CN106390930B - A kind of method that glycine prepares active carbon loading silver with silver nitrate complexing - Google Patents
A kind of method that glycine prepares active carbon loading silver with silver nitrate complexing Download PDFInfo
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- CN106390930B CN106390930B CN201611173171.XA CN201611173171A CN106390930B CN 106390930 B CN106390930 B CN 106390930B CN 201611173171 A CN201611173171 A CN 201611173171A CN 106390930 B CN106390930 B CN 106390930B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 90
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 61
- 239000004332 silver Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910001961 silver nitrate Inorganic materials 0.000 title claims abstract description 32
- 239000004471 Glycine Substances 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 238000011068 loading method Methods 0.000 title claims abstract description 14
- 230000000536 complexating effect Effects 0.000 title claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000007654 immersion Methods 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 31
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 230000007306 turnover Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 238000002798 spectrophotometry method Methods 0.000 claims description 2
- 239000012086 standard solution Substances 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000002070 germicidal effect Effects 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 description 9
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002333 glycines Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
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- Carbon And Carbon Compounds (AREA)
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Abstract
The present invention relates to a kind of method that glycine and silver nitrate complexing prepare active carbon loading silver, by with silver nitrate and complexing of glycin solution, then activated carbon is infiltrated, be made by heat resolve and reduction.It is 2~1.5 first to prepare molar ratio:The silver nitrate of 1, Ag mass of ion a concentration of 0.01~0.6%-complexing of glycin liquid；The ratio of activated carbon and complex liquid is to be dehydrated in 50~100 DEG C after 0.25~1Kg/ rises immersion 6~24 hours；160-260 DEG C under circulating nitrogen gas protection, heat preservation thermal decomposition in 0.5~6 hour；It is dry after clear water washing.Gained nano silver grain size of the invention is 10 ~ 60nm；0.01~0.45wt.% of silver carrying amount；Argent grain is high with activated carbon binding force, and Argent grain good dispersion, technological process is short, and reaction temperature is low, improves the germicidal efficiency of active carbon loading silver, reduces silver-colored dosage.
Description
Technical field
The present invention relates to a kind of methods of active carbon loading silver.It is by preparing silver nitrate and complexing of glycin solution, then
Activated carbon is infiltrated, high stability is obtained using the reaction heat of silver nitrate and glycine complexes by heat resolve and reduction
Activated carbon surface adsorbs nano-Ag particles, for pure water purification and sterilization etc..
Technical background
The absorbent charcoal material being modified the invention belongs to the nano particle silver in fields such as purify, sterilize.
Domestic and international drinking water deep purification activated carbon (AC), usually based on load silver.The preparation of active carbon loading silver (AC/Ag)
Method includes mainly infusion process, doping method, electrochemical deposition method, reduction method, supercritical water infusion process etc., and industrial applications are more
Be infusion process and reduction method.
Infusion process be using the film containing silver particles aqueous solution soaking AC such as silver nitrate, silver acetate, adsorbed after dry silver from
Then the activated carbon of son decomposes by heating and obtains silver oxide, then calcines several hours at 400~500 DEG C, utilize silver oxide height
Temperature decomposes and obtains metallic silver.It is required that calcining under inert gas protection, there cannot be free air infiltration to enter in calcination process and temperature-fall period,
Once there is free air infiltration to enter, the metallic silver easily formed can be oxidized to silver oxide again, and end product quality is not easy to control.Infusion process
AC/Ag simple process and low costs are prepared, pollution-free, silver is distributed in the surfaces AC, is conducive to sterilize.But the load silver that the method obtains
The combination of AC and silver is mainly physical absorption in activated carbon, and silver is easy to be lost in, and cannot achieve the effect that persistently to sterilize.
