CN109997871A - A kind of hydro-thermal carbon ball of one-step method loading nano silvery and the preparation method and application thereof - Google Patents
A kind of hydro-thermal carbon ball of one-step method loading nano silvery and the preparation method and application thereof Download PDFInfo
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- CN109997871A CN109997871A CN201910239654.2A CN201910239654A CN109997871A CN 109997871 A CN109997871 A CN 109997871A CN 201910239654 A CN201910239654 A CN 201910239654A CN 109997871 A CN109997871 A CN 109997871A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 238000011068 loading method Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 114
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002028 Biomass Substances 0.000 claims abstract description 43
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004202 carbamide Substances 0.000 claims abstract description 40
- 239000000470 constituent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 27
- 239000004332 silver Substances 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- 238000005119 centrifugation Methods 0.000 claims abstract description 19
- 238000002604 ultrasonography Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 61
- 230000000844 anti-bacterial effect Effects 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 9
- 240000008042 Zea mays Species 0.000 claims description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 9
- 235000005822 corn Nutrition 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 235000009566 rice Nutrition 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 241000609240 Ambelania acida Species 0.000 claims description 6
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 6
- 244000105624 Arachis hypogaea Species 0.000 claims description 6
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 6
- 235000018262 Arachis monticola Nutrition 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 239000010905 bagasse Substances 0.000 claims description 6
- 235000020232 peanut Nutrition 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 5
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000010907 stover Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 241000143432 Daldinia concentrica Species 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 241000588724 Escherichia coli Species 0.000 description 9
- 241000209094 Oryza Species 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 241000191967 Staphylococcus aureus Species 0.000 description 6
- -1 be uniformly mixed Substances 0.000 description 6
- 239000010815 organic waste Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000035613 defoliation Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241001478240 Coccus Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 240000006365 Vitis vinifera Species 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000606153 Chlamydia trachomatis Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000588653 Neisseria Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940038705 chlamydia trachomatis Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
-
- 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
-
- 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
Abstract
The present invention relates to hydro-thermal carbon balls of a kind of one-step method loading nano silvery and the preparation method and application thereof, after the biomass full constituent being collected into removal impurity washing drying, fine particle is prepared under the effect of the mechanical external force of pulverizer and ball mill, then the biomass full constituent low temperature is dissolved in sodium hydroxide/urea system, after the dissolution of above-mentioned solution, the silver ammino solution prepared is instilled to be uniformly mixed, and solution after mixing is poured into together and carries out hydro-thermal reaction in high-temperature high-pressure reaction kettle, after hydro-thermal reaction is complete, solution is through being centrifuged, washing, ultrasound, centrifugation, freeze-drying obtains the hydro-thermal carbon ball of final loading nano silvery.The present invention can improve nano silver disadvantage unstable, leakage is too fast easy to reunite, expand application range of the hydro-thermal carbon ball as nano silver carrier, make full use of the biomass full constituent such as agricultural-forestry biomass waste.
Description
Technical field
The present invention relates to biomass full constituents to utilize field, in particular to a kind of hydro-thermal carbon ball of one-step method loading nano silvery
And the preparation method and application thereof.
Background technique
Nano silver refers to the metallic silver simple substance that partial size is accomplished to Nano grade.Common nano silver simple substance partial size exists mostly
25nm or so, it has the characteristics that broad-spectrum sterilization, to tens of kinds of Escherichia coli, gonococcus, chlamydia trachomatis etc. micro- lifes of causing a disease
Object has strong inhibition and killing effect, and will not generate drug resistance, makes it in the fresh-keeping antibacterial field of food and fruit
With highly important status.However, higher surface can make nano silver have dual character, nano silver is on the one hand improved
On the other hand reactivity reduces the stability of nano silver.And nano silver is easy to reunite, oxidizable, unstable in application process
Fixed, poor adhesive force, rate of release are too fast.Among these, the stability and rate of release of nano silver are to influence the master of its antibacterial effect
Want factor.
Biomass full constituent is a kind of general designation of renewable green resource being used directly without separating-purifying process,
Including agriculture and forestry organic waste material, animal husbandry waste and renewable house refuse etc..Fresh-keeping antibiotic packaging material, including preservative film, guarantor
Fresh paper, anti-bacteria paper, antibacterial gel etc. play very important work in the daily fresh-keeping, packaging, transportational process of food fruit
With.China generates a large amount of biomass agriculture and forestry organic waste material every year, how efficient green by these biological materials and nano silver
Preparation and application combine, and method is simple, low in cost, effect is obvious and can apply to food antibacterial fresh-keeping packaging field
It will be a very promising technology.
