CN114505053B - Platinum-absorbing modified carbon fiber containing organic chelating group and preparation method and application thereof - Google Patents

Platinum-absorbing modified carbon fiber containing organic chelating group and preparation method and application thereof Download PDF

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CN114505053B
CN114505053B CN202110342506.0A CN202110342506A CN114505053B CN 114505053 B CN114505053 B CN 114505053B CN 202110342506 A CN202110342506 A CN 202110342506A CN 114505053 B CN114505053 B CN 114505053B
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CN114505053A (en
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姚丹丹
谭清倩
蒋晓云
何劲松
李英杰
李亿
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Changsha Hasky Environmental Protection Technology Development Co ltd
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    • 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
    • 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
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a platinum-absorbing modified carbon fiber containing organic chelating groups, and a preparation method and application thereof. The preparation method comprises the oxidation reaction of the carbon fiber and hydrogen peroxide and the organic condensation reaction of the oxidized carbon fiber and organic matters containing amino in an organic solvent. The platinum-absorbing modified carbon fiber can be used for adsorbing platinum ions in an acidic aqueous solution containing platinum ions, can efficiently adsorb platinum ions with high, medium and low concentrations in a complex acidic environment, and has the advantages of strong adsorption selectivity, high saturated adsorption quantity and wide pH application range.

Description

Platinum-absorbing modified carbon fiber containing organic chelating group and preparation method and application thereof
Technical Field
The invention belongs to the technical field of platinum ion enrichment and recovery, relates to a platinum ion selective enrichment carbon fiber and a preparation method and application thereof, and particularly relates to a platinum absorption modified carbon fiber containing organic chelating groups and a preparation method and application thereof.
Background
Platinum is present in the earth's crust in very small amounts, often associated with other metal minerals in very low compositional content, in addition to being present in the form of natural alloys, platinum minerals or solid solutions. Therefore, at present, while the metallurgical industry extracts main metal components, trace platinum group valuable metals contained in a leaching solution are also extracted and recovered, complex enrichment and separation means such as a precipitation method and an extraction method are often required, the grade of a recovered part is not high, a subsequent separation step is required to be added, and the tail solution still contains low-concentration valuable metals which can be further recovered. The process is also influenced by pH and acid components, and additional waste water and waste residues are generated in the water sample adjusting process, so that the problems of long process, increased output of the waste water and the waste residues and the like are caused.
At present, solid phase adsorbents such as activated carbon, weak anion exchange resin, silicon-based or mineral adsorbents and the like are commonly used for recovering low-concentration valuable metals, but the problems of low selectivity, contention of adsorption sites by base metals, low saturated adsorption capacity and the like exist all the time. These problems are caused by the low saturated adsorption amount of the adsorbent itself and the low selectivity of the active group. Researchers try to modify carbon fibers, but the existing carbon fiber material modification method mainly adopts inorganic modification, has single type of active groups and limited selectivity and adsorption capacity to specific metals (such as platinum ions). Some grafted carbon fibers using high polymers have large molecules, increase air resistance, and fill and occupy the original gaps of the carbon fibers, so that the adsorption amount and the adsorption rate of target ions are greatly influenced. Therefore, the development of a platinum adsorption material with rich active groups, large saturated adsorption capacity and strong selectivity has good practical application value.
Disclosure of Invention
The invention aims to overcome the defects of the existing material modification technology, and provides a platinum-absorbing modified carbon fiber containing an organic chelating group, which can be used for platinum ions with high, medium and low concentrations in a complex environment, and has the advantages of strong adsorption selectivity, high saturated adsorption quantity and wide pH application range, and a preparation method and application thereof.
The platinum-absorbing modified carbon fiber comprises carbon fiber and an organic chelating group bonded to the carbon fiber, wherein the organic chelating group is a platinum-absorbing organic chelating group which is mainly obtained by condensation reaction of an active group and an organic matter containing amino, and the active group at least comprises carboxyl.
In the platinum-adsorbing modified carbon fiber containing an organic chelating group, preferably, the terminal group of the amino-containing organic substance is an amino group.
Preferably, the amino-containing organic substance further includes a hydroxyl group, and the terminal group of the amino-containing organic substance is an amino group or a hydroxyl group.
Preferably, the amino-containing organic substance includes one or more of tetraethylenepentamine, diethylenetriamine, ethylenediamine and N, N' -tetrakis (2-hydroxyethyl) ethylenediamine.
