CN106698616A - Method for reduction preparation of silver loaded activated carbon from citric acid - Google Patents
Method for reduction preparation of silver loaded activated carbon from citric acid Download PDFInfo
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- CN106698616A CN106698616A CN201611173162.0A CN201611173162A CN106698616A CN 106698616 A CN106698616 A CN 106698616A CN 201611173162 A CN201611173162 A CN 201611173162A CN 106698616 A CN106698616 A CN 106698616A
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- silver
- activated carbon
- citric acid
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 87
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000009467 reduction Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 238000007654 immersion Methods 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 12
- UZVQOEUTOCRSJN-UHFFFAOYSA-N silver 2-hydroxypropane-1,2,3-tricarboxylic acid nitrate Chemical compound [N+](=O)([O-])[O-].[Ag+].C(CC(O)(C(=O)O)CC(=O)O)(=O)O UZVQOEUTOCRSJN-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
- 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
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000005516 engineering 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
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 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
- 238000004448 titration Methods 0.000 claims description 2
- RRXWRHLYVPTSIF-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;silver Chemical compound [Ag].OC(=O)CC(O)(C(O)=O)CC(O)=O RRXWRHLYVPTSIF-UHFFFAOYSA-N 0.000 claims 1
- 239000002384 drinking water standard Substances 0.000 claims 1
- 238000009413 insulation 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 19
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000001954 sterilising effect Effects 0.000 abstract description 5
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 description 21
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 6
- 235000013399 edible fruits Nutrition 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002070 germicidal effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 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
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 fruit shell carbon Chemical compound 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Carbon And Carbon Compounds (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention relates to a method for reduction preparation of silver loaded activated carbon from citric acid. The method comprises the following steps: soaking activated carbon into a complex solution of silver nitrate and citric acid, and performing heating decomposition and reduction, namely, firstly, preparing a 0.01-0.6% complex solution of silver nitrate and citric acid in a mole ratio of (3.6-3):1; soaking the activated carbon into the complex solution for 6-24 hours in a ratio of 0.25-1Kg/liter; performing heating decomposition in the presence of circulated nitrogen; and washing with clean water, and drying, thereby obtaining the silver loaded activated carbon, wherein the particle size of obtained nano silver is 10-60nm, and the silver loading capacity is 0.01-0.5wt%. By adopting the method, the process procedures are shortened, the reaction temperature is reduced, the sterilization efficiency of the silver loaded activated carbon is improved, and the silver amount is reduced.
Description
Technical field
The present invention relates to a kind of method of active carbon loading silver.It is by with silver nitrate and citric acid complex solution, then to soak
Activated carbon is oozed, by heat resolve and reduction, using silver nitrate and the reaction heat of citric acid complex, the work of high stability is obtained
Property carbon surface absorption Nano Silver, for aspects such as pure water purification and sterilizations.
Technical background
The invention belongs to purify, the modified absorbent charcoal material of the nano particle silver in the field such as sterilization.
Domestic and international drinking water deep purification activated carbon (AC), generally based on load silver.The preparation of active carbon loading silver (AC/Ag)
Method is mainly including infusion process, doping method, electrochemical deposition method, reducing process, supercritical water infusion process etc., and industrial applications are more
Be infusion process and reducing process.
Infusion process be using the film containing silver particles aqueous solution soaking AC such as silver nitrate, silver acetate, adsorbed after drying silver from
The activated carbon of son, then obtains silver oxide by intensification decomposition, then is calcined some hours at 400~500 DEG C, high using silver oxide
Temperature is decomposed and obtains argent.It is required that being calcined under inert gas shielding, there can not be free air infiltration to enter in calcination process and temperature-fall period,
Once there is free air infiltration to enter, the argent for easily being formed can be oxidized to silver oxide again, and its end product quality is difficult to control.Infusion process
AC/Ag process is simples are prepared, low cost is pollution-free, and silver is distributed in AC surfaces, is conducive to sterilization.But AC is mainly physics to silver
Absorption, silver is easily lost in, it is impossible to reach the effect of lasting sterilization.
