CN114601099B - High-reliability deoxidizer and preparation method thereof - Google Patents
High-reliability deoxidizer and preparation method thereof Download PDFInfo
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- CN114601099B CN114601099B CN202210329930.6A CN202210329930A CN114601099B CN 114601099 B CN114601099 B CN 114601099B CN 202210329930 A CN202210329930 A CN 202210329930A CN 114601099 B CN114601099 B CN 114601099B
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 91
- 239000010439 graphite Substances 0.000 claims abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 86
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 74
- 239000001110 calcium chloride Substances 0.000 claims abstract description 74
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000003792 electrolyte Substances 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002250 absorbent Substances 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004806 packaging method and process Methods 0.000 claims abstract description 12
- 238000009830 intercalation Methods 0.000 claims abstract description 11
- 230000002687 intercalation Effects 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 12
- 230000002745 absorbent Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 235000011850 desserts Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013332 fish product Nutrition 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 235000013606 potato chips Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
- A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
- A23L3/3436—Oxygen absorbent
Abstract
The application discloses a high-reliability deoxidizer, which comprises the following components: the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin are prepared by the following components in percentage by mass: 30-60:10-20:2-8; the carbon-coated calcium chloride composite graphite is obtained by intercalation of acidified graphite with calcium chloride, thermal expansion and coating of a carbon layer on the surface of the product; the electrolyte composite water-absorbent resin is obtained by mixing electrolyte aqueous solution with water-absorbent resin. The application discloses a preparation method of the high-reliability deoxidizer, which comprises the steps of adding reduced iron powder into carbon-coated calcium chloride composite graphite, sealing and mixing, adding silicon dioxide and electrolyte composite water-absorbing resin, uniformly stirring, sieving, packaging and vacuumizing to obtain the high-reliability deoxidizer.
Description
Technical Field
The application relates to the technical field of deoxidizers, in particular to a high-reliability deoxidizer and a preparation method thereof.
Background
Deoxidizing agent, also called free oxygen absorber, free oxygen remover or deoxidizing agent, etc. It is a class of substances that can absorb free oxygen. When the deoxidizer is sealed in the same package together with the food, the deoxidizer can absorb free oxygen in the package and dissolved oxygen in the food through a certain chemical reaction or other actions, so that the damage to the food due to oxidation, microorganism growth and pests can be prevented. Effectively maintains the color, fragrance and taste of food, prevents the oxidation and destruction of nutrients such as vitamins, prolongs the shelf life of food, etc. The deoxidizer is used for storing foods, is convenient to use, low in price and reliable in storage, solves the problem of long-term storage of a plurality of foods, and ensures that various foods are hardly limited by seasons, thereby radically changing the food industry.
In recent years, along with the development of the food industry and the improvement of packaging materials, deoxidizers are increasingly valued in China, and the application is also becoming wider. Deoxidizing agents have been widely used in various foods such as wet bread flour, wet noodles, wet vermicelli, wet desserts, and semi-dry fish products. Recently, there have been expanded fields such as foods containing high moisture and distributed foods having short shelf lives and medical and health foods having long shelf lives, in which it has been difficult to use deoxidizers before.
With the intensive research and popularization of use of deoxidizers and successful application in the food industry, more and more deoxidizers will be developed and put into wider use. However, in the use process of the existing deoxidizer for food, the reaction rate is low, and the deoxidizing reaction rate is low; in addition, most of the existing deoxidizers for food have poor water retention performance, and moisture carried by the deoxidizers in the use process easily causes food moisture regain, so that the storage effect of the food is affected.
Disclosure of Invention
The application aims to solve the defects in the prior art and provides a high-reliability deoxidizer and a preparation method thereof.
A high reliability deoxidizer comprising: the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin are prepared by the following components in percentage by mass: 30-60:10-20:2-8; the carbon-coated calcium chloride composite graphite is obtained by intercalation of acidified graphite with calcium chloride, thermal expansion and coating of a carbon layer on the surface of the product; the electrolyte composite water-absorbent resin is obtained by mixing electrolyte aqueous solution with water-absorbent resin.
