CN112481494A - Method for recovering rhodium from residual liquid of waste rhodium catalyst in oxo synthesis reaction - Google Patents
Method for recovering rhodium from residual liquid of waste rhodium catalyst in oxo synthesis reaction Download PDFInfo
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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
- 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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- C22B11/00—Obtaining noble metals
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- C22B11/042—Recovery of noble metals from waste materials
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Abstract
The invention relates to a method for recovering rhodium from waste rhodium catalyst residues, which comprises the following steps: distilling the residual liquid of the waste rhodium catalyst in the oxo reaction to prepare rhodium-containing residue; roasting the rhodium-containing residue to prepare rhodium ash; dissolving the rhodium ash in a hydrochloric acid and hydrogen peroxide solution to prepare a crude chlororhodic acid solution; concentrating the crude chlororhodic acid solution to prepare a chlororhodic acid solution; and reducing the rhodium ions in the chlororhodic acid solution to form a rhodium simple substance under the action of a reducing agent. The method of the invention has the recovery rate of rhodium in the waste rhodium catalyst residue of more than 96 percent and the purity of the recovered rhodium of not less than 99.95 percent.
Description
Technical Field
The invention belongs to the technical field of precious metal recovery, and particularly relates to a method for recovering rhodium from waste rhodium catalyst residual liquid in a oxo synthesis reaction.
Background
The field of oxo synthesis has always been the focus in chemical production and has always held great importance in the petrochemical industry. The existing carbonyl synthesis field commonly uses rhodium-phosphine complex organic homogeneous catalysts which have the characteristics of high catalytic activity, good selectivity and the like and are widely applied to hydroformylation reaction. In industrial production, as the rhodium-phosphine complex catalyst is easy to be deactivated by high temperature and trace impurities, because the rhodium is expensive, the residual liquid of the waste rhodium catalyst is a valuable secondary resource, and the rhodium in the waste catalyst needs to be recycled based on the requirement of sustainable development, therefore, the efficient and economic recovery of the rhodium in the waste rhodium catalyst has extremely important significance.
The method for recovering rhodium from the waste rhodium catalyst of oxo synthesis mainly comprises an incineration method and an extraction method. Since the residual liquid of the waste rhodium catalyst contains low rhodium content, the incineration method is relatively common, the method has the advantage of high efficiency, but if the rhodium content is too low, organic components or the temperature is too high, part of rhodium is vaporized and lost in the incineration process, so that the yield is reduced. For example, in CN101362207A, a method of incinerating a rhodium-containing waste liquid is adopted, the waste liquid is incinerated and incinerated at 600-1000 ℃, rhodium is recovered from a soluble rhodium salt obtained after high-temperature melting, and the yield of rhodium can reach more than 87%. In the Chinese patent CN1414125A, carbonate of alkali metal or alkali earth metal is used as an additive, and added into waste rhodium catalyst raffinate of oxo synthesis reaction for incineration, the waste rhodium catalyst raffinate is ashed at the temperature of 650 plus 700 ℃, the residual residue is reacted with alkali metal acid sulfate in a molten state to generate soluble rhodium salt, then rhodium is separated by adopting an electrolysis technology, and the final recovery rate of rhodium is more than 90%. The method needs to add a large amount of alkaline compounds as an auxiliary agent, has low applicability, generates more rhodium ash impurities, has a long recovery period and influences the final yield.
In view of the above-mentioned disadvantages of the existing methods for recovering rhodium, there is a need to develop a method for recovering rhodium from the residual liquid of waste rhodium catalyst in oxo reaction with high efficiency, green and economical efficiency.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for recovering rhodium from rhodium catalyst raffinate after oxo reaction aiming at the defects of the prior art. The method comprises the steps of distilling and roasting the residual liquid of the waste rhodium catalyst in the oxo synthesis reaction to obtain rhodium ash, preparing the rhodium ash into a crude chlororhodic acid solution, removing base metal cations from the crude chlororhodic acid solution through ion exchange, and reducing the chlororhodic acid solution to reduce rhodium ions in the chlororhodic acid solution to form a rhodium simple substance. The method can recover the rhodium metal in a green, efficient and economic manner, and has great economic benefit.
