CN111996386B - Method for recovering rhodium from rhodium-containing homogeneous phase waste catalyst - Google Patents
Method for recovering rhodium from rhodium-containing homogeneous phase waste catalyst Download PDFInfo
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- CN111996386B CN111996386B CN202010884010.1A CN202010884010A CN111996386B CN 111996386 B CN111996386 B CN 111996386B CN 202010884010 A CN202010884010 A CN 202010884010A CN 111996386 B CN111996386 B CN 111996386B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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 disclosesA method for recovering rhodium from a rhodium-containing homogeneous phase waste catalyst is provided, a recovery method of acidification, oxidation, complex precipitation and sulfide precipitation is adopted, firstly, acidification, oxidation is utilized to break the 'bridging' of rhodium in rhodium-phosphine catalysis in the waste catalyst, then a specific complex precipitator is adopted to generate complex precipitation of rhodium, so that the recovery rate of rhodium reaches 95.23% in one step, a rhodium main body in the waste catalyst is recovered in one step, the dispersion of rhodium is effectively reduced, and the recovery rate of rhodium is improved; in addition, a small portion of the rhodium is directly oxidized to Rh in the acidification-oxidation process step3+And the part is recovered by a sulfide precipitation method, and the final recovery rate of the rhodium combined with the part can reach more than 97 percent. The complex precipitate and the sulfide precipitate generated in the recovery process are easy to treat, do not generate highly toxic substances, and are safe, green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of secondary resources of noble metals, relates to recovery of noble metal rhodium, and particularly relates to a method for recovering rhodium from a rhodium-containing homogeneous phase waste catalyst.
Background
The rhodium homogeneous organic complex catalyst has the advantages of high catalytic activity, good selectivity and the like, and plays an important role in chemical processes such as catalytic hydrogenation, hydroformylation, oxo synthesis and the like. However, in commercial applications, it has been found that various high boiling by-products and impurities in their feedstocks deactivate portions of the homogeneous rhodium catalyst after a period of use. The inactivated homogeneous rhodium catalyst has rhodium content of 100-800ppm, which is much higher than that in the crust, and is an important rhodium secondary resource. Because the resource of the noble metal rhodium in China is deficient, the noble metal rhodium mainly depends on import, the circular economy is greatly developed, the efficient recovery of the rhodium from the waste has important significance in the fields of economic development, scientific research, environmental protection and the like, and the economic benefit is considerable.
At present, the commonly used methods for recovering rhodium mainly comprise an immersion combustion method, an extraction method, an adsorption separation method and the like. The immersion combustion method is that the homogeneous rhodium-containing waste catalyst is placed in a combustion chamber for combustion, sufficient air is provided at the same time, and the resultant is washed by water and filtered to obtain rhodium. In the incineration process, rhodium in the homogeneous phase waste catalyst volatilizes along with smoke dust to cause rhodium loss, so that the recovery rate of rhodium can only reach 90% at most, meanwhile, high-temperature incineration is easy to generate explosion, and highly toxic substances such as dioxin and the like are generated, so that the method is high in danger and serious in environmental pollution.
The extraction method is characterized in that acid and peroxide are added into a homogeneous waste catalyst to generate a water-polar organic two-phase mixture, and a rhodium complex in the waste catalyst enters a water phase to separate rhodium from an organic phase. However, because the rhodium content concentration in the homogeneous catalyst is low, the binding capacity of metal rhodium and the organic phosphine compound is very strong, the polynuclear rhodium complex is stable, the waste rhodium solution is very viscous, and the like, the final recovery rate is not high and can only reach about 85%.
The adsorption separation method is characterized in that a selective adsorbent is added into a homogeneous phase waste catalyst to adsorb a rhodium-phosphine complex catalyst, then benzene is used as a solvent to thoroughly wash high-boiling-point byproducts in the catalyst, and the recovery rate of rhodium can reach 90% after desorption-purification.
