CN111802556A - Composite impregnated cellulose-based aerogel solid matter and preparation method thereof - Google Patents
Composite impregnated cellulose-based aerogel solid matter and preparation method thereof Download PDFInfo
- Publication number
- CN111802556A CN111802556A CN202010711763.2A CN202010711763A CN111802556A CN 111802556 A CN111802556 A CN 111802556A CN 202010711763 A CN202010711763 A CN 202010711763A CN 111802556 A CN111802556 A CN 111802556A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- root
- aerogel
- cyperus
- cyperus rotundus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 89
- 239000001913 cellulose Substances 0.000 title claims abstract description 89
- 239000004964 aerogel Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000007787 solid Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 31
- 244000285774 Cyperus esculentus Species 0.000 claims abstract description 22
- 235000005853 Cyperus esculentus Nutrition 0.000 claims abstract description 22
- 244000173166 Pyrus ussuriensis Species 0.000 claims abstract description 18
- 235000011572 Pyrus ussuriensis Nutrition 0.000 claims abstract description 18
- 239000000284 extract Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 5
- 244000075634 Cyperus rotundus Species 0.000 claims description 47
- 235000016854 Cyperus rotundus Nutrition 0.000 claims description 47
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 244000099162 Cyperus alternifolius Species 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 230000003113 alkalizing effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000002137 ultrasound extraction Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 244000185180 Pyrus betulifolia Species 0.000 claims 1
- 235000006877 Pyrus betulifolia Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- 230000003449 preventive effect Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000002609 medium Substances 0.000 description 5
- 230000003385 bacteriostatic effect Effects 0.000 description 4
- 241000411851 herbal medicine Species 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 235000017454 sodium diacetate Nutrition 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 2
- 241000233732 Fusarium verticillioides Species 0.000 description 2
- 239000004330 calcium propionate Substances 0.000 description 2
- 235000010331 calcium propionate Nutrition 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019764 Soybean Meal Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- -1 organic acid salt Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004455 soybean meal Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Images
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
- A23L3/3454—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 liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3562—Sugars; Derivatives thereof
-
- 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
- A23L3/3454—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 liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3472—Compounds of undetermined constitution obtained from animals or plants
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a composite impregnated cellulose-based aerogel solid and a preparation method thereof, wherein the composite impregnated cellulose-based aerogel solid is prepared from 100 parts by weight of shredded cyperus esculentus root cellulose aerogel microporous powder and 80-350 parts by weight of a pyrus ussuriensis young leaf extract, wherein the average particle size of the shredded cyperus esculentus root cellulose aerogel microporous powder is not more than 0.72 mu m, and the volume of micropores accounts for not less than 75%. According to the composite impregnated cellulose-based aerogel solid matter disclosed by the embodiment of the invention, the time for generating mildew of the feed can be delayed, and the mildew degree of the feed can be reduced; compared with the prior art, the cost is obviously reduced, and the mildew-proof effect is equivalent, so that the chemical mildew-proof agent and the composite mildew-proof agent are effectively replaced, and the mildew-proof agent is green and non-toxic.
Description
Technical Field
The invention belongs to the technical field of feeds, and particularly relates to a composite impregnated cellulose-based aerogel solid matter and a preparation method thereof.