Summary of the invention
In order to solve nano silver unstable feature easy to reunite, while agricultural-forestry biomass full constituent is efficiently utilized, the present invention
A kind of preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery, effective use agricultural-forestry biomass full constituent reduction preparation are provided
The lesser nano silver simple substance of partial size out, and in its uniform load to carbon ball, will solve nano silver it is easy to reunite, it is unstable and leakage
Too fast deficiency, and by the carbon ball of loading nano silvery with nano-cellulose is compound that paper base material is prepared, continue to improve and receive
The sustained-release antibacterial performance of meter Yin.
The present invention is using the functional group for containing a large amount of reproducibilities in biomass full constituent, by one step hydro thermal method, with silver-colored ammonia
Solution is silver-colored source, and biomass full constituent is reducing agent and stabilizer, hydro-thermal carbon ball is obtained while preparing nano silver, and will receive
The directly load of rice silver is fixed on carbon ball surface, obtains the carbon ball of loading nano silvery, it is easy to reunite unstable both to have solved nano silver
Deficiency also makes the nano silver being supported in carbon ball achieve the purpose that sustained release in application.The loading nano silvery being prepared
Carbon ball can uniformly mix copy paper with multiple fiber raw material and be prepared into composite antibacterial paper, the sustained release for field of food packaging material
Antibacterial.
The technical solution adopted by the present invention is as follows.
The present invention provides a kind of preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery, and biomass full constituent is dissolved
In sodium hydroxide/urea system, biomass solution is obtained；Silver salt solution is instilled to the biomass solution, in high-temperature high-voltage reaction
Hydro-thermal reaction is carried out in kettle；The biomass solution generates carbon ball through hydro-thermal reaction high temperature degradation, while silver salt solution is through hydro-thermal
Reaction is reduced into nano silver under the action of biomass solution is as reducing agent, and the nano-silver loaded is on carbon ball surface.
Further, the preparation method specifically includes the following steps:
(1) after biomass full constituent removal impurity being washed drying, through under the effect of the mechanical external force of pulverizer and ball mill
Be prepared into granular biomass full constituent, then -15~-12 DEG C at a temperature of be dissolved in sodium hydroxide/urea system, it is described
After particle is completely dissolved, biomass solution is obtained；
(2) silver salt solution is instilled into step (1), is uniformly mixed, is obtained mixed solution；
(3) mixed solution in step (2) is poured into together and carries out hydro-thermal reaction in high-temperature high-pressure reaction kettle；
(4) after hydro-thermal reaction, the solution in reaction kettle is successively centrifuged, is washed, ultrasound, last time centrifugation, done
It is dry, obtain the carbon ball of loading nano silvery.
Preferably, the biomass full constituent includes corn stover, wheat stalk, bagasse, rice straw, peanut shell.
Preferably, the weight ratio of sodium hydroxide, urea and water is 5~7:10~12 in the sodium hydroxide/urea system:
81~85, biomass full constituent and sodium hydroxide/urea system mass volume ratio are 0.5~1:100~120, g/mL, biology
The time that matter full constituent particle dissolves in sodium hydroxide/urea system is 4~6h.
Preferably, the silver salt includes silver ammino solution, and silver nitrate solution, the concentration of silver salt is 0.01~0.05mol/L, silver
The volume ratio of salting liquid and the biomass solution is 2~12:100~120.
Preferably, the temperature of the hydro-thermal reaction is 210~270 DEG C, and soaking time is 6~12h, stirring rate 100
~200rpm, the time of stirring are 6~12h.
Preferably, in step (1), the mesh number that the pulverizer crushes biomass material is 40~60 mesh, ball mill ball
Grinding speed is 200~220rpm, and Ball-milling Time is 8~10h.
Preferably, the centrifugation rate in step (4) is 3000~4000rpm, and centrifugation time is 5~20min；The washing
It is ultrapure water with water, centrifugation adds ultrapure water progress ultrasound after repeating 4~6 times with washing step, last time is centrifuged, freezing
It is dry；The ultrasonic power is 400~600W, and ultrasonic time is 5~10min；The drying mode is freeze-drying, dry temperature
Degree be -40~-60 DEG C, drying time be 10~for 24 hours.
