CN108950233A - A method of rhodium is recycled from inactivation rhodium-containing homogeneous catalyst - Google Patents
A method of rhodium is recycled from inactivation rhodium-containing homogeneous catalyst Download PDFInfo
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- CN108950233A CN108950233A CN201810681935.9A CN201810681935A CN108950233A CN 108950233 A CN108950233 A CN 108950233A CN 201810681935 A CN201810681935 A CN 201810681935A CN 108950233 A CN108950233 A CN 108950233A
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
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Abstract
The present invention principally falls into the recovery technology field of rhodium, and in particular to a method of rhodium is recycled from inactivation rhodium-containing homogeneous catalyst.Described method includes following steps: organic matter in rhodium-containing homogeneous catalyst being recovered by distillation first and obtains rhodium enriched substance；Then rhodium enriched substance is mixed with transition metal M, reducing agent and slag former, rhodium is restored using method of smelting and forms low melting point Rh-M alloy with transition metal M, Rh-M alloy is subjected to electrolysis afterwards again or acidolysis obtains rhodium powder, finally smelts rhodium powder to obtain rhodium ingot with electric arc furnaces.The present invention is suitable for a variety of inactivation rhodium-containing homogeneous catalysts, avoids organic matter and directly burns generation air pollution, while can convert high-melting-point rhodium to low melting point, high reaction activity Rh-M alloy, purifies convenient for the smelting of subsequent rhodium.The present invention has rhodium rate of recovery height, high production efficiency, pollution-free, is suitable for industrial applications.
Description
Technical field
The present invention principally falls into the recovery technology field of rhodium, and in particular to a kind of to recycle from inactivation rhodium-containing homogeneous catalyst
The method of rhodium.
Background technique
Rhodium-containing homogeneous catalyst has many advantages, such as that high catalytic activity, reaction condition are mild, good selective, is widely applied
In fields such as petrochemical industry, fine chemistry industry, bio-pharmaceuticals.Rhodium homogeneous catalyst is because generating various high boiling pairs in use process
Impurity poisoning, carrier structure variation, microcrystalline aggregation or loss in product, catalystic converter system etc. cause catalytic activity to drop
It is low until scrap.It inactivates rhodium-containing homogeneous catalyst and is rich in rhodium, be valuable secondary resource.
Rhodium homogeneous catalyst complicated component, recycling are difficult.Removal process needs to overcome the problems, such as follows: (1) in catalyst
Content of organics be up to 95%, wherein the compounds such as organic phosphine are easily in conjunction with rhodium, it is difficult to directly carry out reduction purification, routine side
Method removal organic matter is easy to produce dioxin contamination；(2) rhodium has chemical inertness, and the solubility in chloroazotic acid is extremely low, efficiently
Quickly dissolution is always a problem；(3) in chloride media, the chemical form of rhodium is sufficiently complex, with chlorine ion concentration, acidity
With the difference of standing time and hydration occurs, reaction, the Rh (III) such as hydroxyl closes, dissociation produce a series of chlorine water complex [Rh
(H2O)nCl6-n]n-3, it is suppressed that it is extracted by general organic reagent.
By years of researches, a series of method for having been developed that rhodiums recycling, to sum up can be divided into incineration method and
Wet process.
Incineration method recycling rhodium is the existing method generallyd use in the industrial production.Chinese patent CN102247841A is disclosed
Industrial waste liquid of carbonyl synthesis of acetic anhydride is burned and is ashed, a certain proportion of sodium peroxide and sodium hydroxide mixing are added
Object, melt oxidation at a temperature of 800~900 DEG C.With hydrochloric acid and NaClO3Oxidation complexation rhodium, then zinc powder reduction is settled out rhodium
Powder.Chinese patent CN1414125A, which is disclosed, adds alkali or alkaline earth metal into the spent rhodium catalyst of carbongl group synthesis reaction
Carbonate is burned at 650~700 DEG C, and residual residue is raw again with the alkali metal bisulphate reactant salt under molten condition
At soluble rhodium salt, then rhodium is separated using electrolysis tech.Incineration method rhodium ash leaching rate is undesirable, smoke pollution is serious.
