Efficient deoxidizer suitable for low-temperature environment and preparation method thereof
By using modified nanozeolite powder, modified polyethylene glycol and modified nano tourmaline in the deoxidant, combined with electric field treatment, the problem of poor deoxidation effect of existing deoxidants in low temperature environments is solved, and efficient and long-lasting deoxidation effect is achieved.
Patent Information
- Application Number
- CN202510346229.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-24
- Publication Date
- 2025-06-13
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing iron-based and non-ferrous deoxidants have poor deoxidation effects in low temperature environments, high moisture regain rate, and low oxygen absorption rate, resulting in poor preservation and corrosion protection effects.
A formulation including reduced iron powder, sodium chloride, modified nanozeolite powder, sodium sulfite, modified polyethylene glycol, modified nano tourmaline and nanotitanium dioxide is used to improve the reactive activity and dispersion of the deoxidant through modified nanomaterials and electric field treatment.
In low temperature environments, the reaction rate and deoxygenation effect of the deoxidant are significantly improved, the action time is extended, and the preservation and corrosion resistance are enhanced.
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Figure CN120130530A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of deoxidants, and particularly relates to a high-efficiency deoxidant applicable to low-temperature environments and a preparation method thereof. Background Art
[0002] A deoxidant, also known as an oxygen remover or oxygen absorber, is an additive that can absorb oxygen and slow down the oxidation of food. It is a new product being used in food preservation. It is a group of chemical mixtures that easily react with free oxygen or dissolved oxygen. Packed in a sealed paper bag with a certain air permeability and strength, like a desiccant bag, it is sealed and packaged with food in a food bag, can remove the oxygen remaining in the air in the bag, prevent food from changing color, deteriorating due to oxidation, and the rancidity of oils and fats, and also has an inhibitory effect on the growth of molds, aerobic bacteria, and grain pests. Deoxidants are not only used to maintain food quality.
[0003] Iron-based deoxidants generally use iron powder as the basic raw material and have been widely used in various foods such as wet bread flour, wet noodles, wet vermicelli, wet pastries, and semi-dried fish products. However, at present, iron-based deoxidants still have problems such as poor deoxidation effect at low temperatures, high moisture regain rate after use, and low oxygen absorption rate, resulting in poor freshness preservation and anti-corrosion effects. Non-iron-based deoxidants mainly use reducing organic substances such as vitamin C, tea polyphenols, and oleic acid as raw materials. They can all react with oxygen to become oxidation products, thereby removing the oxygen in the food. However, non-iron-based organic materials have poor activity and deoxidation effect at low temperatures. Summary of the Invention
[0004] The present invention provides a high-efficiency deoxidant applicable to low-temperature environments, aiming to solve the above problems.
[0005] The present invention is realized as follows. A high-efficiency deoxidant applicable to low-temperature environments includes the following raw materials in parts by weight: 70 - 100 parts of reduced iron powder, 1 - 5 parts of sodium chloride, 25 - 35 parts of modified nano-zeolite powder, 2 - 8 parts of sodium sulfite, 10 - 20 parts of modified polyethylene glycol, 5 - 15 parts of modified nano-tourmaline, 2 - 6 parts of nano-titanium dioxide, and 10 - 20 parts of water.
[0006] Preferably, it includes the following raw materials in parts by weight: 75 - 95 parts of reduced iron powder, 2 - 4 parts of sodium chloride, 28 - 32 parts of modified nano-zeolite powder, 3 - 7 parts of sodium sulfite, 12 - 18 parts of modified polyethylene glycol, 8 - 13 parts of modified nano-tourmaline, 3 - 5 parts of nano-titanium dioxide, and 13 - 18 parts of water.
[0007] Preferably, it includes the following raw materials in parts by weight: 85 parts of reduced iron powder, 3 parts of sodium chloride, 30 parts of modified nano-zeolite powder, 5 parts of sodium sulfite, 15 parts of modified polyethylene glycol, 10 parts of modified nano-tourmaline, 4 parts of nano-titanium dioxide, and 15 parts of water.