Therefore, the invention provides a method for recovering rhodium from rhodium catalyst raffinate after oxo reaction, which comprises the following steps:
distilling the residual liquid of the waste rhodium catalyst in the oxo reaction to prepare rhodium-containing residue;
roasting the rhodium-containing residue to prepare rhodium ash;
dissolving the rhodium ash in a hydrochloric acid and hydrogen peroxide solution to prepare a crude chlororhodic acid solution;
concentrating the crude chlororhodic acid solution to prepare a chlororhodic acid solution;
and reducing the rhodium ions in the chlororhodic acid solution to form a rhodium simple substance under the action of a reducing agent.
In some embodiments, the method of distillation treatment comprises:
and distilling the residual liquid of the rhodium catalyst after the oxo synthesis reaction under normal pressure until no distillate of light components is distilled out, and then distilling under reduced pressure until no distillate of heavy components is distilled out.
In some embodiments, the atmospheric distillation is conducted at a temperature of 150-; and/or the reduced pressure distillation is carried out under the conditions that the temperature is 250-280 ℃ and the vacuum degree is 400-650 Pa.
In some embodiments, after the reduced pressure distillation is complete, the method further comprises: under the reduced pressure condition of the reduced pressure distillation, the reduced pressure distillation product was cooled to room temperature.
In some embodiments, the temperature of the calcination is 500-650 ℃, and the calcination time is 3-5 h.
In some embodiments, after the firing treatment, the method further comprises: washing and drying the product obtained by roasting to obtain rhodium ash;
preferably, the roasted product is washed by adopting an anhydrous methanol solution and deionized water in sequence.
In some embodiments, a method of dissolving the rhodium ash in an aqueous solution of hydrochloric acid and hydrogen peroxide to produce a crude chlororhodic acid solution comprises:
adding a hydrochloric acid solution to the rhodium ash to form a hydrochloric acid solution comprising rhodium ash;
under the heating and stirring state, dropwise adding hydrogen peroxide solution into the hydrochloric acid solution containing rhodium ash to form a hydrochloric acid and hydrogen peroxide mixed solution containing rhodium ash;
and reacting the mixed solution of hydrochloric acid containing rhodium ash and hydrogen peroxide at the temperature of 100-120 ℃ for 2-4h, and then cooling and filtering to obtain the crude chlororhodic acid solution.
In some embodiments, the hydrochloric acid solution is added in an amount of 15 to 18mL/g, preferably 16 to 17mL/g, based on the ratio of the volume of the hydrochloric acid solution to the mass of the rhodium ash; and/or
The adding amount of the hydrogen peroxide solution is 1.2-1.8, preferably 1.4-1.6 according to the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution; and/or
The concentration of the hydrochloric acid solution is 30-37 wt%, and the concentration of the hydrogen peroxide solution is 30-50 wt%.
In some embodiments, the method of subjecting the crude chlororhodic acid solution to a concentration treatment comprises:
enabling the crude chlororhodic acid solution to sequentially pass through an LX-110 cation exchange resin column and an LSD-396 cation exchange resin column to remove base metal cations;
concentrating the solution obtained by column chromatography to obtain chlororhodic acid solution;
preferably, the mass content of rhodium in the chlororhodic acid solution is 20000-35000 ppm.
In some embodiments, the reducing agent comprises formic acid, and the reduction is carried out at a pH of 5 to 7 and a temperature of 70 to 90 ℃.
In some embodiments, after the reduction is complete, the method further comprises: sequentially roasting and reducing the rhodium black obtained by reduction to obtain rhodium powder;
preferably, the temperature of the roasting treatment is 600-800 ℃; the roasting treatment time is 2-5 h;
the temperature of the reduction treatment is 600-800 ℃; the time of the reduction treatment is 3-5 h.