Disclosure of Invention
The invention aims to provide a method for recovering rhodium from a rhodium-containing homogeneous spent catalyst, which can effectively reduce the dispersion of rhodium in the recovery process, improve the recovery rate of rhodium, does not produce highly toxic substances, and is safe, green and environment-friendly.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a process for recovering rhodium from a rhodium-containing homogeneous spent catalyst, said process comprising the steps of:
step 1: taking a certain amount of waste catalyst, firstly adding inorganic acid and an oxidant into the waste catalyst at normal temperature, heating to 70-90 ℃, and carrying out heat preservation stirring reaction for 0.5-2 h; wherein the addition of the inorganic acid is 5-20% of the amount of the waste catalyst, and the addition of the oxidant is 3-30% of the amount of the waste catalyst;
step 2: step 1, after the heat preservation is finished, adding a mixed solution of oxalic acid and formic acid, continuing to preserve heat, stirring and reacting for 1-2.5 h, and cooling and filtering after the heat preservation is finished; wherein the adding amount of oxalic acid is 4-25% of the amount of the waste catalyst, and the adding amount of formic acid is 3-18% of the amount of the waste catalyst;
and step 3: stirring and heating the filtrate obtained by filtering in the step 2 to 60-90 ℃, dropwise adding a sodium sulfide solution, preserving heat for 1-3 hours, and cooling and filtering after heat preservation; wherein the adding amount of the sodium sulfide is 2 to 15 percent of the amount of the waste catalyst;
and 4, step 4: mixing the filter residue obtained by filtering in the step 2 and the filter residue obtained by filtering in the step 3, and dissolving the mixture by using aqua regia; adjusting the pH value of the leachate to 8-9 by using an alkali solution to obtain rhodium hydroxide precipitate;
and 5: dissolving rhodium hydroxide with acid, concentrating the solution to contain 15-200 g/L of rhodium, reducing and filtering with formic acid to obtain rhodium black powder, and reducing the rhodium black powder with closed hydrogen to obtain rhodium powder.
Preferably, in step 1, the inorganic acid is selected from hydrochloric acid or sulfuric acid.
Preferably, in step 1, the oxidizing agent is one selected from hydrogen peroxide, sodium chlorate, sodium hypochlorite and nitric acid.
Preferably, in step 4, the alkali solution is a NaOH solution or a KOH solution.
More preferably, in the step 4, the mass fraction of the alkali solution is 15% to 20%.
Preferably, in step 5, the acid is hydrochloric acid or sulfuric acid.
More preferably, in the step 5, the concentration of the acid is 2-6 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
1. firstly, interrupting rhodium 'bridging' in a waste rhodium-phosphine homogeneous catalyst by utilizing acidification and oxidation, so that a rhodium cluster complex is dispersed, the rhodium-phosphine complex is decomposed, and an inhibitor is gradually damaged; then, when oxalic acid is combined with transition metal elements, a soluble complex is formed due to the coordination effect of oxalic acid, the solubility of the complex is greatly increased, and rhodium and oxalic acid in the homogeneous rhodium catalyst are coordinated into a light yellow coordination compound colloidal precipitate. The recovery rate of rhodium can reach 95.23 percent, the main body of rhodium in the homogeneous phase waste catalyst is recovered in one step, the dispersion of rhodium is effectively reduced, the loss of rhodium in the recovery process is greatly reduced, and the recovery rate is greatly improved.
2. In the acidification oxidation step, there will be a small portion of Rh3+After precipitating in the channels and collaterals, a small amount of Rh is generated in the channels and collaterals3+The obtained Rh enters an organic phase and is recovered by adding sulfide to generate Rh2S3Can be dissolved by aqua regia, and the subsequent purification is simple and easy. By adopting a two-step precipitation method with the main complexing precipitation and the auxiliary vulcanizing precipitation, the recovery rate can reach more than 97 percent, and the recovery rate is greatly improved.
In conclusion, the method combines the two steps of complex precipitation and sulfide precipitation, takes the complex precipitation as a main step, recovers the main part of rhodium in the homogeneous phase waste catalyst in one step, effectively reduces the dispersion of the rhodium, ensures that the recovery rate of the rhodium can reach 95.23 percent, takes the sulfide precipitation as an auxiliary step, and ensures that a small part of Rh in an organic phase is obtained after the complex precipitation3+The recovery rate of rhodium can reach more than 97% by adopting a mode of adding sulfide and combining a two-step precipitation method, and the complex precipitate generated in the recovery processThe material and the sulfide precipitate are easy to treat, do not generate highly toxic substances, and are safe, green and environment-friendly.
Drawings
FIG. 1 is a flow diagram of the process of the present invention for recovering rhodium from rhodium-containing homogeneous spent catalysts.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The reagents used in the following examples are commercially available products, and the purity thereof was analytical purity or higher.
The spent catalyst to be treated in the following examples is a deactivated rhodium-phosphine homogeneous complex catalyst.