[0008] Preferably, the preparation method of the modified nano-zeolite powder is as follows: By weight, take 40-50 parts of zeolite, roast it at 400-500 °C for 3-5 h, and then grind it to obtain nano-zeolite powder. Add a hydrochloric acid solution with a weight 8-12 times that of the nano-zeolite powder and a concentration of 20-30%, soak it for 1-2 h while stirring, filter and wash it 2-3 times. Mix it with 2-6 parts of activated carbon and soak it in an ethanol solution of 3-aminopropyltriethoxysilane with a weight 10-15 times that of the mixture and a concentration of 10-30%. Heat it to 60-80 °C, filter and wash it 2-3 times after reacting for 1-2 h to obtain an intermediate. Spread the intermediate evenly in a microwave container, and place it in a microwave device for treatment for 10-30 min to obtain the modified nano-zeolite powder. By roasting, the water in different states in the structure is removed, making the internal structure loose and porous, increasing the specific surface area. Then, surface corrosion modification is carried out with hydrochloric acid to form a stable porous structure on the surface. Through the treatment of 3-aminopropyltriethoxysilane, various hydrophilic groups are introduced on the zeolite surface, enhancing its water adsorption capacity, promoting the reaction of oxygen and reducing substances at low temperatures. Microwave treatment heats the zeolite through electromagnetic waves, changes its surface properties and microstructure, and improves its activity.
[0009] Preferably, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 10-15%. Add succinic anhydride with a mass of 5-10% of the PEG solution, and stir and react at 60-80 °C for 2-3 h. After the reaction, precipitate and wash the product with ethanol, and dry it under vacuum to obtain the modified polyethylene glycol.
[0010] Through carboxylation modification, polyethylene glycol has higher hydrophilicity and reactivity, adjusts the humidity of the environment around the deoxidizer, promotes the deoxidation reaction at low temperatures, synergistically acts with other components to enhance the reactivity of the deoxidizer, can prevent the aggregation of nano-iron particles, improve its dispersibility and reactivity, and can also coat the nano-iron particles, control its reaction rate, and extend the action time of the deoxidizer.
[0011] Preferably, the preparation method of the modified nano-tourmaline is as follows: By weight, take 20-25 parts of tourmaline, put the tourmaline into a ball mill and grind it for 40-60 min. Then soak the tourmaline powder in a hydrochloric acid solution with a weight 6-10 times that of the tourmaline powder and a concentration of 5-15%, stir it at 60-80 °C for 50-60 min, filter and wash it. Disperse the tourmaline powder in 10-20 parts of water, add 1-3 parts of sodium dodecyl sulfate and 1-2 parts of nano-activated carbon powder, mix them evenly and transfer them to a high-pressure reaction kettle, and carry out hydrothermal reaction at 150-180 °C for 12-24 h. Filter, wash and dry to obtain the product.
[0012] Surface corrosion modification is carried out with hydrochloric acid to form a stable porous structure on the surface of tourmaline. Modification with sodium dodecyl sulfate increases its specific surface area and surface activity, thereby improving the adsorption capacity and reaction efficiency. By adding nano-activated carbon powder, the high specific surface area of activated carbon and the far-infrared radiation characteristics of tourmaline are utilized to synergistically improve the deoxidation effect. The modified nano-tourmaline has a permanent electrode polarity, can generate a microelectric field, release negative ions, improve the oxygen distribution in the environment, and emit far-infrared rays to promote molecular vibration and chemical reactions.
[0013] Preferably, the preparation method of the modified nano-tourmaline further includes: evenly spreading the product on a tray; placing the tray in a plasma treatment chamber, starting the plasma generator, and treating for 5 - 10 min to obtain the modified nano-tourmaline. The power of the plasma generator is 100 - 200 W, and the gas atmosphere is air or inert gas.
[0014] Plasma treatment uses high-energy particles (such as electrons, ions) to bombard the surface of the product, change its surface chemical properties and microstructure, improve the reaction activity, introduce active groups (such as hydroxyl groups, carboxyl groups) on the surface, enhance its adsorption capacity for oxygen and moisture, and improve the deoxidation effect.
[0015] The present invention also provides a preparation method of the above-mentioned high-efficiency deoxidizer applicable to low-temperature environments, including the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir and mix evenly; Next, add modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide, stir and mix evenly to obtain a mixture, and package it in a breathable packaging material to obtain the deoxidizer.
[0016] Preferably, before packaging into the packaging bag, evenly spread the mixture on a conductive tray with a spreading thickness of 1 - 5 mm, place the conductive tray between the two poles of an electric field generator, and apply an electric field treatment for 5 - 10 min; specifically, use a DC or pulsed electric field generator with a voltage range of 1 - 10 kV and an electric field intensity of 1 - 10 kV / cm.