Hydrometallurgic recovery rhodium is also common technique.Chinese patent CN103540749A, which is disclosed in rhodium caprylate organic liquid waste, to be added
After water adjusts pH, after complexing agent and phase transfer catalyst progress complexometric extraction is added, the water soluble complex of rhodium is generated, carbon is added
Sour sodium or sodium hydroxide pellets obtain rhodium hydroxide.Chinese patent CN102373335A, which is disclosed, dissolves inactivation rhodium with organic solvent
Alkaline matter is added with gaseous oxidant or the mixed solution of peroxide treatment in phosphine complex catalyst, and stirring is sunk
It forms sediment, obtained rhodium-containing insoluble matter and alcohol mixed solution is filtered, washed, is dried to obtain rhodium oxide.Wet processing long flow path,
The complex compound contact break processing of rhodium is not thorough, the rate of recovery is low, tail washings amount is big.
Therefore, need to develop the technology of the efficient green recycling rhodium from rhodium-containing homogeneous catalyst.
Summary of the invention
Decomposed for organic matter during inactivation rhodium-containing homogeneous catalyst recycling rhodium generate toxic and harmful gas, material consumption it is high,
The problem low with leaching rate that product purity is low, the present invention provides it is a kind of efficiently, environmental protection from inactivation rhodium-containing homogeneous catalyst
The method for recycling rhodium.
The present invention is achieved by the following technical solutions:
A method of rhodium being recycled from inactivation rhodium-containing homogeneous catalyst, the described method comprises the following steps:
(1) organic matter in inactivation rhodium-containing homogeneous catalyst is recycled by the way of distillation, obtains rhodium enriched substance；
(2) transition metal M is mixed with rhodium enriched substance, reducing agent, slag former, obtains mixture；
(3) mixture for obtaining step (2) carries out melting, obtains Rh-M alloy and metallurgical slag；
(4) separation that Rh-M alloy is realized to rhodium and transition metal M by electrolysis or acidolysis, is obtained by filtration rhodium powder.
Further, the inactivation rhodium-containing homogeneous catalyst is carbonylation synthesis rhodium-containing dead catalyst, hydroformylation reaction contains
One of rhodium dead catalyst, Cyclopropanated rhodium-containing dead catalyst and rhodium caprylate organic liquid waste or more than one.
Further, in step (1), by the way of distillation remove the organic matter include triphenylphosphine, triphenylphosphine oxide,
Acetylacetone,2,4-pentanedione, alcohol, ethyl acetate, acetonitrile, methylene chloride, toluene and aldehyde one of condensation polymer or more than one；It is described
The condition of the way of distillation specifically: vapo(u)rizing temperature is 100-350 DEG C, distillation time 1-10h.Wherein, vapo(u)rizing temperature control is organic
Below object flash-point.
Further, transition metal M described in step (2) be one of Fe, Co, Cr, Mn, Zr or more than one, institute
The Rh mass for stating transition metal M and the rhodium enriched substance is respectively XM± 10% and XRh± 10%, XM、XRhRespectively Rh-M alloy
Eutectic composition；
Further, the reducing agent is hydrogen or carbonizable substance, and the carbonizable substance is one of coke, coal, graphite and charcoal
Or more than one；
When using hydrogen as reducing agent, control hydrogen flow rate is 10~100mL/min；When using carbonizable substance as reducing agent, control
The additional amount of carbonizable substance is 10 ~ 60wt.% of the rhodium enriched substance.
Further, the slag former is calcium oxide, silica, calcirm-fluoride, aluminium oxide, magnesia, sodium carbonate and boron
One of sand or more than one, the additional amount of the slag former is 5 ~ 25wt.% of rhodium enriched substance.
Further, in step (3), the condition of the melting is controlled are as follows: 800 ~ 1600 DEG C of smelting temperature, smelting time 1 ~
6h。
Further, in step (4):
The isolated actual conditions of rhodium and transition metal M are realized using electrolysis are as follows: using Rh-M alloying substance as anode, with platinized platinum or
Titanium plate is cathode；Electrolytic condition are as follows: voltage -0.4 ~ 0.7V, electrolytic efficiency 80-98%, electrolysis temperature are 25 ~ 90 DEG C；
Using acidolysis realize rhodium and transition metal M isolated actual conditions are as follows: acid hydrolysis solution used in acidolysis be sulfuric acid, hydrochloric acid,
One of nitric acid, hydrofluoric acid or more than one, acidolysis condition are as follows: in acid hydrolysis solution hydrogen ion concentration be 1 ~ 8.0mol/L, acidolysis
20 ~ 90 DEG C of temperature.
