CN107232229A - A kind of preparation method of nano silver antimicrobials - Google Patents
A kind of preparation method of nano silver antimicrobials Download PDFInfo
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- CN107232229A CN107232229A CN201710424757.7A CN201710424757A CN107232229A CN 107232229 A CN107232229 A CN 107232229A CN 201710424757 A CN201710424757 A CN 201710424757A CN 107232229 A CN107232229 A CN 107232229A
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- nano silver
- constant temperature
- activated carbon
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- silver
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000004599 antimicrobial Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical class [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 abstract description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000845 anti-microbial effect Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 150000003904 phospholipids Chemical class 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 16
- 241000894006 Bacteria Species 0.000 description 14
- 230000002421 anti-septic effect Effects 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 12
- 239000010985 leather Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 235000021463 dry cake Nutrition 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000012149 noodles Nutrition 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 229940098458 powder spray Drugs 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- VDIQGOWLVYFDOU-UHFFFAOYSA-H [Ca+]O.[Ca+]O.[Ca+]O.[O-]P([O-])([O-])=O Chemical compound [Ca+]O.[Ca+]O.[Ca+]O.[O-]P([O-])([O-])=O VDIQGOWLVYFDOU-UHFFFAOYSA-H 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical group N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of preparation method of nano silver antimicrobials, belong to antimicrobial technology field.The present invention is mixed after activated carbon is crushed with phosphorus pentoxide to be scattered in absolute ethyl alcohol, phosphorus pentoxide is dissolved in ethanol formation phosphatide, and it is adsorbed in activated carbon surface, under alkalescence condition, calcium nitrate is set slowly to be combined with the hydroxyl on phospholipid hydrolysis product, form calcium hydroxy phosphate nucleus, and be adsorbed in activated carbon pore structure, avoid reuniting, calcined again after scrubbed drying, remove activated carbon kernel, obtain the calcining material of loose structure, and to calcine material for carrier, using glucose as reducing agent, reduce silver ammino solution, the nano-Ag particles of generation are made to be adsorbed by the calcining material of loose structure, eventually pass and be dried in vacuo after filter washing, produce nano silver antimicrobials.Nano silver antimicrobials stability of the present invention is good, is uniformly dispersed during use, with higher Durability of antimicrobial effect.
Description
Technical field
The present invention relates to a kind of preparation method of nano silver antimicrobials, belong to antimicrobial technology field.
Background technology
Antiseptic is commonly divided into natural antibacterial agent, organic antibacterial agent and inorganic antiseptic three major types.Natural antibacterial agent has
Have the advantages that safety non-toxic, wide spectrum, colour stability are good, but turn into restriction the shortcomings of processing difficulties, poor heat resistance, resource-constrained
The problem of it develops.Organic antibacterial agent can effectively suppress harmful bacteria, the growth and breeding of mould, instant effect, but heat endurance
The defects such as poor, easy decomposition, are just gradually eliminated.There is antibacterial wide spectrum due to inorganic antiseptic, it is heat-resist, easily
Industrialization, the study hotspot as antiseptic field.
Inorganic antiseptic is resisted using a class made from the metals such as silver, copper, zinc, titanium and its sterilization of ion or bacteriostasis
Microbial inoculum.Ag+With broad-spectrum antibacterial property, be not likely to produce the resistance to the action of a drug the features such as, the representative substances as inorganic antiseptic, in recent years
It is further development of nano silver antimicrobials.
Particle diameter is exactly accomplished nano level argent simple substance by nano silver antimicrobials, and particle diameter is mostly in 25 rans.It is
Refer within a certain period of time, make certain micro-organisms(Bacterium, fungi, saccharomycete, algae and virus etc.)Growth or breeding protect
Hold in necessary chemical substance below horizontal.Nano silver antimicrobials are with antibacterial and material or product of bactericidal property.
Haptoreaction Antibacterial Mechanism:Silver ion haptoreaction, causes microorganism to have component damage or produces dysfunction.
When micro silver ion reaches microbial cell film, because the latter is negatively charged, by Coulomb attraction, both are made firmly to adsorb,
Silver ion penetration cell wall enters intracellular, and is reacted with sulfydryl, makes protein coagulating, destroys the activity of cell synzyme, cell
Lose division growth ability and it is dead.