Background
The feed mildew preventive is a common feed additive and is used for inhibiting the generation of mildew and toxin, preventing the loss of nutrient components of the feed during the storage period, slowing down the mildew of the feed and prolonging the storage time of the feed. The existing feed mildew-proof additive mainly comprises a chemical mildew-proof agent, a composite mildew-proof agent and a Chinese herbal medicine mildew-proof agent. The chemical mildew inhibitor mainly comprises propionic acid and its salts, sodium diacetate, sorbic acid, etc. The chemical mildew inhibitor has the defects that the mildew-proof effect is inversely proportional to the corrosivity, and toxic and side effects are easy to generate. The compound mildew preventive is prepared by mixing a plurality of organic acids or organic acid salt mildew preventives according to a certain proportion, the mildew preventive effect of the compound mildew preventive is superior to that of a single chemical mildew preventive, but the compound mildew preventive is easy to damage the whole nutrition level of the feed. The anti-mildew effect of the Chinese herbal medicine mildew preventive is realized by bacteriostatic growth and reproduction, has no residue, no drug resistance and no toxic or side effect, and is an important development direction of the feed mildew preventive. In practical application, the Chinese herbal medicine feed mildew-proof additive also has the following defects: 1) the stability of the device is not high, and the device is easily influenced by light, heat, moisture and the like in the application process and is inconvenient to store; 2) the slow release effect is not obvious, and the mould-proof aging is not durable; 3) the variety of Chinese herbal medicines is various, and how to adopt proper raw materials and preparation process, the raw materials and the manufacturing cost are reduced and the cost performance is improved while the excellent mildew-proof effect is obtained, and continuous and deep research is needed.
The shredded cyperus rotundus is almost spread all over the country, especially grows in farmlands, is harmful to the growth of rice, soybeans, cotton, vegetables and fruit trees, and is a harmful plant. However, the root of the cyperus rotundus L is rich in the special total alkaloids, has the bacteriostatic action, and the difficulty in preparation is how to change the cyperus rotundus L which is low in cost and rich in source into valuable and is worthy of attention and research, and how to ensure the stability of the cyperus rotundus L, and simultaneously ensure the slow-release effect and finally obtain the reasonable mildew-proof bacteriostatic effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a composite impregnated cellulose-based aerogel solid and a preparation method thereof, and the gist of the invention is as follows:
according to one aspect of the invention, the composite impregnated cellulose-based aerogel solid is prepared from 100 parts by weight of shredded cyperus esculentus root cellulose aerogel microporous powder and 80-350 parts by weight of an extract of young leaves of pyrus ussuriensis, wherein the average particle size of the shredded cyperus esculentus root cellulose aerogel microporous powder is not more than 0.72 mu m, and the volume of micropores accounts for not less than 75%.
According to another aspect of the invention, a method of preparing composite impregnated cellulose-based aerogel solids, the method comprising:
extraction of cellulose from root of cyperus alternifolius
1) Pretreatment: cutting, drying, crushing and sieving the cleaned root of the cyperus rotundus to obtain 50-micron powder of the root of the cyperus rotundus;
2) acidifying pretreatment: soaking the ground cyperus esculentus root powder for 60min at 35 ℃ by adopting 0.1mol/L oxalic acid solution according to the solid-to-liquid ratio of 1:30, and drying after suction filtration to obtain a first intermediate product;
3) alkalizing and leaching: according to the solid-liquid ratio of 1:15, 0.2mol/L sodium hydroxide solution is adopted to leach the first intermediate product for 80min at 90 ℃, and the second intermediate product is obtained after leaching and drying;
4) and (3) purification treatment: according to the solid-liquid ratio of 1:10, carrying out thermostatic water bath on the second intermediate product for 60min at 80 ℃ by adopting 0.2mol/L sodium hypochlorite solution; washing with anhydrous alcohol to neutrality, and vacuum drying at 60 deg.C to obtain cellulose of root of shredded cyperus esculentus.
Preparation of crushed cyperus esculentus root cellulose aerogel microporous powder
1) Preparation of shredded cyperus esculentus root cellulose aerogel precursor
And (3) activating treatment of the cellulose at the root of the cyperus rotundus: adding 100 parts by weight of the cyperus rotundus root cellulose into 280 and 400 parts by weight of N, N-dimethylacetamide solvent according to the weight part ratio, and stirring for 20min in a constant-temperature water bath at 100 ℃ to obtain an activated cyperus rotundus root cellulose solution;
dissolving the cellulose in the root of the cyperus rotundus: cooling the cellulose solution at the root of the activated shredded cyperus rotundus to 70 ℃, adding 15 parts by weight of sodium chloride, and stirring at constant temperature for 2 hours to obtain an intermediate cellulose solution;
microfibrillation treatment: carrying out microfibrillation treatment on the intermediate cellulose solution by adopting a high-frequency ultrasonic cell disruptor under the ice-water bath condition to obtain microfibrillated sol;
preparing a gel precursor: standing the microfibrillated sol at 10 +/-1 ℃ for 8h, and fully washing the microfibrillated sol by using absolute ethyl alcohol to obtain a precursor of the cellulose aerogel at the root of the cyperus rotundus.