[0017] Through the electric field treatment, the surface charge density of the deoxidizer particles is increased, promoting the contact and reaction between oxygen and the deoxidizer, accelerating the electrochemical corrosion reaction of iron powder, improving the oxygen absorption efficiency, regulating the moisture distribution in the deoxidizer, ensuring the humidity conditions required for the reaction, making the deoxidizer particles more evenly dispersed, avoiding caking, increasing the contact area with oxygen, and in a low-temperature environment, the electric field treatment can overcome the limitation of a relatively high reaction activation energy and improve the reaction rate of the deoxidizer.
[0018] Compared with the prior art, the embodiments of the present application mainly have the following beneficial effects: The high-efficiency deoxidizer applicable to low-temperature environments provided by the present invention enhances the adsorption capacity of zeolite for moisture and oxygen by adding modified nano-zeolite powder, thereby enhancing the reaction activity of the deoxidizer in low-temperature environments. By adding modified polyethylene glycol, it has higher hydrophilicity and reaction activity, adjusts the humidity of the environment around the deoxidizer, promotes the deoxidation reaction at low temperatures, and synergistically enhances the reaction activity of the deoxidizer with other components. It can prevent the aggregation of nano-iron particles, improve their dispersibility and reaction activity, and can also coat the nano-iron particles, control their reaction rate, and extend the action time of the deoxidizer. By adding modified nano-tourmaline, it has a permanent electrode polarity, can generate a microelectric field, can release negative ions, improve the oxygen distribution in the environment, can emit far-infrared rays, promote molecular vibration and chemical reactions, and improve the deoxidation effect. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 is a flowchart of a preparation method of a high-efficiency deoxidizer applicable to low-temperature environments provided by the present invention; Figure 2 is another flowchart of a preparation method of a high-efficiency deoxidizer applicable to low-temperature environments provided by the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this application belongs; the terms used in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above drawings are intended to cover non-exclusive inclusion. The terms "first", "second", etc. in the specification and claims of this application or the above drawings are used to distinguish different objects and not to describe a specific order.
[0021] Reference to "embodiment" herein means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of this application. The phrase appears in various places in the specification and does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.
[0022] Embodiment 1 The embodiments of the present invention provide a high-efficiency deoxidizer applicable to low-temperature environments, as Figure 1As shown, it includes the following raw materials by weight: 70 parts of reduced iron powder, 1 part of sodium chloride, 25 parts of modified nano-zeolite powder, 2 parts of sodium sulfite, 10 parts of modified polyethylene glycol, 5 parts of modified nano-tourmaline, 2 parts of nano-titanium dioxide, and 10 parts of water. The preparation method of the high-efficiency deoxidizer applicable to low-temperature environments includes the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir and mix evenly; Next, add modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide, stir and mix evenly to obtain a mixture, and sub-pack it with a breathable packaging material to obtain a deoxidizer.
[0023] Among them, the preparation method of the modified nano-zeolite powder is as follows: By weight, take 40 parts of zeolite, place it in a roasting furnace at 400 °C for 3 h, then grind it to obtain nano-zeolite powder, add a hydrochloric acid solution with a concentration of 20% and a weight 8 times that of the nano-zeolite powder, soak it while stirring for 1 h, filter and wash it 2 times, mix it with 2 parts of activated carbon and soak it in an ethanol solution of 3-aminopropyltriethoxysilane with a weight 10 times that of the mixture and a concentration of 10%, heat it to 60 °C, filter and wash it 2 times after reacting for 1 h to obtain an intermediate product, spread the intermediate product evenly in a microwave container, put it into a microwave device and process it for 10 min to obtain the modified nano-zeolite powder.
[0024] In this embodiment, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 10%, add succinic anhydride with a mass of 5% of the PEG solution, stir and react at 60 °C for 2 h. After the reaction, precipitate and wash the product with ethanol, and dry it under vacuum to obtain the modified polyethylene glycol.