Compared with the prior art, the invention has the following beneficial effects:
the method for recovering rhodium from the residual liquid of the waste rhodium catalyst in the oxo synthesis reaction provided by the invention comprises the steps of distilling and roasting the residual liquid of the waste rhodium catalyst in the oxo synthesis reaction to obtain rhodium ash, preparing the rhodium ash into a crude chlororhodic acid solution, removing base metal cations from the crude chlororhodic acid solution through ion exchange resin, and reducing the obtained chlororhodic acid solution to reduce rhodium ions in the chlororhodic acid solution to form a rhodium simple substance. Compared with the chemical complexing method in the prior art, the method disclosed by the invention has the advantages that the rhodium is purified by adopting an ion exchange resin method, the use of a large amount of organic matters and the emission of nitrogen oxides are avoided, the low-carbon recovery of the rhodium is realized, and the method is simple and convenient, can be repeatedly used, and is environment-friendly and economical. The method has the advantages of high rhodium recovery efficiency, low rhodium loss, high rhodium yield of more than 96 percent and high purity of not less than 99.95 percent, and has great economic benefit.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
In view of the defects of low rhodium yield, large amount of addition agent, long recovery period and the like of the conventional method for recovering rhodium from the waste rhodium catalyst in the oxo synthesis, repeated experimental research by the inventor of the invention finds that rhodium ash is obtained by distilling and roasting the residual liquid of the waste rhodium catalyst in the oxo synthesis reaction, then the rhodium ash is prepared into a crude chlororhodic acid solution, the crude chlororhodic acid solution is subjected to ion exchange resin to remove base metal cations, and then the obtained chlororhodic acid solution is concentrated and subjected to reduction treatment, so that rhodium ions in the chlororhodic acid solution are reduced to form simple rhodium. The present invention has been made based on the above findings.
Accordingly, the present invention provides a process for recovering rhodium from a spent rhodium catalyst raffinate from an oxo reaction, which comprises the steps of:
s1, distilling the residual liquid of the waste rhodium catalyst in the oxo reaction to obtain rhodium-containing residue;
s2, roasting the rhodium-containing residue to obtain rhodium ash;
s3, dissolving the rhodium ash in a hydrochloric acid and hydrogen peroxide solution to prepare a crude chlororhodic acid solution;
s4, treating the crude chlororhodic acid solution with ion exchange resin, and concentrating to obtain a chlororhodic acid solution;
s5, reducing rhodium ions in the chlororhodic acid solution under the action of a reducing agent to prepare rhodium black;
and S6, sequentially roasting and reducing the rhodium black to obtain rhodium powder.
In step S1, the method of distillation processing includes: the residual liquid of rhodium catalyst after carbonyl synthesis reaction is distilled under normal pressure until no light component (mainly comprising low-carbon aldehydes, oligomers of aldehydes and the like) distillate is distilled out, and then is distilled under reduced pressure until no heavy component (mainly comprising polymers of aldehydes, organic matters containing phosphine and the like) distillate is distilled out.
Preferably, the atmospheric distillation is carried out at a temperature of 150 ℃ and 200 ℃. More preferably, the atmospheric distillation is carried out at a temperature of 160 ℃ and 180 ℃. Preferably, the reduced pressure distillation is carried out under the conditions that the temperature is 250-280 ℃ and the vacuum degree is 400-650 Pa. More preferably, the reduced pressure distillation is carried out under the conditions of the temperature of 250-275 ℃ and the vacuum degree of 400-600 Pa.
The invention adopts atmospheric distillation and reduced pressure distillation to concentrate the waste rhodium catalyst raffinate, and controls the distillation temperature and the vacuum degree at the same time to reduce the loss of noble metal rhodium, improve the yield of rhodium and reduce the cost.
In step S1, after the reduced pressure distillation is completed, the method further includes: under the reduced pressure condition of the reduced pressure distillation, the reduced pressure distillation product is cooled to room temperature to obtain rhodium-containing residue.
In step S2, the baking temperature is 500-650 ℃, and the baking time is 3-5 h. After the roasting treatment, the method further comprises the following steps: and washing and drying the product obtained by roasting to obtain rhodium ash. Preferably, the roasted product is washed with a boiled absolute methanol solution and deionized water in this order. Through washing treatment, the organic matters which are not burnt completely can be removed, and the dissolution rate of subsequent rhodium is improved.