2) Crosslinking treatment
Preparing acetic acid and sodium acetate solution into a crosslinking initiation solution according to the mass ratio of 4: 1; and fully soaking the precursor of the cellulose aerogel at the root of the cyperus rotundus by using a crosslinking initiation solution at the temperature of 45 +/-2 ℃ for 5 hours to obtain the crosslinking-reinforced cyperus rotundus root cellulose gel.
3) Purification treatment
And (3) immersing the crosslinked and strengthened cellulose gel at the root of the cyperus rotundus into a supercritical purifier which stores absolute ethyl alcohol for purification treatment.
4) Shaping process
And (3) carrying out molding treatment on the purified gel to obtain the shredded cyperus esculentus root cellulose aerogel microporous powder.
Preparation of extract of young leaf of pyrus ussuriensis maxim
Adding the young leaves of the pyrus ussuriensis maxim into absolute ethyl alcohol according to the solid-liquid ratio of 1:15, carrying out ultrasonic extraction for 80min, filtering, drying at 121 ℃ and sterilizing for 20s to obtain the extract of the young leaves of the pyrus ussuriensis maxim.
Preparation of composite impregnated cellulose-based aerogel solid
The weight ratio of: 100 parts of shredded cyperus rotundus root cellulose aerogel microporous powder and 80-350 parts of pyrus ussuriensis young leaf extract by weight are mixed;
adding the extract of the young leaves of the pyrus ussuriensis into absolute ethyl alcohol, fully stirring and dissolving in a sealed reaction kettle, adding the cellulose aerogel microporous powder at the root of the cyperus rotundus, electromagnetically stirring for 100min at the temperature of 60 ℃ under the pressure of 5MPa in the sealed reaction kettle, and evaporating and drying to obtain the composite impregnated cellulose base aerogel solid.
According to the exemplary embodiment of the present invention, the microfibrillation treatment is performed at an ultrasonic frequency of 15.5 to 17.5kHz, an ultrasonic time of 10min, and a pulse interval of 5 s.
According to an exemplary embodiment of the present invention, the concentration of acetic acid is 0.1mol/L and the concentration of sodium acetate solution is 0.15mol/L in the crosslinking treatment.
Exemplary according to the inventionIn the example, the temperature in the supercritical purifier is-5 deg.C, the pressure is 5.2MPa, and the purification medium is liquid CO2。
According to the exemplary embodiment of the present invention, the molding temperature is 105 ℃ and the molding time is 2h to 6.5 h.
The preparation of the composite impregnated cellulose-based aerogel solid matter is realized by extracting the cellulose at the root of the cyperus rotundus, preparing microporous powder of the cellulose aerogel at the root of the cyperus rotundus and preparing extract of the young leaves of the pyrus ussuriensis. According to the composite impregnated cellulose-based aerogel solid matter disclosed by the embodiment of the invention, the time for generating mildew of the feed can be delayed, and the mildew degree of the feed can be reduced; compared with the prior art, the cost is obviously reduced, and the mildew-proof effect is equivalent, so that the chemical mildew-proof agent and the composite mildew-proof agent are effectively replaced, and the mildew-proof agent is green and non-toxic.
