes at least one of tapioca starch, potato starch, corn starch, sweet potato starch, and taro starch.
4. A method for preparing the solid rust remover composition according to any one of claims 1 to 3, characterized in that, The first viscous substance is obtained by mixing the natural starch, wheat protein and a first portion of water. The first viscous substance and the alginate are mixed to obtain a second viscous substance; The acid-soluble chitosan, the second portion of water, and the acid are mixed to obtain a third viscous substance; The second viscous substance is mixed with the third viscous substance and then fumigated to obtain a solid rust remover.
5. The preparation method according to claim 4, characterized in that, The process of mixing also includes cutting.
6. The preparation method according to claim 4, characterized in that, The volume ratio of the first part of water to the second part of water is (1-3):
5.
7. The preparation method according to claim 4, characterized in that, The natural starch and the first portion of water are mixed to obtain a natural starch solution, wherein the mass-to-volume ratio of the natural starch to the first portion of water is (4-2):1; and the mass ratio of the natural starch solution to the wheat protein is (7-3):
1. The mass ratio of the first viscous substance to the alginate is (8-16):1; The mass-to-volume ratio of the acid-soluble chitosan to the second portion of water is 1:(3-7); the acid-soluble chitosan and the second portion of water are mixed to obtain an acid-soluble chitosan system; the amount of phosphoric acid added is 5%-15% of the volume of the acid-soluble chitosan system.
8. The preparation method according to claim 4, characterized in that, The fumigation temperature is 50-70℃, and the time is 4-6 hours. The fumigation includes deionized water fumigation, and the fumigant used during fumigation is deionized water.
9. The use of the solid rust remover composition according to any one of claims 1 to 3 or the solid rust remover composition obtained by the preparation method according to any one of claims 4 to 8 in protecting carbon dioxide electrochemical conversion catalysts.
10. A method for protecting a catalyst for the electrochemical conversion of carbon dioxide, characterized in that, The solid rust remover composition is placed in the pipeline of the carbon dioxide electrochemical conversion device; the solid rust remover composition is the solid rust remover composition according to any one of claims 1 to 3 or the solid rust remover composition obtained by the preparation method according to any one of claims 4 to 8.