Reducing process is that AC is immersed in into 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 as a example by, detailed process be activated carbon activation process, when long under the conditions of lucifuge
Between be impregnated into AgNO3In solution, afterwards with distillation water washing until without silver ion detection in cleaning solution, then impregnating above-mentioned AC
In NaBH4In solution for a long time, washing removes residue NaBH afterwards4, dried for a long time in 70 DEG C of vacuum.The method can realize AC
With the good combination of Argent grain.But reducing process process flow is long；Repeatedly washing is needed, water resource requirement is high；Use lucifuge, vacuum
Etc. technique, equipment requirement is high；And Argent grain is mainly distributed in the outer surface and hole of AC with reunion shape, the Argent grain ratio of load
It is larger, and germicidal efficiency is not high.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the active carbon loading silver with efficient, lasting bactericidal action.
The technical solution adopted for the present invention to solve the technical problems is that complexing can occur with silver particles using one kind
Reducing agent, by silver ion with complex form adsorb in the surface and micropore of activated carbon, it is then fast at a lower temperature
Speed reduction, decomposition, the active carbon loading silver for obtain good dispersion, not easily runing off.It is specific as follows：
(1) prepared by silver nitrate-citric acid complex liquid：A certain amount of silver nitrate crystal and Citric acid crystal are weighed, it is water-soluble with distilling
Solution, obtains silver-colored ammonium nitrate complex liquid.Wherein, silver nitrate and the molar ratio of citric acid are 3.6~3:Between 1, preparation it is water-soluble
Ag mass of ions concentration is 0.01~0.6% in liquid.
(2) silver ion immersion, dry activated carbon：By commercially available water purification active carbon, such as fruit shell carbon, ature of coal charcoal, with distillation
Water is cleaned, dries, cooled.With the silver nitrate for preparing-citric acid complex liquid shaken at room temperature, immersion activated carbon, soak time is 6
~24 hours；The ratio of activated carbon and complex liquid is 0.25~1Kg/ liters during immersion；Filtered in ventilated environment, light protected environment after immersion
It is dry；Then in hot blast, such as electric drying oven with forced convection, 40~90 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up to 120-200 DEG C after immersion is dried, and soaking time is 0.5~6 hour.
Protected using dry circulating nitrogen gas during thermal decomposition, can also be protected using ammonia is decomposed when having ready conditions.Done using boat stove, net belt type is pushed away
The continuous furnace such as dry stove or rotary furnace, realizes continuous production.Programming rate is controlled at 0.1~2 DEG C/min, it is to avoid thermal decomposition
Reaction excessively acutely influences Nano Silver dispersiveness and the interface binding power with activated carbon surface.
(4) wash：By above-mentioned activated carbon pure water washing 2~4 times, the reactant of remnants is washed away.In order to avoid silver granuel
Son oxidation, the drying temperature after cleaning is controlled at 50~120 DEG C.Silver-colored remaining quantity≤the 10ppb of the water after cleaning（Micrograms per litre),
Reach the standard of drinking water.
(5) detect：Sodium sulfocyanate standard liquid titration determination silver carrying amount, scanning electron microscopic observation Argent grain shape are used per batch
Looks and size, and in 25 DEG C, 150 r/min, constant temperature oscillation is after 600 hours, with the anti-current of the swollen Spectrophotometric Determination of Silver of double sulphur
Lose performance, turnover rate≤25% of silver, silver carrying amount receptor 1 activity charcoal specific surface and absorption property, complex liquid silver content, soaking technology and
The influence of the parameter of thermal decomposition process, when silver carrying amount is less than desired 0.01~0.50wt.% of interval, repeat step（2）Silver from
Son immersion, dry activated carbon and step（3）Pyrolysis are increasing silver carrying amount.
Described silver nitrate is 3.5~3 with the mol ratio of citric acid:1.
Described Ag mass of ions concentration is 0.1~0.6%.
Described step（3）Middle dry activated carbon is warming up to 140-180 DEG C.
By silver nitrate (AgNO3) as oxidant, citric acid (C6H8O7) as complexing reducing agent, it is configured to the aqueous solution.Lemon
Lemon acid forms the chelate of stabilization with Ag ions, and solution gradually evaporates can form gel, micropore surface of the absorption in activated carbon.This
Planting gel can rapidly react at 120~200 DEG C, release a large amount of gases and heat, can obtain scattered nano level superfine argent
Powder.Citric acid (CH2COOH-C(OH)-COOHCH2COOH fusing point) only has 153 DEG C, and rapid burning under an oxygen-containing atmosphere is formed
CO2And H2O, but in the case of anoxic, reacted with nitrate anion and silver ion, obtain Nano Silver and CO2、H2O、N2O、N2Deng gas
Body.