In step S3, the method of dissolving the rhodium ash in an aqueous solution of hydrochloric acid and hydrogen peroxide to obtain a crude chlororhodic acid solution includes:
adding a hydrochloric acid solution to the rhodium ash to form a hydrochloric acid solution comprising rhodium ash;
under the heating and stirring state, dropwise adding hydrogen peroxide solution into the hydrochloric acid solution containing rhodium ash to form a hydrochloric acid and hydrogen peroxide mixed solution containing rhodium ash;
and reacting the mixed solution of hydrochloric acid containing rhodium ash and hydrogen peroxide at the temperature of 100-120 ℃ for 2-4h, and then cooling and filtering to obtain the crude chlororhodic acid solution.
Preferably, the addition amount of the hydrochloric acid solution is 15-18mL/g, preferably 16-17mL/g, based on the ratio of the volume of the hydrochloric acid solution to the mass of the rhodium ash. The addition amount of the hydrogen peroxide solution is 1.2-1.8, preferably 1.4-1.6 based on the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution. The concentration of the hydrochloric acid solution is 30-37 wt%, and the concentration of the hydrogen peroxide solution is 30-50 wt%.
In step S4, the method of treating the crude chlororhodic acid solution with an ion exchange resin and then concentrating to obtain a chlororhodic acid solution includes:
enabling the crude chlororhodic acid solution to sequentially pass through an LX-110 cation exchange resin column and an LSD-396 cation exchange resin column to remove base metal cations;
concentrating the solution obtained by column chromatography to obtain chlororhodic acid solution;
preferably, the mass content of rhodium in the chlororhodic acid solution is 20000-35000 ppm.
According to the invention, through concentration treatment, the chlororhodic acid reaches a proper concentration, the subsequent reduction efficiency is improved, the time is saved, and the pollution and the cost are reduced.
The LX-110 cation exchange resin and the LSD-396 cation exchange resin are cation exchange resins produced by Seisan blue Xiao scientific Co.
In step S5, the reducing agent includes formic acid, and the reduction is performed at a pH of 5 to 7 and a temperature of 70 to 90 ℃. Preferably, the reduction is carried out at a pH of 5.5 to 6.5 and a temperature of 75 to 85 ℃.
In step S6, the present invention employs a baking process to further remove some residual organic matters, since the baking process oxidizes part of the rhodium, a further reduction process is required after the baking process, and the reduction process is also a process of removing impurities.
Preferably, in step S6, the temperature of the roasting treatment is 600-; the roasting treatment time is 2-5h, preferably 3-4.5 h. The temperature of the reduction treatment is 600-800 ℃, preferably 600-750 ℃; the time of the reduction treatment is 3 to 5 hours, and preferably 3 to 4.5 hours.
The starting materials used in the present invention are commercially available unless otherwise specified.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
The test method or the calculation method provided by the invention is as follows:
the rhodium recovery is calculated as:
rhodium yield was 106(rhodium powder mass g x rhodium powder purity%)/(rhodium mass content ppm in the rhodium catalyst raffinate from oxo reaction x rhodium catalyst raffinate from oxo reaction) x 100%
The mass content of rhodium in the rhodium catalyst raffinate after the oxo reaction is analyzed by ICP (inductively coupled plasma emission spectrometer), and the purity of rhodium powder is analyzed by ICP after the rhodium powder is electrified and dissolved by concentrated hydrochloric acid (37 wt%).