[0025] In a specific implementation, the preparation method of the modified nano-tourmaline is as follows: By weight, take 20 parts of tourmaline, put the tourmaline into a ball mill and grind it for 40 min. Then soak the tourmaline powder in a hydrochloric acid solution with a weight 6 times that of the powder and a concentration of 5%, stir at 60 °C for 50 min, filter and wash it, disperse the tourmaline powder in 10 parts of water, add 1 part of sodium dodecyl sulfate and 1 part of nano-activated carbon powder, mix evenly and transfer it to a high-pressure reaction kettle, carry out hydrothermal reaction at 150 °C for 12 h, filter, wash and dry to obtain a product; spread the product evenly on a tray; put the tray into a plasma treatment chamber, start the plasma generator, and process it for 5 min to obtain the modified nano-tourmaline. The power of the plasma generator is 100 W, and the gas atmosphere is air or inert gas.
[0026] Example 2 The embodiment of the present invention provides a high-efficiency deoxidizer applicable to low-temperature environments, such asFigure 1 As shown, it includes the following raw materials in parts by weight: 75 parts of reduced iron powder, 2 parts of sodium chloride, 28 parts of modified nano-zeolite powder, 3 parts of sodium sulfite, 12 parts of modified polyethylene glycol, 8 parts of modified nano-tourmaline, 3 parts of nano-titanium dioxide, and 13 parts of water. The preparation method of the high-efficiency deoxidizer applicable to low-temperature environments includes the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir and mix evenly; Next, add modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide, stir and mix evenly to obtain a mixture, and sub-pack it with a breathable packaging material to obtain a deoxidizer.
[0027] Among them, the preparation method of the modified nano-zeolite powder is as follows: By weight, take 40 parts of zeolite, place it in a roasting furnace at 400 °C for 3 h, then grind it to obtain nano-zeolite powder, add a hydrochloric acid solution with a concentration of 20% and a weight 8 times that of the nano-zeolite powder, soak it while stirring for 1 h, filter and wash it 2 times, mix it with 2 parts of activated carbon and soak it in an ethanol solution of 3-aminopropyltriethoxysilane with a concentration of 10% and a weight 10 times that of the mixture, heat it to 60 °C, filter and wash it 2 times after reacting for 1 h to obtain an intermediate, evenly spread the intermediate in a microwave container, and place it in a microwave device for 10 min to obtain modified nano-zeolite powder.
[0028] In this embodiment, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 10%, add succinic anhydride with a mass of 5% of the PEG solution, stir and react at 60 °C for 2 h. After the reaction, precipitate and wash the product with ethanol, and dry it under vacuum to obtain modified polyethylene glycol.
[0029] In a specific implementation, the preparation method of the modified nano-tourmaline is as follows: By weight, take 20 parts of tourmaline, put the tourmaline into a ball mill and grind it for 40 min. Then soak the tourmaline powder in a hydrochloric acid solution with a concentration of 5% and a weight 6 times that of the tourmaline powder, stir at 60 °C for 50 min, filter and wash it, disperse the tourmaline powder in 10 parts of water, add 1 part of sodium dodecyl sulfate and 1 part of nano-activated carbon powder, mix evenly and transfer it to a high-pressure reaction kettle, carry out hydrothermal reaction at 150 °C for 12 h, filter, wash and dry to obtain a product; evenly spread the product on a tray; place the tray in a plasma treatment chamber, start the plasma generator, and treat it for 5 min to obtain modified nano-tourmaline. The power of the plasma generator is 100 W, and the gas atmosphere is air or inert gas.
[0030] Example 3 An embodiment of the present invention provides an efficient deoxidizer suitable for low-temperature environments, such as Figure 1 shown, comprising the following raw materials by weight: 85 parts of reduced iron powder, 3 parts of sodium chloride, 30 parts of modified nanozeolite powder, 5 parts of sodium sulfite, 15 parts of modified polyethylene glycol, 10 parts of modified nano-tourmaline, 4 parts of nano-titanium dioxide, and 15 parts of water. The preparation method of the efficient deoxidizer suitable for low-temperature environments includes the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir and mix evenly; Next, add modified nanozeolite powder, modified nano-tourmaline and nano-titanium dioxide, stir and mix evenly to obtain a mixture, and sub-pack it with a breathable packaging material to obtain a deoxidizer.