Preferably, the adsorption rate of the organic chelating group-containing platinum-adsorbing modified carbon fiber on platinum ions in the acidic aqueous solution containing the platinum ions is more than 99%, the saturated adsorption capacity is 80 mg/g-160 mg/g, and the lower adsorption limit is less than 0.5mg/L.
As a general technical concept, the present invention also provides a preparation method of the platinum-adsorbing modified carbon fiber containing the organic chelating group, which comprises the following steps:
(1) Adding carbon fibers into hydrogen peroxide for oxidation reaction, so that the carbon fibers are modified to obtain active groups, wherein the active groups at least comprise carboxyl groups, and obtaining oxidized carbon fibers after the oxidation reaction;
(2) And adding the oxidized carbon fiber and an organic matter containing amino into an organic solvent, and carrying out heating reflux under an anhydrous or nearly anhydrous condition to carry out organic condensation reaction to form an organic chelating group with a function of adsorbing platinum ions, thereby obtaining the platinum-adsorbing modified carbon fiber containing the organic chelating group.
Preferably, in the step (2), the organic solvent comprises one or more of ethanol, toluene, xylene, dimethylformamide and dimethyl sulfoxide, the heating reflux time is 5-10 h, after the heating reflux is finished, the organic solvent is evaporated and recovered, after the reaction product is cooled, the reaction product is firstly washed by alcohol, then washed by water, and then dried at 60-100 ℃ for 24-48 h. The alcohol is preferably methanol or ethanol. The amino-containing organic matter comprises one or more of tetraethylenepentamine, diethylenetriamine, ethylenediamine and N, N, N ', N' -tetra (2-hydroxyethyl) ethylenediamine.
In the preparation method of the platinum-adsorbing modified carbon fiber containing the organic chelating group, preferably, in the step (2), the theoretical adding molar ratio of the effective reaction functional group of the oxidized carbon fiber to the effective reaction functional group of the amino-containing organic substance is 1: 1-2.5.
In the preparation method of the platinum-adsorbing modified carbon fiber containing the organic chelating group, preferably, in the step (1), the oxidation reaction time is 2-5 h, and after the oxidation reaction is finished, the solvent is dried under suction filtration and pressure for 24-48 h at 60-100 ℃.
As a general technical concept, the invention also provides application of the platinum-absorbing modified carbon fiber containing the organic chelating group or the platinum-absorbing modified carbon fiber containing the organic chelating group prepared by the preparation method in treatment of acidic aqueous solution containing platinum ions.
In the above application, preferably, the pH of the acidic aqueous solution containing platinum ions is not more than 5, the applicable range of platinum ion concentration is 0.5mg/L to 1700mg/L, and the acid component of the solution includes one or more of hydrochloric acid, sulfuric acid and nitric acid.
Compared with the prior art, the invention has the advantages that:
(1) The invention relates to a platinum-absorbing modified carbon fiber containing organic chelating groups, which is characterized in that carbon fibers are used as a matrix, active groups (mainly carboxyl) obtained by oxidation on the carbon fibers are subjected to chemical reaction with organic micromolecules containing amino groups, and the platinum-absorbing organic chelating groups are obtained by organic condensation reaction. In the prior art, the surface modification of the carbon fiber is mainly inorganic modification, and organic modification only modifies organic molecules or macromolecules on the surface of the carbon fiber by methods such as deposition, coating and the like, and chemical bonding of the organic molecules or macromolecules is not realized, so that subsequent washing by using an organic solvent is usually not adopted. According to the invention, the micromolecule chelating group is modified on the surface of the carbon fiber through chemical bond linkage, and compared with materials prepared by other carbon fiber deposition and coating methods, the carbon fiber composite material avoids the blockage of the original pore passage of the carbon fiber and the desorption of organic groups in high-acidity wastewater. The platinum-absorbing modified carbon fiber containing the organic chelating group has strong selectivity on platinum, has high saturation adsorption capacity on platinum ions in an acid solution, can reach 80-160 mg/g, has an adsorption lower limit of less than 0.5mg/L, can adsorb the platinum ions to a level of dozens of micrograms per liter or even picograms per liter, has a platinum-absorbing capacity of specific activity about 100 times higher than that of a commercially available ion exchange resin and exceeds that of a foreign resin adsorption material when applied to the same experimental conditions of real wastewater.