Examples
Example 1
1544.9g of rhodium catalyst raffinate from the oxo reaction is transferred into a 5000mL three-neck flask (the mass content of rhodium is 379ppm), the light components are distilled out by adopting a normal pressure distillation method, the temperature is slowly raised to 150 ℃ until the distillate is not distilled out, and the distillate is condensed and recovered. And (3) continuing to adopt a reduced pressure distillation method, reacting at constant temperature under the conditions of vacuum degree of 400Pa and kettle temperature of 250 ℃ until distillate is not distilled out, and condensing and recycling the distillate to obtain 28.9g of rhodium-containing residue. Transferring the rhodium-containing residue into a muffle furnace for aerobic roasting, and reacting for 3 hours at constant temperature when the temperature is raised to 500 ℃ to obtain 7.2g of rhodium ash containing a small amount of impurity metals; adding 108mL of hydrochloric acid with the concentration of 37 wt% (the addition amount of the hydrochloric acid solution is 15mL/g according to the volume ratio of the hydrochloric acid solution to the rhodium ash) into the obtained rhodium ash for dissolving, stirring and heating to 100 ℃, gradually dropwise adding 130mL of hydrogen peroxide with the concentration of 30 wt% (the addition amount of the hydrogen peroxide solution is 1.2 according to the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution) for continuously reacting for 3h, stopping the reaction, filtering, and collecting the acid solution after filtering to obtain the crude chlororhodic acid solution. And (3) enabling the obtained crude chlororhodic acid solution to sequentially pass through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin, and concentrating the solution after passing through the chromatographic columns to obtain the chlororhodic acid solution with the rhodium content of 20057 ppm. Adjusting the pH value of the chlororhodic acid solution to 5, slowly adding formic acid at 70 ℃, boiling and reducing to obtain rhodium black. And putting the obtained rhodium black into a muffle furnace to react for 2h at the temperature of 600 ℃ to obtain rhodium oxide. Putting rhodium oxide into a hydrogen reduction furnace, and reacting for 3 hours at 600 ℃ in a hydrogen atmosphere to obtain 0.5701g of high-purity rhodium powder, wherein the recovery rate of the rhodium is 97.32 percent, and the purity is 99.95 percent.
Example 2
1613.5g of rhodium catalyst raffinate from the oxo reaction is transferred into a 5000mL three-neck flask (the mass content of rhodium is 379ppm), the light components are distilled out by adopting a normal pressure distillation method, the temperature is slowly raised to 200 ℃ until no distillate is distilled out, and the distillate is condensed and recovered. And (3) continuing to adopt a reduced pressure distillation method, reacting at constant temperature under the conditions of vacuum degree of 650Pa and kettle temperature of 280 ℃ until distillate is not distilled out, and condensing and recycling the distillate to obtain 27.5g of rhodium-containing residue. Transferring the rhodium-containing residue into a muffle furnace for aerobic roasting, and reacting for 5 hours at constant temperature when the temperature is raised to 600 ℃ to obtain 6.4g of rhodium ash containing a small amount of impurity metals; adding 102mL of 30 wt% hydrochloric acid (the addition amount of the hydrochloric acid solution is 16mL/g based on the volume ratio of the hydrochloric acid solution to the rhodium ash) into the obtained rhodium ash for dissolving, stirring and heating to 110 ℃, gradually dropwise adding 143mL of 40 wt% hydrogen peroxide (the addition amount of the hydrogen peroxide solution is 1.4 based on the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution) for continuously reacting for 3h, stopping the reaction, filtering, and collecting the acid solution after filtering to obtain the crude chlororhodic acid solution. And (3) enabling the obtained crude chlororhodic acid solution to sequentially pass through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin, and concentrating the solution after passing through the chromatographic columns to obtain the chlororhodic acid solution with the rhodium content of 35162 ppm. Adjusting the pH value of the chlororhodic acid solution to 6, slowly adding formic acid at 90 ℃, boiling and reducing to obtain rhodium black. And putting the obtained rhodium black into a muffle furnace to react for 3h at 800 ℃ to obtain rhodium oxide. Putting rhodium oxide into a hydrogen reduction furnace, and reacting for 5 hours at 800 ℃ in a hydrogen atmosphere to obtain 0.5938g of high-purity rhodium powder, wherein the recovery rate of rhodium is 97.05 percent, and the purity is 99.95 percent.