Reduction method is that AC is immersed in a period of time in Ag-containing solution, then with a kind of reducing agent silver ion reduction Cheng Dan
The process of matter silver.With NaBH4Reduction prepare AC/Ag for, detailed process be activated carbon activation process, it is long under the conditions of being protected from light when
Between be impregnated into AgNO3In solution, it is washed with distilled water later until without silver ion detection in cleaning solution, then impregnates above-mentioned AC
In NaBH4In solution for a long time, washing removes residue NaBH later4, dry for a long time in 70 DEG C of vacuum.AC may be implemented in the method
With the good combination of Argent grain.But reduction method process flow is long；It needs repeatedly to wash, water consumption is big, and water resource purity requirement is high；
Need to be protected from light, techniques, the equipment requirement such as vacuum it is high；And Argent grain is mainly distributed in reunion shape in the outer surface and hole of AC,
The Argent grain of load is bigger, and germicidal efficiency is not high.
Invention content
The object of the present invention is to provide a kind of preparation methods of the active carbon loading silver with efficient, lasting bactericidal effect.
The technical solution adopted by the present invention to solve the technical problems is complexing to occur with silver particles using a kind of
Reducing agent, silver ion is adsorbed on complex form in the surface and micropore of activated carbon, it is then fast at a lower temperature
Speed reduction is decomposed, the active carbon loading silver for obtaining good dispersion, not easily runing off.It is specific as follows：
(1) prepared by silver nitrate-complexing of glycin liquid：A certain amount of silver nitrate crystal and Glycine crystals are weighed, with distillation
Water dissolution obtains silver-colored ammonium nitrate complex liquid.Wherein, the molar ratio of silver nitrate and glycine is 2~1.5:1, preparation it is water-soluble
Ag mass of ions a concentration of 0.01~0.6% in liquid.
(2) silver ion immersion, dry activated carbon：By water purification active carbon, such as fruit shell carbon, coal quality charcoal, washed with distillation
Only it, dries, cool.With prepared silver nitrate-complexing of glycin liquid shaken at room temperature, activated carbon is impregnated, soaking time is 6~24
Hour；The ratio of activated carbon and complex liquid is 0.25~1Kg/ liters when immersion；It is filtered dry in ventilated environment, light protected environment after immersion；
Then in hot wind, such as electric drying oven with forced convection, 50~100 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 160-260 DEG C after drying will be impregnated, and soaking time is 0.5~6 small
When.It is protected using dry circulating nitrogen gas when thermal decomposition, can also be used when having ready conditions and decompose ammonia protection.Using pushing away boat stove, guipure
The continuous furnaces such as formula drying oven, rotary furnace can realize continuous production.Heating rate is controlled at 0.1~2 DEG C/min, avoids heat
Decomposition reaction excessively acutely influences nano silver dispersibility and the interface binding power with activated carbon surface.
(4) it washs：By above-mentioned activated carbon pure water washing 2~4 times, remaining reactant is washed away.In order to avoid silver granuel
Son oxidation, the drying temperature after cleaning are controlled at 50~120 DEG C.Silver-colored remaining quantity≤10ppb of water after cleaning（Micrograms per litre),
Reach the standard of drinking water.
(5) it detects：Every batch of is using sodium sulfocyanate standard solution titration determination silver carrying amount, scanning electron microscopic observation Argent grain
Morphology and size, and in 25 DEG C, 150 r/min, constant temperature oscillation is after 600 hours, with resisting for the swollen Spectrophotometric Determination of Silver of double sulphur
Flow and failure property, silver-colored turnover rate≤20%, silver carrying amount receptor 1 activity charcoal specific surface and absorption property, complex liquid silver content, soaking technology
With the influence of the parameter of thermal decomposition process step is repeated when silver carrying amount is less than desired 0.01~0.45wt.% of section（2）Silver
Ion immersion, dry activated carbon and step（3）Pyrolysis is to increase silver carrying amount.
The molar ratio of the silver nitrate and alanine is 1.8~1.5:1.
The Ag mass of ions a concentration of 0.1~0.6%.
The dry activated carbon heating is 180-250 DEG C.