[0031] Among them, the preparation method of the modified nanozeolite powder is as follows: By weight, take 45 parts of zeolite, place it in a roasting furnace at 450 °C for 4 h, and then grind it to obtain nanozeolite powder. Add a hydrochloric acid solution with a concentration of 25% and a weight 10 times that of the nanozeolite powder, soak it while stirring for 1.5 h, filter and wash it 2 times, mix it with 4 parts of activated carbon, and soak it in an ethanol solution of 3-aminopropyltriethoxysilane with a concentration of 20% and a weight 12 times that of the mixture. Heat it to 70 °C, filter and wash it 3 times after reacting for 1.5 h to obtain an intermediate product. Spread the intermediate product evenly in a microwave container, put it into a microwave device and process it for 20 min to obtain the modified nanozeolite powder.
[0032] In this embodiment, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 13%. Add succinic anhydride with a mass of 8% of the PEG solution, stir and react at 70 °C for 2.5 h. After the reaction, precipitate and wash the product with ethanol, and dry it under vacuum to obtain the modified polyethylene glycol.
[0033] In a specific implementation, the preparation method of the modified nano-tourmaline is as follows: By weight, take 22.5 parts of tourmaline, put the tourmaline into a ball mill and grind it for 50 min. Then soak the tourmaline powder in a hydrochloric acid solution with a concentration of 10% and a weight 8 times that of the tourmaline powder, stir at 70 °C for 55 min, filter and wash it. Disperse the tourmaline powder in 15 parts of water, add 2 parts of sodium dodecyl sulfate and 1.5 parts of nano-activated carbon powder, mix evenly and transfer it to a high-pressure reaction kettle, and carry out hydrothermal reaction at 165 °C for 18 h. Filter, wash and dry to obtain a product; Spread the product evenly on a tray; Put the tray into a plasma treatment chamber, start the plasma generator, and process it for 8 min to obtain the modified nano-tourmaline. The power of the plasma generator is 150 W, and the gas atmosphere is air or inert gas.
[0034] Example 4 An embodiment of the present invention provides an efficient deoxidizer suitable for low-temperature environments, such as Figure 1 shown, including the following raw materials by weight: 95 parts of reduced iron powder, 4 parts of sodium chloride, 32 parts of modified nano-zeolite powder, 7 parts of sodium sulfite, 18 parts of modified polyethylene glycol, 13 parts of modified nano-tourmaline, 5 parts of nano-titanium dioxide, and 18 parts of water. The preparation method of the efficient deoxidizer suitable for low-temperature environments includes the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir to mix evenly; Next, add modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide, stir and mix evenly to obtain a mixture, and sub-pack it with a breathable packaging material to obtain a deoxidizer.
[0035] Among them, the preparation method of the modified nano-zeolite powder is as follows: By weight, take 50 parts of zeolite, place it in a 500°C oven and roast for 5 hours, then grind to obtain nano-zeolite powder. Add a hydrochloric acid solution with a concentration of 30% and a weight 12 times that of the nano-zeolite powder, stir and soak for 2 hours, filter and wash 3 times, mix with 6 parts of activated carbon, and soak in an ethanol solution of 3-aminopropyltriethoxysilane with a concentration of 30% and a weight 15 times that of the mixture. Heat to 80°C, filter and wash 3 times after reacting for 2 hours to obtain an intermediate. Spread the intermediate evenly in a microwave container, place it in a microwave device and process for 30 minutes to obtain the modified nano-zeolite powder.
[0036] In this embodiment, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 15%. Add succinic anhydride with a mass of 10% of the PEG solution, stir and react at 80°C for 3 hours. After the reaction, precipitate and wash the product with ethanol, and dry it under vacuum to obtain the modified polyethylene glycol.
[0037] In a specific implementation, the preparation method of the modified nano-tourmaline is as follows: By weight, take 25 parts of tourmaline, put the tourmaline into a ball mill and grind for 60 minutes. Then soak the tourmaline powder in a hydrochloric acid solution with a concentration of 15% and a weight 10 times that of the tourmaline powder, stir at 80°C for 60 minutes, filter and wash. Disperse the tourmaline powder in 20 parts of water, add 3 parts of sodium dodecyl sulfate and 2 parts of nano-activated carbon powder, mix evenly and transfer to a high-pressure reaction kettle, carry out hydrothermal reaction at 180°C for 24 hours, filter, wash and dry to obtain a product; spread the product evenly on a tray; place the tray in a plasma treatment chamber, start the plasma generator, and process for 10 minutes to obtain the modified nano-tourmaline. The power of the plasma generator is 200W, and the gas atmosphere is air or inert gas.