(2) The preparation method of the invention is that under the condition of condensation reaction (anhydrous or nearly anhydrous environment), the oxidized carbon fiber and organic matter micromolecule modify the organic chelating group on the surface of the carbon fiber in a chemical bond connection mode. The invention firstly modifies carbon fiber through oxidation reaction to generate a large amount of active groups, such as carboxyl, hydroxyl, lactone group and the like, which mainly take carboxyl, and then the carboxyl and organic matter containing amino carry out organic condensation reaction in an organic solvent, wherein the reaction process is in an anhydrous solvent environment or in the presence of water removing equipment. The organic chelating group is prepared through the chemical reaction, namely, the carboxyl on the carbon fiber is bonded with the organic matter containing amino through a chemical bond to form a group, and compared with the surface modification of a deposition and coating method, the preparation method provided by the invention is beneficial to improving the stability of the modified carbon fiber. The yield of the platinum-absorbing modified carbon fiber containing the organic chelating group prepared by the preparation method is mostly more than 85 percent and even more than 94 percent.
(3) The preparation method of the invention takes the carbon fiber as the matrix material, can fully utilize the characteristics of large specific surface area and relatively abundant surface active groups of the carbon fiber, and preferentially uses the oxidized carbon fiber obtained by oxidation treatment to increase the carboxyl active groups on the surface in order to improve the modifiability of the chemical reaction. The method has the advantages that hydrogen peroxide is used as an oxidant, the reaction condition is mild, the carboxyl yield is high, the hydrogen peroxide is a cleaning reagent, the method is environment-friendly, no waste acid is generated, and the industrial application is greatly facilitated.
(4) The platinum-adsorbing modified carbon fiber containing the organic chelating group can be widely and efficiently applied to acidic aqueous solutions containing platinum ions, particularly can be applied to selective recovery of platinum resources in acidic aqueous solutions with different concentrations and ionic components, has a wide adsorption range and a wide pH application range, can adsorb platinum ions in complex acid component environments such as sulfuric acid, hydrochloric acid, nitric acid or mixed acid, can be applied to the platinum-containing ion aqueous solutions from weak acid with the pH of less than or equal to 5 to strong acid, and solves the problems that the existing adsorbing materials are narrow in pH, limited in acid components in use environments and the like. The material can selectively enrich, refine and secondarily recover high-concentration and medium-concentration platinum ions and low-concentration platinum in a complex multi-ion environment, the concentration of the platinum ions is 0.5-1700 mg/L, particularly, high enrichment factor, adsorption rate and saturated adsorption capacity of trace platinum ion waste liquid are kept, the material can be applied to further adsorption and recovery of low-concentration platinum ions in waste liquid enriched by an acid leaching solution, a precipitation method or an extraction method, meanwhile, the selectivity of the material can enable enrichment and purification to be carried out simultaneously, and the grade of platinum containing after pyrolysis ash is greatly improved.
(5) The platinum-adsorbing modified carbon fiber is a carbon-based material, the group playing a role in metal chelation is also an organic group, and a metal or inorganic salt refractory substance is not introduced, so that the carbon fiber is environment-friendly and easy to treat.
Drawings
FIG. 1 is a graph showing adsorption volume-concentration curves of platinum ion-containing acidic aqueous solutions having concentrations of 550mg/L with respect to platinum ion-containing modified carbon fibers having organic chelating groups according to example 1 of the present invention.
FIG. 2 is a graph showing the adsorption volume-concentration curve of platinum ion-containing acidic aqueous solution of low concentration in 28mg/L with respect to platinum ion-containing acidic carbon fiber having an organic chelating group in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. Unless otherwise specified, the raw materials and equipment used in the following examples are commercially available.
Example 1:
the invention relates to a platinum-absorbing modified carbon fiber containing an organic chelating group, which comprises carbon fiber and an organic chelating group bonded on the carbon fiber, wherein the organic chelating group is a platinum-absorbing organic chelating group, the platinum-absorbing organic chelating group is obtained by condensation reaction of an active group and an organic matter containing amino, the active group is mainly carboxyl, and the organic matter containing amino is tetraethylenepentamine.