When silver nitrate and citric acid are in molar ratio 18:Reaction equation when 5 is as follows：
18AgNO3+ 5C6H8O7→18Ag+30CO2+20H2O+9N2O
When silver nitrate and citric acid are in molar ratio 3:Reaction equation when 1 is as follows：
6AgNO3+2C6H8O7→6Ag+12CO2+8H2O+N2
When silver nitrate is excessive, reaction occurs the oxide of silver；When reducing agent citric acid is further excessive, it is necessary to oxygen is joined
With reaction, or ammonia is discharged.
The present invention for producing active carbon loading silver, with reaction temperature is low and the characteristics of efficiency high, generally at 120-200 DEG C
Between, the heat promotion reaction of decomposition reaction release is carried out.Compared with conventional dipping and thermal decomposition process, technique stream is shortened
Journey, reduce reaction temperature, avoid the occurrence of the Ag particles caused due to pyroreaction combined with carbon surface loosely and easily occur
The problem of silver oxide.Compared with conventional reduction method, dipping time is reduced, and due to complexing Ag chemical combination of the present invention
Thing is decomposed and produces a large amount of gas such as H2O、CO2、N2, N2O etc., disperses the Ag nano particles to be formed, and overcomes General N aBH4Reduction
The Ag particle agglomeration phenomenons of AC/Ag are prepared, the germicidal efficiency of active carbon loading silver is improved, silver-colored consumption is reduced.
Present invention process process is simple, easily operated, yield is high, be easy to industrialized production, with clean, environmental protection and
Characteristics of energy saving.Gained Nano Silver particle diameter is 10 ~ 60nm；0.01~0.5wt.% of silver carrying amount；Argent grain is high with activated carbon adhesion,
150r/min, vibrates in 25 DEG C of thermostatted waters, after 600 hours, turnover rate≤25% of silver；Argent grain good dispersion, germicidal efficiency
It is high.
Specific embodiment
The present invention is elaborated below by way of specific embodiment.
Embodiment 1
(1) prepared by silver nitrate-citric acid complex liquid：17g silver nitrates and 6.4g citric acids are weighed, with distillation water dissolves, is obtained
100 liters of silver-colored ammonium nitrate complex liquids.Wherein, silver nitrate and the molar ratio of citric acid are 3:1, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.01%.
(2) silver ion immersion, dry activated carbon：Commercially available coconut fruit shell carbon distilled water is cleaned, dry, cooled.With
Ag mass of ion concentration is about 0.01%, and molar ratio is 3:1 silver nitrate-citric acid complex liquid shaken at room temperature, immersion activity
Charcoal, soak time is 6 hours；The ratio of activated carbon and complex liquid is 1Kg/ liters during immersion；In ventilated environment, lucifuge ring after immersion
Border is filtered dry；In electric drying oven with forced convection, 40 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 120 DEG C after immersion is dried, and soaking time is 6 hours.Thermal decomposition
Dried in the dry circulating nitrogen gas protection tube furnaces of Shi Caiyong, programming rate is 2 DEG C/min.
(4) wash：By above-mentioned activated carbon pure water washing 2 times, the reactant of remnants is washed away.In electric heating air blast after cleaning
Drying box, 50 DEG C of dryings to constant weight.
(5) detect：Gained Nano Silver particle diameter is 10nm；Silver carrying amount 0.01%；Argent grain is high with activated carbon adhesion, 150r/
Min, vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 9%.
Embodiment 2
(1) prepared by silver nitrate-citric acid complex liquid：17g silver nitrates and 6.4g citric acids are weighed, with distillation water dissolves, 18 is obtained
Rise silver-colored ammonium nitrate complex liquid.Wherein, silver nitrate and the molar ratio of citric acid are 3:1, Ag mass of ions in the aqueous solution of preparation
Concentration is about 0.6%.
(2) silver ion immersion, dry activated carbon：Commercially available ature of coal charcoal distilled water is cleaned, dry, cooled.Use Ag ions
Mass concentration is about 0.6% silver nitrate-citric acid complex liquid shaken at room temperature, immersion activated carbon, and soak time is 24 hours；Leaching
The ratio of activated carbon and complex liquid is 1Kg/ liters during bubble；It is filtered dry in ventilated environment, light protected environment after immersion；In electric heating forced air drying
Case, 90 DEG C of dryings to constant weight remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 200 DEG C after immersion is dried, and soaking time is 0.5 hour.Heat point
Protected using dry circulating nitrogen gas at 0.1 DEG C/min using net belt type drying oven, programming rate control during solution.
