CN114427027A - Method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues and obtained rhodium trichloride - Google Patents
Method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues and obtained rhodium trichloride Download PDFInfo
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- CN114427027A CN114427027A CN202011055128.XA CN202011055128A CN114427027A CN 114427027 A CN114427027 A CN 114427027A CN 202011055128 A CN202011055128 A CN 202011055128A CN 114427027 A CN114427027 A CN 114427027A
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000010948 rhodium Substances 0.000 title claims abstract description 148
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 147
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 title claims abstract description 29
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 73
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 28
- 230000009467 reduction Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 5
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 50
- 238000010438 heat treatment Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
-
- 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
- C22B11/06—Chloridising
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues, which comprises the following steps: step 1, carrying out aerobic roasting on waste rhodium slag, and then washing and drying to obtain primary rhodium ash; step 2, carrying out reduction treatment on the primary rhodium ash to obtain secondary rhodium ash; step 3, sequentially adding acid and hydrogen peroxide into the secondary rhodium ash for reaction, and filtering to obtain a crude chlororhodic acid solution; and 4, passing the crude chlororhodic acid solution through a cation exchange resin column to obtain a chlororhodic acid solution, and performing post-treatment to obtain rhodium trichloride. According to the method, the obtained rhodium ash is washed by the boiled absolute ethyl alcohol solution and the deionized water, so that organic matters which are not burnt completely can be removed, and the subsequent reduction of rhodium and the dissolution rate of rhodium are improved; the rhodium ash is subjected to hydrogenation reduction, so that rhodium oxidized at high temperature is reduced, and the subsequent rhodium dissolution rate is improved.
Description
Technical Field
The invention relates to the technical field of precious metal recovery, particularly relates to recovery of rhodium from waste rhodium slag, and particularly provides a method for preparing rhodium trichloride by recovering rhodium from waste rhodium slag.
Background
Rhodium as a noble metal has excellent performance, stable resistance and conductivity, high-temperature oxidation resistance and high catalytic activity, and is widely applied to the petrochemical industry and the metallurgical industry, and is also indispensable to the fields of automotive electronics, aerospace, fuel cells and the like.
In industrial production, the rhodium-phosphine complex catalyst has the characteristics of high catalytic activity, good selectivity and the like, so the catalyst is widely applied to hydroformylation reaction, but the catalyst is easy to be inactivated by trace impurities and high temperature in the reaction, a large amount of invalid rhodium-phosphine complex catalyst needs to be replaced every year, and the waste rhodium catalyst is precious secondary resource because the rhodium is expensive, and the method has important economic benefit and social benefit for recovering the noble metal rhodium from the waste rhodium. The waste rhodium catalyst of the hydroformylation reaction has a plurality of impurities, and a plurality of high-boiling-point organic matters are generated in the using process, so that the difficulty of rhodium purification is very high. At present, the main methods for recycling are incineration method, wet method, etc., wherein the incineration method is generally adopted in industry.
Chinese patent CN108950233A is an alloy obtained by melting a transition metal, a reducing agent and rhodium residues together, and then obtaining rhodium powder by electrolysis or acidolysis. Such processes require the addition of large amounts of other transition metals, and the recovery period is long, and the final yield is affected.
Chinese patent CN1414125A provides a method for recovering rhodium from waste rhodium catalyst in oxo reaction. The recovery treatment comprises three steps, (1) adding carbonate of alkali metal or alkaline earth metal into the waste catalyst, wherein the addition amount of the carbonate is 10-20 times of the rhodium content in the waste catalyst, and carrying out constant temperature for 4-5 hours at 650-700 ℃, namely carrying out incineration on the waste catalyst; (2) adding alkali metal acid sulfate into rhodium ash formed after incineration, wherein the addition amount of the alkali metal acid sulfate is 20-30 times of the rhodium content in the refined slag, putting the rhodium ash into an incinerator, heating to 400 ℃, melting the acid sulfate, heating to 550 ℃, and keeping the temperature for 2 hoursThe reaction produces soluble rhodium salts Rh2(SO4)3Other metals such as copper, iron, nickel and the like also generate corresponding sulfate, and then are dissolved by deionized water or 2M hydrochloric acid at the temperature of 80-90 ℃; (3) the rhodium salt solution is placed in a cathode chamber of an electrolysis device, the anode chamber is a 10% ammonium chloride solution, a saturated calomel electrode is used as a reference electrode, the cathode potential is controlled to be-1.10V-1.15V, electrolysis is carried out for 4-5 hours, and rhodium powder is reduced and separated out at the cathode. However, the processing thereof is very complicated.