Drawings
Fig. 1 is a graph comparing MIC values of composite impregnated cellulose based aerogel solids samples according to embodiments of the present invention and prior art samples.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the present invention is further described in detail by the following specific examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example (b):
preparation of composite impregnated cellulose-based aerogel solid
Extraction of cellulose from root of cyperus alternifolius
1) Pretreatment: cutting, drying, crushing and sieving the cleaned root of the cyperus rotundus to obtain 50-micron powder of the root of the cyperus rotundus;
2) acidifying pretreatment: soaking the ground cyperus esculentus root powder for 60min at 35 ℃ by adopting 0.1mol/L oxalic acid solution according to the solid-to-liquid ratio of 1:30, and drying after suction filtration to obtain a first intermediate product;
3) alkalizing and leaching: according to the solid-liquid ratio of 1:15, 0.2mol/L sodium hydroxide solution is adopted to leach the first intermediate product for 80min at 90 ℃, and the second intermediate product is obtained after leaching and drying;
4) and (3) purification treatment: according to the solid-liquid ratio of 1:10, carrying out thermostatic water bath on the second intermediate product for 60min at 80 ℃ by adopting 0.2mol/L sodium hypochlorite solution; washing with deionized water and absolute ethyl alcohol to neutrality, and vacuum drying at 60 deg.C to obtain shredded cyperus rotundus root cellulose.
Preparation of crushed cyperus esculentus root cellulose aerogel microporous powder
1) Preparation of shredded cyperus esculentus root cellulose aerogel precursor
And (3) activating treatment of the cellulose at the root of the cyperus rotundus: adding 100 parts by weight of the cyperus rotundus root cellulose into 280 and 400 parts by weight of N, N-dimethylacetamide solvent according to the weight part ratio, and stirring for 20min in a constant-temperature water bath at 100 ℃ to obtain an activated cyperus rotundus root cellulose solution;
dissolving the cellulose in the root of the cyperus rotundus: cooling the cellulose solution at the root of the activated shredded cyperus rotundus to 70 ℃, adding 15 parts by weight of sodium chloride, and stirring at constant temperature for 2 hours to obtain an intermediate cellulose solution;
microfibrillation treatment: microfibrillating the intermediate cellulose solution by using a high-frequency ultrasonic cell disruptor under the ice-water bath condition, wherein the ultrasonic frequency is 15.5-17.5kHz, the ultrasonic time is 10min, and the pulse interval is 5s to obtain microfibrillated sol;
preparing a gel precursor: standing the microfibrillated sol at 10 +/-1 ℃ for 8h, and fully washing the microfibrillated sol by using absolute ethyl alcohol to obtain a precursor of the cellulose aerogel at the root of the cyperus rotundus.
2) Crosslinking treatment
Preparing 0.1mol/L acetic acid and 0.15mol/L sodium acetate solution into a crosslinking initiation solution according to the mass ratio of 4: 1; and fully soaking the precursor of the cellulose aerogel at the root of the cyperus rotundus by using a crosslinking initiation solution at the temperature of 45 +/-2 ℃ for 5 hours to obtain the crosslinking-reinforced cyperus rotundus root cellulose gel.
3) Purification treatment
Soaking the crosslinked and strengthened shredded cyperus esculentus root cellulose gel into a supercritical purifier which stores absolute ethyl alcohol, wherein the temperature in the supercritical purifier is-5 ℃, the pressure in the supercritical purifier is 5.2MPa, and the purification medium is liquid CO2And (4) carrying out purification treatment.
4) Shaping process
And (3) carrying out molding treatment on the purified gel at the molding temperature of 105 ℃ for 2-6.5 h to obtain the shredded cyperus esculentus root cellulose aerogel microporous powder.
Preparation of extract of young leaf of pyrus ussuriensis maxim
Adding the young leaves of the pyrus ussuriensis maxim into absolute ethyl alcohol according to the solid-liquid ratio of 1:15, carrying out ultrasonic extraction for 80min, filtering, drying at 121 ℃ and sterilizing for 20s to obtain the extract of the young leaves of the pyrus ussuriensis maxim.
Preparation of composite impregnated cellulose-based aerogel solid
The weight ratio of: 100 parts of shredded cyperus rotundus root cellulose aerogel microporous powder and 80-350 parts of pyrus ussuriensis young leaf extract by weight are mixed;
adding the extract of the young leaves of the pyrus ussuriensis into absolute ethyl alcohol, fully stirring and dissolving in a sealed reaction kettle, adding the cellulose aerogel microporous powder at the root of the cyperus rotundus, electromagnetically stirring for 100min at the temperature of 60 ℃ under the pressure of 5MPa in the sealed reaction kettle, and evaporating and drying to obtain the composite impregnated cellulose base aerogel solid.