[0038] Example 5 The embodiment of the present invention provides an efficient deoxidizer suitable for low-temperature environments, such as Figure 1 shown, including the following raw materials in parts by weight: 100 parts of reduced iron powder, 5 parts of sodium chloride, 35 parts of modified nano-zeolite powder, 8 parts of sodium sulfite, 20 parts of modified polyethylene glycol, 15 parts of modified nano-tourmaline, 6 parts of nano-titanium dioxide, and 20 parts of water. The preparation method of the efficient deoxidizer suitable for low-temperature environments includes the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir to mix evenly; Next, add modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide, stir and mix evenly to obtain a mixture, and sub-pack it with a breathable packaging material to obtain a deoxidizer.
[0039] Among them, the preparation method of the modified nano-zeolite powder is as follows: By weight, take 50 parts of zeolite, calcine it at 500 °C for 5 h, and then grind it to obtain nano-zeolite powder. Add a hydrochloric acid solution with a concentration of 30% and a weight 12 times that of the nano-zeolite powder, soak it while stirring for 2 h, filter and wash it 3 times, mix it with 6 parts of activated carbon, and soak it in an ethanol solution of 3-aminopropyltriethoxysilane with a concentration of 30% and a weight 15 times that of the mixture. Heat it to 80 °C, filter and wash it 3 times after reacting for 2 h to obtain an intermediate. Spread the intermediate evenly in a microwave container, put it into a microwave device and process it for 30 min to obtain the modified nano-zeolite powder.
[0040] In this embodiment, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 15%. Add succinic anhydride with a mass of 10% of the PEG solution, stir and react at 80 °C for 3 h. After the reaction, precipitate and wash the product with ethanol, and dry it under vacuum to obtain the modified polyethylene glycol.
[0041] In a specific implementation, the preparation method of the modified nano-tourmaline is as follows: By weight, take 25 parts of tourmaline, put the tourmaline into a ball mill, grind it for 60 min, then soak the tourmaline powder in a hydrochloric acid solution with a weight 10 times and a concentration of 15%, stir at 80 °C for 60 min, filter and wash, then disperse the tourmaline powder in 20 parts of water, add 3 parts of sodium dodecyl sulfate and 2 parts of nano-activated carbon powder, transfer the mixture to a high-pressure reactor after mixing evenly, carry out hydrothermal reaction at 180 °C for 24 h, filter, wash and dry to obtain the product; spread the product evenly on a tray; put the tray into a plasma treatment chamber, start the plasma generator, treat for 10 min to obtain the modified nano-tourmaline, the power of the plasma generator is 200 W, and the gas atmosphere is air or inert gas.
[0042] Example 6 The embodiment of the present invention provides an efficient deoxidizer applicable to low-temperature environments, such as Figure 2 shown, including the following raw materials by weight: 85 parts of reduced iron powder, 3 parts of sodium chloride, 30 parts of modified nano-zeolite powder, 5 parts of sodium sulfite, 15 parts of modified polyethylene glycol, 10 parts of modified nano-tourmaline, 4 parts of nano-titanium dioxide, and 15 parts of water. The preparation method of the efficient deoxidizer applicable to low-temperature environments includes the following steps: Prepare each raw material according to the ratio; Add sodium chloride and sodium sulfite to water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, and stir and mix evenly; Next, add modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide, and stir and mix evenly to obtain a mixture; Spread the mixture evenly on a conductive tray with a spreading thickness of 1 - 5 mm, place the conductive tray between the two poles of an electric field generator, and apply an electric field treatment for 5 - 10 min; specifically, use a DC or pulsed electric field generator, the voltage range is 1 - 10 kV, the electric field strength is 1 - 10 kV / cm, and it is packaged with a breathable packaging material to obtain the deoxidizer.
[0043] Among them, the preparation method of the modified nano-zeolite powder is as follows: By weight, take 45 parts of zeolite, calcine it at 450 °C for 4 h, then grind it to obtain nano-zeolite powder, add a hydrochloric acid solution with a weight 10 times and a concentration of 25% of the nano-zeolite powder, soak while stirring for 1.5 h, filter and wash 2 times, mix with 4 parts of activated carbon and soak in an ethanol solution of 3-aminopropyltriethoxysilane with a weight 12 times and a concentration of 20%, heat to 70 °C, filter and wash 3 times after reacting for 1.5 h to obtain an intermediate, spread the intermediate evenly in a microwave container, and put it into a microwave device for treatment for 20 min to obtain the modified nano-zeolite powder.