Therefore, it is important to develop a technology for efficiently and economically recovering rhodium from waste rhodium residues.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues, and the method can be used for efficiently and economically preparing rhodium trichloride and realizing economic and social benefits.
(1) A method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues comprises the following steps:
step 1, carrying out aerobic roasting on waste rhodium slag, and then washing and drying to obtain primary rhodium ash;
step 2, carrying out reduction treatment on the primary rhodium ash to obtain secondary rhodium ash;
step 3, sequentially adding acid and hydrogen peroxide into the secondary rhodium ash for reaction, and filtering to obtain a crude chlororhodic acid solution;
and 4, passing the crude chlororhodic acid solution through a cation exchange resin column to obtain a chlororhodic acid solution, and performing post-treatment to obtain rhodium trichloride.
(2) The preparation method according to the above (1), wherein in the step 1, the roasting temperature is 500-1200 ℃ and the roasting time is 2-10 hours;
preferably, the roasting temperature is 700-1000 ℃ and the roasting time is 4-8 hours.
(3) The production method according to the above (1), wherein in the step 1, washing is performed with a boiled organic solvent, and then washing is performed with boiled water until the pH value of the water becomes neutral;
preferably, the organic solvent is selected from water-soluble organic solvents, preferably from organic alcohols.
(4) The production method according to the above (1), wherein, in the step 2, the reduction treatment is performed in a hydrogen atmosphere;
preferably, the temperature of the reduction treatment is 500-1000 ℃, and the time is 2-10 hours;
more preferably, the temperature of the reduction treatment is 600-900 ℃ and the time is 3-8 hours.
(5) The production method according to the above (1), wherein, in the step 3, the acid is selected from hydrochloric acid.
(6) The preparation method according to the above (5), wherein in the step 3, the amount of the acid is 10 to 25mL/g of the secondary rhodium ash, preferably 15 to 18mL/g of the secondary rhodium ash.
(7) The preparation method according to the above (1), wherein in the step 3, the hydrogen peroxide is added dropwise;
preferably, the concentration of the hydrogen peroxide is 30-50 wt%, and the addition amount of the hydrogen peroxide is 1-2 mL/mL of acid.
(8) The production method according to the above (1), wherein, in the step 3,
the reaction was carried out under reflux, then cooled to room temperature and filtered; and/or
The reaction time is 1-8 hours, preferably 2-5 hours; and/or
And 3, repeating the step 2-4 times, preferably 2-3 times.
(9) The production process according to any one of the above (1) to (8), wherein, in step 4, the crude chlororhodic acid solution is passed through an LX-110 cation exchange resin column and an LSD-396 cation exchange resin column in this order to remove cationic impurities therefrom.
(10) Rhodium trichloride obtained by the production method according to any one of the above (1) to (9).
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
One of the purposes of the invention is to provide a method for preparing rhodium trichloride by recovering rhodium from waste rhodium slag, which comprises the following steps:
step 1, carrying out aerobic roasting on waste rhodium slag, and then washing and drying to obtain primary rhodium ash;
step 2, carrying out reduction treatment on the primary rhodium ash to obtain secondary rhodium ash;
step 3, sequentially adding acid and hydrogen peroxide into the secondary rhodium ash for reaction, and filtering to obtain a crude chlororhodic acid solution;
and 4, passing the crude chlororhodic acid solution through a cation exchange resin column to obtain a chlororhodic acid solution, and performing post-treatment to obtain rhodium trichloride.
In a preferred embodiment, in step 1, the temperature of the roasting is 500 to 1200 ℃ and the time is 2 to 10 hours.
In a further preferred embodiment, in the step 1, the roasting temperature is 700 to 1000 ℃ and the roasting time is 4 to 8 hours.
In a preferred embodiment, in step 1, washing is first carried out with a boiled organic solvent.
Preferably, the organic solvent is selected from water-soluble organic solvents, more preferably, the organic solvent is selected from at least one of organic alcohol, dimethylformamide, tetrahydrofuran, and dimethyl sulfoxide, such as organic alcohol. Wherein the organic solvent is colorless after the washing.