By silver nitrate (AgNO3) as oxidant, glycine (C2H5NO2) as complexing reducing agent, it is configured to aqueous solution；
Solution, which is gradually evaporated, can form gel.This gel can react rapidly at 160~260 DEG C, release bulk gas and heat, can
The nano level superfine silver powder disperseed.Glycine (H has occurred first during this2N-CH2- COOH) hydrolysis it is anti-
It answers, NH occurs4 +.With the progress of heating, water evaporation, the NH in solution4 +And NO3 -Ion is then with NH4NO3The form of crystal is analysed
Go out, finally obtains AgOH, Ag2O and NH4NO3The mixture of crystal.Above-mentioned mixed crystal further heats, it may occur that multiple
Miscellaneous decomposition reaction obtains nano silver and CO2、H2O、N2O、N2Equal gases.
When silver nitrate and glycine are 2 in molar ratio:Reaction equation when 1 is as follows：
4AgNO3+2C2H5NO2→4Ag+4CO2+5H2O+3N2O
When silver nitrate and glycine are 3 in molar ratio:Reaction equation when 2 is as follows：
6AgNO3+4C2H5NO2→6Ag+8CO2+10H2O+5N2
When silver nitrate excess, reaction will appear the oxide of silver, but due to exothermic heat of reaction, local temperature increases, silver-colored
Oxidation product decomposes and obtains elemental silver；When reducing agent glycine is further excessive, oxygen is needed to participate in reaction, or release
Go out ammonia.
The present invention has the characteristics that reaction temperature is low and efficient, usually at 160-260 DEG C for producing active carbon loading silver
Between, the heat of decomposition reaction release promotes reaction to carry out.Compared with conventional dipping and thermal decomposition process, technique stream is shortened
Journey, reduce reaction temperature, avoid the occurrence of due to pyroreaction and caused by Ag particles combined with carbon surface and loosely and easily occurred
The problem of silver oxide.Compared with conventional reduction method, reduce dipping time, and due to complexing Ag chemical combination of the present invention
Object, which decomposes, generates bulk gas such as NH3、H2O、CO2、N2, N2O etc. makes the Ag nano particles to be formed disperse, overcomes General N aBH4
Reduction prepares the Ag particle agglomeration phenomenons of AC/Ag, improves the germicidal efficiency of active carbon loading silver, reduces silver-colored dosage.
Present invention process process is simple, easily operated, yield is high, is easy to industrialized production, have it is clean, environmentally protective and
Characteristics of energy saving.Gained nano silver grain size is 10 ~ 60nm；0.01~0.45wt.% of silver carrying amount；Argent grain and activated carbon binding force
Height, 150r/min vibrate in 25 DEG C of thermostatted waters, after 600 hours, silver-colored turnover rate≤25%；Argent grain good dispersion, sterilization effect
Rate is high.
Specific implementation mode
It elaborates to the present invention below by way of specific embodiment.
Embodiment 1
(1) prepared by silver nitrate-complexing of glycin liquid：17g silver nitrates and 5.0g glycine are weighed, with distillation water dissolution, is obtained
Obtain 100 liters of silver-colored ammonium nitrate complex liquids.Wherein, the molar ratio of silver nitrate and glycine is 3:2, Ag ions in the aqueous solution of preparation
Mass concentration is about 0.01%.
(2) silver ion immersion, dry activated carbon：Commercially available coconut fruit shell carbon is cleaned with distilled water, dry, is cooled.With
Ag mass of ion concentration is about 0.01%, molar ratio 3:2 silver nitrate-complexing of glycin liquid shaken at room temperature impregnates activity
Charcoal, soaking time are 6 hours；The ratio of activated carbon and complex liquid is 1Kg/ liters when immersion；After immersion in ventilated environment, be protected from light ring
Border is filtered dry；In electric drying oven with forced convection, 50 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 160 DEG C after drying will be impregnated, and soaking time is 6 hours.Thermal decomposition
Dry in the circulating nitrogen gas protection tube furnace of Shi Caiyong dryings, heating rate is 2 DEG C/min.
(4) it washs：By above-mentioned activated carbon pure water washing 2 times, remaining reactant is washed away.It is roused in electric heating after cleaning
Wind drying box, 50 DEG C of dryings to constant weight.
(5) it detects：Gained nano silver grain size is 25nm；Silver carrying amount 0.01%；Argent grain is high with activated carbon binding force,
150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, silver-colored turnover rate is 12%.
