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CN1233855C - Method for promoting activated carbon fibers to reduction and adsorbing noble metal ions by organic chelating agent - Google Patents

Method for promoting activated carbon fibers to reduction and adsorbing noble metal ions by organic chelating agent Download PDF

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Publication number
CN1233855C
CN1233855C CNB031142788A CN03114278A CN1233855C CN 1233855 C CN1233855 C CN 1233855C CN B031142788 A CNB031142788 A CN B031142788A CN 03114278 A CN03114278 A CN 03114278A CN 1233855 C CN1233855 C CN 1233855C
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China
Prior art keywords
activated carbon
carbon fiber
sequestering agent
metal ion
precious metal
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CNB031142788A
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CN1445373A (en
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曾汉民
安小宁
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Sun Yat Sen University
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Sun Yat Sen University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The present invention relates to a method for promoting the reduction and the adsorption of the noble metal ions of activated carbon fiber by an organic chelating agent, which comprises the following steps: the activated carbon fiber adsorbing the organic chelating agent is put in solution comprising the noble metal ions; a mixing process and an adsorbing process are carried out for 12 to 48 hours under 10 to 60 DEG C; a solid phase and a liquid phase are separated by filtration to obtain the activated carbon fiber adsorbed with the noble metal ions. The present invention carries out the surface modification of the activated carbon fiber by organic chelating agents, such as 1, 10-phenanthroline, 8-hydroxyquinoline or dithizone, etc., and effectively promotes the reduction and the adsorption of the noble metal ions of the activated carbon fiber.

