CN116445726A - Method for enriching and recovering rhodium from waste rhodium park catalyst - Google Patents
Method for enriching and recovering rhodium from waste rhodium park catalyst Download PDFInfo
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- CN116445726A CN116445726A CN202310326001.4A CN202310326001A CN116445726A CN 116445726 A CN116445726 A CN 116445726A CN 202310326001 A CN202310326001 A CN 202310326001A CN 116445726 A CN116445726 A CN 116445726A
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- rhodium
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- roasting
- catalyst
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- 239000010948 rhodium Substances 0.000 title claims abstract description 125
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 235000013312 flour Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- -1 triphenylphosphine carbonyl acetyl acetone rhodium Chemical compound 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IDYWQONQVXWFQP-UHFFFAOYSA-N butan-1-ol;octan-1-ol Chemical compound CCCCO.CCCCCCCCO IDYWQONQVXWFQP-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011273 tar residue Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
- C22B11/028—Recovery of noble metals from waste materials from spent catalysts using solid sorbents, e.g. getters or catchment gauzes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for enriching and recovering rhodium from waste rhodium park catalyst, which comprises the following steps: (1) roasting in an inert atmosphere: placing the waste rhodium park catalyst into a closed reactor, introducing inert gas into the reactor, and roasting at a certain temperature to obtain rhodium-containing solid. (2) oxidizing roasting: adding solid sodium carbonate into the rhodium-containing solid obtained in the step (1) according to a certain mass ratio, and oxidizing and roasting for a period of time at a certain temperature to enable the phosphorus-containing component to generate sodium phosphate. (3) water immersion: leaching the roasting product obtained in the step (2) by water, and filtering to obtain rhodium concentrate. The invention adopts inert atmosphere high-temperature roasting, improves the recovery rate of rhodium, does not generate toxic and harmful substances, and is environment-friendly.
Description
Technical Field
The invention belongs to the field of precious metal secondary resource recovery, and relates to a method for enriching and recovering rhodium from a waste rhodium park catalyst.
Background
The rhodium-phosphine complex catalyst commonly used for producing butanol and octanol by propylene low-pressure oxo-synthesis method is triphenylphosphine carbonyl acetyl acetone rhodium (I)
[Rh(C 5 H 7 O 2 )(CO)(PPh 3 )]The trade name is rhodium park. Rhodium park catalysts are often deactivated by the presence of various high boiling byproducts generated during the reaction and impurities in the feedstock, and the spent rhodium park catalysts generated are usually in liquid form and contain a large amount of organics such as triphenylphosphine, triphenylphosphine oxide, high boiling byproducts of oxo synthesis, and polycondensates of butyraldehyde, etc. Rhodium resources are few, extraction is difficult and expensive. Therefore, the recovery of rhodium from spent catalyst is of great socioeconomic significance.
The current recovery method of the rhodium-containing dead catalyst comprises a regeneration method, a precipitation method, an incineration method, an extraction method, an adsorption method and the like.
U.S. patent No. 4363765 discloses a process for the internal regeneration of rhodium deactivated catalysts. Oxygen treatment, and then under the hydroformylation condition, 70% of the activity of the catalyst is reduced, and the catalyst returns to the hydroformylation reaction system for continuous use.
Chinese patent CN107021983A refers to a recycling method of rhodium-containing waste liquid of butanol-octanol device, rhodium is replaced by resin mixed exchange adsorption from triphenylphosphine ligand, rhodium-containing solution is obtained by desorption, and rhodium chloride is obtained after separation and purification. The rhodium-removed reaction mother liquor is treated to obtain triphenylphosphine, and rhodium trichloride and triphenylphosphine are used for preparing a novel rhodium park catalyst. And (3) burning the mixed solvent distilled in the treatment process, and discharging the tail gas reaching the standard after desulfurization and denitration treatment.
German patent DE4326076A1 discloses a process for the recovery of rhodium catalysts by adding an organic solution of an organophosphorus compound containing rhodium to a basic compound and then burning and incinerating the same at a controlled temperature below 1000 ℃. After ashing, the soluble salts in the ash are removed from the elements other than rhodium by a cleaning liquid containing a reducing agent, thereby efficiently and proportionally recovering rhodium.
German patent DE2438847A1 discloses a submerged combustion method for rhodium catalyst recovery, in which spent rhodium catalyst raffinate is fed into a submerged combustion chamber together with air, combustion gas is absorbed by water, rhodium is left in suspension in the water, and rhodium is obtained after filtration, with a recovery rate of rhodium of about 94%.
Chinese patent CN102925699a discloses a method for recovering rhodium from waste rhodium-containing catalyst in hydroformylation reaction by hydrogen peroxide, which comprises treating waste rhodium liquid with hydrogen peroxide, recovering about 90% of rhodium in the form of precipitate, concentrating the remaining rhodium solution containing about 10% to obtain rhodium slag, burning the rhodium slag in an electric furnace, removing residual carbon deposit in the slag to obtain rhodium metal containing other metal impurities, and finally combining the rhodium metals obtained in the two steps to obtain the raw material rhodium trichloride hydrate for preparing rhodium-phosphine complex catalyst.