Preferably, the electrolyte is at least one of sodium chloride, calcium nitrate, ferrous sulfate, ammonium acetate.
Preferably, the electrolyte comprises sodium chloride and calcium chloride according to a mass ratio of 10: 1-5.
The electrolyte is defined as the mixture of sodium chloride and calcium chloride, and the proportion of the electrolyte is controlled, so that the three-phase balance point of water is changed, the humidity is maintained at a lower level, the water activity of the food is lower than that of the food, the water is not transferred out, and the stable operation of the deoxidizing process is further ensured.
Preferably, the water absorbent resin is a polyacrylic acid-based high molecular water absorbent resin and/or a polyacrylamide-based water absorbent resin.
Preferably, the mass ratio of the electrolyte to the water absorbing resin is 1-3:5-15:1-5.
Preferably, the carbon-coated calcium chloride composite graphite is prepared by the following specific steps: intercalation treatment of acidified graphite by calcium chloride, thermal expansion at 600-700 ℃ for 30-60s, crushing, adding water, adding glucose and ethylenediamine into the mixture under stirring, uniformly stirring, carrying out hydrothermal reaction at 200-220 ℃ for 4-6h, filtering, drying, calcining at 300-400 ℃ for 10-20min in nitrogen atmosphere, and cooling to room temperature to obtain the carbon-coated calcium chloride composite graphite.
Preferably, the mass ratio of the calcium nitrate, the acidified graphite, the glucose and the ethylenediamine is 1-5:10-20:1-5:0.1-1.
Preferably, the above acidified graphite is prepared by the following process: uniformly mixing 40-60% of nitric acid and 70-80% of phosphoric acid, adding flake graphite, stirring, adding potassium permanganate, stirring at 40-60 ℃ for 1-2h, washing with water, filtering, and drying to obtain acidified graphite.
Preferably, the mass ratio of nitric acid, phosphoric acid, potassium permanganate and crystalline flake graphite is 5-10:10-20:5-15:1-4.
According to the preparation method of the high-reliability deoxidizer, the reducing iron powder is added into the carbon-coated calcium chloride composite graphite for sealing and mixing, then the silicon dioxide and the electrolyte composite water-absorbing resin are added for stirring uniformly, sieving is carried out, and vacuum pumping is carried out after packaging, so that the high-reliability deoxidizer is obtained.
The technical effects of the application are as follows:
the application adopts nitric acid and phosphoric acid to compound and acidify the crystalline flake graphite, which not only can effectively and synergistically improve the oxidation effect of potassium permanganate, but also can promote calcium chloride to enter the lamellar structure of crystalline flake graphite more fully by adopting calcium chloride and co-intercalation. And then the flake graphite lamellar structure is opened through thermal expansion, the expansion rate can reach 250ml/g, and the calcium chloride nano particles are uniformly dispersed in the lamellar structure, so that the dispersion uniformity is extremely high.
According to the application, a layer of carbon structure is further coated on the surface of the expanded graphite powder under the cooperation of ethylenediamine, wherein the ethylenediamine promotes generated carbon to be positively charged and is electrostatically combined with a large amount of oxygen-containing functional groups on the surface of the expanded graphite powder, so that the porous carbon layer structure is promoted to be coated on the surface of the expanded graphite powder; because the surface of the carbon-coated calcium chloride composite graphite contains a large number of oxygen-containing functional groups, the carbon-coated calcium chloride composite graphite has strong adsorption capacity on the reductive iron powder, and can realize high loading of the reductive iron powder by matching with a large number of lamellar structures in the carbon-coated calcium chloride composite graphite.
The application utilizes the lamellar structure of the internal load calcium chloride of the carbon-coated calcium chloride composite graphite and the porous carbon structure on the surface to promote the uniform distribution of the reductive iron powder therein, so that the oxidative reaction of the reductive iron powder is more sufficient and uniform in the use process, the reductive iron powder is compounded with silicon dioxide, the absorbed oxygen and water are transferred to the reductive iron powder to carry out chemical reaction by virtue of the strong dispersibility and flowability of the silicon dioxide, and meanwhile, the calcium chloride distributed in the reductive iron powder can further adsorb moisture, thereby having comprehensive effect and high deoxidizing speed and effectively maintaining the dry environment in the deoxidizer packaging bag.