In a further preferred embodiment, the washing is carried out again with boiling water and is carried out until the pH of the water is neutral.
The roasted rhodium ash is washed by boiled organic alcohol and water, so that organic matters which are not burnt completely can be removed, and the subsequent reduction of rhodium and the dissolution rate of rhodium are improved.
In a preferred embodiment, in step 2, the reduction treatment is performed under a hydrogen atmosphere.
In a further preferred embodiment, in the step 2, the temperature of the reduction treatment is 500 to 1000 ℃ and the time is 2 to 10 hours.
In a further preferred embodiment, in the step 2, the temperature of the reduction treatment is 600 to 900 ℃ and the time is 3 to 8 hours.
Through a great deal of experimental research, the inventor finds that the dissolution rate of rhodium in acid can be obviously improved by carrying out reduction treatment before acid treatment.
In a preferred embodiment, in step 3, the acid is selected from hydrochloric acid.
In a further preferred embodiment, in step 3, the amount of the acid is 10 to 25mL/g of secondary rhodium ash, preferably 15 to 18mL/g of secondary rhodium ash.
In a preferred embodiment, in step 3, the hydrogen peroxide solution is added dropwise.
Wherein, the dropwise addition can ensure that the reaction is completely and fully carried out; the direct addition results in violent reaction, large gas generation and sudden spraying.
In a further preferred embodiment, in step 3, the concentration of the hydrogen peroxide is 30 to 50 wt%, and the addition amount of the hydrogen peroxide is 1 to 2mL/mL of acid, preferably 1.2 to 1.7mL/mL of acid.
In a preferred embodiment, in step 3, the reaction is carried out under reflux, then cooled to room temperature and filtered.
In a further preferred embodiment, in step 3, the reaction time is 1 to 8 hours, preferably 2 to 5 hours.
In a further preferred embodiment, step 3 is repeated 2 to 4 times, preferably 2 to 3 times.
In a preferred embodiment, in step 4, the crude chlororhodic acid solution is passed through an LX-110 cation exchange resin column and an LSD-396 cation exchange resin column in sequence to remove cationic impurities therein.
The second purpose of the invention is to provide rhodium trichloride obtained by the preparation method of the first purpose of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, the obtained rhodium ash is washed by the boiled absolute ethyl alcohol solution and the deionized water, so that organic matters which are not burnt completely can be removed, and the subsequent reduction of rhodium and the dissolution rate of rhodium are improved;
(2) the rhodium ash is subjected to hydrogenation reduction, so that rhodium oxidized at high temperature is reduced, and the subsequent rhodium dissolution rate is improved.
Examples
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
LX-110 cation exchange resin column and LSD-396 cation exchange resin column were purchased from Seisan blue Xiao scientific Co.
The rhodium yield is calculated by the following formula:
the rhodium yield is (the mass of rhodium trichloride is multiplied by the mass percent of rhodium in the rhodium trichloride)/(the mass percent of rhodium in the waste rhodium slag is multiplied by the mass of the waste rhodium slag) multiplied by 100 percent
And (3) after digesting the mass percentage content of rhodium in the waste rhodium slag, analyzing by ICP, and analyzing the rhodium content in rhodium trichloride by a gravimetric method.
[ example 1 ]
30g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and is ashed for 4 hours at 700 ℃ to obtain rhodium ash.
And (3) washing the obtained rhodium ash by using a boiled absolute ethyl alcohol solution and deionized water in sequence until the pH value of the washed deionized water is neutral, putting the dried rhodium ash into a hydrogen reduction furnace, and reacting for 3 hours at 600 ℃ in a hydrogen atmosphere to obtain 12.11g of rhodium ash.
Adding 182mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 218mL of 30 wt% hydrogen peroxide for assisting in dissolving, heating and refluxing for 2 hours, collecting the acid solution after filtering, repeating the acid dissolving treatment on the filter residue for three times according to the steps, and combining the filtrate to obtain the crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.3036g of rhodium trichloride, wherein the content of rhodium is 37.86 percent, and the yield of rhodium is 97.07 percent.
[ example 2 ]
40g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and is ashed for 6 hours at 800 ℃ to obtain rhodium ash.