Embodiment 2
(1) prepared by silver nitrate-complexing of glycin liquid：17g silver nitrates and 5.0g glycine are weighed, with distillation water dissolution, is obtained
Obtain 18 liters of silver-colored ammonium nitrate complex liquids.Wherein, the molar ratio of silver nitrate and glycine is 3:2, Ag ions in the aqueous solution of preparation
Mass concentration is about 0.6%.
(2) silver ion immersion, dry activated carbon：Commercially available coal quality charcoal is cleaned with distilled water, dry, is cooled.With Ag ions
Mass concentration is about 0.6%, molar ratio 3:2 silver nitrate-complexing of glycin liquid shaken at room temperature impregnates activated carbon, when immersion
Between be 24 hours；The ratio of activated carbon and complex liquid is 1Kg/ liters when immersion；It is filtered dry in ventilated environment, light protected environment after immersion；
In electric drying oven with forced convection, 100 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 260 DEG C after drying will be impregnated, and soaking time is 0.5 hour.Heat point
It is protected using dry circulating nitrogen gas at 0.1 DEG C/min using net belt type drying oven, heating rate control when solution.
(4) it washs：By above-mentioned activated carbon pure water washing 4 times, remaining reactant is washed away.Guipure is used in after cleaning
In formula drying oven, 120 DEG C of dryings to constant weight.
(5) it detects：Gained nano silver grain size is 58nm；Silver carrying amount 0.44%；Argent grain is high with activated carbon binding force,
150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, silver-colored turnover rate is 24%.
Embodiment 3
(1) prepared by silver nitrate-complexing of glycin liquid：17g silver nitrates and 3.8g glycine are weighed, with distillation water dissolution, is obtained
Obtain 18 liters of silver-colored ammonium nitrate complex liquids.Wherein, the molar ratio of silver nitrate and glycine is 2:1, Ag ions in the aqueous solution of preparation
Mass concentration is about 0.6%.
(2) silver ion immersion, dry activated carbon：Commercially available fruit shell carbon is cleaned with distilled water, dry, is cooled.With Ag ions
Mass concentration is about 0.6%, molar ratio 2:1 silver nitrate-complexing of glycin liquid shaken at room temperature impregnates activated carbon, when immersion
Between be 12 hours；The ratio of activated carbon and complex liquid is 0.25Kg/ liters when immersion；It is filtered in ventilated environment, light protected environment after immersion
It is dry；It is dried to constant weight in 80 DEG C of heated-air drying cylinders, removes water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 200 DEG C after drying will be impregnated, and soaking time is 3 hours.Thermal decomposition
Shi Caiyong pushes away boat drying oven, heating rate control at 0.5 DEG C/min automatically, is protected using dry circulating nitrogen gas.
(4) it washs：By above-mentioned activated carbon pure water washing 3 times, remaining reactant is washed away.It is used in after cleaning automatic
Push away boat drying oven, 110 DEG C of dryings to constant weight.
(5) it detects：Gained nano silver grain size is 60nm；Silver carrying amount 0.32%；Argent grain is high with activated carbon binding force,
150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, silver-colored turnover rate is 14%.
Embodiment 4
(1) prepared by silver nitrate-complexing of glycin liquid：Weigh 17g silver nitrates and 4.68g glycine, with distillation water dissolution,
Obtain 36 liters of silver-colored ammonium nitrate complex liquids.Wherein, the molar ratio of silver nitrate and glycine is 1.6:1, Ag in the aqueous solution of preparation
Mass of ion concentration is about 0.3%.
(2) silver ion immersion, dry activated carbon：Commercially available fruit shell carbon is cleaned with distilled water, dry, is cooled.With Ag ions
Mass concentration is about 0.3%, molar ratio 1.6:1 silver nitrate-complexing of glycin liquid shaken at room temperature impregnates activated carbon, impregnates
Time is 12 hours；The ratio of activated carbon and complex liquid is 0.5Kg/ liters when immersion；It is filtered in ventilated environment, light protected environment after immersion
It is dry；It is dried to constant weight in 100 DEG C of heated-air drying cylinders, removes water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 220 DEG C after drying will be impregnated, and soaking time is 3 hours.Thermal decomposition
Shi Caiyong pushes away boat drying oven, heating rate control at 0.5 DEG C/min automatically, is protected using dry circulating nitrogen gas.