(4) wash：By above-mentioned activated carbon pure water washing 4 times, the reactant of remnants is washed away.Net belt type is used in after cleaning
In drying oven, 120 DEG C of dryings to constant weight.
(5) detect：Gained Nano Silver particle diameter is 58nm；Silver carrying amount 0.49%；Argent grain is high with activated carbon adhesion, 150r/
Min, vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 23%.
Embodiment 3
(1) prepared by silver nitrate-citric acid complex liquid：17g silver nitrates and 6.0g citric acids are weighed, with distillation water dissolves, 18 is obtained
Rise silver-colored ammonium nitrate complex liquid.Wherein, silver nitrate and the molar ratio of citric acid are 18:5.5, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.6%.
(2) silver ion immersion, dry activated carbon：Commercially available fruit shell carbon distilled water is cleaned, dry, cooled.Use Ag ions
Mass concentration is about 0.6%, and molar ratio is 18:5.5 silver nitrate-citric acid complex liquid shaken at room temperature, immersion activated carbon, leaching
The bubble time is 12 hours；The ratio of activated carbon and complex liquid is 0.25Kg/ liters during immersion；In ventilated environment, lucifuge ring after immersion
Border is filtered dry；Dried to constant weight in 80 DEG C of heated-air drying cylinders, remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 180 DEG C after immersion is dried, and soaking time is 3 hours.Thermal decomposition
Shi Caiyong pushes away boat drying oven, programming rate control at 0.5 DEG C/min automatically, is protected using dry circulating nitrogen gas.
(4) wash：By above-mentioned activated carbon pure water washing 3 times, the reactant of remnants is washed away.It is used in after cleaning and is pushed away automatically
Boat drying oven, 110 DEG C of dryings to constant weight.
(5) detect：Gained Nano Silver particle diameter is 50nm；Silver carrying amount 0.3%；Argent grain is high with activated carbon adhesion, 150r/
Min, vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 12%.
Embodiment 4
(1) prepared by silver nitrate-citric acid complex liquid：17g silver nitrates and 6.4g citric acids are weighed, with distillation water dissolves, 36 is obtained
Rise silver-colored ammonium nitrate complex liquid.Wherein, silver nitrate and the molar ratio of citric acid are 3:1, Ag mass of ions in the aqueous solution of preparation
Concentration is about 0.3%.
(2) silver ion immersion, dry activated carbon：Commercially available fruit shell carbon distilled water is cleaned, dry, cooled.Use Ag ions
Mass concentration is about 0.3%, and molar ratio is 3:1 silver nitrate-citric acid complex liquid shaken at room temperature, immersion activated carbon, during immersion
Between be 12 hours；The ratio of activated carbon and complex liquid is 0.5Kg/ liters during immersion；Filtered in ventilated environment, light protected environment after immersion
It is dry；Dried to constant weight in 100 DEG C of heated-air drying cylinders, remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 180 DEG C after immersion is dried, and soaking time is 3 hours.Thermal decomposition
Shi Caiyong pushes away boat drying oven, programming rate control at 0.5 DEG C/min automatically, is protected using dry circulating nitrogen gas.
(4) wash：By above-mentioned activated carbon pure water washing 2 times, the reactant of remnants is washed away.It is used in after cleaning and is pushed away automatically
Boat drying oven, 120 DEG C of dryings to constant weight.
(5) detect：Gained Nano Silver particle diameter is 30nm；Silver carrying amount 0.3%；Argent grain is high with activated carbon adhesion, 150r/
Min, vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 14%.
Embodiment 5
(1) prepared by silver nitrate-citric acid complex liquid：8.5g silver nitrates and 3.2g citric acids are weighed, with distillation water dissolves, is obtained
36 liters of silver-colored ammonium nitrate complex liquids.Wherein, silver nitrate and the molar ratio of citric acid are 3:1, Ag ions matter in the aqueous solution of preparation
Amount concentration is about 0.15%.