Example 3
1569.3g of rhodium catalyst raffinate from the oxo reaction is transferred into a 5000mL three-neck flask (the mass content of rhodium is 379ppm), the light components are distilled out by a normal pressure distillation method, the temperature is slowly raised to 180 ℃ until no distillate is distilled out, and the distillate is condensed and recovered. And (3) continuing to adopt a reduced pressure distillation method, reacting at constant temperature under the conditions of vacuum degree of 500Pa and kettle temperature of 275 ℃ until distillate is not distilled out, and condensing and recycling the distillate to obtain 27.8g of rhodium-containing residue. Transferring the rhodium-containing residue into a muffle furnace for aerobic roasting, and reacting for 4 hours at constant temperature when the temperature is raised to 650 ℃ to obtain 6.1g of rhodium ash containing a small amount of impurity metals; adding 104mL of 35 wt% hydrochloric acid (the addition amount of the hydrochloric acid solution is 17mL/g based on the volume ratio of the hydrochloric acid solution to the rhodium ash) into the obtained rhodium ash for dissolving, stirring and heating to 100 ℃, gradually dropwise adding 166mL of 40 wt% hydrogen peroxide (the addition amount of the hydrogen peroxide solution is 1.6 based on the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution) for continuously reacting for 3h, stopping the reaction, filtering, and collecting the acid solution after filtering to obtain the crude chlororhodic acid solution. And (3) enabling the obtained crude chlororhodic acid solution to sequentially pass through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin, and concentrating the solution after passing through the chromatographic columns to obtain the chlororhodic acid solution with the rhodium content of 26143 ppm. Adjusting the pH value of the chlororhodic acid solution to 7, slowly adding formic acid at the temperature of 80 ℃, boiling and reducing to obtain rhodium black. And putting the obtained rhodium black into a muffle furnace to react for 5 hours at 700 ℃ to obtain rhodium oxide. Putting rhodium oxide into a hydrogen reduction furnace, and reacting at 750 ℃ for 4h in a hydrogen atmosphere to obtain 0.5758g of high-purity rhodium powder, wherein the recovery rate of the rhodium is 96.76% and the purity is 99.95%.
Example 4
1557.6g of rhodium catalyst raffinate from the oxo reaction is transferred into a 5000mL three-neck flask (the mass content of rhodium is 379ppm), the light components are evaporated by adopting a normal pressure distillation method, the temperature is slowly raised to 160 ℃ until the distillate is not evaporated any more, and the distillate is condensed and recovered. And (3) continuing to adopt a reduced pressure distillation method, reacting at constant temperature under the conditions of vacuum degree of 650Pa and kettle temperature of 280 ℃ until distillate is not distilled out, and condensing and recycling the distillate to obtain 25.4g of rhodium-containing residue. Transferring the rhodium-containing residue into a muffle furnace for aerobic roasting, and reacting for 3 hours at constant temperature when the temperature is raised to 550 ℃ to obtain 5.8g of rhodium ash containing a small amount of impurity metals; adding 104mL of 36 wt% hydrochloric acid (the addition amount of the hydrochloric acid solution is 18mL/g according to the volume ratio of the hydrochloric acid solution to the rhodium ash) into the obtained rhodium ash for dissolving, stirring and heating to 120 ℃, gradually dropwise adding 188mL of 30 wt% hydrogen peroxide (the addition amount of the hydrogen peroxide solution is 1.8 according to the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution) for continuously reacting for 3h, stopping the reaction, filtering, and collecting the acid solution after filtering to obtain the crude chlororhodic acid solution. And (3) enabling the obtained crude chlororhodic acid solution to sequentially pass through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin, and concentrating the solution after passing through the chromatographic columns to obtain the chlororhodic acid solution with the rhodium content of 29471 ppm. Adjusting the pH value of the chlororhodic acid solution to 5.5, slowly adding formic acid at 85 ℃, boiling and reducing to obtain rhodium black. And putting the obtained rhodium black into a muffle furnace to react for 3.5 hours at 750 ℃ to obtain rhodium oxide. Putting rhodium oxide into a hydrogen reduction furnace, and reacting for 5 hours at 650 ℃ in a hydrogen atmosphere to obtain 0.5755g of high-purity rhodium powder, wherein the recovery rate of rhodium is 97.44% and the purity is 99.95%.