The present invention provides a kind of hydro-thermal carbon balls of one-step method loading nano silvery prepared by made as described above method.
The present invention also provides the hydro-thermal carbon balls of one-step method loading nano silvery described above to lead in food fruit anti-bacterial refreshing
Application in domain
The present invention first carries out sodium hydroxide/urea system dissolution powdered biomass, then the rear silver ammino solution that instills carries out water
The reason of thermal response is that agricultural-forestry biomass is as the base with a large amount of reproducibilities in a kind of natural plant fiber material structure
Group, under the premise of not adding other reducing agents and stabilizer can green reduction silver ammino solution be prepared nano silver, and hydrogen-oxygen
Change sodium/urea system can high-efficiency dissolution biomass full constituent, this carries out the reduction reaction of silver ammino solution in solution system,
And hydro-thermal reaction may make biomass full constituent high temperature degradation to occur to react generation at the same time at nuclear reaction generation carbon ball
Nano silver will be supported on carbon ball surface, achieve the purpose that dispersing nano silver reduces its reunion and oxidation, real in subsequent antibacterial
The effect of slow release nanometer silver can also be played in testing.The advantages of the present invention are mainly reflected in two aspects: being on the one hand using natural
Reducing agent and stabilizer of the biomass full constituent as nano silver, do not need to add any other surfactant and reduction
Agriculture and forestry organic waste material is not only utilized in agent, but also green is prepared for nano silver, and environmentally protective sustainability is strong；It on the other hand is to react
The hydro-thermal carbon ball generated in journey can be used as the carrier of nano silver due to specific surface area with higher, restore reaction
Nano-silver loaded reduces the reunion and oxidation of nano silver, improves its reactivity, realize and receive during antibacterial to carbon ball surface
The slow release effect of meter Yin.
According to the demand of the hydro-thermal carbon ball of final loading nano silvery, the load capacity of carbon ball nano surface silver is mainly detected,
The degree of oxidation of nano silver and the anti-microbial property (to the anti-microbial property of Escherichia coli, staphylococcus aureus, mould) of carbon ball, it is raw
The additive amount of substance full constituent and the additive amount of silver ammino solution can be adjusted accordingly.
The beneficial effects of the present invention are:
(1) present invention makes the nanometer of preparation using the carbon ball with high specific surface area as a kind of dispersing agent and carrier
Silver is supported in carbon ball, reduces the reunion and oxidation of nano silver, prevents the too fast leakage of nano silver.
(2) present invention prepares the reducing agent and stabilizer of nano silver using agriculture and forestry organic waste material full constituent as silver ammino solution,
It does not need to add other any surfactants and reducing agent, the biomass full constituent of recyclable regenerative had not only been utilized, but also reduce
The use of the chemicals of other reproducibilities, has saved drug, has protected environment.
(3) by sodium hydroxide/urea, this green dissolution system dissolves biomass full constituent, does not need additionally to biology
Matter raw material is separated and is purified, while reducing pre-treatment of raw material step, moreover it is possible to the fully dissolved for realizing raw material, after being conducive to
The progress of continuous hydro-thermal reaction and reduction reaction.
(4) present invention utilizes biomass using high-temperature high-pressure reaction kettle one-step method hydro-thermal preparation carbon ball and loading nano silvery
Full constituent is prepared hydro-thermal carbon ball and makes on nano-silver loaded to carbon ball, and the two carries out simultaneously, does not need substep and prepares hydro-thermal
Loading nano silvery, reaction efficiency improve rapidly carbon ball again.
(5) present invention improves the utility value of agriculture and forestry organic waste material, expands the application range of biomass full constituent, can solve
Certainly China's agriculture and forestry organic waste material burns discarded resource and environmental problem wantonly.
Detailed description of the invention
Fig. 1 is the SEM figure of the hydro-thermal carbon ball of loading nano silvery prepared by embodiment 1；
Fig. 2 is the SEM figure of the hydro-thermal carbon ball of loading nano silvery prepared by embodiment 2；
Fig. 3 is the SEM figure of the hydro-thermal carbon ball of loading nano silvery prepared by embodiment 3, and interior attached primary school's figure is carbon ball nano surface
The distribution of silver, particle size is Nano grade.