A plurality of test sets were prepared according to the above preparation method, the test sample sets were numbered T1, T2, T3, T4 and T5, and the proportions of the tests in each set are shown in Table 1.
TABLE 1
Detection of specification of shredded cyperus esculentus root cellulose aerogel microporous powder
According to the technical scheme for preparing the composite impregnated cellulose-based aerogel solid matter in the embodiment 1, a sample group of shredded cyperus esculentus root cellulose aerogel microporous powder is obtained after molding treatment, and the sample group is respectively numbered as S1, S2, S3, S4 and S5.
Measuring the average particle size of the cellulose aerogel microporous powder at the root of the cyperus rotundus according to ASTM E2980-2014 Standard test method for evaluating the average particle size of powder by air permeability; measuring the volume ratio of micropores in the cellulose aerogel microporous powder at the root part of the cyperus rotundus according to GB/T21650-2008 mercury intrusion method and gas adsorption method for measuring the pore size distribution and porosity of the solid material; the results are shown in Table 2.
TABLE 2
Test of mildew-proof effect of composite impregnated cellulose aerogel solid
The common feed is adopted as a solid matter for carrying out mildew-proof effect verification on the composite impregnated cellulose-based aerogel prepared in the embodiment of the application, and the feed formula for the test is as follows: 67% of corn, 25% of soybean meal, 6% of pre-powder and 2% of soybean oil;
the composite impregnated cellulose-based aerogel solid prepared by the embodiment of the application is used as a mildew-proof additive and is added into a test feed, wherein the sample components are respectively numbered as F1, F2, F3, F4 and F5, and the addition proportion is 0.3%. Sodium diacetate, citric acid and calcium propionate were added to the test feeds as anti-mold additives at a ratio of 0.3% to form control groups D1, D2 and D3, respectively; the test feed without the addition of the mold preventive additive was control group D4.
Uniformly mixing all groups of samples, placing the samples in a constant-temperature incubator with the temperature of 30 ℃ and the relative humidity of 90%, setting 5 times of repetition for each treatment, and sampling and analyzing the samples on days 1, 2, 4, 6, 8, 10, 15 and 30 respectively; sensory evaluation was performed on each sample group by observing the odor, caking and mildew of the sample groups, and the evaluation criteria were: whether the odor has rancidity odor, mildew odor and other peculiar smells; whether the shape viscosity is increased, whether the material is caked or not and whether the feed is vermin or not; the evaluation results are shown in Table 3 (the larger the number of "+" indicates the more serious the mildew).
TABLE 3
As can be seen from table 3, the composite impregnated cellulose-based aerogel solid prepared in the examples of the present application can delay the occurrence time of feed mildew and can reduce the degree of feed mildew; compared with the prior art, the mould-proof effect is equivalent under the same test condition.
Composite impregnated cellulose based aerogel solid matter bacteriostasis test
Test indicator bacteria: fusarium moniliforme is used as indicator bacterium.
Test medium: tryptone 1%, yeast extract 0.5%, glucose 2%, pH 6.8.
The test method comprises the following steps: taking a 250mL triangular flask, adding 50mL of culture medium into each flask, and sterilizing at high temperature; cleaning fusarium moniliforme spores by using sterile normal saline, and adding 0.5mL of spore water into each bottle of culture medium; the composite impregnated cellulose-based aerogel solid prepared by the embodiment of the application is used as a mildew-proof additive and is added into a culture medium, and the sample groups are respectively numbered as T1, T2, T3, T4 and T5. Sodium diacetate, citric acid and calcium propionate were added to the medium as anti-mold additives to form control groups d1, d2 and d3, respectively; the medium without the addition of the mildew preventive additive was control d 4. Culturing at constant temperature for 20h under the test conditions of 28 ℃ and 200r/min, and observing the test result, wherein each adding concentration without mould growth is the minimum inhibitory concentration MIC value (mg/mL).