According to the application, the electrolyte is dissolved in water, then the water-absorbent resin is added for standing, and then the water transfer is balanced, so that the electrolyte composite water-absorbent resin is obtained, and is matched with the carbon-coated calcium chloride composite graphite, and the water absorption and discharge functions of the electrolyte composite water-absorbent resin are utilized to regulate and control the water in the deoxidizer, so that the reaction speed with oxygen can be effectively controlled.
Drawings
FIG. 1 is a graph showing the comparison of the deoxidizing rates of the deoxidizers obtained in example 5 and comparative examples 1 to 2.
FIG. 2 is a graph showing the comparison of the dehumidification rates of the deoxidizers obtained in example 5 and comparative examples 1 to 2.
FIG. 3 is a graph showing the comparison of the water return rates of the deoxidizers obtained in example 5 and comparative examples 1 to 2.
Detailed Description
The application is further illustrated below in connection with specific embodiments.
Example 1
A high reliability deoxidizer comprising: the mass ratio of the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin is 15:30:10:2.
the carbon-coated calcium chloride composite graphite is prepared by adopting the following specific steps: intercalation treatment is carried out on 10kg of acidified graphite by adopting 1kg of calcium chloride, then the 10kg of acidified graphite is sent into a muffle furnace, thermal expansion is carried out for 30s at 600 ℃, crushing is carried out, 30kg of water is added, 1kg of glucose and 0.1kg of ethylenediamine are added into the mixture under the stirring state, the mixture is stirred uniformly, the mixture is sent into a polytetrafluoroethylene lining hydrothermal kettle, the mixture is subjected to hydrothermal reaction for 4h at 200 ℃, filtration and drying are carried out, then the mixture is added into the muffle furnace, calcination is carried out for 10min at 300 ℃, and cooling is carried out to room temperature, thus obtaining the carbon-coated calcium chloride composite graphite.
The acidified graphite is prepared by the following process: uniformly mixing 5kg of nitric acid with the mass fraction of 40% and 10kg of phosphoric acid with the mass fraction of 70%, adding 5kg of crystalline flake graphite into the mixture, adding 1kg of potassium permanganate into the mixture under stirring, stirring for 1h at 40 ℃, washing with water, filtering and drying to obtain acidified graphite.
The electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 1kg of calcium nitrate is dissolved in 5kg of water, 1kg of polyacrylic acid type high polymer water absorbent resin is added under stirring, and the electrolyte composite water absorbent resin is obtained after even stirring and standing.
The preparation method of the high-reliability deoxidizer comprises the following steps: 30kg of reducing iron powder is added into 15kg of carbon-coated calcium chloride composite graphite, the mixture is sealed and mixed for 10min, then 10kg of silicon dioxide and 2kg of electrolyte composite water-absorbing resin are added, the mixture is stirred uniformly, a 60-mesh sieve is adopted, and the mixture is packaged and vacuumized, so that the high-reliability deoxidizer is obtained.
Example 2
A high reliability deoxidizer comprising: the mass ratio of the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin is 25:60:20:8.
the carbon-coated calcium chloride composite graphite is prepared by adopting the following specific steps: intercalation treatment is carried out on 20kg of acidified graphite by 5kg of calcium chloride, then the acidified graphite is sent into a muffle furnace, thermal expansion is carried out for 60s at 700 ℃, crushing is carried out, 60kg of water is added, 5kg of glucose and 1kg of ethylenediamine are added into the mixture under stirring, stirring is uniform, the mixture is sent into a polytetrafluoroethylene lining hydrothermal kettle, hydrothermal reaction is carried out for 6h at 220 ℃, filtering and drying are carried out, then the mixture is added into the muffle furnace, calcination is carried out for 20min at 400 ℃, and cooling to room temperature is carried out, thus obtaining the carbon-coated calcium chloride composite graphite.