[0044] In this embodiment, the preparation method of the modified polyethylene glycol is as follows: Dissolve PEG in deionized water to prepare a PEG solution with a concentration of 13%. Add succinic anhydride accounting for 8% of the mass of the PEG solution, and stir and react at 70°C for 2.5 h. After the reaction, precipitate and wash the product with ethanol, and then dry it under vacuum to obtain the modified polyethylene glycol.
[0045] In a specific implementation, the preparation method of the modified tourmaline nanoparticles is as follows: By weight, take 22.5 parts of tourmaline, put the tourmaline into a ball mill and grind it for 50 min. Then soak the tourmaline powder in a hydrochloric acid solution with a concentration of 10% and 8 times the weight, stir at 70°C for 55 min, filter and wash, and then disperse the tourmaline powder in 15 parts of water. Add 2 parts of sodium dodecyl sulfate and 1.5 parts of nano-activated carbon powder, mix evenly and transfer to a high-pressure reaction kettle, carry out hydrothermal reaction at 165°C for 18 h, filter, wash and dry to obtain the product; spread the product evenly on a tray; put the tray into a plasma treatment chamber, start the plasma generator, and treat for 8 min to obtain the modified tourmaline nanoparticles. The power of the plasma generator is 150 W, and the gas atmosphere is air or inert gas.
[0046] Comparative Example 1: Compared with Example 3, the modified nano-zeolite powder is replaced with ordinary nano-zeolite powder.
[0047] Comparative Example 2: Compared with Example 3, the modified tourmaline nanoparticles are replaced with ordinary tourmaline nanoparticles.
[0048] Comparative Example 3: Compared with Example 3, the modified polyethylene glycol is replaced with ordinary polyethylene glycol.
[0049] Comparative Example 4: Compared with Example 3, the modified nano-zeolite powder is replaced with ordinary nano-zeolite powder, the modified tourmaline nanoparticles are replaced with ordinary tourmaline nanoparticles, and the modified polyethylene glycol is replaced with ordinary polyethylene glycol.
[0050] Comparative Example 5: A commercially available iron-based deoxidizer.
[0051] Performance Test Put the deoxidizers prepared in Examples 1-6 and Comparative Examples 1-5 into a gas-barrier bag made of polyethylene laminated film, fill it with 2000 ml of a mixed gas with a humidity of 50% (oxygen accounts for 95% and air accounts for 5%), and then seal it. Keep the bag at a low temperature of 1°C (refrigerated), measure the oxygen absorption amount after 1 day, 3 days and 5 days. The dosage of the deoxidizer is 10 g, and the oxygen absorption amount is measured by the method of "SBT10514-2008 Food Deoxidizer". The test results are shown in Table 1 below: Table 1 Oxygen Absorption Test Results As can be seen from the above results, the deoxidizer prepared by the present invention has excellent deoxidation effect at low temperature. In particular, by adding modified nano zeolite powder, modified nano tourmaline and modified polyethylene glycol, the three have a synergistic effect and can further improve the low-temperature deoxidation effect.
[0052] It should be noted that for the foregoing embodiments, for the sake of simple description, they are all expressed as a series of action combinations. However, those skilled in the art should know that the present invention is not limited by the described action sequence, because according to the present invention, certain steps may be performed in other sequences or simultaneously. Secondly, those skilled in the art should also know that the embodiments described in the specification are all preferred embodiments, and the actions and modules involved are not necessarily essential to the present invention.
[0053] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting the protection scope of the invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all embodiments. Based on these embodiments, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of the present invention to be protected. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art can still, without conflict, make combinations, additions, deletions or other adjustments to the features in the embodiments of the present invention according to the situation without creative efforts, so as to obtain different technical solutions that essentially do not deviate from the concept of the present invention, and these technical solutions also fall within the scope of the present invention to be protected.
Claims
1. A high-efficiency deoxidizer suitable for use in low-temperature environments, characterized in that: The invention comprises the following raw materials in parts by weight: 70-100 parts of reduced iron powder, 1-5 parts of sodium chloride, 25-35 parts of modified nano zeolite powder, 2-8 parts of sodium sulfite, 10-20 parts of modified polyethylene glycol, 5-15 parts of modified nano tourmaline, 2-6 parts of nano titanium dioxide and 10-20 parts of water.