Chinese patent CN111848674a discloses a method for recovering the effective components of spent rhodium park catalyst step by step, which comprises the following steps: the waste rhodium park catalyst is subjected to normal pressure rectification for removing light component and reduced pressure rectification, the overhead component and heavy rhodium-containing tar residue are burnt and the tail gas is treated to become ammonium phosphate fertilizer, and the burnt residue is subjected to high-temperature activation, liquid making and rhodium powder reduction refining to obtain rhodium powder.
Chinese patent CN111996386a discloses a method for recovering rhodium from rhodium-containing homogeneous phase spent catalyst, which adopts a recovery method of acidification oxidation-complexation precipitation-sulfuration precipitation, the recovery rate of rhodium reaches 95.23%, the rhodium main body in the spent catalyst is recovered in one step, the dispersion of rhodium is effectively reduced, and the recovery rate of rhodium is improved; during the acidification-oxidation process step, a small portion of rhodium is directly oxidized to Rh 3+ The part is recovered by a sulfuration precipitation method, and the final recovery rate of the rhodium combined in two sections can reach more than 97 percent.
Chinese patent CN113462900a discloses a method for recovering rhodium from a spent rhodium park catalyst, wherein the spent rhodium park catalyst is subjected to oxidation extraction to obtain an oil phase and a water phase respectively, and the rhodium-containing water phase is precipitated, purified or used for producing other rhodium compounds by DETA; the residual rhodium in the oil phase is burnt, slag-making smelting and trapping, dissolving, rhodium molecular recognition resin separation and purification, hydrazine hydrate reduction to obtain rhodium powder, and the recovery rate of rhodium is more than or equal to 96%.
In summary, the current technology research on recovering rhodium from waste rhodium catalysts at home and abroad mainly comprises a pyrogenic process and a wet process. The loss of the directly oxidized incineration metal is large, and the rhodium recovery rate is low; wet treatment involves the reaction of organic matter and strong oxidant, and the reaction is intense, inflammable and explosive, and the safety problem is outstanding.
Disclosure of Invention
In order to overcome the deficiencies of the above techniques, the present invention provides a method for enriching rhodium from spent rhodium park catalyst.
The invention is realized mainly by the following technical scheme:
a method for enriching and recovering rhodium from spent rhodium-containing park catalyst, comprising the following steps:
(1) Roasting in an inert atmosphere: placing a waste rhodium park catalyst into a quartz boat, placing the quartz boat into a tube furnace, introducing nitrogen, argon or helium, controlling the flow to be 30-100 mL/min, and roasting at 600-800 ℃ for 2-5 h to convert macromolecular organic matters such as triphenylphosphine and the like in the catalyst into gaseous and solid components with smaller molecular weight, and allowing rhodium and phosphorus to enter the solid components to obtain rhodium-containing solid matters; roasting tail gas is oxidized and combusted at high temperature and then discharged after reaching the standard;
(2) Oxidizing and roasting: mixing the rhodium-containing solid obtained in the step (1) according to the mass ratio of rhodium-containing solid to solid sodium carbonate of 1:0.1-0.5, and roasting at 500-600 ℃ for 1-2 h;
(3) Soaking in water: leaching the roasting product obtained in the step (2) for 0.5-1 h by using water at normal temperature, leaching water-soluble sodium phosphate and the like, and filtering to obtain rhodium concentrate.
In the step 1, the waste rhodium park catalyst is added with active carbon powder or starch-rich plant powder according to the mass ratio of 1:0.1-0.5, and the mixture is roasted after mixing.
Further, the starch-enriched plant powder comprises wheat flour and/or corn flour.
Mechanism of the invention
The invention calcines liquid waste rhodium park catalyst in inert atmosphere, under the combined action of decomposition and condensation under the condition of no oxygen, macromolecular organic matters such as triphenylphosphine and the like are cracked and converted into gaseous matters with smaller molecular weight and solid carbon; rhodium and phosphorus in the spent catalyst generate rhodium phosphide or remain in solid components in the form of simple substances during roasting in inert atmosphere; the rhodium-containing solid obtained is added with sodium carbonate for oxidation roasting, so that carbon in the rhodium-containing solid is combusted, a phosphorus-containing phase is converted into sodium phosphate, rhodium-containing components do not react and remain in roasting slag, water is used for leaching water-soluble sodium phosphate and the like from an oxidation roasting product, and the rhodium-containing components enter filter residues to realize rhodium enrichment.
The beneficial effects of the invention include:
(1) Compared with the traditional oxidation incineration method, the method has the advantages that the waste rhodium park catalyst is roasted at high temperature in inert atmosphere, high-temperature oxidation reaction does not occur, and toxic and harmful substances are not generated; the solid carbon generated or added by roasting adsorbs rhodium, so that the recovery rate of rhodium is improved; gaseous components with smaller molecular weight, which are generated by breaking carbon chains in macromolecular organic matters such as triphenylphosphine, are discharged after being oxidized, combusted and absorbed, and the environment is friendly.