And (3) washing the obtained rhodium ash by using a boiled absolute ethyl alcohol solution and deionized water in sequence until the pH value of the washed deionized water is neutral, placing the dried rhodium ash into a hydrogen reduction furnace, and reacting for 5 hours at 800 ℃ in a hydrogen atmosphere to obtain 16.85g of rhodium ash.
Adding 303mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 455mL of 50 wt% hydrogen peroxide for dissolving, heating and refluxing for reaction for 3 hours, collecting the acid solution after filtering, repeating the acid dissolving treatment on the filter residue for three times according to the steps, and combining the filtrate to obtain the crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.4015g of rhodium trichloride, wherein the content of rhodium is 38.25 percent, and the yield of rhodium is 97.27 percent.
[ example 3 ]
40g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and incinerated for 8 hours at 1000 ℃ to obtain rhodium ash.
And (3) washing the obtained rhodium ash by using a boiled absolute ethyl alcohol solution and deionized water in sequence until the pH value of the washed deionized water is neutral, placing the dried rhodium ash into a hydrogen reduction furnace, and reacting for 8 hours at 900 ℃ in a hydrogen atmosphere to obtain 15.77g of rhodium ash.
And adding 252mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 404mL of 40 wt% hydrogen peroxide for assisting in dissolving, heating and refluxing for 5 hours, collecting an acid solution after filtering, repeating acid dissolving treatment on filter residues for three times according to the steps, and combining the filtrate to obtain a crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.4012g of rhodium trichloride, wherein the content of rhodium is 38.54 percent, and the yield of rhodium is 97.94 percent.
[ example 4 ]
40g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and incinerated at 950 ℃ for 5 hours to obtain rhodium ash.
And (3) washing the obtained rhodium ash by using a boiled absolute ethyl alcohol solution and deionized water in sequence until the pH value of the washed deionized water is neutral, placing the dried rhodium ash into a hydrogen reduction furnace, and reacting for 6 hours at 700 ℃ in a hydrogen atmosphere to obtain 15.89g of rhodium ash.
And adding 270mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 460mL of 35 wt% hydrogen peroxide for assisting in dissolving, heating for reflux reaction for 4 hours, collecting an acid solution after filtering, repeating acid dissolving treatment on filter residues for three times according to the steps, and combining the filtrate to obtain a crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.4072g of rhodium trichloride, wherein the content of rhodium is 37.69 percent, and the yield of rhodium is 97.21 percent.
[ example 5 ]
45g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and is ashed at 750 ℃ for 5.5 hours to obtain rhodium ash.
And (3) washing the obtained rhodium ash by using a boiled absolute ethyl alcohol solution and deionized water in sequence until the pH value of the washed deionized water is neutral, placing the dried rhodium ash into a hydrogen reduction furnace, and reacting at 800 ℃ for 4.5 hours in a hydrogen atmosphere to obtain 14.93g of rhodium ash.
239mL of concentrated hydrochloric acid is added into the obtained rhodium ash for dissolving, 30 wt% of hydrogen peroxide solution is gradually added dropwise for dissolving assistance when the mixture is stirred and heated to 80 ℃, the mixture is heated and refluxed for reaction for 3 hours, the acid solution is collected after filtration, the acid dissolving treatment is repeated for three times on filter residues according to the steps, and the filtrate is combined to obtain the crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.4525g of rhodium trichloride, wherein the content of rhodium is 38.17 percent, and the yield of rhodium is 97.24 percent.
Comparative example
Comparative example 1
30g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and is ashed for 4 hours at 700 ℃ to obtain rhodium ash.
The obtained rhodium ash was washed with a normal temperature absolute ethyl alcohol solution and deionized water in sequence, and the amounts of absolute ethyl alcohol and water were the same as those in example 1. And (3) putting the dried rhodium ash into a hydrogen reduction furnace, and reacting at 600 ℃ for 3 hours in a hydrogen atmosphere to obtain 12.75g of rhodium ash.
Adding 182mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 218mL of 30 wt% hydrogen peroxide for assisting in dissolving, heating and refluxing for 2 hours, collecting the acid solution after filtering, repeating the acid dissolving treatment on the filter residue for three times according to the steps, and combining the filtrate to obtain the crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.3082g of rhodium trichloride, wherein the content of rhodium is 36.49 percent, and the yield of rhodium is 94.98 percent.
Comparative example 2
30g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and is ashed for 4 hours at 700 ℃ to obtain rhodium ash.