But current nano silver antimicrobials have following not enough:Nano Silver is easy to change, and stability is poor, easily reunite, point
Dissipate uneven, cause its Durability of antimicrobial effect poor;And contain substantial amounts of nitrate anion, salt acid group and various organic matters etc. in silver system solution
Noxious material, the Nano silver solution toxicity manufactured is larger.
Therefore, how to realize that a kind of stability is good, be uniformly dispersed, the use of the good antiseptic of rear Durability of antimicrobial effect is in the industry urgently
Technical problem to be solved.
The content of the invention
The technical problems to be solved by the invention:For Conventional nano silver antibacterial agent, stability is poor in use, point
Dissipate uneven, easily reunite, causing the problem of Durability of antimicrobial effect is poor, there is provided a kind of preparation method of nano silver antimicrobials.
In order to solve the above technical problems, the present invention is using technical scheme as described below:
(1)400~600mL mass fractions are measured for 2% silver nitrate solution, under constant temperature stirring, are dripped into silver nitrate solution
Plus mass fraction is continuation dropwise addition ammoniacal liquor after 2~4% ammoniacal liquor, precipitation to be generated, until the precipitation produced is completely dissolved, obtains silver-colored ammonia
Solution;
(2)Activated carbon powder obtained by 20~30g is weighed successively, and 10~15g phosphorus pentoxides pour into 100~120mL absolute ethyl alcohols
In, after 20~30min of ultrasonic disperse, constant temperature 45~60min of stirring reaction, then be added dropwise 100~150mL mass fractions for 30~
35% calcium nitrate solution, control is dripped off in 30~45min, and is that 10% sodium hydroxide solution adjusts pH to 9.6 with mass fraction
~10.0, continue after 45~60min of constant temperature stirring reaction, be transferred in autoclave, it is closed under the conditions of temperature is 170~180 DEG C
8~10h is reacted, treats that confined reaction terminates, is filtered, washing, drying and calcination must calcine material;
(3)10~12g calcining material are weighed, are poured into 100~150mL silver ammino solutions, after 20~30min of ultrasonic disperse, side constant temperature
Stirring side adds 100~120mL mass fractions into silver ammino solution for 5~10% glucose solutions, end to be added, continues permanent
Warm 20~30min of stirring reaction, filtering is dried to constant weight after washing, produces nano silver antimicrobials.
Step(2)Described activated carbon powder particle diameter is 80~120 mesh.
Step(2)2~4mL mass fractions can also be added in described absolute ethyl alcohol for 98% sulfuric acid solution.
Step(2)Described constant temperature stirring reaction condition is that reaction temperature is 55~60 DEG C, speed of agitator be 400~
600r/min。
Step(3)During described constant temperature stirring reaction, moreover it is possible to be passed through with 8~10mL/min speed into silver ammino solution
Nitrogen.
The present invention is compared with other method, and advantageous effects are:
(1)The present invention, which first mixes activated carbon powder with phosphorus pentoxide, to be scattered in absolute ethyl alcohol, using the concentrated sulfuric acid as catalyst,
Phosphorus pentoxide and ethanol synthesis formation phosphide are catalyzed, the phosphatide of generation is tightly held by activated carbon, and is filled in activated carbon pore structure
In, then using activated carbon as carrier, calcium nitrate is added into system, under alkalescence condition, phosphatide is slowly hydrolyzed, hydrolysate and nitre
Sour calcium is slowly combined, and forms calcium hydroxy phosphate nucleus, once forming calcium hydroxy phosphate crystal, that is, is tightly held by activated carbon, it is to avoid brilliant
Body further growth is reunited, then activated carbon kernel is removed through calcining, and the carbon dioxide produced in calcination process can
The pore structure of calcium hydroxy phosphate is further enriched, and calcium hydroxy phosphate is activated in calcination process;
(2)The present invention is using obtained adsorbed property of porous hydroxyl calcium phosphate as carrier, and deposition of silver ammonia is molten in the pore structure of calcium hydroxy phosphate
The silver nano-grain that liquid is produced with glucose redox reaction, the pore structure and molecule space steric hindrance of calcium hydroxy phosphate can have
Effect avoids nano-Ag particles from reuniting, and calcium hydroxy phosphate good biocompatibility, Nano Silver during product is used as antiseptic
Particle is wrapped up by pore structure, can effectively be alleviated silver and is oxidized, antibacterial effect can be played for a long time.