2. The high-efficiency deoxidizer suitable for use in low-temperature environments according to claim 1, characterized in that: The invention comprises the following raw materials in parts by weight: 75-95 parts of reduced iron powder, 2-4 parts of sodium chloride, 28-32 parts of modified nano zeolite powder, 3-7 parts of sodium sulfite, 12-18 parts of modified polyethylene glycol, 8-13 parts of modified nano tourmaline, 3-5 parts of nano titanium dioxide and 13-18 parts of water.
3. The high-efficiency deoxidizer suitable for use in low-temperature environments as claimed in claim 2, characterized in that: The invention comprises the following raw materials in parts by weight: 85 parts of reduced iron powder, 3 parts of sodium chloride, 30 parts of modified nano zeolite powder, 5 parts of sodium sulfite, 15 parts of modified polyethylene glycol, 10 parts of modified nano tourmaline, 4 parts of nano titanium dioxide and 15 parts of water.
4. The high-efficiency deoxidizer suitable for use in low-temperature environments as claimed in claim 1, characterized in that: 40-50 parts of zeolite are taken by weight, calcined at 400-500°C for 3-5h, and then ground to obtain nano zeolite powder, and a hydrochloric acid solution with a concentration of 20-30% and 8-12 times of the weight of the nano zeolite powder is added, and the mixture is immersed for 1-2h while stirring, filtered and washed 2-3 times, mixed with 2-6 parts of activated carbon, and then immersed in an ethanol solution of 3-aminopropyltriethoxysilane with a concentration of 10-15 times and 10-30%, heated to 60-80°C, reacted for 1-2h, filtered, washed 2-3 times to obtain an intermediate, and the intermediate is evenly spread in a microwave container, and placed in a microwave device for treatment for 10-30min to obtain a modified nano zeolite powder.
5. The high-efficiency deoxidizer suitable for use in low-temperature environments as claimed in claim 1, characterized in that: The preparation method of the modified polyethylene glycol is as follows: PEG is dissolved in deionized water to prepare a PEG solution with a concentration of 10-15%, succinic anhydride is added at 5-10% of the mass of the PEG solution, and the mixture is stirred at 60-80° C. for 2-3 hours. After the reaction is completed, the product is precipitated and washed with ethanol, and vacuum dried to obtain the modified polyethylene glycol.
6. The high-efficiency deoxidizer suitable for use in low-temperature environments according to claim 1, characterized in that: The preparation method of the modified nano tourmaline is as follows: taking 20-25 parts of tourmaline by weight, putting the tourmaline into a ball mill, grinding for 40-60 minutes, then soaking the tourmaline powder in a hydrochloric acid solution with a concentration of 5-15% and a weight of 6-10 times, stirring for 50-60 minutes at 60-80° C., filtering and washing, dispersing the tourmaline powder in 10-20 parts of water, adding 1-3 parts of sodium dodecyl sulfate and 1-2 parts of nano activated carbon powder, mixing evenly, transferring to a high-pressure reactor, hydrothermally reacting at 150-180° C. for 12-24 hours, filtering, washing and drying to obtain the product.
7. The high-efficiency deoxidizer suitable for use in low-temperature environments as claimed in claim 6, characterized in that: The preparation method of the modified nano-tourmaline also includes: evenly spreading the product on a tray; placing the tray into a plasma treatment chamber, starting a plasma generator, and treating for 5-10 minutes to obtain the modified nano-tourmaline, wherein the power of the plasma generator is 100-200W, and the gas atmosphere is air or inert gas.
8. The method for preparing a high-efficiency deoxidizer suitable for use in a low-temperature environment according to any one of claims 1 to 7, characterized in that: The steps include: Prepare the raw materials according to the ratio; Add sodium chloride and sodium sulfite into water, mix and stir to dissolve; Then add reduced iron powder and modified polyethylene glycol, stir and mix evenly; Then, modified nano-zeolite powder, modified nano-tourmaline and nano-titanium dioxide are added, stirred and mixed to obtain a mixed product, which is packaged with air-permeable packaging materials to obtain a deoxidizer.
9. The method for preparing a high-efficiency deoxidizer suitable for use in a low-temperature environment according to claim 8, characterized in that: Before being divided into packaging bags, the mixture is evenly spread on a conductive tray with a thickness of 1-5 mm. The conductive tray is placed between the two poles of an electric field generator and an electric field treatment is applied for 5-10 minutes.