(2) silver ion immersion, dry activated carbon：Commercially available fruit shell carbon distilled water is cleaned, dry, cooled.Use Ag ions
Mass concentration is about 0.15%, and molar ratio is 3:1 silver nitrate-citric acid complex liquid shaken at room temperature, immersion activated carbon, immersion
Time is 9 hours；The ratio of activated carbon and complex liquid is 0.25Kg/ liters during immersion；Filtered in ventilated environment, light protected environment after immersion
It is dry；Dried to constant weight in 80 DEG C of heated-air drying cylinders, remove water and the crystallization water.
(3) pyrolysis：Activated carbon is warming up at 160 DEG C after immersion is dried, and soaking time is 2 hours.Thermal decomposition
The dry circulating nitrogen gas protection tube furnaces of Shi Caiyong, programming rate is controlled at 1 DEG C/min.
(4) wash：By above-mentioned activated carbon pure water washing 2 times, the reactant of remnants is washed away.With 80 DEG C of air blast after cleaning
Drying box drying is to constant weight.
(5) detect：Gained Nano Silver particle diameter is 30nm；Silver carrying amount 0.03%；Argent grain is high with activated carbon adhesion, 150r/
Min, vibrates in 25 DEG C of thermostatted waters, and after 600 hours, the turnover rate of silver is 10%.
Claims (4)
1. a kind of method that citric acid reduction prepares active carbon loading silver, it is characterised in that comprise the following steps：
(1) prepared by silver nitrate-citric acid complex liquid：Silver nitrate crystal and Citric acid crystal are weighed, with distillation water dissolves, is obtained
Silver-colored ammonium nitrate complex liquid, silver nitrate is 3.6~3 with the molar ratio of citric acid:1, Ag mass of ions are dense in the aqueous solution of preparation
Spend is 0.01~0.6%；
(2) silver ion immersion, dry activated carbon：Water purification active carbon is cleaned with distilled water, dry, cooled down, with the nitre for preparing
Sour silver-citric acid complex liquid shaken at room temperature, immersion activated carbon, soak time is 6~24 hours；Activated carbon and complex liquid during immersion
Ratio be 0.25~1Kg/ liters；It is filtered dry in ventilation, light protected environment after immersion；Then in hot blast, such as electric drying oven with forced convection, 40
~90 DEG C of dryings remove water and the crystallization water to constant weight；
(3) pyrolysis：Activated carbon is warming up to 120-200 DEG C after immersion is dried, and insulation carries out heat point for 0.5~6 hour
Solution, is protected during thermal decomposition using dry circulating nitrogen gas, or is protected using ammonia is decomposed；Using push away boat stove, net belt type drying oven or
Rotary furnace continuous furnace, realizes continuous production；Programming rate is controlled at 0.1~2 DEG C/min, it is to avoid pyrolysis are excessively
Acutely influence Nano Silver dispersiveness and the interface binding power with activated carbon surface；
(4) wash：By above-mentioned activated carbon pure water washing 2~4 times, the reactant of remnants is washed away；In order to avoid silver particles
Oxidation, the drying temperature after cleaning is controlled at 50~120 DEG C；Silver-colored remaining quantity≤the 10ppb of the water after cleaning, reaches drinking water
Standard；
(5) detect：Sodium sulfocyanate standard liquid titration determination silver carrying amount, scanning electron microscopic observation Argent grain pattern are used per batch
And size, and in 25 DEG C, 150 r/min, constant temperature oscillation is lost after 600 hours with the anti-current of the swollen Spectrophotometric Determination of Silver of double sulphur
Performance, turnover rate≤25% of silver, 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, when silver carrying amount is less than desired 0.01~0.50wt.% of interval, repeat step（2）Silver ion
Immersion, dry activated carbon and step（3）Pyrolysis are increasing silver carrying amount.
2. the method that citric acid reduction as claimed in claim 1 prepares active carbon loading silver, it is characterised in that described silver nitrate
It is 3.5~3 with the mol ratio of citric acid:1.
3. the method that citric acid reduction as claimed in claim 1 prepares active carbon loading silver, it is characterised in that：Described Ag ions
Mass concentration is 0.1~0.6%.
4. the method that citric acid reduction as claimed in claim 1 prepares active carbon loading silver, it is characterised in that：Step（3）Middle institute
Dry activated carbon is warming up to 140-180 DEG C after the immersion stated is dried.
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| CN116078347A (en) * | 2022-12-23 | 2023-05-09 | 大连理工大学 | Preparation method of Cu (I)/ZSM-5 desulfurizing agent and application of desulfurizing agent in removal of carbonyl sulfide in gas |
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