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 PDFInfo
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- 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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- Prior art keywords
- activated carbon
- carbon fiber
- sequestering agent
- metal ion
- precious metal
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 6
- 150000002500 ions Chemical class 0.000 title abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 title abstract 5
- 239000002738 chelating agent Substances 0.000 title abstract 4
- 230000001737 promoting effect Effects 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000001914 filtration Methods 0.000 claims abstract description 15
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 abstract description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 239000003352 sequestering agent Substances 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 239000010970 precious metal Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 229960003540 oxyquinoline Drugs 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 14
- 229910052737 gold Inorganic materials 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000000274 adsorptive effect Effects 0.000 description 9
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- -1 gold ion Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- 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
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.
Priority Applications (1)
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CNB031142788A CN1233855C (en) | 2003-04-24 | 2003-04-24 | Method for promoting activated carbon fibers to reduction and adsorbing noble metal ions by organic chelating agent |
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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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