Further, the method also includes step (5): obtaining rhodium ingot using rhodium powder described in electric arc furnace smelting.
Further, in the step (5), electric arc furnace smelting condition are as follows: temperature is 2000-3000 DEG C, the duration of heat 5
~30min.
Advantageous effects of the invention:
1) the method for the invention recycles the organic matter in inactivation rhodium-containing homogeneous catalyst by the way of distillation, can effectively avoid
Machine object, such as triphenylphosphine, triphenylphosphine oxide, acetylacetone,2,4-pentanedione, alcohol, ethyl acetate, acetonitrile, methylene chloride, toluene and aldehyde
Air pollution caused by condensation polymer directly burns, and organic matter after the recovery can recycle.
2) type (transition metal M Fe, Co, Cr, Mn, Zr that the method for the invention passes through control addition transition metal M
One of or more than one), high-melting-point rhodium can be converted to low melting point, high reaction activity Rh-M alloy, the eutectic of formation
Point Rh-M eutectic alloy, reduces smelting reduction temperature, improves the reactivity of Rh-M eutectic alloy, is conducive to subsequent electricity
Solution or acidolysis purify rhodium.
3) the alloying transition metal M that the method for the invention is selected is cheap, fusing point is moderate, activation capacity is strong；
4) the method for the invention controls basicity, slag is further adjusted, by the fusing point of alloy phase and slag phase by selection slag type
Increase with viscosity differences, can be easily separated alloy phase and slag phase；
5) present invention can effectively remove impurity using electric arc furnace smelting, and temperature is easy to regulate and control；
6) material consumption of the present invention the advantages that low energy consumption, adaptability to raw material is wide, product purity is high, at low cost, it is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the method schematic diagram for recycling rhodium in the embodiment of the present invention from inactivation rhodium-containing homogeneous catalyst.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
The present invention can also be understood completely in description.
Embodiment 1
Inactivation rhodium-containing homogeneous catalyst is distilled into 10h recycling organic matter at 100 DEG C and obtains rhodium enriched substance.Iron is as alloy member
Element, the composition proportion of Rh, Fe are Rh:92wt%, Fe:8wt%.For coke as reducing agent, additional amount is the 60wt% of rhodium enriched substance.
For calcium oxide as slag former, additional amount is the 25wt% of rhodium enriched substance.Above-mentioned raw materials mixing, which is placed in induction furnace at 800 DEG C, melts
Refine 6h.Through the isolated Rh-Fe alloy of slag.Rh-Fe alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage -0.4V,
25 DEG C of electrolysis temperature, electrolytic efficiency 98%.Rhodium powder obtains rhodium ingot using 2000 DEG C of smelting 5min of electric arc furnaces.Through detecting, rhodium recycling
Rate reaches 98.5%.
Embodiment 2
Inactivation rhodium-containing homogeneous catalyst is distilled into 9h recycling organic matter at 120 DEG C and obtains rhodium enriched substance.Iron is as alloy member
Element, the composition proportion of Rh, Fe are Rh:88wt%, Fe:12wt%.As reducing agent, coke additional amount is rhodium enriched substance for coke, coal
40wt%, the additional amount of coal is the 10wt% of rhodium enriched substance.As slag former, calcium oxide additional amount is rhodium for calcium oxide, aluminium oxide
The 10wt% of enriched substance, aluminium oxide additional amount are the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace at 900 DEG C
Melting 5.5h.Through the isolated Rh-Fe alloy of slag.Rh-Fe alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) be
1mol/L, 20 DEG C of acidolysis temperature.Rhodium powder obtains rhodium ingot using 2050 DEG C of smelting 10min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches
98.7%。
Embodiment 3
Inactivation rhodium-containing homogeneous catalyst is distilled into 8h recycling organic matter at 130 DEG C and obtains rhodium enriched substance.Iron is as alloy member
Element, the composition proportion of Rh, Fe are Rh:84wt%, Fe:16wt%.As reducing agent, coke additional amount is rhodium for coke, coal and graphite
The 40wt% of enriched substance, the additional amount of coal are the 10wt% of rhodium enriched substance, and the additional amount of graphite is the 10wt% of rhodium enriched substance.Fluorination
For calcium as slag former, calcirm-fluoride additional amount is the 25wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace at 1000 DEG C
Melting 5.5h.Through the isolated Rh-Fe alloy of slag.Rh-Fe alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage-
0.3V, 40 DEG C of electrolysis temperature, electrolytic efficiency 96%.Rhodium powder obtains rhodium ingot using 2100 DEG C of smelting 10min of electric arc furnaces.Through detecting,
The rhodium rate of recovery reaches 98.5%.