The preparation method of the platinum-adsorbing modified carbon fiber containing the organic chelating group comprises the following steps:
(1) Preparing oxidized carbon fibers: weighing 20g of carbon fiber material, putting the carbon fiber material into a 1000mL beaker, adding hydrogen peroxide to immerse the carbon fiber, wherein the mass fraction of the hydrogen peroxide is 30%, the reaction time is usually 2-5 h, the self temperature of the reaction is firstly increased and then decreased, and the reaction is finished after the temperature is reduced to room temperature. The carbon fiber is kept immersed in the solution system during the whole reaction period, after the reaction is finished, the carbon fiber is filtered and pressed to be dry, and the carbon fiber is placed in a drying oven at 100 ℃ for drying for 24-48 h to obtain the oxidized carbon fiber C O The yield is 60-70%.
(2) Preparing the platinum absorbing carbon fiber containing the organic chelating group: weighing 8g of carbon oxide fiber, adding the carbon oxide fiber into a 500mL double-mouth round-bottom flask, adding 200mL of organic solvent toluene to immerse the carbon oxide fiber, adding about 2mL of amino-containing organic substance tetraethylenepentamine, wherein the adding amount of the carbon oxide fiber and the amino-containing organic substance is in accordance with the theoretical adding molar ratio of effective reaction functional groups of the carbon oxide fiber and the amino-containing organic substance of 1: 1-2.5, and heating and refluxing for 5 hours to perform organic condensation reaction. After the heating reflux is finished, evaporating the organic solvent and recovering, and after the reaction product is cooled, washing the carbon fibers respectively 3 times by using methanol and deionized water which are slightly excessive in volume compared with the reaction product. Placing the carbon fiber in a drying oven at 80 ℃ for 24 to 48 hours until the carbon fiber is dried to prepare the platinum-absorbing modified carbon fiber containing the organic chelating group, namely the aminated carbon fiber C NH The yield was 94% (based on the oxidized carbon fiber as the starting material).
In this example, diethylenetriamine, ethylenediamine or N, N' -tetrakis (2-hydroxyethyl) ethylenediamine may be used as the amino group-containing organic substance, and dimethylformamide, dimethylsulfoxide, ethanol or the like may be used as the organic solvent.
The following are effect tests, i.e., application examples.
Platinum absorption measurement and saturated adsorption measurement of platinum-absorbing modified carbon fiber containing organic chelating group on high-concentration acidic aqueous solution containing platinum ions
0.5g of the platinum-adsorbing modified carbon fiber containing the organic chelating group prepared in the embodiment 1 is weighed and filled into an adsorption column, the diameter of the adsorption column is 2cm, 50mL of 1700mg/L high-concentration acidic aqueous solution containing platinum ions (pH < 1) is pumped into the adsorption column at a constant speed at a speed of 0.3mL/min to 0.4mL/min through a peristaltic pump, and the high-concentration acidic aqueous solution is naturally flowed out under normal pressure. The concentration of the solution after adsorption was measured by an absorbance method or ICP-MS, and the saturated adsorption amount was calculated.
The calculation shows that the saturated adsorption capacity of the platinum-absorbing modified carbon fiber containing the organic chelating group to platinum is in the range of 80mg/g to 160 mg/g. Under the same experimental conditions, the saturated adsorption capacity of the commercial anion resin to platinum ions is 10 mg/g-30 mg/g.
Adsorption determination of platinum-containing solution in medium concentration by platinum-absorbing modified carbon fiber containing organic chelating group
0.5g of the platinum-adsorbing modified carbon fiber containing the organic chelating group prepared in the example 1 is weighed and filled into an adsorption column, the diameter of the adsorption column is 2cm, 170mL of 550mg/L acid aqueous solution containing platinum ions with medium concentration (pH < 1) is pumped into the adsorption column at a constant speed through a peristaltic pump at the speed of 0.4mL/min, and the solution is naturally flowed out under normal pressure. The post-adsorption solution was collected every 10mL, 17 bottles of post-adsorption solution were counted, the concentration of the post-adsorption solution was measured by the absorbance method or ICP-MS, and as shown in Table 1, a post-adsorption solution concentration-adsorption volume curve was plotted as shown in FIG. 1. Wherein the first 6 vials are received above the absorbance detection limit (below 1 mg/L).
TABLE 1 concentration table of platinum-adsorbing modified carbon fibers containing organic chelating groups after adsorption of acidic aqueous solution containing platinum ions at medium concentration
Serial number 1 2 3 4 5 6 7 8
V(mL) 10 10 10 10 10 10 10 10
C(mg/L) <1 <1 <1 <1 <1 <1 4.30 86.07
Serial number 9 10 11 13 14 15 16 17
V(mL) 10 10 10 10 10 10 10 10
C(mg/L) 204.04 346.01 436.11 505.37 523.74 529.00 547.37 547.37
Note: the measured concentration of the solution after the adsorption of the 1-6 bottles is lower than the lower limit of linear measurement, the 12 th bottle (0.12L) is subjected to supplementary adsorption because the column adsorption material is not saturated, the 13-17 bottles are subjected to supplementary adsorption, and the data of the 12 th bottle is not continuous adsorption data and is discarded.