Example 5
1602.1g of rhodium catalyst raffinate from the oxo reaction is transferred into a 5000mL three-neck flask (with the mass content of rhodium being 379ppm), the light components are distilled out by a normal pressure distillation method, the temperature is slowly raised to 180 ℃ until no distillate is distilled out, and the distillate is condensed and recovered. And (3) continuing to adopt a reduced pressure distillation method, reacting at constant temperature under the conditions of the vacuum degree of 600Pa and the kettle temperature of 270 ℃ until distillate is not distilled out, and condensing and recycling the distillate to obtain 26.9g of rhodium-containing residue. Transferring the rhodium-containing residue into a muffle furnace for aerobic roasting, and reacting for 5 hours at constant temperature when the temperature is raised to 650 ℃ to obtain 5.2g of rhodium ash containing a small amount of impurity metals; adding 83mL of 34 wt% hydrochloric acid (the addition amount of the hydrochloric acid solution is 16mL/g based on the volume ratio of the hydrochloric acid solution to the rhodium ash) into the obtained rhodium ash for dissolving, stirring and heating to 100 ℃, gradually dropwise adding 133mL of 50 wt% hydrogen peroxide (the addition amount of the hydrogen peroxide solution is 1.6 based on the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution) for continuously reacting for 3h, stopping the reaction, filtering, and collecting the acid solution after filtering to obtain the crude chlororhodic acid solution. And (3) enabling the obtained crude chlororhodic acid solution to sequentially pass through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin, and concentrating the solution after passing through the chromatographic columns to obtain the chlororhodic acid solution with the rhodium content of 23603 ppm. Adjusting the pH value of the chlororhodic acid solution to 6, slowly adding formic acid at 75 ℃, boiling and reducing to obtain rhodium black. And putting the obtained rhodium black into a muffle furnace to react for 5 hours at 800 ℃ to obtain rhodium oxide. Putting rhodium oxide into a hydrogen reduction furnace, and reacting for 4 hours at 800 ℃ in a hydrogen atmosphere to obtain 0.5901g of high-purity rhodium powder, wherein the recovery rate of rhodium is 97.14 percent, and the purity is 99.95 percent.
Example 6
1596.4g of rhodium catalyst raffinate from the oxo reaction is transferred into a 5000mL three-neck flask (the mass content of rhodium is 379ppm), the light components are distilled out by adopting a normal pressure distillation method, the temperature is slowly raised to 170 ℃ until no distillate is distilled out, and the distillate is condensed and recovered. And (3) continuing to adopt a reduced pressure distillation method, reacting at constant temperature under the conditions of the vacuum degree of 600Pa and the kettle temperature of 270 ℃ until distillate is not distilled out, and condensing and recycling the distillate to obtain 25.3g of rhodium-containing residue. Transferring the rhodium-containing residue into a muffle furnace for aerobic roasting, and reacting for 3 hours at constant temperature when the temperature is raised to 600 ℃ to obtain 5.8g of rhodium ash containing a small amount of impurity metals; adding 99mL of hydrochloric acid with the concentration of 37 wt% (the addition amount of the hydrochloric acid solution is 17mL/g according to the volume ratio of the hydrochloric acid solution to the rhodium ash) into the obtained rhodium ash for dissolving, stirring and heating to 100 ℃, gradually dropwise adding 148mL of hydrogen peroxide with the concentration of 40 wt% (the addition amount of the hydrogen peroxide solution is 1.5 according to the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution) for continuously reacting for 3h, stopping the reaction, filtering, and collecting the acid solution after filtering to obtain the crude chlororhodic acid solution. And (3) enabling the obtained crude chlororhodic acid solution to sequentially pass through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin, and concentrating the solution after passing through the chromatographic columns to obtain the chlororhodic acid solution with the rhodium content of 31043 ppm. Adjusting the pH value of the chlororhodic acid solution to 6.5, slowly adding formic acid at the temperature of 80 ℃, boiling and reducing to obtain rhodium black. And putting the obtained rhodium black into a muffle furnace to react for 4.5h at 750 ℃ to obtain rhodium oxide. Putting rhodium oxide into a hydrogen reduction furnace, and reacting at 750 ℃ for 4.5h in a hydrogen atmosphere to obtain 0.5851g of high-purity rhodium powder, wherein the recovery rate of rhodium is 96.66% and the purity is 99.95%.