(4) it washs：By above-mentioned activated carbon pure water washing 2 times, remaining reactant is washed away.It is used in after cleaning automatic
Push away boat drying oven, 120 DEG C of dryings to constant weight.
(5) it detects：Gained nano silver grain size is 30nm；Silver carrying amount 0.3%；Argent grain is high with activated carbon binding force,
150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, silver-colored turnover rate is 14%.
Embodiment 5
(1) prepared by silver nitrate-complexing of glycin liquid：Weigh 8.5g silver nitrates and 4.4g glycine, with distillation water dissolution,
Obtain 36 liters of silver-colored ammonium nitrate complex liquids.Wherein, the molar ratio of silver nitrate and glycine is 1.7:1, Ag in the aqueous solution of preparation
Mass of ion concentration is about 0.15%.
(2) silver ion immersion, dry activated carbon：Commercially available fruit shell carbon is cleaned with distilled water, dry, is cooled.With Ag ions
Mass concentration is about 0.15%, molar ratio 1.7:1 silver nitrate-complexing of glycin liquid shaken at room temperature impregnates activated carbon, leaching
It is 9 hours to steep the time；The ratio of activated carbon and complex liquid is 0.25Kg/ liters when immersion；In ventilated environment, light protected environment after immersion
It is filtered dry；It is dried to constant weight in 90 DEG C of heated-air drying cylinders, removes water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 200 DEG C after drying will be impregnated, and soaking time is 2 hours.Thermal decomposition
The circulating nitrogen gas of Shi Caiyong dryings protects tube furnace, heating rate to control at 1 DEG C/min,.
(4) it washs：By above-mentioned activated carbon pure water washing 2 times, remaining reactant is washed away.With 90 DEG C of drums after cleaning
Wind drying box is dried to constant weight.
(5) it detects：Gained nano silver grain size is 25nm；Silver carrying amount 0.03%；Argent grain is high with activated carbon binding force,
150r/min vibrates in 25 DEG C of thermostatted waters, and after 600 hours, silver-colored turnover rate is 9%.
Claims (4)
1. a kind of method that glycine prepares active carbon loading silver with silver nitrate complexing, it is characterised in that include the following steps：
(1) prepared by silver nitrate-complexing of glycin liquid：Silver nitrate crystal and Glycine crystals are weighed, with distillation water dissolution, is obtained
The molar ratio of silver nitrate-complexing of glycin liquid, silver nitrate and glycine is 2~1.5:1, Ag ion matter in the aqueous solution of preparation
Measure a concentration of 0.01~0.6%；
(2) silver ion immersion, dry activated carbon：Water purification active carbon distilled water is cleaned, is dried, is cooling, with prepared nitre
Sour silver-complexing of glycin liquid shaken at room temperature impregnates activated carbon, and soaking time is 6~24 hours；Activated carbon and complex liquid when immersion
Ratio be 0.25~1Kg/ liters；It is filtered dry in ventilation, light protected environment after immersion；Then it is dried extremely in 50~100 DEG C of hot wind
Constant weight removes water and the crystallization water；
(3) pyrolysis：Activated carbon is warming up to 160-260 DEG C after drying will be impregnated, and keeps the temperature 0.5~6 hour and carries out heat point
Solution is protected using dry circulating nitrogen gas when thermal decomposition；Using boat stove, net belt type drying oven or rotary furnace is pushed away, realize continuous raw
Production；Heating rate is controlled at 0.1~2 DEG C/min；
(4) it washs：The product that step (3) is obtained pure water washing 2~4 times, washes away the reactant of remnants；In order to avoid
Silver particles aoxidize, and the drying temperature after cleaning is controlled at 50~120 DEG C；Silver-colored remaining quantity≤10ppb of water after cleaning, reaches drink
With the standard of water；
(5) it detects：Every batch of is using sodium sulfocyanate standard solution titration determination silver carrying amount, scanning electron microscopic observation Argent grain pattern
And size, and in 25 DEG C, 150 r/min, constant temperature oscillation after 600 hours, lose by the anti-current that silver is measured with dithizone spectrophotometry
Performance, silver-colored turnover rate≤20%, silver carrying amount receptor 1 activity charcoal specific surface and absorption property, complex liquid silver content, soaking technology and heat
The influence of the parameter of decomposition technique repeats step when silver carrying amount is less than desired 0.01wt.%（2）Silver ion impregnates, is dry
Activated carbon and step（3）Pyrolysis is to increase silver carrying amount.