Specific embodiment
In following embodiment, in addition to having special instruction, other all percentages are mass percent.
Embodiment 1:
The fresh corn stover being collected into prepares the hydro-thermal carbon of loading nano silvery according to the following steps after drying defoliation and removing root
Ball:
(1) by corn straw smashing and ball milling pretreatment, adjustable speed ball mill is MITR-YXQM-1L planetary ball mill,
Pretreatment condition are as follows: pulverizer crushes raw material to 40 mesh, and drum's speed of rotation 220rpm, Ball-milling Time 8h obtain granular jade
Rice stalk；
(2) corn stalk pellets are dissolved in sodium hydroxide/urea system, hydrogen-oxygen in the sodium hydroxide/urea system
The mass ratio for changing sodium, urea and water is 5:10:85, sodium hydroxide/urea system volume 100mL, dissolution conditions are as follows: temperature-
15 DEG C, time 4h, corn stalk pellets dosage 0.5g；
(3) silver ammino solution prepared is instilled into above-mentioned steps (2) dissolved solution, be uniformly mixed, silver ammino solution
Adding conditional are as follows: concentration 0.05mol/L, dosage 2mL；
(4) solution for being uniformly mixed step (3) moves into high-temperature high-pressure reaction kettle, carries out hydro-thermal reaction, reaction condition
Are as follows: 210 DEG C of temperature, heating rate is 5 DEG C/min, soaking time 12h, mixing speed 100rpm, mixing time 12h；
(5) solution after above-mentioned steps (4) reaction is moved into 100mL centrifuge tube and is centrifuged 5min at speed 4000rpm,
Ultrapure water is added after outwelling supernatant liquor, continues to be centrifuged, so be repeated 6 times, last time solution before centrifugation is through ultrasonic disruption
Machine ultrasound 5min at power 600W, finally centrifugation obtain be deposited at -60 DEG C of temperature be freeze-dried 10h obtain it is final
The hydro-thermal carbon ball of loading nano silvery；The hydro-thermal carbon ball and nano-cellulose of loading nano silvery manufactured in the present embodiment are according to mass ratio
1:100g/g compound anti-bacteria paper can form the inhibition zone of radius 10mm to Escherichia coli army, form half to staphylococcus aureus
The inhibition zone of diameter 10.2mm.The Escherichia coli and staphylococcus aureus that the present embodiment and following all examples are used be
What same time was cultivated under the conditions of.
Embodiment 2:
The fresh wheat stalk raw material being collected into prepares the water of loading nano silvery according to the following steps after drying defoliation and removing root
Hot carbon ball:
(1) wheat stalk is crushed and ball milling pretreatment, adjustable speed ball mill is MITR-YXQM-1L planetary ball mill,
Pretreatment condition are as follows: pulverizer crushes raw material to 40 mesh, and drum's speed of rotation 220rpm, Ball-milling Time 8h are obtained granular small
Wheat Straw；
(2) particle is dissolved in sodium hydroxide/urea system, sodium hydroxide, urea in sodium hydroxide/urea system
Mass ratio with water is 5:10:85, and sodium hydroxide/urea system volume is 100mL, dissolution conditions are as follows: -15 DEG C of temperature, when
Between 4h, wheat stalk amount of particles 0.5g；
(3) silver ammino solution prepared is instilled into above-mentioned steps (2) dissolved solution, be uniformly mixed, silver ammino solution
Adding conditional are as follows: concentration 0.05mol/L, dosage 4mL；
(4) solution for being uniformly mixed step (3) moves into high-temperature high-pressure reaction kettle, carries out hydro-thermal reaction, reaction condition
Are as follows: 230 DEG C of temperature, heating rate is 5 DEG C/min, soaking time 6h, mixing speed 100rpm, mixing time 6h；
(5) solution after above-mentioned steps (4) reaction is moved into 100mL centrifuge tube and is centrifuged 5min at speed 4000rpm,
Ultrapure water is added after outwelling supernatant liquor, continues to be centrifuged, so be repeated 6 times, last time solution before centrifugation is through ultrasonic disruption
Machine ultrasound 5min at power 600W, finally centrifugation obtain be deposited at -60 DEG C of temperature be freeze-dried 10h obtain it is final
The hydro-thermal carbon ball of loading nano silvery；The hydro-thermal carbon ball and nano-cellulose of loading nano silvery manufactured in the present embodiment are according to mass ratio
1:100g/g compound anti-bacteria paper can form the inhibition zone of radius 10.4mm to Escherichia coli army, be formed to staphylococcus aureus
The inhibition zone of radius 9.9mm.