Embodiment
400~600mL mass fractions are measured first for 2% silver nitrate solution, are poured into beaker, then beaker is moved into digital display
In the constant temperature blender with magnetic force that tests the speed, in temperature be 55~60 DEG C, rotating speed be 300~500r/min under the conditions of, into beaker be added dropwise
Mass fraction is 2~4% ammoniacal liquor, continues that ammoniacal liquor is added dropwise after precipitation is produced in beaker, until the precipitation produced is completely dissolved, obtains
Silver ammino solution;80~100g activated carbons are weighed, are poured into pulverizer, 80~120 mesh sieves are crossed after crushing, activated carbon powder is obtained, then according to
Secondary to weigh activated carbon powder obtained by 20~30g, 10~15g phosphorus pentoxides pour into fill 100~120mL absolute ethyl alcohols three mouthfuls
In flask, and three-necked flask is moved into sonic oscillation instrument, 20~30min of ultrasonic disperse under the conditions of frequency is 40~45kHz, then
Three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, is 55~60 DEG C in temperature, rotating speed is 400~600r/min conditions
Under, 45~60min of constant temperature stirring reaction;It is 600~800r/min in rotating speed, temperature is 60~65 after after constant temperature stirring reaction
Under the conditions of DEG C, 100~150mL mass fractions are added dropwise for 30~35% calcium nitrate solutions into three-necked flask by dropping funel, control
System dripped off in 30~45min, and with mass fraction be 10% sodium hydroxide solution adjust three-necked flask in material pH to 9.6~
10.0, continue after constant temperature stirring reaction 45~60min, material in three-necked flask be transferred in autoclave, in temperature be 170~
8~10h of confined reaction under the conditions of 180 DEG C;Then treat that confined reaction terminates, by material filtering in autoclave, obtain filter cake, with anhydrous
After ethanol washing gained filter cake 3~5 times, then it is washed with deionized until cleaning solution is in neutrality, then after deionized water is washed
Filter cake be transferred in baking oven, in temperature be 105~110 DEG C under the conditions of dry to constant weight, obtain dry cake;Gained is dried again and filtered
Cake is transferred to Muffle furnace, is warming up to 500~550 DEG C with 8~10 DEG C/min rate programs, insulation 2~4h of calcining cools to room with the furnace
Temperature, discharging, must calcine material;Calcining material obtained by 10~12g is weighed, the four-hole boiling flask for filling 100~150mL silver ammino solutions is poured into
In, then four-hole boiling flask is placed in sonic oscillation instrument, 20~30min of ultrasonic disperse under the conditions of frequency is 40~45kHz, then by four
Mouth flask immigration digital display tests the speed in constant temperature blender with magnetic force, is 400~500r/min in rotating speed, temperature is 40~45 DEG C of conditions
Under, it is 5~10% glucose solutions that 100~120mL mass fractions are added into four-hole boiling flask, then with 8~10mL/min speed to
Nitrogen is passed through in four-hole boiling flask, end to be added under nitrogen guard mode, continues constant temperature 20~30min of stirring reaction, mistake
Filter, obtains deposit filter residue;Gained deposit filter residue is finally washed with deionized, until cleaning solution is in neutrality, then by after washing
Deposit filter residue be transferred in vacuum drying chamber, be to dry to constant weight under the conditions of 105~110 DEG C in temperature, then will be dried
Deposit filter residue sealing preserve, produces nano silver antimicrobials.