Description

Organic chelating promotes the method for active carbon fiber reduction absorption precious metal ion
Technical field
The present invention relates to a kind of method of utilizing organic sequestering agent to promote active carbon fiber reduction absorption precious metal ion.
Background technology
Activated carbon fiber be nineteen sixties along with the high-tech product that carbon fiber industry progressively grows up, be a kind of high-effect and broad-spectrum sorbing material.The chemical property on activated carbon fiber (ACF) surface greatly influences character such as its absorption, electrochemistry, catalysis, redox and close and distant water.For example, reactive hydrogen atom, hydroxyl and carbonyl isoreactivity center energy and metal ion generation redox reaction on activated carbon fiber (ACF) surface, and redox electromotive force E is linear relevant with the activity of active centre and metal ion; The adsorptive capacity of acid oxy radical content and polar adsorption matter is proportional on activated carbon fiber (ACF) surface.Activated carbon fiber (ACF) can increase its content of surface oxygen by oxidizing reaction, complex operation, and content of surface oxygen increases limited.There is the research report to adopt reductive agents such as activated carbon fiber absorption methylene blue and aniline to change its surface, improves Ag (NH 3) 2 +Reduction efficiency.At present, adopt cost-effective activated carbon fiber surface modifying method, developing activated carbon fiber Application Areas remains the problem that people endeavour to study.
Summary of the invention
The purpose of this invention is to provide the method that organic sequestering agent promotes active carbon fiber reduction absorption precious metal ion, this method is passed through with organic chelating the activated carbon fiber surface modification, make the activated carbon fiber functionalisation of surfaces, thereby promote the absorption of activated carbon fiber precious metal ion.
Method of the present invention is: will adsorb the activated carbon fiber of organic sequestering agent, and place the solution that contains precious metal ion, and in 5~70 ℃ of following whip attachment 12~24 hours, filtering separation solid-liquid two-phase, obtain being adsorbed with the activated carbon fiber of precious metal ion.
The activated carbon fiber of used absorption organic sequestering agent can prepare by the following method: activated carbon fiber is placed the saturated ethanolic soln of organic sequestering agent, 20~40 ℃ of following whip attachment 24~48 hours, filtering separation solid-liquid two-phase, the activated carbon fiber drying obtains the activated carbon fiber of surface-functionalized absorption organic sequestering agent.
Used organic sequestering agent is 1,10-phenanthroline, oxine or dithizone.
The solid-to-liquid ratio of used activated carbon fiber and the saturated ethanolic soln of organic sequestering agent is generally 1: 100~l: 1000g/ml.
The acidity of used precious metal ion solution is generally pH=1.0~6.0.
The concentration of used precious metal ion solution is generally 0.01~0.5mol/L.
The activated carbon fiber of used absorption organic sequestering agent and the solid-to-liquid ratio of precious metal ion solution are generally 1: 100~1: 5000g/ml.
The invention described above method activated carbon fiber surface reduction absorption precious metal ion amount adopts X-ray photoelectron spectroscopy and ICP-aes determination.
The inventive method adopts activated carbon fiber to adsorb organic integrated agent to the activated carbon fiber surface modification.Oxine, 1, sequestrant molecules such as 10-phenanthroline and dithizone can promote the absorption of activated carbon fiber to precious metal ion, and under different acidity and concentration conditions adsorbable precious metal ion, so the present invention has broad application prospects.
Embodiment
The invention will be further described by the following examples.
Embodiment 1: with the activated carbon fiber of 100mg through 120 ℃ of vacuum-dryings, constant weight, place 50ml oxine, 1, in the saturated ethanolic solns of organic sequestering agent such as 10-phenanthroline or dithizone, 20 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase, activated carbon fiber obtains surface-functionalized activated carbon fiber through 100 ℃ of vacuum-dryings.
Take by weighing the surface-functionalized activated carbon fiber of 100mg, place and contain 0.1mol/L, in the 50ml chlorogold solution, 30 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase.Adopt the XPS method to measure the gold content of activated carbon fiber absorption, its result is as shown in table 1.Table 1 explanation oxine, 1, sequestrant molecules such as 10-phenanthroline and dithizone can promote the absorption of activated carbon fiber to gold ion.
The percentage composition (%) of gold in table 1. activated carbon fiber
The activated carbon fiber type The load oxine Load 1, the 10-phenanthroline The load dithizone Load organic sequestering agent not
The percentage composition of gold 38.01 20.18 17.57 17.04
Embodiment 2: with the activated carbon fiber of 100mg through 120 ℃ of vacuum-dryings, constant weight, place the saturated ethanolic soln of 100ml oxine, 30 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase, activated carbon fiber obtains surface-functionalized activated carbon fiber through 100 ℃ of vacuum-dryings.
Take by weighing 100mg and obtain surface-functionalized activated carbon fiber, place and contain 0.01mol/L, the pH value is respectively: 1.0, in 1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0 and 6.0 the 500ml chlorogold solution, 30 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase.Adopt the gold content of ICP-aes determination activated carbon fiber absorption, its analytical results is as shown in table 2.Can be observed adsorptive capacity by table 2 result and one maximum value is arranged with the increase of pH value.The pH value raises, and the redox electromotive force value of activated carbon fiber increases, and has reduced the protonation reaction of organic chelating, helps the increase of adsorptive capacity, makes it reach maximum value.Along with the increase of pH value, make AuCl 4 1-Form the alkali formula and cooperate ion [Au (OH) Cl 3] 1-Or [Au (OH) 2Cl 2] 1-, even Au (OH) 3Precipitation, this has just reduced AuCl 4 1-Activity and electrode potential value, cause the adsorptive capacity of gold to reduce.
Table 2.pH value is to the influence (mg/g) of golden adsorptive capacity
pH 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 6.0
Activated carbon fiber (ACF) 171 185 189 198 206 203 199 180 167 149
Surface-functionalized ACF 552 568 571 589 601 610 591 578 563 526
Embodiment 3: with the activated carbon fiber of 100mg through 120 ℃ of vacuum-dryings, constant weight, place the saturated ethanolic soln of 10ml oxine, 30 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase, activated carbon fiber obtains surface-functionalized activated carbon fiber through 100 ℃ of vacuum-dryings.
Take by weighing the surface-functionalized activated carbon fiber of 100mg, place and contain 0.2mol/L, in the 100ml chlorogold solution of pH 3.0, respectively 5,25,40,55 and 70 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase.Adopt the gold content of ICP-aes determination activated carbon fiber absorption, its analytical results is as shown in table 3.The course of activated carbon fiber ADSORPTION OF GOLD comprises physical adsorption and redox absorption, and adsorption temp raises and helps redox absorption but be unfavorable for physical adsorption, and both actings in conjunction make activated carbon fiber vary with temperature the adsorptive capacity of gold and change.The result can be observed by table 3: when 5 ℃ were increased to 40 ℃, the adsorptive capacity of gold increased with temperature, and in the time of 40 ℃, reaches maximum value; When temperature was higher than 40 ℃, the adsorptive capacity of gold increased with temperature and reduces.
Table 3. temperature is to the influence (mg/g) of golden adsorptive capacity
Adsorption temp ℃ 5 25 40 55 70
Activated carbon fiber ACF 170 201 211 184 167
Surface-functionalized ACF 529 601 618 591 540
Embodiment 4: with the activated carbon fiber of 100mg through 120 ℃ of vacuum-dryings, constant weight, place the saturated ethanolic soln of 100ml oxine, 20 ℃ of following whip attachment 48 hours.Filtering separation solid-liquid two-phase, activated carbon fiber obtains surface-functionalized activated carbon fiber through 100 ℃ of vacuum-dryings.
Take by weighing the surface-functionalized activated carbon fiber of 100mg, place and contain 0.5mol/L, in the 10ml silver nitrate solution of pH 3.0,30 ℃ of following whip attachment 12 hours.Filtering separation solid-liquid two-phase.Adopt the XPS method to measure the silver content of activated carbon fiber absorption, its analytical results is as shown in table 4.Table 4 explanation oxine can promote the absorption of activated carbon fiber to silver ions.
Analytical element percentage composition (%) in table 4. activated carbon fiber
The activated carbon fiber type Analytical element
Cls Ols N2p Ag3d
Not surface-functionalized activated carbon fiber 85.33 9.25 2.19 3.24
Surface-functionalized activated carbon fiber 61.71 22.34 3.91 12.04
Embodiment 5: with the activated carbon fiber of 100mg through 120 ℃ of vacuum-dryings, constant weight, place the saturated ethanolic soln of 100ml oxine, 40 ℃ of following whip attachment 24 hours.Filtering separation solid-liquid two-phase, activated carbon fiber obtains surface-functionalized activated carbon fiber through 100 ℃ of vacuum-dryings.
Take by weighing the surface-functionalized activated carbon fiber of 100mg, place and contain 0.1mol/L, in the 100ml potassium platinichloride solution of pH 3.0,10 ℃ of constant temperature whip attachment 24 hours.Filtering separation solid-liquid two-phase.Adopt the XPS method to measure the platinum content of activated carbon fiber absorption, its analytical results is as shown in table 5.Table 5 explanation oxine can promote the absorption of activated carbon fiber to platinum ion.
Analytical element percentage composition (%) in table 5. activated carbon fiber
The activated carbon fiber type Analytical element
Cls Ols Cl2p K2p Pt4f
Not surface-functionalized activated carbon fiber 87.13 9.41 2.63 / 0.82
Surface-functionalized activated carbon fiber 66.78 9.63 15.47 4.37 3.76