Embodiment 4
Inactivation rhodium-containing homogeneous catalyst is distilled into 8h recycling organic matter at 170 DEG C and obtains rhodium enriched substance.Iron is as alloy member
Element, the composition proportion of Rh, Fe are Rh:82wt%, Fe:18wt%.As reducing agent, coke additional amount is rhodium enrichment for coke, graphite
The 30wt% of object, the additional amount of graphite are the 20wt% of rhodium enriched substance.As slag former, calcium oxide adds for calcium oxide, aluminium oxide, borax
Enter the 5wt% that amount is rhodium enriched substance, aluminium oxide additional amount is the 10wt% of rhodium enriched substance, and aluminium oxide additional amount is rhodium enriched substance
5wt%.Above-mentioned raw materials mixing is placed in induction furnace melting 5h at 1100 DEG C.Through the isolated Rh-Fe alloy of slag.Rh-Fe is closed
Gold is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage -0.2V, 50 DEG C of electrolysis temperature, and electrolytic efficiency 94%.Rhodium powder is using electricity
2150 DEG C of smelting 10min of arc furnace obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 95.2%.
Embodiment 5
Inactivation rhodium-containing homogeneous catalyst is distilled into 8h recycling organic matter at 190 DEG C and obtains rhodium enriched substance.Cobalt is as alloy member
Element, the composition proportion of Rh, Co are Rh:35wt%, Co:65wt%.As reducing agent, coke additional amount is that rhodium is rich for coke, coal, charcoal
Collect the 20wt% of object, the additional amount of coal is the 20wt% of rhodium enriched substance, and the additional amount of charcoal is the 10wt% of rhodium enriched substance.Calcium oxide,
As slag former, calcium oxide additional amount is the 15wt% of rhodium enriched substance for sodium carbonate, borax, and sodium carbonate additional amount is rhodium enriched substance
10wt%, borax additional amount are the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 5h at 1200 DEG C.Through
The isolated Rh-Co alloy of slag.Rh-Co alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) it is 3mol/L, acidolysis
40 DEG C of temperature.Rhodium powder obtains rhodium ingot using 2200 DEG C of smelting 15min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 98.7%.
Embodiment 6
Inactivation rhodium-containing homogeneous catalyst is distilled into 7h recycling organic matter at 210 DEG C and obtains rhodium enriched substance.Cobalt is as alloy member
Element, the composition proportion of Rh, Co are Rh:39wt%, Co:61wt%.As reducing agent, coke additional amount is rhodium for coke, graphite, charcoal
The 10wt% of enriched substance, the additional amount of graphite are the 20wt% of rhodium enriched substance, and the additional amount of charcoal is the 30wt% of rhodium enriched substance.Oxygen
Change calcium, aluminium oxide, sodium carbonate as slag former, calcium oxide additional amount is the 5wt% of rhodium enriched substance, and aluminium oxide additional amount is that rhodium is rich
Collect the 5wt% of object, sodium carbonate additional amount is the 15wt% of rhodium enriched substance.Above-mentioned raw materials mixing, which is placed in induction furnace at 1200 DEG C, melts
Refine 5h.Through the isolated Rh-Co alloy of slag.Rh-Co alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) is
3mol/L, 50 DEG C of acidolysis temperature.Rhodium powder obtains rhodium ingot using 2300 DEG C of smelting 15min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches
99.3%。
Embodiment 7
Inactivation rhodium-containing homogeneous catalyst is distilled into 7h recycling organic matter at 210 DEG C and obtains rhodium enriched substance.Cobalt is as alloy member
Element, the composition proportion of Rh, Co are Rh:43wt%, Co:57wt%.As reducing agent, coke additional amount is rhodium enrichment for coke, charcoal
The 20wt% of object, the additional amount of charcoal are the 20wt% of rhodium enriched substance.As slag former, silica adds for silica, calcirm-fluoride
Enter the 20wt% that amount is rhodium enriched substance, calcirm-fluoride additional amount is the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace
Melting 4.5h at 1300 DEG C.Through the isolated Rh-Co alloy of slag.Rh-Co alloy is electrolysed to obtain rhodium powder, electrolytic condition
Are as follows: voltage -0.1V, 60 DEG C of electrolysis temperature, electrolytic efficiency 92%.Rhodium powder obtains rhodium using 2350 DEG C of smelting 20min of electric arc furnaces
Ingot.Through detecting, the rhodium rate of recovery reaches 98.4%.