Example 1
400mL mass fractions are measured first for 2% silver nitrate solution, are poured into beaker, then beaker immigration digital display is tested the speed constant temperature magnetic
It it is 55 DEG C in temperature, rotating speed is under the conditions of 300r/min, it is 2% ammoniacal liquor that mass fraction, which is added dropwise, into beaker, is treated in power agitator
Produced in beaker and continue that ammoniacal liquor is added dropwise after precipitation, until the precipitation produced is completely dissolved, obtain silver ammino solution;80g activated carbons are weighed,
Pour into pulverizer, 80 mesh sieves are crossed after crushing, activated carbon powder is obtained, then weigh activated carbon powder obtained by 20g, the oxidations of 10g five two successively
Phosphorus, is poured into the three-necked flask for filling 100mL absolute ethyl alcohols, and by three-necked flask move into sonic oscillation instrument, in frequency be 40kHz
Under the conditions of ultrasonic disperse 20min, then three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, in temperature be 55 DEG C, rotating speed
Under the conditions of 400r/min, constant temperature stirring reaction 45min;It is 600r/min in rotating speed, temperature is 60 after after constant temperature stirring reaction
Under the conditions of DEG C, 100mL mass fractions are added dropwise for 30% calcium nitrate solution into three-necked flask by dropping funel, controlled in 30min
Inside drip off, and be that 10% sodium hydroxide solution adjusts material pH to 9.6 in three-necked flask with mass fraction, continue constant temperature stirring anti-
Answer after 45min, material in three-necked flask is transferred in autoclave, the confined reaction 8h under the conditions of temperature is 170 DEG C;Then treat close
Close reaction to terminate, by material filtering in autoclave, obtain filter cake, washed with absolute ethyl alcohol after gained filter cake 3 times, then use deionized water
Washing is until cleaning solution is in neutrality, then the filter cake after deionized water is washed is transferred in baking oven, is to do under the conditions of 105 DEG C in temperature
It is dry to constant weight, obtain dry cake;Gained dry cake is transferred to Muffle furnace again, 500 DEG C are warming up to 8 DEG C/min rate programs,
Insulation calcining 2h, cools to room temperature with the furnace, discharges, must calcine material;Calcining material obtained by 10g is weighed, pours into that to fill the silver-colored ammonia of 100mL molten
In the four-hole boiling flask of liquid, then four-hole boiling flask is placed in sonic oscillation instrument, the ultrasonic disperse 20min under the conditions of frequency is 40kHz, then
Four-hole boiling flask immigration digital display is tested the speed in constant temperature blender with magnetic force, is 400r/min in rotating speed, temperature is Xiang Si under the conditions of 40 DEG C
It is 5% glucose solution to add 100mL mass fractions in mouth flask, then nitrogen is passed through into four-hole boiling flask with 8mL/min speed,
It is to be added to terminate, under nitrogen guard mode, continue constant temperature stirring reaction 20min, filtering obtains deposit filter residue;Finally spend
Deposit filter residue obtained by ion water washing, until cleaning solution is in neutrality, then is transferred to vacuum drying by the deposit filter residue after washing
In case, dried under the conditions of temperature is 105 DEG C to constant weight, then by dried deposit filter residue sealing preserve, produce Nano Silver
Antiseptic.
It is put into powder spray rifle, and is uniformly sprayed in shoe lining leather skin after nano silver antimicrobials produced by the present invention are crushed
Sample flesh noodles, it is 65g/m to control the amount of spraying2, spray and finish.Nano silver antimicrobials of the present invention have preferably dispersed and anti-
Bacterium persistence, not only reduces the processing cost of shoe lining leather, also effectively increases bacteriostasis rate of the shoe lining leather to mould and bacterium,
After xerotripsis 25 times, wet rubbing 21 times, to mould bacteriostasis rate still up to 91.7%, to bacterium bacteriostasis rate still up to 93.5%, and conventional nano silver
Antiseptic is used in after shoe lining leather, after xerotripsis 25 times, wet rubbing 21 times, is 81.2% to mould bacteriostasis rate, is to bacterium bacteriostasis rate
82.3%。
Example 2
500mL mass fractions are measured first for 2% silver nitrate solution, are poured into beaker, then beaker immigration digital display is tested the speed constant temperature magnetic
It it is 58 DEG C in temperature, rotating speed is under the conditions of 400r/min, it is 3% ammoniacal liquor that mass fraction, which is added dropwise, into beaker, is treated in power agitator
Produced in beaker and continue that ammoniacal liquor is added dropwise after precipitation, until the precipitation produced is completely dissolved, obtain silver ammino solution;90g activated carbons are weighed,