Claims (4)

1. an organic sequestering agent promotes active carbon fiber reduction to adsorb the method for precious metal ion, it is characterized in that: the activated carbon fiber that will adsorb organic sequestering agent, place the solution that contains precious metal ion, 5~70 ℃ of following whip attachment 12~24 hours, filtering separation solid-liquid two-phase; The activated carbon fiber of used absorption organic sequestering agent prepares by the following method: activated carbon fiber is placed the saturated ethanolic soln of organic sequestering agent, 20~40 ℃ of following whip attachment 24~48 hours, filtering separation solid-liquid two-phase, the activated carbon fiber drying obtains the activated carbon fiber of surface-functionalized absorption organic sequestering agent; Used organic sequestering agent is 1,10-phenanthroline, oxine or dithizone; The acidity of used precious metal ion solution is pH=1.0~6.0.
2. in accordance with the method for claim 1, the solid-to-liquid ratio that it is characterized in that used activated carbon fiber and the saturated ethanolic soln of organic sequestering agent is 1: 100~1: 1000g/ml.
3. according to claim 1 or 2 described methods, the concentration that it is characterized in that used precious metal ion solution is 0.01~0.5mol/L.
4. according to claim 1 or 2 described methods, the solid-to-liquid ratio that it is characterized in that used activated carbon fiber and precious metal ion solution is 1: 100~1: 5000g/ml.
CNB031142788A 2003-04-24 2003-04-24 Method for promoting activated carbon fibers to reduction and adsorbing noble metal ions by organic chelating agent Expired - Fee Related CN1233855C (en)

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CN100435934C (en) * 2007-02-02 2008-11-26 华南理工大学 Organic complex supported activated carbon adsorbent and its preparation method and application
JP5885463B2 (en) * 2010-11-02 2016-03-15 三菱マテリアル株式会社 Carbon nanofiber dispersion, coating composition and paste composition
CN103451931B (en) * 2012-06-04 2015-10-21 金发科技股份有限公司 Carbon fiber surface modifier, modified carbon fiber, matrix material and their preparation method
CN103993480B (en) * 2013-02-18 2016-06-15 广州金发碳纤维新材料发展有限公司 Carbon fiber surface modification emulsion and preparation method thereof and its modified carbon fiber prepared, moulding compound
CN104745819B (en) * 2013-12-27 2016-10-05 中国科学院宁波材料技术与工程研究所 Utilize the method that metal is reclaimed in conducting polymer nanometer spinning from electron wastes
CN105536783A (en) * 2015-12-23 2016-05-04 上海大学 A preparing method of an ordered mesoporous carbon-supported Ru nanometer catalyst
CN114505053B (en) * 2021-03-30 2022-12-09 长沙华时捷环保科技发展股份有限公司 Platinum-absorbing modified carbon fiber containing organic chelating group and preparation method and application thereof

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