The acidified graphite is prepared by the following process: uniformly mixing 10kg of nitric acid with the mass fraction of 60% and 20kg of phosphoric acid with the mass fraction of 80%, adding 15kg of crystalline flake graphite into the mixture, adding 4kg of potassium permanganate into the mixture under stirring, stirring for 2 hours at 60 ℃, washing with water, filtering and drying to obtain acidified graphite.
The electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 3kg of ammonium acetate is dissolved in 15kg of water, 5kg of polyacrylic acid type high polymer water absorbent resin is added under stirring, and the electrolyte composite water absorbent resin is obtained after even stirring and standing.
The preparation method of the high-reliability deoxidizer comprises the following steps: 60kg of reducing iron powder is added into 25kg of carbon-coated calcium chloride composite graphite, the mixture is sealed and mixed for 15min, then 20kg of silicon dioxide and 8kg of electrolyte composite water-absorbing resin are added, the mixture is stirred uniformly, a 60-mesh sieve is adopted, and the mixture is packaged and vacuumized, so that the high-reliability deoxidizer is obtained.
Example 3
A high reliability deoxidizer comprising: the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin are prepared from the following components in percentage by mass: 50:12:6.
the carbon-coated calcium chloride composite graphite is prepared by adopting the following specific steps: intercalation treatment is carried out on 18kg of acidified graphite by adopting 2kg of calcium chloride, then the mixture is sent into a muffle furnace, thermal expansion is carried out for 50s at 620 ℃, crushing is carried out, 40kg of water is added, 4kg of glucose and 0.3kg of ethylenediamine are added into the mixture under the stirring state, the mixture is stirred uniformly, the mixture is sent into a polytetrafluoroethylene lining hydrothermal kettle, hydrothermal reaction is carried out for 4.5h at 215 ℃, filtration and drying are carried out, then the mixture is added into the muffle furnace, calcination is carried out for 12min at 380 ℃, and cooling is carried out to room temperature, thus obtaining the carbon-coated calcium chloride composite graphite.
The acidified graphite is prepared by the following process: uniformly mixing 8kg of nitric acid with the mass fraction of 45% and 17kg of phosphoric acid with the mass fraction of 73%, adding 12kg of crystalline flake graphite into the mixture, adding 2kg of potassium permanganate into the mixture under stirring, stirring for 1.3 hours at 55 ℃, washing with water, filtering and drying to obtain acidified graphite.
The electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 2.273kg of sodium chloride and 0.227kg of calcium chloride are dissolved in 8kg of water, 4kg of polyacrylamide water-absorbent resin is added under stirring, and the electrolyte composite water-absorbent resin is obtained after uniform stirring and standing.
The preparation method of the high-reliability deoxidizer comprises the following steps: 50kg of reducing iron powder is added into 18kg of carbon-coated calcium chloride composite graphite, the mixture is sealed and mixed for 13min, then 12kg of silicon dioxide and 6kg of electrolyte composite water-absorbing resin are added, the mixture is stirred uniformly, a 60-mesh sieve is adopted, and the mixture is packaged and vacuumized, so that the high-reliability deoxidizer is obtained.
Example 4
A high reliability deoxidizer comprising: the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin are prepared from the following components in percentage by mass: 40:18:4.
the carbon-coated calcium chloride composite graphite is prepared by adopting the following specific steps: intercalation treatment is carried out on 12kg of acidified graphite by 4kg of calcium chloride, then the acidified graphite is sent into a muffle furnace, thermal expansion is carried out for 40s at 680 ℃, crushing is carried out, 50kg of water is added, 2kg of glucose and 0.7kg of ethylenediamine are added into the mixture under the stirring state, the mixture is stirred uniformly, the mixture is sent into a polytetrafluoroethylene lining hydrothermal kettle, the hydrothermal reaction is carried out for 5.5h at 205 ℃, filtration and drying are carried out, then the mixture is added into the muffle furnace, calcination is carried out for 18min at 320 ℃, and cooling is carried out to room temperature, thus obtaining the carbon-coated calcium chloride composite graphite.