TABLE 4
As can be seen from table 4 and fig. 1, the composite impregnated cellulose-based aerogel solid prepared in the examples of the present application has bacteriostatic and mildewproof effects; compared with the prior art, the antibacterial and mildewproof effects are equivalent under the same test conditions.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. The composite impregnated cellulose-based aerogel solid is characterized by being prepared from 100 parts by weight of shredded cyperus rotundus root cellulose aerogel microporous powder and 80-350 parts by weight of a pyrus betulaefolia young leaf extract, wherein the average particle size of the shredded cyperus rotundus root cellulose aerogel microporous powder is not more than 0.72 mu m, and the volume of micropores accounts for not less than 75%.
2. A method of preparing a composite impregnated cellulose-based aerogel solids, the method comprising:
extraction of cellulose from root of cyperus alternifolius
1) Pretreatment: cutting, drying, crushing and sieving the cleaned root of the cyperus rotundus to obtain 50-micron powder of the root of the cyperus rotundus;
2) acidifying pretreatment: soaking the ground cyperus esculentus root powder for 60min at 35 ℃ by adopting 0.1mol/L oxalic acid solution according to the solid-to-liquid ratio of 1:30, and drying after suction filtration to obtain a first intermediate product;
3) alkalizing and leaching: according to the solid-liquid ratio of 1:15, 0.2mol/L sodium hydroxide solution is adopted to leach the first intermediate product for 80min at 90 ℃, and the second intermediate product is obtained after leaching and drying;
4) and (3) purification treatment: according to the solid-liquid ratio of 1:10, carrying out thermostatic water bath on the second intermediate product for 60min at 80 ℃ by adopting 0.2mol/L sodium hypochlorite solution; washing with anhydrous ethanol to neutrality, and vacuum drying at 60 deg.C to obtain cellulose of root of herba Cyperi;
preparation of crushed cyperus esculentus root cellulose aerogel microporous powder
1) Preparation of shredded cyperus esculentus root cellulose aerogel precursor
And (3) activating treatment of the cellulose at the root of the cyperus rotundus: adding 100 parts by weight of the cyperus rotundus root cellulose into 280 and 400 parts by weight of N, N-dimethylacetamide solvent according to the weight part ratio, and stirring for 20min in a constant-temperature water bath at 100 ℃ to obtain an activated cyperus rotundus root cellulose solution;
dissolving the cellulose in the root of the cyperus rotundus: cooling the cellulose solution at the root of the activated shredded cyperus rotundus to 70 ℃, adding 15 parts by weight of sodium chloride, and stirring at constant temperature for 2 hours to obtain an intermediate cellulose solution;
microfibrillation treatment: carrying out microfibrillation treatment on the intermediate cellulose solution by adopting a high-frequency ultrasonic cell disruptor under the ice-water bath condition to obtain microfibrillated sol;
preparing a gel precursor: standing the microfibrillated sol at 10 +/-1 ℃ for 8 hours, and fully washing the microfibrillated sol by using absolute ethyl alcohol to obtain a precursor of the cellulose aerogel at the root of the chopped cyperus esculentus;
2) crosslinking treatment
Preparing acetic acid and sodium acetate solution into a crosslinking initiation solution according to the mass ratio of 4: 1; fully soaking the precursor of the cellulose aerogel at the root of the cyperus rotundus by using a crosslinking initiation solution at the temperature of 45 +/-2 ℃ for 5 hours to obtain crosslinked and reinforced cyperus rotundus root cellulose gel;
3) purification treatment
Soaking the crosslinked and strengthened shredded cyperus esculentus root cellulose gel into a supercritical purifier which stores absolute ethyl alcohol for purification treatment;
4) shaping process
Molding the purified gel to obtain shredded cyperus esculentus root cellulose aerogel microporous powder;
preparation of extract of young leaf of pyrus ussuriensis maxim
Adding the young leaves of the pyrus ussuriensis maxim into absolute ethyl alcohol according to the solid-liquid ratio of 1:15, carrying out ultrasonic extraction for 80min, filtering, drying at 121 ℃ and sterilizing for 20s to obtain an extract of the young leaves of the pyrus ussuriensis maxim;
preparation of composite impregnated cellulose-based aerogel solid
The weight ratio of: 100 parts of shredded cyperus rotundus root cellulose aerogel microporous powder and 80-350 parts of pyrus ussuriensis young leaf extract by weight are mixed;
adding the extract of the young leaves of the pyrus ussuriensis into absolute ethyl alcohol, fully stirring and dissolving in a sealed reaction kettle, adding the cellulose aerogel microporous powder at the root of the cyperus rotundus, electromagnetically stirring for 100min at the temperature of 60 ℃ under the pressure of 5MPa in the sealed reaction kettle, and evaporating and drying to obtain the composite impregnated cellulose base aerogel solid.