Example 1
A process for recovering rhodium from a rhodium-containing homogeneous spent catalyst, as shown in figure 1, comprising the steps of:
step 1: taking a certain amount of waste catalyst, firstly adding hydrochloric acid with 5% of the amount of the waste catalyst into the waste catalyst at normal temperature, then adding hydrogen peroxide with 3% of the amount of the waste catalyst, heating to 90 ℃, and carrying out heat preservation and stirring reaction for 2 hours;
step 2: after the heat preservation of the step 1 is finished, adding a mixed solution of oxalic acid with the waste catalyst amount of 4% and formic acid with the waste catalyst amount of 3%, continuing to preserve heat, stirring and reacting for 2.5h, and cooling and filtering after the heat preservation is finished;
and step 3: stirring and heating the filtrate obtained by filtering in the step 2 to 90 ℃, and dropwise adding Na with the mass fraction of 10%2S solution, adding Na2The S amount is 2 percent of the amount of the waste catalyst, the heat is preserved for 3 hours, and the cooling and the filtration are carried out after the heat preservation is finished;
2Rh3++3S2-→Rh2S3↓
and 4, step 4: mixing the filter residue obtained by filtering in the step 2 and the filter residue obtained by filtering in the step 3, and dissolving the mixture by using aqua regia; adjusting the pH value of the leachate to 8 by using NaOH solution with the mass fraction of 15% to obtain rhodium hydroxide precipitate;
and 5: dissolving rhodium hydroxide by adopting 2mol/L HCl, concentrating the solution until the rhodium content is 15g/L, reducing and filtering by using formic acid to obtain rhodium black powder, and reducing the rhodium black powder by closed hydrogen to obtain rhodium powder with the purity of 99.95 percent.
Rh(OH)3+3HCl→RhCl3+3H2O
| Numbering | Rhodium content (g/t) | Sample (mL) | Rhodium content (g/L) of the precipitation slag | Rhodium recovery (%) |
| 1 | 110 | 500 | 0.05109 | 97.17 |
The sediment residue is the sum of the complexing filter residue obtained by filtering in the step 2 and the vulcanized filter residue obtained by filtering in the step 3.
Example 2
A process for recovering rhodium from a rhodium-containing homogeneous spent catalyst, as shown in figure 1, comprising the steps of:
step 1: taking a certain amount of waste catalyst, firstly adding sulfuric acid with the waste catalyst amount being 20% into the waste catalyst at normal temperature, then adding hydrogen peroxide with the waste catalyst amount being 30%, heating to 70 ℃, and carrying out heat preservation and stirring reaction for 0.5 h;
step 2: after the heat preservation of the step 1 is finished, adding a mixed solution of oxalic acid with the waste catalyst amount of 25% and formic acid with the waste catalyst amount of 18%, continuing to preserve heat, stirring and reacting for 1h, and cooling and filtering after the heat preservation is finished;
and step 3: stirring and heating the filtrate obtained by filtering in the step 2 to 60 ℃, and dropwise adding Na with the mass fraction of 30%2S solution, adding Na2The S amount is 15 percent of the amount of the waste catalyst, the heat is preserved for 1 hour, and the mixture is cooled and filtered after the heat preservation is finished;
and 4, step 4: mixing the filter residue obtained by filtering in the step 2 and the filter residue obtained by filtering in the step 3, and dissolving the mixture by using aqua regia; adjusting the pH value of the leachate to 9 by using NaOH solution with the mass fraction of 20 percent to obtain rhodium hydroxide precipitate;
and 5: rhodium hydroxide was used in an amount of 6mol/L H2SO4Dissolving, concentrating the solution to 200g/L of rhodium, reducing and filtering with formic acid to obtain rhodium black powder, and reducing the rhodium black powder under sealed hydrogen to obtain rhodium powder with the purity of 99.95%.
| Numbering | Rhodium content (g/t) | Sample (mL) | Rhodium content (g/L) of the precipitated slag | Rhodium recovery (%) |
| 2 | 110 | 500 | 0.03822 | 96.92 |
Example 3
A process for recovering rhodium from a rhodium-containing homogeneous spent catalyst, as shown in figure 1, comprising the steps of:
step 1: taking a certain amount of waste catalyst, firstly adding hydrochloric acid with the waste catalyst amount of 15% into the waste catalyst at normal temperature, then adding sodium chlorate with the waste catalyst amount of 16%, heating to 80 ℃, and carrying out heat preservation and stirring reaction for 1 h;
step 2: step 1, after the heat preservation is finished, adding a mixed solution of oxalic acid with the waste catalyst amount of 15% and formic acid with the waste catalyst amount of 10%, continuing to preserve heat, stirring and reacting for 2 hours, and cooling and filtering after the heat preservation is finished;
and step 3: stirring and heating the filtrate obtained by filtering in the step 2 to 75 ℃, and dropwise adding Na with the mass fraction of 20%2S solution, adding Na2The S amount is 9 percent of the amount of the waste catalyst, the heat is preserved for 2 hours, and the cooling and the filtration are carried out after the heat preservation is finished;
and 4, step 4: mixing the filter residue obtained by filtering in the step 2 and the filter residue obtained by filtering in the step 3, and dissolving the mixture by using aqua regia; adjusting the pH value of the leachate to 8 by using a KOH solution with the mass fraction of 15 percent to obtain rhodium hydroxide precipitate;
and 5: dissolving rhodium hydroxide by adopting 4mol/L HCl, concentrating the solution until the solution contains 120g/L of rhodium, reducing and filtering the solution by using formic acid to obtain rhodium black powder, and reducing the rhodium black powder by closed hydrogen to obtain rhodium powder with the purity of 99.95 percent.