Embodiment 3:
The fresh bagasse being collected into prepares the hydro-thermal of loading nano silvery according to the following steps after drying the impurity such as removal dust
Carbon ball:
(1) bagasse is crushed and ball milling pretreatment, adjustable speed ball mill is MITR-YXQM-1L planetary ball mill, pre- place
Manage bar part are as follows: pulverizer crushes raw material to 50 mesh, and drum's speed of rotation 210rpm, Ball-milling Time 9h obtain granular bagasse；
(2) particle is dissolved in sodium hydroxide/urea system, sodium hydroxide, urea in sodium hydroxide/urea system
Mass ratio with water is 6:11:83, sodium hydroxide/urea system volume 110mL, dissolution conditions are as follows: -15 DEG C of temperature, the time
5h, bagasse amount of particles 1g；
(3) silver ammino solution prepared is instilled into above-mentioned steps (2) dissolved solution, be uniformly mixed, silver ammino solution
Adding conditional are as follows: concentration 0.03mol/L, dosage 6mL；
(4) solution for being uniformly mixed step (3) moves into high-temperature high-pressure reaction kettle, carries out hydro-thermal reaction, reaction condition
Are as follows: 250 DEG C of temperature, heating rate is 7 DEG C/min, soaking time 6h, mixing speed 150rpm, mixing time 6h；
(5) solution after above-mentioned steps (4) reaction is moved into 100mL centrifuge tube and is centrifuged at speed 3500rpm
Ultrapure water is added after outwelling supernatant liquor in 10min, continues to be centrifuged, so be repeated 5 times, and last time solution before centrifugation is through ultrasound
Wave crusher ultrasound 7min at power 500W is finally centrifuged the obtained freeze-drying 18h at -50 DEG C of temperature that is deposited in and obtains
The hydro-thermal carbon ball of final loading nano silvery；The hydro-thermal carbon ball of loading nano silvery manufactured in the present embodiment and nano-cellulose according to
Mass ratio 1:100g/g compound anti-bacteria paper can form the inhibition zone of radius 10.5mm to Escherichia coli army, to Staphylococcus aureus
The inhibition zone of bacterium formation radius 10.3mm.
Embodiment 4:
The fresh rice straw being collected into prepares the hydro-thermal carbon ball of loading nano silvery according to the following steps after drying defoliation and removing root:
(1) rice straw is crushed and ball milling pretreatment, adjustable speed ball mill is MITR-YXQM-1L planetary ball mill, pre- place
Manage bar part are as follows: pulverizer crushes raw material to 50 mesh, and drum's speed of rotation 210rpm, Ball-milling Time 9h obtain granular rice straw；
(2) particle is dissolved in sodium hydroxide/urea system, sodium hydroxide, urea in sodium hydroxide/urea system
Mass ratio with water is 6:11:83, and sodium hydroxide/urea system volume is 110mL, dissolution conditions are as follows: -12 DEG C of temperature, when
Between 6h, rice straw amount of particles 0.5g；
(3) silver ammino solution prepared is instilled into above-mentioned steps (2) dissolved solution, be uniformly mixed, silver ammino solution
Adding conditional are as follows: concentration 0.03mol/L, dosage 8mL；
(4) solution for being uniformly mixed step (3) moves into high-temperature high-pressure reaction kettle, carries out hydro-thermal reaction, reaction condition
Are as follows: 270 DEG C of temperature, heating rate is 7 DEG C/min, soaking time 8h, mixing speed 150rpm, mixing time 8h；
(5) solution after above-mentioned steps (4) reaction is moved into 100mL centrifuge tube and is centrifuged at speed 3500rpm
Ultrapure water is added after outwelling supernatant liquor in 10min, continues to be centrifuged, so be repeated 5 times, and last time solution before centrifugation is through ultrasound
Wave crusher ultrasound 7min at power 500W is finally centrifuged the obtained freeze-drying 18h at -50 DEG C of temperature that is deposited in and obtains
The hydro-thermal carbon ball of final loading nano silvery；The hydro-thermal carbon ball of loading nano silvery manufactured in the present embodiment and nano-cellulose according to
Mass ratio 1:100g/g compound anti-bacteria paper can form the inhibition zone of radius 10.5mm to Escherichia coli army, to Staphylococcus aureus
The inhibition zone of bacterium formation radius 9.8mm.