3. The preparation method according to claim 2, wherein the microfibrillation treatment is carried out at an ultrasonic frequency of 15.5 to 17.5kHz, an ultrasonic time of 10min and a pulse interval of 5 s.
4. The method according to claim 2, wherein the concentration of acetic acid is 0.1mol/L and the concentration of the sodium acetate solution is 0.15mol/L in the crosslinking treatment.
5. The method according to claim 2, wherein the supercritical purifier has a temperature of-5 deg.C and a pressure of 5.2MPa, and the purification medium is liquid CO2。
6. The preparation method according to claim 2, wherein the molding temperature is 105 ℃ and the molding time is 2h to 6.5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010711763.2A CN111802556B (en) | 2020-07-22 | 2020-07-22 | Composite impregnated cellulose-based aerogel solid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010711763.2A CN111802556B (en) | 2020-07-22 | 2020-07-22 | Composite impregnated cellulose-based aerogel solid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111802556A true CN111802556A (en) | 2020-10-23 |
| CN111802556B CN111802556B (en) | 2023-05-26 |
Family
ID=72862006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010711763.2A Active CN111802556B (en) | 2020-07-22 | 2020-07-22 | Composite impregnated cellulose-based aerogel solid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111802556B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115812850A (en) * | 2022-11-28 | 2023-03-21 | 上海邦成生物工程有限公司 | Preparation method of calcium propionate powder with composite gel coating layer and corresponding powder |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008231258A (en) * | 2007-03-20 | 2008-10-02 | Univ Of Tokyo | Cellulose aerogel and method for producing the same |
| CN102443180A (en) * | 2011-09-15 | 2012-05-09 | 复旦大学 | Method for preparing cellulose composite aerogel |
| CN105542218A (en) * | 2016-01-22 | 2016-05-04 | 昆明理工大学 | Preparation method of citric acid cross-linking reinforced cellulose aerogel |
| CN108086029A (en) * | 2017-12-05 | 2018-05-29 | 成都中医药大学 | A kind of Leaf of Magnolia officinalis cellulose and preparation method thereof purposes |
| CN108252143A (en) * | 2017-12-28 | 2018-07-06 | 潍坊友容实业有限公司 | A kind of method that plant salt and cellulose are extracted from Suaeda salsa |
| CN109898358A (en) * | 2019-03-07 | 2019-06-18 | 天津科技大学 | A kind of preparation method of plant source sustained-release antibacterial aeroge |
| CN111280369A (en) * | 2020-04-14 | 2020-06-16 | 上海邦成生物工程有限公司 | Plant extract-impregnated nano microporous zinc oxide solid and preparation method thereof |
-
2020
- 2020-07-22 CN CN202010711763.2A patent/CN111802556B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008231258A (en) * | 2007-03-20 | 2008-10-02 | Univ Of Tokyo | Cellulose aerogel and method for producing the same |
| CN102443180A (en) * | 2011-09-15 | 2012-05-09 | 复旦大学 | Method for preparing cellulose composite aerogel |
| CN105542218A (en) * | 2016-01-22 | 2016-05-04 | 昆明理工大学 | Preparation method of citric acid cross-linking reinforced cellulose aerogel |
| CN108086029A (en) * | 2017-12-05 | 2018-05-29 | 成都中医药大学 | A kind of Leaf of Magnolia officinalis cellulose and preparation method thereof purposes |
| CN108252143A (en) * | 2017-12-28 | 2018-07-06 | 潍坊友容实业有限公司 | A kind of method that plant salt and cellulose are extracted from Suaeda salsa |
| CN109898358A (en) * | 2019-03-07 | 2019-06-18 | 天津科技大学 | A kind of preparation method of plant source sustained-release antibacterial aeroge |