As can be seen from the above examples, the method for recovering rhodium from waste rhodium catalyst residues of oxo synthesis provided by the invention has the advantages that the recovery rate of rhodium is more than 96%, the purity of the recovered rhodium is not less than 99.95%, and good effects are achieved. Therefore, the invention provides a method for efficiently, greenly and economically recovering rhodium, which has great economic efficiency.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A process for recovering rhodium from a spent rhodium catalyst raffinate from an oxo reaction, comprising the steps of:
distilling the residual liquid of the waste rhodium catalyst in the oxo reaction to prepare rhodium-containing residue;
roasting the rhodium-containing residue to prepare rhodium ash;
dissolving the rhodium ash in a hydrochloric acid and hydrogen peroxide solution to prepare a crude chlororhodic acid solution;
concentrating the crude chlororhodic acid solution to prepare a chlororhodic acid solution;
and reducing the rhodium ions in the chlororhodic acid solution to form a rhodium simple substance under the action of a reducing agent.
2. The method of claim 1, wherein the distillation process comprises:
and distilling the residual liquid of the rhodium catalyst after the oxo synthesis reaction under normal pressure until no distillate of light components is distilled out, and then distilling under reduced pressure until no distillate of heavy components is distilled out.
3. The method as claimed in claim 2, wherein the atmospheric distillation is carried out at a temperature of 150 ℃ and 200 ℃; and/or the reduced pressure distillation is carried out under the conditions that the temperature is 250-280 ℃ and the vacuum degree is 400-650 Pa.
4. The method according to claim 2 or 3, wherein after the distillation under reduced pressure is completed, the method further comprises: under the reduced pressure condition of the reduced pressure distillation, the reduced pressure distillation product was cooled to room temperature.
5. The method as claimed in any one of claims 1 to 4, wherein the calcination temperature is 500-650 ℃, and the calcination time is 3-5 h.
6. The method of any one of claims 1-5, further comprising, after the firing step: washing and drying the product obtained by roasting to obtain rhodium ash;
preferably, the roasted product is washed by adopting an anhydrous methanol solution and deionized water in sequence.
7. The method according to any one of claims 1 to 6, wherein the step of dissolving the rhodium ash in an aqueous solution of hydrochloric acid and hydrogen peroxide to obtain a crude chlororhodic acid solution comprises:
adding a hydrochloric acid solution to the rhodium ash to form a hydrochloric acid solution comprising rhodium ash;
under the heating and stirring state, dropwise adding hydrogen peroxide solution into the hydrochloric acid solution containing rhodium ash to form a hydrochloric acid and hydrogen peroxide mixed solution containing rhodium ash;
and reacting the mixed solution of hydrochloric acid containing rhodium ash and hydrogen peroxide at the temperature of 100-120 ℃ for 2-4h, and then cooling and filtering to obtain the crude chlororhodic acid solution.
8. The method according to any one of claims 1 to 7, wherein the hydrochloric acid solution is added in an amount of 15 to 18mL/g, preferably 16 to 17mL/g, in terms of the ratio of the volume of the hydrochloric acid solution to the mass of the rhodium ash; and/or
The adding amount of the hydrogen peroxide solution is 1.2-1.8, preferably 1.4-1.6 according to the volume ratio of the hydrogen peroxide solution to the hydrochloric acid solution; and/or
The concentration of the hydrochloric acid solution is 30-37 wt%, and the concentration of the hydrogen peroxide solution is 30-50 wt%.
9. The method according to any one of claims 1 to 8, wherein the method for subjecting the crude chlororhodic acid solution to concentration treatment comprises:
enabling the crude chlororhodic acid solution to sequentially pass through an LX-110 cation exchange resin column and an LSD-396 cation exchange resin column to remove base metal cations;
concentrating the solution obtained by column chromatography to obtain chlororhodic acid solution;
preferably, the mass content of rhodium in the chlororhodic acid solution is 20000-35000 ppm.
10. The method according to any one of claims 1 to 9, wherein the reducing agent comprises formic acid and the reduction is carried out at a pH of 5 to 7 and a temperature of 70 to 90 ℃.
11. The method according to any of claims 1-10, wherein after the reduction is completed, the method further comprises: sequentially roasting and reducing the rhodium black obtained by reduction to obtain rhodium powder;
preferably, the temperature of the roasting treatment is 600-800 ℃; the roasting treatment time is 2-5 h;
the temperature of the reduction treatment is 600-800 ℃; the time of the reduction treatment is 3-5 h.
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