The rhodium ash was placed in a hydrogen reduction furnace and reacted at 600 ℃ for 3 hours in a hydrogen atmosphere to obtain 12.96g of rhodium ash.
Adding 182mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 218mL of 30 wt% hydrogen peroxide for assisting in dissolving, heating and refluxing for 2 hours, collecting the acid solution after filtering, repeating the acid dissolving treatment on the filter residue for three times according to the steps, and combining the filtrate to obtain the crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.3065g of rhodium trichloride, wherein the content of rhodium is 36.27 percent, and the yield of rhodium is 93.88 percent.
Comparative example 3
30g of waste rhodium slag (with the rhodium content of 0.3947%) is transferred into a muffle furnace to be incinerated and is ashed for 4 hours at 700 ℃ to obtain rhodium ash.
And (3) washing the obtained rhodium ash by using a boiled absolute ethyl alcohol solution and deionized water in sequence until the pH value of the washed deionized water is neutral, and drying to obtain 14.66g of rhodium ash.
Adding 182mL of concentrated hydrochloric acid into the obtained rhodium ash for dissolving, stirring and heating to 80 ℃, gradually dropwise adding 218mL of 30 wt% hydrogen peroxide for assisting in dissolving, heating and refluxing for 2 hours, collecting the acid solution after filtering, repeating the acid dissolving treatment on the filter residue for three times according to the steps, and combining the filtrate to obtain the crude chlororhodic acid solution.
The obtained crude chlororhodic acid solution passes through a chromatographic column of LX-110 cation exchange resin and a chromatographic column of LSD-396 cation exchange resin in sequence, and the chlororhodic acid solution after passing through the chromatographic columns is concentrated and dried to obtain 0.2964g of rhodium trichloride, wherein the content of rhodium is 36.45 percent, and the yield of rhodium is 91.24 percent.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for preparing rhodium trichloride by recovering rhodium from waste rhodium residues comprises the following steps:
step 1, carrying out aerobic roasting on waste rhodium slag, and then washing and drying to obtain primary rhodium ash;
step 2, carrying out reduction treatment on the primary rhodium ash to obtain secondary rhodium ash;
step 3, sequentially adding acid and hydrogen peroxide into the secondary rhodium ash for reaction, and filtering to obtain a crude chlororhodic acid solution;
and 4, passing the crude chlororhodic acid solution through a cation exchange resin column to obtain a chlororhodic acid solution, and performing post-treatment to obtain rhodium trichloride.
2. The preparation method according to claim 1, wherein in the step 1, the roasting temperature is 500-1200 ℃ and the roasting time is 2-10 hours; preferably, the roasting temperature is 700-1000 ℃ and the roasting time is 4-8 hours.
3. The method according to claim 1, wherein in step 1, the washing is carried out with a boiled organic solvent and then with a boiled water until the pH of the water becomes neutral; preferably, the organic solvent is selected from water-soluble organic solvents, preferably from organic alcohols.
4. The production method according to claim 1, wherein in step 2, the reduction treatment is performed under a hydrogen atmosphere; preferably, the temperature of the reduction treatment is 500-1000 ℃, and the time is 2-10 hours; more preferably, the temperature of the reduction treatment is 600-900 ℃ and the time is 3-8 hours.
5. The method according to claim 1, wherein in step 3, the acid is selected from hydrochloric acid.
6. The preparation method according to claim 5, wherein in the step 3, the amount of the acid is 10 to 25mL/g of the secondary rhodium ash, preferably 15 to 18mL/g of the secondary rhodium ash.
7. The preparation method according to claim 1, wherein in step 3, the hydrogen peroxide is added dropwise; preferably, the concentration of the hydrogen peroxide is 30-50 wt%, and the addition amount of the hydrogen peroxide is 1-2 mL/mL of acid.
8. The production method according to claim 1, wherein, in step 3,
the reaction was carried out under reflux, then cooled to room temperature and filtered; and/or
The reaction time is 1-8 hours, preferably 2-5 hours; and/or
And 3, repeating the step 2-4 times, preferably 2-3 times.
9. The method according to any one of claims 1 to 8, wherein in step 4, the crude chlororhodic acid solution is passed through an LX-110 cation exchange resin column and an LSD-396 cation exchange resin column in this order to remove cationic impurities therefrom.
10. Rhodium trichloride obtained by the production method according to any one of claims 1 to 9.
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