Embodiment 5:
The fresh peanut shell being collected into is washed dry after prepare the hydro-thermal carbon ball of loading nano silvery according to the following steps:
(1) peanut shell is crushed and ball milling pretreatment, adjustable speed ball mill is MITR-YXQM-1L planetary ball mill, in advance
Treatment conditions are as follows: pulverizer crushes raw material to 60 mesh, and drum's speed of rotation 200rpm, Ball-milling Time 10h obtain granular peanut
Shell；
(2) particle is dissolved in sodium hydroxide/urea system, sodium hydroxide, urea in sodium hydroxide/urea system
Mass ratio with water is 7:12:81, and sodium hydroxide/urea system volume is 120mL, dissolution conditions are as follows: -12 DEG C of temperature, when
Between 6h, peanut shell granular dosage 1g；
(3) silver ammino solution prepared is instilled into above-mentioned steps (2) dissolved solution, be uniformly mixed, silver ammino solution
Adding conditional are as follows: concentration 0.01mol/L, dosage 10mL；
(4) solution for being uniformly mixed step (3) moves into high-temperature high-pressure reaction kettle, carries out hydro-thermal reaction, reaction condition
Are as follows: 270 DEG C of temperature, heating rate is 10 DEG C/min, soaking time 8h, mixing speed 200rpm, mixing time 8h；
(5) solution after above-mentioned steps (4) reaction is moved into 100mL centrifuge tube and is centrifuged at speed 3000rpm
Ultrapure water is added after outwelling supernatant liquor in 20min, continues to be centrifuged, so be repeated 4 times, and last time solution before centrifugation is through ultrasound
Wave crusher ultrasound 10min at power 400W, what finally centrifugation obtained is deposited at -40 DEG C of temperature and is freeze-dried for 24 hours to obtain the final product
To the hydro-thermal carbon ball of final loading nano silvery；Hydro-thermal carbon ball and the nano-cellulose of loading nano silvery manufactured in the present embodiment are pressed
The inhibition zone that radius 10.5mm can be formed to Escherichia coli army according to mass ratio 1:100g/g compound anti-bacteria paper, to golden yellow grape
The inhibition zone of coccus formation radius 9.8mm.
Embodiment 6:
The fresh corn stover being collected into prepares the hydro-thermal carbon of loading nano silvery according to the following steps after drying defoliation and removing root
Ball:
(1) by corn straw smashing and ball milling pretreatment, adjustable speed ball mill is MITR-YXQM-1L planetary ball mill,
Pretreatment condition are as follows: pulverizer crushes raw material to 60 mesh, and drum's speed of rotation 200rpm, Ball-milling Time 10h obtain granular jade
Rice stalk；
(2) particle is dissolved in sodium hydroxide/urea system, sodium hydroxide, urea in sodium hydroxide/urea system
Mass ratio with water is 7:12:81, and sodium hydroxide/urea system volume is 120mL, dissolution conditions are as follows: -12 DEG C of temperature, when
Between 6h, corn stalk pellets dosage 1g；
(3) silver ammino solution prepared is instilled into above-mentioned steps (2) dissolved solution, be uniformly mixed, silver ammino solution
Adding conditional are as follows: concentration 0.01mol/L, dosage 12mL；
(4) solution for being uniformly mixed step (3) moves into high-temperature high-pressure reaction kettle, carries out hydro-thermal reaction, reaction condition
Are as follows: 270 DEG C of temperature, heating rate is 10 DEG C/min, soaking time 12h, mixing speed 200rpm, mixing time 12h；
(5) solution after above-mentioned steps (4) reaction is moved into 100mL centrifuge tube and is centrifuged at speed 3000rpm
Ultrapure water is added after outwelling supernatant liquor in 20min, continues to be centrifuged, so be repeated 4 times, and last time solution before centrifugation is through ultrasound
Wave crusher ultrasound 10min at power 400W, what finally centrifugation obtained is deposited at -40 DEG C of temperature and is freeze-dried for 24 hours to obtain the final product
To the hydro-thermal carbon ball of final loading nano silvery；Hydro-thermal carbon ball and the nano-cellulose of loading nano silvery manufactured in the present embodiment are pressed
The inhibition zone that radius 10.4mm can be formed to Escherichia coli army according to mass ratio 1:100g/g compound anti-bacteria paper, to golden yellow grape
The inhibition zone of coccus formation radius 10.5mm.