The acidified graphite is prepared by the following process: mixing 6kg of 55% nitric acid and 13kg of 77% phosphoric acid evenly, adding 8kg of crystalline flake graphite, adding 3kg of potassium permanganate under stirring, stirring at 45 ℃ for 1.7h, washing with water, filtering, and drying to obtain acidified graphite.
The electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 1kg of sodium chloride and 0.5kg of calcium chloride are dissolved in 12kg of water, 2kg of polyacrylamide water-absorbent resin is added under stirring, and after uniform stirring, the electrolyte composite water-absorbent resin is obtained by standing.
The preparation method of the high-reliability deoxidizer comprises the following steps: adding 40kg of reducing iron powder into 22kg of carbon-coated calcium chloride composite graphite, sealing and mixing for 11min, then adding 18kg of silicon dioxide and 4kg of electrolyte composite water-absorbing resin, uniformly stirring, sieving with a 60-mesh sieve, packaging, and vacuumizing to obtain the high-reliability deoxidizer.
Example 5
A high reliability deoxidizer comprising: the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin are prepared from the following components in percentage by mass: 45:15:5.
the carbon-coated calcium chloride composite graphite is prepared by adopting the following specific steps: intercalation treatment is carried out on 15kg of acidified graphite by 3kg of calcium chloride, then the 15kg of acidified graphite is sent into a muffle furnace, thermal expansion is carried out for 45s at 650 ℃, crushing is carried out, 45kg of water is added, 3kg of glucose and 0.5kg of ethylenediamine are added into the mixture under stirring, the mixture is stirred uniformly, the mixture is sent into a polytetrafluoroethylene lining hydrothermal kettle, hydrothermal reaction is carried out for 5h at 210 ℃, filtration and drying are carried out, then the mixture is added into the muffle furnace, calcination is carried out for 15min at 350 ℃, and cooling is carried out to room temperature, thus obtaining the carbon-coated calcium chloride composite graphite.
The acidified graphite is prepared by the following process: uniformly mixing 7kg of nitric acid with the mass fraction of 50% and 15kg of phosphoric acid with the mass fraction of 75%, adding 10kg of crystalline flake graphite into the mixture, adding 2.5kg of potassium permanganate into the mixture under stirring, stirring for 1.5 hours at 50 ℃, washing with water, filtering and drying to obtain the acidified graphite.
The electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 1.538kg of sodium chloride and 0.462kg of calcium chloride are dissolved in 10kg of water, 3kg of polyacrylamide water-absorbent resin is added under stirring, and the electrolyte composite water-absorbent resin is obtained after uniform stirring and standing.
The preparation method of the high-reliability deoxidizer comprises the following steps: 45kg of reducing iron powder is added into 20kg of carbon-coated calcium chloride composite graphite, the mixture is sealed and mixed for 12min, then 15kg of silicon dioxide and 5kg of electrolyte composite water-absorbing resin are added, the mixture is stirred uniformly, a 60-mesh sieve is adopted, and the mixture is packaged and vacuumized, so that the high-reliability deoxidizer is obtained.
Comparative example 1
A deoxidizer, comprising: the mass ratio of the calcium chloride composite graphite to the reducing iron powder is 20:45:15:5.
the calcium chloride composite graphite is prepared by the following specific steps: 3kg of calcium chloride and 15kg of crystalline flake graphite were mixed to obtain calcium chloride composite graphite.
The electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 1.538kg of sodium chloride and 0.462kg of calcium chloride are dissolved in 10kg of water, 3kg of polyacrylamide water-absorbent resin is added under stirring, and the electrolyte composite water-absorbent resin is obtained after uniform stirring and standing.
The preparation method of the deoxidizer comprises the following steps: 45kg of reducing iron powder is added into 20kg of calcium chloride composite graphite, the mixture is sealed and mixed for 12min, then 15kg of silicon dioxide and 5kg of electrolyte composite water-absorbing resin are added, the mixture is stirred uniformly, a 60-mesh sieve is adopted, and vacuum pumping is carried out after packaging, so as to obtain the deoxidizer.