Pour into pulverizer, 100 mesh sieves are crossed after crushing, activated carbon powder is obtained, then weigh activated carbon powder obtained by 25g, the oxidations of 13g five two successively
Phosphorus, is poured into the three-necked flask for filling 110mL absolute ethyl alcohols, and by three-necked flask move into sonic oscillation instrument, in frequency be 43kHz
Under the conditions of ultrasonic disperse 25min, then three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, in temperature be 58 DEG C, rotating speed
Under the conditions of 500r/min, constant temperature stirring reaction 52min;It is 700r/min in rotating speed, temperature is 63 after after constant temperature stirring reaction
Under the conditions of DEG C, 130mL mass fractions are added dropwise for 33% calcium nitrate solution into three-necked flask by dropping funel, controlled in 38min
Inside drip off, and be that 10% sodium hydroxide solution adjusts material pH to 9.8 in three-necked flask with mass fraction, continue constant temperature stirring anti-
Answer after 52min, material in three-necked flask is transferred in autoclave, the confined reaction 9h under the conditions of temperature is 175 DEG C;Then treat close
Close reaction to terminate, by material filtering in autoclave, obtain filter cake, washed with absolute ethyl alcohol after gained filter cake 4 times, then use deionized water
Washing is until cleaning solution is in neutrality, then the filter cake after deionized water is washed is transferred in baking oven, is to do under the conditions of 108 DEG C in temperature
It is dry to constant weight, obtain dry cake;Gained dry cake is transferred to Muffle furnace again, 530 DEG C are warming up to 9 DEG C/min rate programs,
Insulation calcining 3h, cools to room temperature with the furnace, discharges, must calcine material;Calcining material obtained by 11g is weighed, pours into that to fill the silver-colored ammonia of 130mL molten
In the four-hole boiling flask of liquid, then four-hole boiling flask is placed in sonic oscillation instrument, the ultrasonic disperse 25min under the conditions of frequency is 43kHz, then
Four-hole boiling flask immigration digital display is tested the speed in constant temperature blender with magnetic force, is 450r/min in rotating speed, temperature is Xiang Si under the conditions of 43 DEG C
It is 8% glucose solution to add 110mL mass fractions in mouth flask, then nitrogen is passed through into four-hole boiling flask with 9mL/min speed,
It is to be added to terminate, under nitrogen guard mode, continue constant temperature stirring reaction 25min, filtering obtains deposit filter residue;Finally spend
Deposit filter residue obtained by ion water washing, until cleaning solution is in neutrality, then is transferred to vacuum drying by the deposit filter residue after washing
In case, dried under the conditions of temperature is 108 DEG C to constant weight, then by dried deposit filter residue sealing preserve, produce Nano Silver
Antiseptic.
It is put into powder spray rifle, and is uniformly sprayed in shoe lining leather skin after nano silver antimicrobials produced by the present invention are crushed
Sample flesh noodles, it is 68g/m to control the amount of spraying2, spray and finish.Nano silver antimicrobials of the present invention have preferably dispersed and anti-
Bacterium persistence, not only reduces the processing cost of shoe lining leather, also effectively increases bacteriostasis rate of the shoe lining leather to mould and bacterium,
After xerotripsis 27 times, wet rubbing 23 times, to mould bacteriostasis rate still up to 90.1%, to bacterium bacteriostasis rate still up to 92.9%, and conventional nano silver
Antiseptic is used in after shoe lining leather, after xerotripsis 27 times, wet rubbing 23 times, is 79.8% to mould bacteriostasis rate, is to bacterium bacteriostasis rate
81.4%。
Example 3
600mL mass fractions are measured first for 2% silver nitrate solution, are poured into beaker, then beaker immigration digital display is tested the speed constant temperature magnetic
It it is 60 DEG C in temperature, rotating speed is under the conditions of 500r/min, it is 4% ammoniacal liquor that mass fraction, which is added dropwise, into beaker, is treated in power agitator
Produced in beaker and continue that ammoniacal liquor is added dropwise after precipitation, until the precipitation produced is completely dissolved, obtain silver ammino solution;Weigh 100g activity
Charcoal, is poured into pulverizer, and 120 mesh sieves are crossed after crushing, activated carbon powder is obtained, then weighs activated carbon powder obtained by 30g, the oxygen of 15g five successively
Change two phosphorus, pour into the three-necked flask for filling 120mL absolute ethyl alcohols, and three-necked flask is moved into sonic oscillation instrument, be in frequency
Ultrasonic disperse 30min under the conditions of 45kHz, then three-necked flask immigration digital display is tested the speed constant temperature blender with magnetic force, in temperature be 60 DEG C,