Claims (10)
1. a kind of preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery, which is characterized in that dissolve biomass full constituent
In sodium hydroxide/urea system, biomass solution is obtained；Silver salt solution is instilled into the biomass solution, in high temperature and pressure
Hydro-thermal reaction is carried out in reaction kettle；The biomass solution forms carbon ball through hydro-thermal reaction high temperature degradation polycondensation, while silver salt is molten
Liquid is reduced into nano silver under the action of biomass solution is as reducing agent through hydro-thermal reaction and is supported on carbon ball surface.
2. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 1, which is characterized in that specific
The following steps are included:
(1) by after the removal impurity washing drying of biomass full constituent, lower preparation is acted on through the mechanical external force of pulverizer and ball mill
At granular biomass full constituent, then -15 ~ -12 DEG C at a temperature of be dissolved in sodium hydroxide/urea system, described
After grain is completely dissolved, biomass solution is obtained；
(2) silver salt solution is instilled into step (1), is uniformly mixed, is obtained mixed solution；
(3) mixed solution in step (2) is poured into together and carries out hydro-thermal reaction in high-temperature high-pressure reaction kettle；
(4) after hydro-thermal reaction, the solution in reaction kettle is successively centrifuged, is washed, ultrasound, last time centrifugation, drying, obtained
The carbon ball of loading nano silvery.
3. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 1 or 2, which is characterized in that
The biomass full constituent includes corn stover, wheat stalk, bagasse, rice straw, peanut shell.
4. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 1 or 2, which is characterized in that
The mass ratio of sodium hydroxide, urea and water is 5 ~ 7:10~12:81~85, the life in the sodium hydroxide/urea system
Substance full constituent particle and sodium hydroxide/urea system mass volume ratio are 0.5 ~ 1:100 ~ 120, g/mL, the life
The time that substance full constituent particle dissolves in sodium hydroxide/urea system is 4~6 h.
5. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 1 or 2, which is characterized in that
The silver salt solution includes silver ammino solution, and silver nitrate solution, the concentration of silver salt solution is 0.01~0.05 mol/L, silver salt solution
Volume ratio with the biomass solution is 2 ~ 12:100 ~ 120.
6. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 1 or 2, which is characterized in that
The temperature of the hydro-thermal reaction is 210~270 DEG C, and soaking time is 6~12 h, and heating rate is 5~10 DEG C/min, stirring speed
Rate is 100~200 rpm, and the time of stirring is 6~12 h.
7. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 2, which is characterized in that step
(1) in, the mesh number that the pulverizer crushes biomass material is 40 ~ 60 mesh, and ball mill ball milling speed is 200 ~ 220
Rpm, Ball-milling Time are 8 ~ 10 h.
8. the preparation method of the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 2, which is characterized in that step
(4) centrifugation rate in is 3000 ~ 4000 rpm, and centrifugation time is 5 ~ 20 min；The slurry is ultrapure water, from
The heart and washing step add ultrapure water and carry out ultrasound, last time centrifugation, freeze-drying after repeating 4 ~ 6 times；The ultrasound
Power is 400 ~ 600 W, and ultrasonic time is 5 ~ 10 min；The drying mode be freeze-drying, drying temperature be -40 ~
- 60 DEG C, drying time is 10 ~ 24 h.
9. a kind of hydro-thermal carbon ball of the one-step method loading nano silvery by the preparation method preparation of any one of claim 1 to 8.
10. the hydro-thermal carbon ball of one-step method loading nano silvery according to claim 9 is in food fruit anti-bacterial refreshing field
Application.
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| CN114831136A (en) * | 2022-05-20 | 2022-08-02 | 爱科美材料科技(南通)有限公司 | Preparation method of oleophylic silver-loaded carbon microspheres |
| CN114953072A (en) * | 2022-05-26 | 2022-08-30 | 岳西县鸡笼尖生态农业科技有限公司 | Improved preparation process of ginger straw suitable for weaving |
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