Comparative example 2
A deoxidizer, comprising: the mass ratio of the expanded graphite, the reductive iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin is 20:45:15:5.
the electrolyte composite water-absorbing resin is prepared by adopting the following specific steps: 1.538kg of sodium chloride and 0.462kg of calcium chloride are dissolved in 10kg of water, 3kg of polyacrylamide water-absorbent resin is added under stirring, and the electrolyte composite water-absorbent resin is obtained after uniform stirring and standing.
The preparation method of the deoxidizer comprises the following steps: 45kg of reduced iron powder is added into 20kg of expanded graphite, the mixture is sealed and mixed for 12min, then 15kg of silicon dioxide and 5kg of electrolyte composite water-absorbing resin are added, the mixture is stirred uniformly, a 60-mesh sieve is adopted, and vacuum pumping is carried out after packaging, so as to obtain the deoxidizer.
The deoxidizers obtained in example 5 and comparative examples 1 to 2 were subjected to comparative tests, specifically as follows:
(1) Deoxygenation rate test
The deoxidizing speed, also called first deoxidizing time, refers to the time (min) required for reducing the oxygen content in the packaging container to be depleted (the oxygen content is below 1 per mill). 1g of each group of samples was put into a 500mL packaging container and then sealed, at this time, the oxygen volume in the packaging container was about 105mL, and the content of the reduced iron powder in 1g of each group of samples was 0.5294g, which theoretically absorbed at most about 177mL of oxygen.
The deoxidation rate was as shown in FIG. 1, and the deoxidation rate was the highest in example 5. The inventors consider that: the application utilizes the lamellar structure of the internal load calcium chloride of the carbon-coated calcium chloride composite graphite and the porous carbon structure on the surface to promote the uniform distribution of the reductive iron powder in the carbon-coated calcium chloride composite graphite, on one hand, the calcium chloride in the carbon-coated calcium chloride composite graphite adsorbs moisture and gathers the moisture around the reductive iron powder, and on the other hand, the moisture in the deoxidizer is regulated and controlled by the water absorption and discharge functions of the electrolyte composite water absorption resin, and on the other hand, the oxygen and the water are transferred to the reductive iron powder for chemical reaction by virtue of the strong dispersibility and flowability of the silicon dioxide, so that the oxidation reaction is more sufficient and uniform, and the deoxidizing speed is effectively improved.
II. Moisture absorption test
Each group of samples was placed in a nitrogen atmosphere at a temperature of 26-28 c and a humidity of 50-60%, weighed every 24 hours until the weight was not increased, and the moisture absorption was calculated as follows:
moisture absorption rate= (post-moisture absorption mass-pre-moisture absorption mass)/pre-moisture absorption mass×100%
As shown in FIG. 2, the moisture absorption rate was the highest in example 5, far exceeding that of the existing commercial deoxidizers (about 28%) and desiccants (about 30%). The inventors considered that; on one hand, the water in the environment is efficiently adsorbed by the internal load calcium chloride of the carbon-coated calcium chloride composite graphite, and on the other hand, the water is regulated in the experimental environment by the water absorption and release functions of the electrolyte composite water absorption resin.