Rotating speed be 600r/min under the conditions of, constant temperature stirring reaction 60min;After after constant temperature stirring reaction, in rotating speed be 800r/min, temperature
Under the conditions of 65 DEG C, 150mL mass fractions are added dropwise for 35% calcium nitrate solution into three-necked flask by dropping funel, control exists
Dripped off in 45min, and be that 10% sodium hydroxide solution adjusts material pH to 10.0 in three-necked flask with mass fraction, continue constant temperature
After stirring reaction 60min, material in three-necked flask is transferred in autoclave, the confined reaction 10h under the conditions of temperature is 180 DEG C;
Then treat that confined reaction terminates, by material filtering in autoclave, obtain filter cake, washed with absolute ethyl alcohol after gained filter cake 5 times, then use
Deionized water washing is until cleaning solution is in neutrality, then the filter cake after deionized water is washed is transferred in baking oven, in temperature be 110 DEG C
Under the conditions of dry to constant weight, obtain dry cake;Gained dry cake is transferred to Muffle furnace again, heated up with 10 DEG C/min rate programs
To 550 DEG C, insulation calcining 4h cools to room temperature with the furnace, discharges, must calcine material;Calcining material obtained by 12g is weighed, pours into and fills
In the four-hole boiling flask of 150mL silver ammino solutions, then four-hole boiling flask is placed in sonic oscillation instrument, the ultrasound under the conditions of frequency is 45kHz
Scattered 30min, then four-hole boiling flask immigration digital display is tested the speed in constant temperature blender with magnetic force, it is 500r/min in rotating speed, temperature is 45
Under the conditions of DEG C, it is 10% glucose solution to add 120mL mass fractions into four-hole boiling flask, then with 10mL/min speed to four mouthfuls
Nitrogen is passed through in flask, end to be added under nitrogen guard mode, continues constant temperature stirring reaction 30min, filtering must be deposited
Thing filter residue;Gained deposit filter residue is finally washed with deionized, until cleaning solution is in neutrality, then the deposit after washing is filtered
Slag is transferred in vacuum drying chamber, is dried under the conditions of temperature is 110 DEG C to constant weight, then dried deposit filter residue is sealed into guarantor
Deposit, produce nano silver antimicrobials.
It is put into powder spray rifle, and is uniformly sprayed in shoe lining leather skin after nano silver antimicrobials produced by the present invention are crushed
Sample flesh noodles, it is 72g/m to control the amount of spraying2, spray and finish.Nano silver antimicrobials of the present invention have preferably dispersed and anti-
Bacterium persistence, not only reduces the processing cost of shoe lining leather, also effectively increases bacteriostasis rate of the shoe lining leather to mould and bacterium,
After xerotripsis 28 times, wet rubbing 25 times, to mould bacteriostasis rate still up to 89.6%, to bacterium bacteriostasis rate still up to 92.4%, and conventional nano silver
Antiseptic is used in after shoe lining leather, after xerotripsis 28 times, wet rubbing 25 times, is 78.5% to mould bacteriostasis rate, is to bacterium bacteriostasis rate
80.5%。
Claims (5)
1. a kind of preparation method of nano silver antimicrobials, it is characterised in that specifically preparation process is:
(1)400~600mL mass fractions are measured for 2% silver nitrate solution, under constant temperature stirring, are dripped into silver nitrate solution
Plus mass fraction is continuation dropwise addition ammoniacal liquor after 2~4% ammoniacal liquor, precipitation to be generated, until the precipitation produced is completely dissolved, obtains silver-colored ammonia
Solution;
(2)Activated carbon powder obtained by 20~30g is weighed successively, and 10~15g phosphorus pentoxides pour into 100~120mL absolute ethyl alcohols
In, after 20~30min of ultrasonic disperse, constant temperature 45~60min of stirring reaction, then be added dropwise 100~150mL mass fractions for 30~
35% calcium nitrate solution, control is dripped off in 30~45min, and is that 10% sodium hydroxide solution adjusts pH to 9.6 with mass fraction
~10.0, continue after 45~60min of constant temperature stirring reaction, be transferred in autoclave, it is closed under the conditions of temperature is 170~180 DEG C
8~10h is reacted, treats that confined reaction terminates, is filtered, washing, drying and calcination must calcine material;
(3)10~12g calcining material are weighed, are poured into 100~150mL silver ammino solutions, after 20~30min of ultrasonic disperse, side constant temperature
Stirring side adds 100~120mL mass fractions into silver ammino solution for 5~10% glucose solutions, end to be added, continues permanent
Warm 20~30min of stirring reaction, filtering is dried to constant weight after washing, produces nano silver antimicrobials.