Embodiment 8
Inactivation rhodium-containing homogeneous catalyst is distilled into 6.5h recycling organic matter at 220 DEG C and obtains rhodium enriched substance.Cobalt is as alloy
Element, the composition proportion of Rh, Co are Rh:45wt%, Co:55wt%.For coal as reducing agent, coal additional amount is rhodium enriched substance
30wt%.As slag former, the additional amount of calcium oxide is the 10wt% of rhodium enriched substance, titanium dioxide for calcium oxide, silica, aluminium oxide
Silicon additional amount is the 10wt% of rhodium enriched substance, and aluminium oxide additional amount is the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed on induction
Melting 4.5h at 1300 DEG C in furnace.Through the isolated Rh-Co alloy of slag.Rh-Co alloy is electrolysed to obtain rhodium powder, is electrolysed item
Part are as follows: voltage 0V, 70 DEG C of electrolysis temperature, electrolytic efficiency 90%.Rhodium powder obtains rhodium ingot using 2400 DEG C of smelting 20min of electric arc furnaces.
Through detecting, the rhodium rate of recovery reaches 98.1%.
Embodiment 9
Inactivation rhodium-containing homogeneous catalyst is distilled into 6h recycling organic matter at 230 DEG C and obtains rhodium enriched substance.Chromium is as alloy member
Element, the composition proportion of Rh, Cr are Rh:58wt%, Cr:42wt%.As reducing agent, coal additional amount is rhodium enriched substance for coal, graphite
20wt%, the additional amount of graphite are the 10wt% of rhodium enriched substance.Calcium oxide, dioxy return silicon as slag former, and calcium oxide additional amount is
The 15wt% of rhodium enriched substance, dioxy return the 10wt% that silicon additional amount is rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace
Melting 4.5h at 1350 DEG C.Through the isolated Rh-Cr alloy of slag.Rh-Cr alloy carries out acidolysis and obtains rhodium powder, acidolysis condition
Are as follows: c (H+) be 4mol/L, 60 DEG C of acidolysis temperature.Rhodium powder obtains rhodium ingot using 2450 DEG C of smelting 20min of electric arc furnaces.Through detecting, rhodium
The rate of recovery reaches 99.3%.
Embodiment 10
Inactivation rhodium-containing homogeneous catalyst is distilled into 5.5h recycling organic matter at 240 DEG C and obtains rhodium enriched substance.Chromium is as alloy
Element, the composition proportion of Rh, Cr are Rh:62wt%, Cr:38wt%.As reducing agent, coal additional amount is rhodium enriched substance for coal, graphite
40wt%, the additional amount of charcoal is the 10wt% of rhodium enriched substance.Dioxy returns silicon, aluminium oxide and sodium carbonate as slag former, dioxy
The 5wt% that silicon additional amount is rhodium enriched substance is returned, aluminium oxide additional amount is the 10wt% of rhodium enriched substance, and sodium carbonate additional amount is rhodium enrichment
The 5wt% of object.Above-mentioned raw materials mixing is placed in induction furnace melting 4h at 1400 DEG C.Through the isolated Rh-Cr alloy of slag.Rh-
Cr alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) be 5mol/L, 70 DEG C of acidolysis temperature.Rhodium powder uses electric arc furnaces
2500 DEG C of smelting 20min obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 98.8%.
Embodiment 11
Inactivation rhodium-containing homogeneous catalyst is distilled into 5.5h recycling organic matter at 250 DEG C and obtains rhodium enriched substance.Chromium is as alloy
Element, the composition proportion of Rh, Cr are Rh:66wt%, Cr:34wt%.As reducing agent, coal additional amount is that rhodium is rich for coal, graphite, charcoal
Collect the 20wt% of object, the additional amount of graphite is the 10wt% of rhodium enriched substance, and the additional amount of charcoal is the 20wt% of rhodium enriched substance.Dioxy
Silicon, calcirm-fluoride, aluminium oxide are returned as slag former, dioxy returns the 10wt% that silicon additional amount is rhodium enriched substance, and calcirm-fluoride additional amount is rhodium
The 10wt% of enriched substance, the additional amount of aluminium oxide are the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace 1450 DEG C
Lower melting 3.5h.Through the isolated Rh-Cr alloy of slag.Rh-Cr alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage
0.1V, 70 DEG C of electrolysis temperature, electrolytic efficiency 88%.Rhodium powder obtains rhodium ingot using 2550 DEG C of smelting 20min of electric arc furnaces.Through detecting,
The rhodium rate of recovery reaches 99.1%.