II. Water return test
Filling nitrogen into each group of samples and 50g of potato chips (the moisture content is about 3 percent) for sealing and packaging, taking out 5 bags of sealing and packaging products each day, and respectively placing each group of samples into a drying oven at 105 ℃ for testing the moisture content; the water return rate is calculated as follows:
water return ratio= (sample mass before test-sample mass after test)/sample mass before test×100%
As shown in FIG. 3, the water return rate of example 5 was always low, because the deoxidizer obtained by the present application had a strong water holding capacity, and the moisture was less likely to escape from the oxygen absorbent.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
Claims (6)
1. A high reliability deoxidizer, comprising: the carbon-coated calcium chloride composite graphite, the reducing iron powder, the silicon dioxide and the electrolyte composite water-absorbing resin are prepared by the following components in percentage by mass: 30-60:10-20:2-8;
the carbon-coated calcium chloride composite graphite is obtained by intercalation of acidified graphite with calcium chloride, thermal expansion and coating of a carbon layer on the surface of the product;
the electrolyte composite water-absorbent resin is obtained by mixing an electrolyte aqueous solution with the water-absorbent resin;
the carbon-coated calcium chloride composite graphite is prepared by adopting the following specific steps: intercalation treatment of acidified graphite by calcium chloride, thermal expansion at 600-700 ℃ for 30-60s, crushing, adding water, adding glucose and ethylenediamine into the mixture under stirring, uniformly stirring, carrying out hydrothermal reaction at 200-220 ℃ for 4-6h, filtering, drying, calcining at 300-400 ℃ in nitrogen atmosphere for 10-20min, and cooling to room temperature to obtain carbon-coated calcium chloride composite graphite;
the mass ratio of the calcium chloride to the acidified graphite to the glucose to the ethylenediamine is 1-5:10-20:1-5:0.1-1;
the acidified graphite is prepared by the following process: uniformly mixing 40-60% of nitric acid and 70-80% of phosphoric acid, adding flake graphite into the mixture, adding potassium permanganate into the mixture in a stirring state, stirring the mixture for 1-2h at 40-60 ℃, washing the mixture with water, filtering the mixture, and drying the mixture to obtain acidified graphite;
the mass ratio of nitric acid to phosphoric acid to potassium permanganate to crystalline flake graphite is 5-10:10-20:5-15:1-4.
2. The high-reliability deoxidizer according to claim 1, wherein the electrolyte is at least one of sodium chloride, calcium nitrate, ferrous sulfate, and ammonium acetate.
3. The high-reliability deoxidizer according to claim 1, wherein the electrolyte comprises sodium chloride and calcium chloride in a mass ratio of 10: 1-5.
4. The highly reliable deoxidizer according to claim 1, wherein the water-absorbent resin is a polyacrylic acid-based polymer water-absorbent resin and/or a polyacrylamide-based water-absorbent resin.
5. The high-reliability deoxidizer according to any one of claims 1 to 4, wherein the mass ratio of the electrolyte, water-absorbent resin is 1 to 3:5-15:1-5.
6. A method for preparing the high-reliability deoxidizer according to any one of claims 1 to 5, wherein the deoxidizer is prepared by adding the reductive iron powder into the carbon-coated calcium chloride composite graphite, mixing the mixture in a sealing manner, adding the silicon dioxide and the electrolyte composite water-absorbing resin, stirring the mixture uniformly, sieving the mixture, packaging the mixture, and vacuumizing the mixture.
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| CN111990581A (en) * | 2020-08-12 | 2020-11-27 | 张冬亮 | Iron-based active reaction type deoxidizer with high oxidation rate and water locking function and preparation method thereof |
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| CN101803786A (en) * | 2010-04-09 | 2010-08-18 | 王力 | Dual-effect anti-staling agent and preparation method thereof |
| CN104107678A (en) * | 2014-07-18 | 2014-10-22 | 杭州干将实业有限公司 | Adsorbent with deoxygenation and humidity control functions and preparation method thereof |
| WO2017024720A1 (en) * | 2015-08-07 | 2017-02-16 | 田东 | Preparation method for high capacity lithium-ion battery negative electrode material |
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| CN111990581A (en) * | 2020-08-12 | 2020-11-27 | 张冬亮 | Iron-based active reaction type deoxidizer with high oxidation rate and water locking function and preparation method thereof |
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Effective date of registration: 20240104 Address after: 314000, No. 288 Qin'an Road, Caoqiao Street, Pinghu City, Jiaxing City, Zhejiang Province Patentee after: Ganjiang New Material Co.,Ltd. Address before: Room 4020, building 2, 188 Caoqiao North Road, Caoqiao street, Pinghu City, Jiaxing City, Zhejiang Province, 314200 Patentee before: Ganjiang New Material Co.,Ltd. Patentee before: HANGZHOU GANJIANG INDUSTRY Co.,Ltd. |