| Numbering | Rhodium content (g/t) | Sample (mL) | Rhodium content (g/L) of the precipitated slag | Rhodium recovery (%) |
| 3 | 110 | 500 | 0.06376 | 97.01 |
Claims (5)
1. A process for recovering rhodium from a rhodium-containing homogeneous spent catalyst, the process comprising the steps of:
step 1: taking a certain amount of waste catalyst, firstly adding inorganic acid and an oxidant into the waste catalyst at normal temperature, heating to 70-90 ℃, and carrying out heat preservation stirring reaction for 0.5-2 h; wherein the addition of the inorganic acid is 5-20% of the amount of the waste catalyst, and the addition of the oxidant is 3-30% of the amount of the waste catalyst;
step 2: step 1, after the heat preservation is finished, adding a mixed solution of oxalic acid and formic acid, continuing to preserve heat, stirring and reacting for 1-2.5 h, and cooling and filtering after the heat preservation is finished; wherein the adding amount of oxalic acid is 4-25% of the amount of the waste catalyst, and the adding amount of formic acid is 3-18% of the amount of the waste catalyst;
and step 3: stirring and heating the filtrate obtained by filtering in the step 2 to 60-90 ℃, dropwise adding a sodium sulfide solution, preserving heat for 1-3 hours, and cooling and filtering after heat preservation; wherein the adding amount of the sodium sulfide is 2 to 15 percent of the amount of the waste catalyst; and 4, step 4: mixing the filter residue obtained by filtering in the step 2 and the filter residue obtained by filtering in the step 3, dissolving the mixture by using aqua regia, and adjusting the pH value of the leaching solution to 8-9 by using an alkali solution to obtain rhodium hydroxide precipitate;
and 5: dissolving rhodium hydroxide with acid, concentrating the solution to contain 15-200 g/L of rhodium, reducing and filtering with formic acid to obtain rhodium black powder, and reducing the rhodium black powder with closed hydrogen to obtain rhodium powder;
wherein, in the step 1, the inorganic acid is selected from hydrochloric acid or sulfuric acid; the oxidant is selected from one of hydrogen peroxide, sodium chlorate, sodium hypochlorite and nitric acid.
2. The method for recovering rhodium from rhodium-containing homogeneous spent catalyst according to claim 1, wherein in the step 4, the alkali solution is NaOH solution or KOH solution.
3. The method for recovering rhodium from rhodium-containing homogeneous spent catalyst according to claim 2, wherein the mass fraction of the alkali solution in the step 4 is 15-20%.
4. The method for recovering rhodium from rhodium-containing homogeneous spent catalyst according to claim 1, wherein in step 5, the acid is hydrochloric acid or sulfuric acid.
5. The method for recovering rhodium from the rhodium-containing homogeneous spent catalyst according to claim 4, wherein the concentration of the acid in the step 5 is 2 to 6 mol/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177306A (en) * | 2007-11-12 | 2008-05-14 | 中国海洋石油总公司 | Method for recovering rhodium chloride from waste rhodium catalyst |
| CN104178641A (en) * | 2014-08-27 | 2014-12-03 | 昆明贵金属研究所 | Method for recovering rhodium from waste rhodium plating solution |
| CN104402068A (en) * | 2014-11-07 | 2015-03-11 | 中国海洋石油总公司 | Method for preparing high-purity rhodium trichloride from carbonyl-synthetic-reaction waste rhodium catalyst degradation solution |
| CN105177306A (en) * | 2015-09-14 | 2015-12-23 | 昆明贵金属研究所 | Method for recycling rhodium from sulfuric acid type rhodanized waste liquid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177306A (en) * | 2007-11-12 | 2008-05-14 | 中国海洋石油总公司 | Method for recovering rhodium chloride from waste rhodium catalyst |
| CN104178641A (en) * | 2014-08-27 | 2014-12-03 | 昆明贵金属研究所 | Method for recovering rhodium from waste rhodium plating solution |
| CN104402068A (en) * | 2014-11-07 | 2015-03-11 | 中国海洋石油总公司 | Method for preparing high-purity rhodium trichloride from carbonyl-synthetic-reaction waste rhodium catalyst degradation solution |
| CN105177306A (en) * | 2015-09-14 | 2015-12-23 | 昆明贵金属研究所 | Method for recycling rhodium from sulfuric acid type rhodanized waste liquid |
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