Embodiment 12
Inactivation rhodium-containing homogeneous catalyst is distilled into 5h recycling organic matter at 260 DEG C and obtains rhodium enriched substance.Chromium is as alloy member
Element, the composition proportion of Rh, Cr are Rh:68wt%, Cr:32wt%.Graphite is rhodium enriched substance as reducing agent, the additional amount of graphite
60wt%.For aluminium oxide as slag former, the additional amount of aluminium oxide is the 25wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed on induction
Melting 3.5h at 1450 DEG C in furnace.Through the isolated Rh-Cr alloy of slag.Rh-Cr alloy is electrolysed to obtain rhodium powder, is electrolysed item
Part are as follows: voltage 0.2V, 80 DEG C of electrolysis temperature, electrolytic efficiency 86%.Rhodium powder obtains rhodium using 2600 DEG C of smelting 25min of electric arc furnaces
Ingot.Through detecting, the rhodium rate of recovery reaches 96.6%.
Embodiment 13
Inactivation rhodium-containing homogeneous catalyst is distilled into 4.5h recycling organic matter at 270 DEG C and obtains rhodium enriched substance.Manganese is as alloy
Element, the composition proportion of Rh, Mn are Rh:50wt%, Mn:50wt%.As reducing agent, the additional amount of graphite is rhodium for graphite, charcoal
The 50wt% of enriched substance, the additional amount of charcoal are the 10wt% of rhodium enriched substance.Silica, aluminium oxide, magnesia as slag former,
The additional amount of silica is the 10wt% of rhodium enriched substance, and the additional amount of aluminium oxide is the 10wt% of rhodium enriched substance, and magnesia adds
Enter the 5wt% that amount is rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 3h at 1500 DEG C.It is isolated through slag
Rh-Mn alloy.Rh-Mn alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage 0.3V, 90 DEG C of electrolysis temperature, and electrolytic efficiency
It is 84%.Rhodium powder obtains rhodium ingot using 2650 DEG C of smelting 25min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 99.1%.
Embodiment 14
Inactivation rhodium-containing homogeneous catalyst is distilled into 4h recycling organic matter at 280 DEG C and obtains rhodium enriched substance.Manganese is as alloy member
Element, the composition proportion of Rh, Mn are Rh:54wt%, Mn:46wt%.As reducing agent, the additional amount of coal is rhodium enriched substance for coal, graphite
20wt%, the additional amount of graphite is the 40wt% of rhodium enriched substance.Silica, borax are as slag former, the addition of silica
Amount is the 5wt% of rhodium enriched substance, and the additional amount of borax is the 20wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace
Melting 3h at 1500 DEG C.Through the isolated Rh-Mn alloy of slag.Rh-Mn alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c
(H+) be 6mol/L, 70 DEG C of acidolysis temperature.Rhodium powder obtains rhodium ingot using 2700 DEG C of smelting 25min of electric arc furnaces.Through detecting, rhodium recycling
Rate reaches 97.2%.
Embodiment 15
Inactivation rhodium-containing homogeneous catalyst is distilled into 3.5h recycling organic matter at 290 DEG C and obtains rhodium enriched substance.Manganese is as alloy
Element, the composition proportion of Rh, Mn are Rh:58wt%, Mn:42wt%.As reducing agent, the additional amount of coal is rhodium enrichment for coal, graphite
The 10wt% of object, the additional amount of graphite are the 30wt% of rhodium enriched substance.Calcium oxide, calcirm-fluoride, aluminium oxide are as slag former, calcium oxide
Additional amount be rhodium enriched substance 5wt%, the additional amount of calcirm-fluoride is the 5wt% of rhodium enriched substance, and the additional amount of aluminium oxide is that rhodium is rich
Collect the 5wt% of object.Above-mentioned raw materials mixing is placed in induction furnace melting 2.5h at 1550 DEG C.It is closed through the isolated Rh-Mn of slag
Gold.Rh-Mn alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) be 7mol/L, 80 DEG C of acidolysis temperature.Rhodium powder is using electricity