(2) Sodium carbonate is added into the solid product obtained after roasting in inert atmosphere for oxidizing roasting, so that phosphorus and rhodium phosphide in the solid product react with sodium carbonate to generate sodium phosphate, and rhodium exists in the form of oxide or simple substance, thereby avoiding the generation of harmful substance phosphorus oxide during roasting; the oxidation roasting product is soaked in water to remove water-soluble salts such as sodium phosphate and the like, so that rhodium enrichment is realized.
Detailed Description
Example 1
1L of sticky liquid of waste rhodium park catalyst (rhodium content is 800 mg/L) is filled into a quartz boat, the quartz boat is placed into a tube furnace, nitrogen is introduced, the flow rate of the nitrogen is controlled to be 80mL/min, the tube furnace is started to heat up to 600 ℃, the temperature is kept for roasting for 3 hours, cooling is carried out, roasting slag and 5g of sodium carbonate are mixed, the mixture is placed into a crucible, a muffle furnace is adopted for oxidizing roasting for 2 hours at 600 ℃, cooling is carried out, a roasting product is leached with 100mL of water for 1 hour at normal temperature, filtering and drying are carried out, 1.24g of rhodium-containing enriched material is obtained, analysis of 62.58% of Rh is carried out, and the recovery rate of rhodium is 97%.
Example 2
Mixing 1L of waste rhodium park catalyst (rhodium content is 800 mg/L) viscous liquid with 100g of wheat flour and/or corn flour, putting the quartz boat into a tube furnace, introducing nitrogen, controlling nitrogen flow to 80mL/min, starting the tube furnace to heat up to 800 ℃, preserving heat and roasting for 4h, cooling, mixing roasting slag with 8g of sodium carbonate, placing the mixture into a crucible, oxidizing and roasting for 2h at 600 ℃ by adopting a muffle furnace, cooling, leaching the roasting product with 100mL of water for 1h at normal temperature, filtering, drying to obtain 1.19g of rhodium-containing enriched material, analyzing Rh 64.67%, and recovering rhodium of 96.2%.
Example 3
Mixing 1L of waste rhodium park catalyst (rhodium content is 800 mg/L) viscous liquid with 200g of wheat flour and/or corn flour, putting the quartz boat into a tube furnace, introducing nitrogen, controlling nitrogen flow to 80mL/min, starting the tube furnace to heat up to 700 ℃, preserving heat and roasting for 4h, cooling, mixing roasting slag with 10g of sodium carbonate, placing the mixture into a crucible, oxidizing and roasting for 2h at 600 ℃, cooling, leaching the roasting product with 100mL of water for 1h at normal temperature, filtering, drying to obtain 1.22g of rhodium-containing enriched matters, analyzing Rh 63.80%, and recovering rhodium by 97.3%.
Claims (9)
1. A process for the enriched recovery of rhodium from spent rhodium-park catalyst, comprising the steps of:
(1) Roasting in an inert atmosphere: placing a waste rhodium park catalyst in a closed reactor, introducing inert gas into the reactor, roasting at a certain temperature, and allowing rhodium and phosphorus to enter solid components to obtain rhodium-containing solid;
(2) Oxidizing and roasting: adding solid sodium carbonate into the rhodium-containing solid obtained in the step (1) according to a certain mass ratio, and oxidizing and roasting for a period of time at a certain temperature to enable the phosphorus-containing component to generate sodium phosphate;
(3) Soaking in water: leaching the roasting product obtained in the step (2) by water, and filtering to obtain rhodium concentrate.
2. The method for enriching and recovering rhodium from waste rhodium park catalyst according to claim 1, wherein the inert gas in the step (1) is nitrogen, argon or helium, and the flow is controlled at 30-100 mL/min.
3. The method for enriching and recovering rhodium from waste rhodium park catalyst according to claim 1, wherein the roasting temperature in the step (1) is 600-800 ℃ for 2-5 h.
4. The method for enriching and recovering rhodium from a spent rhodium-containing park catalyst according to claim 1, wherein the mass ratio of rhodium-containing solid to solid sodium carbonate in the step (2) is 1:0.1-0.5.
5. The method for enriching and recovering rhodium from waste rhodium park catalyst according to claim 1, wherein the roasting temperature in the step (2) is 500-600 ℃ for 1-2 h.
6. The method for enriching and recovering rhodium from waste rhodium park catalyst according to claim 1, wherein the water leaching condition in the step (3) is leaching for 0.5-1 h at normal temperature.
7. The method for enriching and recovering rhodium from waste rhodium-park catalyst according to any one of claims 1-6, wherein in step 1, the waste rhodium-park catalyst is added with activated carbon powder or starch-rich plant powder according to a mass ratio of 1:0.1-0.5, and the mixture is roasted.
8. The method of enriching rhodium from a spent rhodium-park catalyst according to claim 7, wherein the starch-enriched plant powder comprises wheat flour and/or corn flour.
9. A method for enriching rhodium from a spent rhodium-party catalyst according to any of claims 1-6, wherein the reactor in step (1) is a tube furnace.
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