2. the method that glycine as described in claim 1 prepares active carbon loading silver with silver nitrate complexing, it is characterised in that：It is described
Silver nitrate and glycine molar ratio be 1.8~1.5:1.
3. the method that glycine as described in claim 1 prepares active carbon loading silver with silver nitrate complexing, it is characterised in that：It is described
Ag mass of ions a concentration of 0.1~0.6%.
4. the method that glycine as claimed in claim 1 or 2 prepares active carbon loading silver with silver nitrate complexing, it is characterised in that：
Activated carbon heating is 180~250 DEG C after the immersion is dry.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376822A (en) * | 2002-04-30 | 2002-10-30 | 中山大学 | Process for preparing antibacterial fibre of activated carbon containing nano silver particles |
| CN101368331A (en) * | 2008-09-25 | 2009-02-18 | 湖南多喜爱纺织科技有限公司 | Cotton fabric inorganic nanometer antibiotic finishing agent and preparation method thereof |
| CN103125524A (en) * | 2013-01-10 | 2013-06-05 | 遵义市大丰农作物研究所 | High-efficiency nano-silver sterilizing agents without selection of media and environment and preparing method thereof |
| CN103232035A (en) * | 2013-03-26 | 2013-08-07 | 赵建树 | Nanometer silver-loaded active carbon and preparation method thereof |
| CN104944537A (en) * | 2015-06-17 | 2015-09-30 | 何素梅 | Bactericide for aquaculture |
| JP5882605B2 (en) * | 2011-06-14 | 2016-03-09 | 株式会社ゼンシン | Method for producing antibacterial composition |
| CN105749865A (en) * | 2016-04-12 | 2016-07-13 | 中国科学院合肥物质科学研究院 | Preparation method and application of three-dimensional graphene/silver composite |
-
2016
- 2016-12-18 CN CN201611173171.XA patent/CN106390930B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376822A (en) * | 2002-04-30 | 2002-10-30 | 中山大学 | Process for preparing antibacterial fibre of activated carbon containing nano silver particles |
| CN101368331A (en) * | 2008-09-25 | 2009-02-18 | 湖南多喜爱纺织科技有限公司 | Cotton fabric inorganic nanometer antibiotic finishing agent and preparation method thereof |
| JP5882605B2 (en) * | 2011-06-14 | 2016-03-09 | 株式会社ゼンシン | Method for producing antibacterial composition |
| CN103125524A (en) * | 2013-01-10 | 2013-06-05 | 遵义市大丰农作物研究所 | High-efficiency nano-silver sterilizing agents without selection of media and environment and preparing method thereof |
| CN103232035A (en) * | 2013-03-26 | 2013-08-07 | 赵建树 | Nanometer silver-loaded active carbon and preparation method thereof |
| CN104944537A (en) * | 2015-06-17 | 2015-09-30 | 何素梅 | Bactericide for aquaculture |
| CN105749865A (en) * | 2016-04-12 | 2016-07-13 | 中国科学院合肥物质科学研究院 | Preparation method and application of three-dimensional graphene/silver composite |
Non-Patent Citations (2)
| Title |
|---|
| Green synthesis of biocidal silver-activated charcoal nanocomposite for disinfecting water;V. Sherly Arputha Kiruba;《Journal of Experimental Nanoscience》;20131018;第10卷(第7期);全文 * |
| 硝酸甘氨酸螯合银（I）的抗菌作用及其制备;秦德华等;《2007年全国化学与生物技术药物学术年会论文集》;20171031;全文 * |
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