2. a kind of preparation method of nano silver antimicrobials according to claim 1, it is characterised in that:Step(2)Described
Activated carbon powder particle diameter is 80~120 mesh.
3. a kind of preparation method of nano silver antimicrobials according to claim 1, it is characterised in that:Step(2)Described
2~4mL mass fractions can also be added in absolute ethyl alcohol for 98% sulfuric acid solution.
4. a kind of preparation method of nano silver antimicrobials according to claim 1, it is characterised in that:Step(2)Described
Constant temperature stirring reaction condition is that reaction temperature is 55~60 DEG C, and speed of agitator is 400~600r/min.
5. a kind of preparation method of nano silver antimicrobials according to claim 1, it is characterised in that:Step(3)Described
During constant temperature stirring reaction, moreover it is possible to nitrogen is passed through into silver ammino solution with 8~10mL/min speed.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107629469A (en) * | 2017-10-19 | 2018-01-26 | 谢新昇 | A kind of chitosan packaging film and preparation method thereof |
CN108620604A (en) * | 2018-06-11 | 2018-10-09 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of high-purity nano silver paste |
CN108821743A (en) * | 2018-07-17 | 2018-11-16 | 仝建川 | A kind of preparation method of the dark-red enameled pottery of health care |
CN112111199A (en) * | 2019-10-16 | 2020-12-22 | 长沙绿叶生物科技有限公司 | Novel nano disinfection coating for disinfection of livestock and poultry breeding places and application thereof |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1587195A (en) * | 2004-07-28 | 2005-03-02 | 同济大学 | Method for synthesizing nano hydroxy-apatite micro powder contaniing carbonate radical |
CN105289497A (en) * | 2015-11-25 | 2016-02-03 | 甘李 | High nanometer sliver loading active carbon and preparation method thereof |
-
2017
- 2017-06-07 CN CN201710424757.7A patent/CN107232229A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1587195A (en) * | 2004-07-28 | 2005-03-02 | 同济大学 | Method for synthesizing nano hydroxy-apatite micro powder contaniing carbonate radical |
CN105289497A (en) * | 2015-11-25 | 2016-02-03 | 甘李 | High nanometer sliver loading active carbon and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
罗民华: "《多孔陶瓷实用技术》", 31 March 2006, 中国建材工业出版社 * |
赵书华,姬红,曹艳霞: "锯末天然模板辅助合成羟基磷灰石", 《中国资源综合利用》 * |
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CN107629469A (en) * | 2017-10-19 | 2018-01-26 | 谢新昇 | A kind of chitosan packaging film and preparation method thereof |
CN108620604A (en) * | 2018-06-11 | 2018-10-09 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of high-purity nano silver paste |
CN108821743A (en) * | 2018-07-17 | 2018-11-16 | 仝建川 | A kind of preparation method of the dark-red enameled pottery of health care |
CN112111199A (en) * | 2019-10-16 | 2020-12-22 | 长沙绿叶生物科技有限公司 | Novel nano disinfection coating for disinfection of livestock and poultry breeding places and application thereof |
CN115530162A (en) * | 2021-12-09 | 2022-12-30 | 沈蓉蓉 | High-temperature-resistant durable antibacterial agent |
CN114232178A (en) * | 2021-12-20 | 2022-03-25 | 深圳市玛依尔科技有限公司 | Composite fiber garment fabric with antibacterial effect and preparation method thereof |
CN114806245A (en) * | 2022-05-10 | 2022-07-29 | 浙江汇丰防腐保温工程有限公司 | Nano modified anticorrosive paint and preparation method thereof |
CN115141575A (en) * | 2022-07-11 | 2022-10-04 | 苏州中廷新材料有限公司 | Nano antibacterial material for hot melt adhesive and preparation method thereof |
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