Fig. 1 shows the adsorption effect of the material on acidic aqueous solution containing platinum ions with medium concentration, the platinum-absorbing modified carbon fiber can well absorb platinum ions, the lower limit of the liquid after adsorption is lower than 1mg/L, the adsorption efficiency is high, and the final adsorption experiment reaches the material saturation state.
Adsorption determination of platinum ion-containing acidic aqueous solution with low concentration in platinum-absorbing modified carbon fiber containing organic chelating group
1.5g of the platinum-adsorbing modified carbon fiber containing the organic chelating group prepared in the example 1 is weighed and filled into an adsorption column, the diameter of the adsorption column is 3cm, 9000mL of 28mg/L medium-low concentration platinum ion-containing acidic aqueous solution (pH is 2-3) is pumped into the adsorption column at a uniform speed at the speed of 1.5 mL/min-1.7 mL/min through a peristaltic pump, and natural outflow is kept under normal pressure. The post-adsorption solution was collected every 1000mL for a total of 9 bottles, and the concentration of the post-adsorption solution was measured by absorbance method or ICP-MS, as shown in Table 2. A graph of the concentration of the post-adsorption solution versus the adsorption volume was plotted as shown in fig. 2.
TABLE 2 table of the concentrations of platinum ion-containing acidic aqueous solutions having low and medium concentrations of platinum ion-containing modified carbon fibers having organic chelating groups adsorbed thereon
Figure BDA0002999642140000051
Figure BDA0002999642140000061
FIG. 2 shows the adsorption effect of acidic aqueous solution containing platinum ions at medium and low concentrations, the lower limit of the adsorbed solution can reach microgram per liter, the adsorption rate is high, the treatment volume is large, and the final adsorption column is approximately saturated.
Selective adsorption performance investigation of platinum-absorbing modified carbon fiber containing organic chelating group on platinum ions in low-concentration multi-ion acidic aqueous solution
Weighing 5mg of the platinum absorption modified carbon fiber containing the organic chelating group prepared in the embodiment 1, adding 10mL of solution containing multiple ions and having a pH value of 2-3, preparing the concentration of each ion in the solution to 0.5mg/L through a standard solution (1000 mg/L), performing shock adsorption for 30min, filtering, detecting the filtrate through ICP-MS, and calculating the adsorption rate, wherein as shown in Table 3, the platinum absorption modified carbon fiber containing the organic chelating group shows very high selective adsorption performance on platinum ions.
TABLE 3 Performance table of platinum ion adsorption performance of platinum-adsorbing modified carbon fiber containing organic chelating group on low-concentration polyion acidic aqueous solution
Figure BDA0002999642140000062
As can be seen from table 3, in the mixed solution containing ten metal ions having a platinum ion concentration of only 0.5mg/L, the platinum-adsorbing modified carbon fiber containing an organic chelating group of the present invention has almost no adsorption effect on As, pb, sb, cd, zn, cu, in, and Ni at the same concentration, while the adsorption on Pt is far from saturated. Therefore, the platinum-absorbing modified carbon fiber containing the organic chelating group has high selective adsorption performance on low-concentration platinum ions in the acidic aqueous solution containing the platinum ions, the lower adsorption limit is lower (0.5 mg/L), and the adsorption rate is more than 99%.
Selective adsorption performance investigation of platinum ion in acidic anode mud leachate by platinum-absorbing modified carbon fiber containing organic chelating group
0.5g of the platinum-adsorbing modified carbon fiber containing the organic chelating group prepared in example 1 is weighed and filled into an adsorption column, the diameter of the adsorption column is 2cm, certain anode mud leachate is pumped into the adsorption column at a constant speed of 0.4mL/min through a peristaltic pump, the anode mud leachate contains sulfuric acid, the pH value is less than 1, the anode mud leachate contains high-concentration metal salt, and the anode mud naturally flows out under normal pressure. Every 200mL of the solution receiving solution was taken, different solution receiving bottles were selected to measure the solution receiving components, and ICP analysis was performed, with the results shown in Table 4.
Table 4 table of platinum ion adsorption performance of platinum ion adsorption modified carbon fiber containing organic chelating group on certain anode mud leachate
Figure BDA0002999642140000063
Figure BDA0002999642140000071
Note: some data are higher than the stock solution composition, and the error is kept within the system error range (80% -120%).
As can be seen from table 4, in the presence of other metal ions at high concentration, the adsorption of the platinum ions at medium and low concentration in the platinum-adsorbing modified carbon fiber containing an organic chelating group according to the present invention is not affected, and the lower limit of the adsorption can still be less than the detection limit of 1 mg/L.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the scope of the invention. Those skilled in the art can make many variations and modifications to the disclosed embodiments, or equivalent variations, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (9)

1. The platinum-absorbing modified carbon fiber containing the organic chelating group is characterized by comprising carbon fiber and the organic chelating group bonded on the carbon fiber, wherein the organic chelating group is a platinum-absorbing organic chelating group which is mainly obtained by condensation reaction of an active group and an organic matter containing amino, and the active group at least comprises carboxyl;
the active groups are obtained by oxidation reaction of carbon fibers by hydrogen peroxide;
the amino-containing organic matter is amino-containing organic matter micromolecules;
the terminal group of the amino-containing organic substance is amino or hydroxyl.
2. The platinum-absorbing modified carbon fiber containing organic chelating groups as claimed in claim 1, wherein the amino-containing organic substance comprises one or more of tetraethylenepentamine, diethylenetriamine, ethylenediamine and N, N' -tetrakis (2-hydroxyethyl) ethylenediamine.
3. The platinum absorbing modified carbon fiber containing the organic chelating group as claimed in claim 1 or 2, wherein the adsorption rate of the platinum ion in the acidic aqueous solution containing the platinum ion by the platinum absorbing modified carbon fiber containing the organic chelating group is more than 99%, the saturated adsorption amount is 80mg/g to 160mg/g, and the lower adsorption limit is less than 0.5mg/L.
4. A method for preparing the platinum-absorbing modified carbon fiber containing an organic chelating group according to any one of claims 1 to 3, comprising the steps of:
(1) Adding carbon fibers into hydrogen peroxide for oxidation reaction, so that the carbon fibers are modified to obtain active groups, wherein the active groups at least comprise carboxyl groups, and obtaining oxidized carbon fibers after the oxidation reaction;
(2) And adding the oxidized carbon fiber and an organic matter containing amino into an organic solvent, and carrying out heating reflux under an anhydrous or nearly anhydrous condition to carry out organic condensation reaction to form an organic chelating group with a function of adsorbing platinum ions, thereby obtaining the platinum-adsorbing modified carbon fiber containing the organic chelating group.
5. The method for preparing the platinum-absorbing modified carbon fiber containing the organic chelating group according to claim 4, wherein in the step (2), the organic solvent comprises one or more of ethanol, toluene, xylene, dimethylformamide and dimethyl sulfoxide, the heating reflux time is 5-10 h, after the heating reflux is finished, the organic solvent is evaporated and recovered, after the reaction product is cooled, the reaction product is firstly washed by alcohol, then washed by water, and then dried at 60-100 ℃ for 24-48 h.
6. The method for preparing the platinum adsorption modified carbon fiber containing the organic chelating group according to the claim 4 or 5, wherein in the step (2), the theoretical adding molar ratio of the effective reaction functional group of the oxidized carbon fiber to the effective reaction functional group of the amino-containing organic substance is 1: 1-2.5.
7. The method for preparing the platinum-adsorbing modified carbon fiber containing the organic chelate group according to claim 4 or 5, wherein in the step (1), the time of the oxidation reaction is 2 to 5 hours, and after the oxidation reaction is finished, the solvent is dried under suction filtration and pressure for 24 to 48 hours at a temperature of between 60 and 100 ℃.
8. Use of the organic chelating group-containing platinum-adsorbing modified carbon fiber according to any one of claims 1 to 3 or the organic chelating group-containing platinum-adsorbing modified carbon fiber prepared by the preparation method according to any one of claims 4 to 7 in treatment of an acidic aqueous solution containing platinum ions.
9. The use of claim 8, wherein the pH of the acidic aqueous solution containing platinum ions is not more than 5, the applicable range of platinum ion concentration is 0.5mg/L to 1700mg/L, and the acid component of the solution comprises one or more of hydrochloric acid, sulfuric acid and nitric acid.
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