| CN111280369A (en) * | 2020-04-14 | 2020-06-16 | 上海邦成生物工程有限公司 | Plant extract-impregnated nano microporous zinc oxide solid and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 周兵等: "碎米莎草根部总生物碱的化感活性及抑菌活性的研究", 《江西农业大学学报》 * |
| 张鑫等: "纤维素基气凝胶材料及其应用研究进展", 《中国材料进展》 * |
| 郭春秋等: "木梨幼叶提取物抑菌防腐作用研究", 《湖南文理学院学报(自然科学版)》 * |
| 魏红芳等: "《养奶牛关键技术招招鲜：常见养奶牛疑难问题破解方案》", 28 February 2015, 中原农民出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115812850A (en) * | 2022-11-28 | 2023-03-21 | 上海邦成生物工程有限公司 | Preparation method of calcium propionate powder with composite gel coating layer and corresponding powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111802556B (en) | 2023-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101114185B1 (en) | Deodorant composition and manufacturing method thereof | |
| CN101829284B (en) | Process for extracting and refining flavone in highland barley seedlings by enzymolysis-membrane ultrafiltration | |
| CN111802555A (en) | Composite aerogel microporous powder impregnated with adinandra nitida leaf extract and preparation method thereof | |
| CN103110549A (en) | Preparation method of olive leaf extract microemulsion containing hydroxytyrosol | |
| CN111802556A (en) | Composite impregnated cellulose-based aerogel solid matter and preparation method thereof | |
| CN1219879C (en) | Hainan variety of lilac grey streptomycete and method for preparing agricultural antibiotic from variety | |
| KR20160117983A (en) | Method for preparing fermented extract enhanced crude saponin contents from platycodon grandiflorum | |
| KR20180119772A (en) | Method for preparing extract of nipa fruticans and nipa fruticans extract thereby | |
| CN102766172A (en) | Industrial production method of rhamnolipid biosurfactant dry powder | |
| CN104031109B (en) | A kind of method of fermentable purifying tea saponin | |
| CN104529885B (en) | Has multiple bioactive pyridone ketone derivatives and application thereof | |
| CN107177579B (en) | Method for preparing alliinase, allicin and garlic polysaccharide by using garlic slice processing wastewater | |
| CN113402626A (en) | Nymphaea hybrid polysaccharide extract and preparation method and application thereof | |
| CN110746659A (en) | Natural preservative film and preparation method thereof | |
| KR102647395B1 (en) | A method for manufacturing cypress leaf extract for removing the smell of the elderly | |
| CN105124716A (en) | Method of preparing food preservative through extraction waste liquid of cinnamon oil | |
| CN107540532B (en) | Diphenyl ether compound with antibacterial activity in honeysuckle and preparation method and application thereof | |
| CN104818306A (en) | Preparation method of aflatoxin B1 | |
| CN108707090A (en) | One kind aromatic compound containing chlorine and its preparation method and application | |
| CN107400015A (en) | A kind of camellia pericarp biological organic fertilizer and preparation method thereof | |
| CN108587331A (en) | A kind of special white-out agent of citrus fruit | |
| CN107865288A (en) | A kind of composite food preservatives and preparation method thereof | |
| CN105559054A (en) | Preparation method of loose dark green tea eurotium cristatum capsules | |
| CN112877218A (en) | Antrodia camphorata fruiting body cultivation and application thereof | |
| CN113424866A (en) | Carcinia Maultflora champ chitin fruit and vegetable fresh-keeping spray and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |