CN117778737A - Method for recovering rhodium from waste rhodium liquid - Google Patents
Method for recovering rhodium from waste rhodium liquid Download PDFInfo
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- CN117778737A CN117778737A CN202410214298.XA CN202410214298A CN117778737A CN 117778737 A CN117778737 A CN 117778737A CN 202410214298 A CN202410214298 A CN 202410214298A CN 117778737 A CN117778737 A CN 117778737A
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 119
- 239000010948 rhodium Substances 0.000 title claims abstract description 119
- 239000002699 waste material Substances 0.000 title claims abstract description 69
- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 24
- 239000004917 carbon fiber Substances 0.000 claims abstract description 24
- 239000003463 adsorbent Substances 0.000 claims abstract description 23
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 20
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of rhodium recovery, and particularly relates to a method for recovering rhodium from waste rhodium liquid. The method takes carbon fiber as a matrix, acrylic fiber is crosslinked on the surface of the carbon fiber, and Cu is introduced into the system 2+ The composite carbon-based adsorbent is obtained, rhodium in the waste liquid can be efficiently enriched with the assistance of the adsorbent, and rhodium is effectively reduced and collected through hydrazine hydrate. The book is provided withThe method for recovering rhodium from the waste rhodium liquid provided by the invention not only can realize high recovery rate (more than 99 percent) of rhodium, but also can keep good stability, can obtain excellent rhodium recovery rate aiming at different types of rhodium-containing waste liquid, is not easily influenced by other substances in the waste liquid, and is more suitable for the recovery and utilization of rhodium in industry.
Description
Technical Field
The invention belongs to the technical field of rhodium recovery, and particularly relates to a method for recovering rhodium from waste rhodium liquid.
Background
The platinum group metal homogeneous catalyst is mainly composed of low valence platinum, palladium and rhodium compounds, wherein rhodium organic carboxylic acid, organic phosphine, carbonyl complex and the like with particularly outstanding catalytic activity are mainly used, and the platinum group metal homogeneous catalyst mainly comprises rhodium acetate, rhodium octoate, triphenylphosphine rhodium chloride, rhodium park. The rhodium homogeneous catalysis complex can generate a large amount of rhodium-containing organic waste liquid in the production and use processes, and if rhodium is purified and reused from the waste liquid efficiently, the scale of rhodium metal resources is effectively enlarged, and the self-supply guarantee of rhodium metal is improved.
In the prior art, the method for recovering rhodium from rhodium-containing organic waste liquid mainly comprises a pyrogenic process and a wet process. The fire method is to concentrate, burn and refine the waste liquid to obtain rhodium, and has the advantage of high recovery rate, but the rhodium loss is caused by flue gas entrainment in the burning process, and the pollution is large and the energy consumption is high. The wet method precipitates rhodium from the waste liquid by adding a precipitant and then refines the rhodium. The wet method and the fire method are combined, rhodium is enriched and settled by the wet method, and then fire refining is performed, so that the method is a reasonable mode, pollution can be relieved to a certain extent, and high recovery rate is obtained. It would therefore be of great importance to explore a process that would allow for the stable recovery of rhodium from different types of spent rhodium solutions.
Disclosure of Invention
Aiming at the problem that the recovery rate is unstable in the prior art of the method for recovering rhodium from rhodium-containing organic waste liquid, the invention provides a method for recovering rhodium from waste rhodium liquid, which takes carbon fiber as a matrix, crosslinks acrylic fiber on the surface of the carbon fiber, and introduces Cu into the system 2+ The composite carbon-based adsorbent is obtained, rhodium in the waste liquid can be efficiently enriched with the assistance of the adsorbent, and rhodium is effectively reduced and collected through hydrazine hydrate. The method for recovering rhodium from the waste rhodium liquid has high recovery rate and stable recovery rate, can obtain excellent rhodium recovery rate aiming at different types of rhodium-containing waste liquid, and is suitable for industrial rhodium recycling.
The first aspect of the present invention provides a process for recovering rhodium from a spent rhodium liquid comprising the steps of:
s1: acrylic fiber, cu (NO) 3 ) 2 Catechol is dissolved in glycol to form a modified solution; then nitric acid is adopted for dissolvingCarrying out surface activation treatment on the cleaned carbon fiber by the liquid, fully soaking the activated carbon fiber in a modified solution under a heating environment, then adding sodium sulfite for heating reflux reaction, and filtering to obtain a composite carbon-based adsorbent;
s2: pouring rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating light components to obtain concentrated solution;
s3: adding the composite carbon-based adsorbent into the concentrated solution, fully stirring and uniformly mixing, filtering, dissolving in a nitric acid solution, adding hydrazine hydrate, and filtering to obtain crude rhodium powder;
s4: and introducing hydrogen into the crude rhodium powder at high temperature for reduction, boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Further, acrylic fiber, cu (NO 3 ) 2 The addition ratio of catechol to ethylene glycol was 3 g/2 g/5 mL/50 mL.
Further, the concentration of the nitric acid solution is 20-30%, and the surface activation treatment mode by using the nitric acid solution is as follows: and soaking the carbon fiber in a nitric acid solution for 3-4 hours, and then filtering and washing the carbon fiber to be neutral.
Further, the addition ratio of the activated carbon fiber to the modifying solution is 2-3 g/50 mL.
Further, the heating temperature of the activated carbon fiber is 80-120 ℃ when the activated carbon fiber is immersed in the modifying solution, and the immersing time is 4-6 hours.
Further, the mass ratio of sodium sulfite to carbon fiber is 1:2.
Further, the heating reflux reaction time is 1-2 h.
Further, the concentration condition of the rhodium-containing waste liquid is that the vacuum degree is 0.08-0.1 MPa, the concentration temperature is 100-200 ℃, and the volume of the concentrated liquid is 20-30% of the total volume of the rhodium-containing waste liquid.
Further, the addition ratio of the composite carbon-based adsorbent to the concentrated solution is 1-2 g/10 mL.
And further, adding the composite carbon-based adsorbent into the concentrated solution, fully stirring and uniformly mixing at 80-100 ℃, filtering, dissolving in a nitric acid solution, adding hydrazine hydrate according to half of the volume of the concentrated solution, adding the hydrazine hydrate, boiling for 2-3 h, cooling to room temperature, and filtering to obtain crude rhodium powder.
Further, the crude rhodium powder is reduced for 2-3 hours by introducing hydrogen at 700-800 ℃.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
1. the carbon fiber is used as the matrix of the adsorbent, a stable structural substrate is built mainly by means of excellent mechanical properties of the carbon fiber, the catechol is used as a medium to crosslink the acrylic fiber on the surface of the carbon fiber, the adsorption activity of rhodium can be enhanced by utilizing the acrylic fiber, and an acrylic fiber network formed by crosslinking among the carbon fibers is more beneficial to building a rich adsorption space, a stable adsorption structure is formed quickly, digestion is difficult, and meanwhile, sodium sulfite is used for carrying out sulfonation treatment on the surface groups, so that the adsorption of rhodium can be further promoted. Furthermore, the invention introduces Cu together in the system 2+ Not only can prevent the agglomeration of the carbon fiber, promote the uniform dispersion of the carbon fiber and further improve the stability of an adsorption system, but also can catalyze the adsorption process of rhodium and improve the adsorption efficiency.
2. The method for recovering rhodium from the waste rhodium liquid provided by the invention not only can realize high recovery rate (more than 99 percent) of rhodium, but also can keep good stability, can obtain excellent rhodium recovery rate for different types of rhodium-containing waste liquid, is not easily influenced by other substances in the waste liquid, and is more suitable for the recovery and utilization of rhodium in industry.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
The embodiment provides a method for recovering rhodium from waste rhodium liquid, which comprises the following specific steps:
s1: 3g of acrylic fiber, 2g of Cu (NO) 3 ) 2 5mL of catechol is dissolved in 50mL of glycol to form a modified solution; soaking 3g of carbon fiber in 20% nitric acid solution for 3 hr, filtering, washing with water to neutrality, and changing at 120deg.C under 50mLFully soaking in the sexual solution for 4 hours, then adding 1.5g of sodium sulfite, heating to reflux reaction, continuing for 2 hours, and filtering to obtain the composite carbon-based adsorbent;
s2: pouring 4 different rhodium-containing waste solutions, namely rhodium park synthetic waste solution, rhodium octanoate synthetic waste solution, rhodium acetate synthetic waste solution and triphenylphosphine rhodium chloride synthetic waste solution, into a concentration kettle for concentration, evaporating light components, wherein the concentration vacuum degree is 0.08MPa, the concentration temperature is 100 ℃, the volume of the concentrated solution is 20% of the total volume of the rhodium-containing waste solution, and 4 concentrated solutions are obtained and marked as sample-A1, sample-A2, sample-A3 and sample-A4;
s3: adding 1g of the composite carbon-based adsorbent into 10mL of the four concentrated solutions, fully stirring and uniformly mixing at 80 ℃, filtering, dissolving in a nitric acid solution, adding 5mL of hydrazine hydrate, adding the hydrazine hydrate, boiling for 2h, cooling to room temperature, and filtering to obtain crude rhodium powder;
s4: and (3) introducing hydrogen into the crude rhodium powder at 800 ℃ for reduction for 2 hours, boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Example 2
The embodiment provides a method for recovering rhodium from waste rhodium liquid, which comprises the following specific steps:
s1: 3g of acrylic fiber, 2g of Cu (NO) 3 ) 2 5mL of catechol is dissolved in 50mL of glycol to form a modified solution; soaking 2g of carbon fiber in a nitric acid solution with the concentration of 20% for 4 hours, filtering, washing to be neutral, fully soaking in 50mL of modified solution for 4 hours in a heating environment at 80 ℃, adding 1g of sodium sulfite, heating to reflux reaction, continuously carrying out 2 hours, and filtering to obtain the composite carbon-based adsorbent;
s2: pouring 4 different rhodium-containing waste solutions, namely rhodium park synthetic waste solution, rhodium octanoate synthetic waste solution, rhodium acetate synthetic waste solution and triphenylphosphine rhodium chloride synthetic waste solution, into a concentration kettle for concentration, evaporating light components, wherein the concentration vacuum degree is 0.1MPa, the concentration temperature is 200 ℃, the volume of the concentrated solution is 30% of the total volume of the rhodium-containing waste solution, and 4 concentrated solutions are obtained and marked as sample-B1, sample-B2, sample-B3 and sample-B4;
s3: adding 1.5g of the composite carbon-based adsorbent into 10mL of the four concentrated solutions, fully stirring and uniformly mixing at 100 ℃, filtering, dissolving in a nitric acid solution, adding 5mL of hydrazine hydrate, adding hydrazine hydrate, boiling for 3h, cooling to room temperature, and filtering to obtain crude rhodium powder;
s4: introducing hydrogen into the crude rhodium powder at 700 ℃ for reduction for 3 hours, then boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Example 3
The embodiment provides a method for recovering rhodium from waste rhodium liquid, which comprises the following specific steps:
s1: 3g of acrylic fiber, 2g of Cu (NO) 3 ) 2 5mL of catechol is dissolved in 50mL of glycol to form a modified solution; soaking 3g of carbon fiber in 30% nitric acid solution for 3h, filtering, washing to neutrality, fully soaking in 50mL of modified solution at 100 ℃ for 6h, adding 1.5g of sodium sulfite, heating to reflux for 1h, and filtering to obtain the composite carbon-based adsorbent;
s2: pouring 4 different rhodium-containing waste solutions, namely rhodium park synthetic waste solution, rhodium octanoate synthetic waste solution, rhodium acetate synthetic waste solution and triphenylphosphine rhodium chloride synthetic waste solution, into a concentration kettle for concentration, evaporating light components, wherein the concentration vacuum degree is 0.08MPa, the concentration temperature is 200 ℃, the volume of the concentrated solution is 20% of the total volume of the rhodium-containing waste solution, and 4 concentrated solutions are obtained and marked as sample-C1, sample-C2, sample-C3 and sample-C4;
s3: adding 2g of the composite carbon-based adsorbent into 10mL of the four concentrated solutions, fully stirring and uniformly mixing at 90 ℃, filtering, dissolving in a nitric acid solution, adding 5mL of hydrazine hydrate, adding hydrazine hydrate, boiling for 3h, cooling to room temperature, and filtering to obtain crude rhodium powder;
s4: and (3) introducing hydrogen into the crude rhodium powder at 750 ℃ for reduction for 3 hours, then boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Example 4
The embodiment provides a method for recovering rhodium from waste rhodium liquid, which comprises the following specific steps:
s1: 3g of acrylic fiber, 2g of Cu (NO) 3 ) 2 5mL catechol in 50mL ethylene glycol, formForming a modified solution; soaking 3g of carbon fiber in a nitric acid solution with the concentration of 20% for 4 hours, filtering, washing to be neutral, fully soaking in 50mL of modified solution for 5 hours in a heating environment at 80 ℃, adding 1.5g of sodium sulfite, heating to reflux for 2 hours, and filtering to obtain the composite carbon-based adsorbent;
s2: pouring 4 different rhodium-containing waste solutions, namely rhodium park synthetic waste solution, rhodium octanoate synthetic waste solution, rhodium acetate synthetic waste solution and triphenylphosphine rhodium chloride synthetic waste solution, into a concentration kettle for concentration, evaporating light components, wherein the concentration vacuum degree is 0.1MPa, the concentration temperature is 100 ℃, the volume of the concentrated solution is 20% of the total volume of the rhodium-containing waste solution, and 4 concentrated solutions are obtained and marked as sample-D1, sample-D2, sample-D3 and sample-D4;
s3: adding 1g of the composite carbon-based adsorbent into 10mL of the four concentrated solutions, fully stirring and uniformly mixing at 90 ℃, filtering, dissolving in a nitric acid solution, adding 5mL of hydrazine hydrate, adding the hydrazine hydrate, boiling for 2h, cooling to room temperature, and filtering to obtain crude rhodium powder;
s4: and (3) introducing hydrogen into the crude rhodium powder at 800 ℃ for reduction for 2 hours, boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Comparative example 1
The comparative example provides a method for recovering rhodium from waste rhodium liquid, which comprises the following specific steps:
s1: 3g of acrylic fiber and 5mL of catechol are dissolved in 50mL of ethylene glycol to form a modified solution; soaking 3g of carbon fiber in a nitric acid solution with the concentration of 20% for 3 hours, filtering, washing to be neutral, fully soaking in 50mL of modified solution for 4 hours in a heating environment at 120 ℃, adding 1.5g of sodium sulfite, heating to reflux for 2 hours, and filtering to obtain a composite carbon-based adsorbent;
s2: pouring 4 different rhodium-containing waste solutions, namely rhodium park synthetic waste solution, rhodium octanoate synthetic waste solution, rhodium acetate synthetic waste solution and triphenylphosphine rhodium chloride synthetic waste solution, into a concentration kettle for concentration, evaporating light components, concentrating the light components at the concentration vacuum degree of 0.08MPa and the concentration temperature of 100 ℃, wherein the volume of the concentrated solution is 20% of the total volume of the rhodium-containing waste solution, so as to obtain 4 concentrated solutions, and marking the 4 concentrated solutions as a sample-E1, a sample-E2, a sample-E3 and a sample-E4;
s3: adding 1g of the composite carbon-based adsorbent into 10mL of the four concentrated solutions, fully stirring and uniformly mixing at 80 ℃, filtering, dissolving in a nitric acid solution, adding 5mL of hydrazine hydrate, adding the hydrazine hydrate, boiling for 2h, cooling to room temperature, and filtering to obtain crude rhodium powder;
s4: and (3) introducing hydrogen into the crude rhodium powder at 800 ℃ for reduction for 2 hours, boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Comparative example 2
The comparative example provides a method for recovering rhodium from waste rhodium liquid, which comprises the following specific steps:
s1: pouring 4 different rhodium-containing waste solutions, namely rhodium park synthetic waste solution, rhodium octanoate synthetic waste solution, rhodium acetate synthetic waste solution and triphenylphosphine rhodium chloride synthetic waste solution, into a concentration kettle for concentration, evaporating light components, concentrating the light components at the concentration vacuum degree of 0.08MPa and the concentration temperature of 100 ℃, wherein the volume of the concentrated solution is 20% of the total volume of the rhodium-containing waste solution, so as to obtain 4 concentrated solutions, and marking the 4 concentrated solutions as samples-F1, sample-F2, sample-F3 and sample-F4;
s2: adding 1g of carbon fiber and 1g of acrylic fiber into 10mL of the four concentrated solutions, fully stirring and uniformly mixing at 80 ℃, filtering, dissolving in a nitric acid solution, adding 5mL of hydrazine hydrate, adding the hydrazine hydrate, boiling for 2h, cooling to room temperature, and filtering to obtain crude rhodium powder;
s3: and (3) introducing hydrogen into the crude rhodium powder at 800 ℃ for reduction for 2 hours, boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
Performance test:
the recovery rates of rhodium finally measured by the methods of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
Therefore, the method for recovering rhodium from the waste rhodium liquid provided by the invention not only can realize high recovery rate (more than 99 percent) of rhodium, but also can keep good stability, can obtain excellent rhodium recovery rate for different types of rhodium-containing waste liquid, is not easily influenced by other substances in the waste liquid, and has excellent recovery effect for different types of rhodium-containing waste liquid, the result difference among different types of waste liquid is small, and the method is more suitable for the recovery and utilization of rhodium in industry.
Claims (10)
1. A process for recovering rhodium from a spent rhodium liquid, characterized by: the method comprises the following steps:
s1: acrylic fiber, cu (NO) 3 ) 2 Catechol is dissolved in glycol to form a modified solution; then nitric acid solution is adopted to carry out surface activation treatment on the cleaned carbon fiber, the activated carbon fiber is fully immersed in the modified solution under a heating environment, sodium sulfite is added to carry out heating reflux reaction, and the composite carbon-based adsorbent is obtained through filtration;
s2: pouring rhodium-containing waste liquid into a concentration kettle for concentration, and evaporating light components to obtain concentrated solution;
s3: adding the composite carbon-based adsorbent into the concentrated solution, fully stirring and uniformly mixing, filtering, dissolving in a nitric acid solution, adding hydrazine hydrate, and filtering to obtain crude rhodium powder;
s4: and introducing hydrogen into the crude rhodium powder at high temperature for reduction, boiling the crude rhodium powder in aqua regia and hydrofluoric acid in sequence, washing the crude rhodium powder with water and drying the crude rhodium powder to obtain pure rhodium powder.
2. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: acrylic fiber, cu (NO) 3 ) 2 The addition ratio of catechol to ethylene glycol was 3 g/2 g/5 mL/50 mL.
3. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: the concentration of the nitric acid solution is 20-30%, and the surface activation treatment mode by using the nitric acid solution is as follows: and soaking the carbon fiber in a nitric acid solution for 3-4 hours, and then filtering and washing the carbon fiber to be neutral.
4. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: the addition ratio of the activated carbon fiber to the modified solution is 2-3 g/50 mL.
5. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: the heating temperature of the activated carbon fiber is 80-120 ℃ when the activated carbon fiber is immersed in the modifying solution, and the immersing time is 4-6 h.
6. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: the mass ratio of the sodium sulfite to the carbon fiber is 1:2.
7. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: the heating reflux reaction time is 1-2 h.
8. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: the adding ratio of the composite carbon-based adsorbent to the concentrated solution is 1-2 g/10 mL.
9. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: and adding the composite carbon-based adsorbent into the concentrated solution, fully stirring and uniformly mixing at 80-100 ℃, filtering, dissolving in a nitric acid solution, adding hydrazine hydrate according to half of the volume of the concentrated solution, adding the hydrazine hydrate, boiling for 2-3 h, cooling to room temperature, and filtering to obtain crude rhodium powder.
10. The method for recovering rhodium from a spent rhodium liquid according to claim 1, wherein: and introducing hydrogen into the crude rhodium powder at 700-800 ℃ for reduction for 2-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410214298.XA CN117778737B (en) | 2024-02-27 | 2024-02-27 | Method for recovering rhodium from waste rhodium liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202410214298.XA CN117778737B (en) | 2024-02-27 | 2024-02-27 | Method for recovering rhodium from waste rhodium liquid |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004292912A (en) * | 2003-03-27 | 2004-10-21 | Nittetsu Mining Co Ltd | Method for recovering high purity rhodium from rhodium-containing metal waste or the like |
| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
| JP2019163502A (en) * | 2018-03-19 | 2019-09-26 | 国立大学法人秋田大学 | Method for recovering rhodium |
| CN110607448A (en) * | 2019-09-27 | 2019-12-24 | 西安凯立新材料股份有限公司 | Method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid |
| CN111910077A (en) * | 2020-07-08 | 2020-11-10 | 武汉工程大学 | Method for efficiently enriching rhodium from rhodium-containing organic waste liquid |
| CN117463304A (en) * | 2023-12-25 | 2024-01-30 | 北京高新利华科技股份有限公司 | Polymer adsorbent and method for recovering rhodium in rhodium-containing waste liquid based on same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004292912A (en) * | 2003-03-27 | 2004-10-21 | Nittetsu Mining Co Ltd | Method for recovering high purity rhodium from rhodium-containing metal waste or the like |
| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
| JP2019163502A (en) * | 2018-03-19 | 2019-09-26 | 国立大学法人秋田大学 | Method for recovering rhodium |
| CN110607448A (en) * | 2019-09-27 | 2019-12-24 | 西安凯立新材料股份有限公司 | Method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid |
| CN111910077A (en) * | 2020-07-08 | 2020-11-10 | 武汉工程大学 | Method for efficiently enriching rhodium from rhodium-containing organic waste liquid |
| CN117463304A (en) * | 2023-12-25 | 2024-01-30 | 北京高新利华科技股份有限公司 | Polymer adsorbent and method for recovering rhodium in rhodium-containing waste liquid based on same |
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