2750 DEG C of smelting 30min of arc furnace obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 98.3%.
Embodiment 16
Inactivation rhodium-containing homogeneous catalyst is distilled into 3h recycling organic matter at 300 DEG C and obtains rhodium enriched substance.Manganese is as alloy member
Element, the composition proportion of Rh, Mn are Rh:60wt%, Mn:40wt%.As reducing agent, the additional amount of coke is that rhodium is rich for coke, graphite
Collect the 5wt% of object, the additional amount of graphite is the 10wt% of rhodium enriched substance.Silica, sodium carbonate as slag former, silica
Additional amount is the 20wt% of rhodium enriched substance, and the additional amount of sodium carbonate is the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed on induction
Melting 2.5h at 1550 DEG C in furnace.Through the isolated Rh-Mn alloy of slag.Rh-Mn alloy is electrolysed to obtain rhodium powder, is electrolysed item
Part are as follows: voltage 0.4V, 85 DEG C of electrolysis temperature, electrolytic efficiency 83%.Rhodium powder obtains rhodium using 2800 DEG C of smelting 30min of electric arc furnaces
Ingot.Through detecting, the rhodium rate of recovery reaches 99.1%.
Embodiment 17
Inactivation rhodium-containing homogeneous catalyst is distilled into 2.5h recycling organic matter at 310 DEG C and obtains rhodium enriched substance.Zirconium is as alloy
Element, the composition proportion of Rh, Zr are Rh:78wt%, Zr:22wt%.Coal is rhodium enriched substance as reducing agent, the additional amount of coal
60wt%.As slag former, the additional amount of calcirm-fluoride is the 20wt% of rhodium enriched substance, the additional amount of aluminium oxide for calcirm-fluoride, aluminium oxide
For the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 2h at 1600 DEG C.Through the isolated Rh-Zr of slag
Alloy.Rh-Zr alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage 0.5V, 90 DEG C of electrolysis temperature, electrolytic efficiency is
82%.Rhodium powder obtains rhodium ingot using 2800 DEG C of smelting 30min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 97.8%.
Embodiment 18
Inactivation rhodium-containing homogeneous catalyst is distilled into 2h recycling organic matter at 320 DEG C and obtains rhodium enriched substance.Zirconium is as alloy member
Element, the composition proportion of Rh, Zr are Rh:82wt%, Zr:18wt%.As reducing agent, the additional amount of coke is rhodium for coke, coal, charcoal
The 10wt% of enriched substance, the additional amount of coal are the 10wt% of rhodium enriched substance, and the additional amount of charcoal is the 40wt% of rhodium enriched substance.Oxidation
As slag former, the additional amount of aluminium oxide is the 20wt% of rhodium enriched substance for aluminium, sodium carbonate, and sodium carbonate additional amount is rhodium enriched substance
5wt%.Above-mentioned raw materials mixing is placed in induction furnace melting 1.5h at 1600 DEG C.Through the isolated Rh-Zr alloy of slag.Rh-Zr
Alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage 0.6V, 90 DEG C of electrolysis temperature, and electrolytic efficiency 81%.Rhodium powder uses
2850 DEG C of smelting 30min of electric arc furnaces obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 98.2%.
Embodiment 19
Inactivation rhodium-containing homogeneous catalyst is distilled into 1.5h recycling organic matter at 330 DEG C and obtains rhodium enriched substance.Zirconium is as alloy
Element, the composition proportion of Rh, Zr are Rh:86wt%, Zr:14wt%.As reducing agent, the additional amount of graphite is rhodium for graphite, charcoal
The 10wt% of enriched substance, the additional amount of charcoal are the 50wt% of rhodium enriched substance.For borax as slag former, borax additional amount is rhodium enrichment
The 25wt% of object.Above-mentioned raw materials mixing is placed in induction furnace melting 1h at 1600 DEG C.Through the isolated Rh-Zr alloy of slag.
Rh-Zr alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) be 8mol/L, 90 DEG C of acidolysis temperature.Rhodium powder uses electric arc
2900 DEG C of smelting 30min of furnace obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 95.8%.
Embodiment 20
Inactivation rhodium-containing homogeneous catalyst is distilled into 1.5h recycling organic matter at 340 DEG C and obtains rhodium enriched substance.Zirconium is as alloy
Element, the composition proportion of Rh, Zr are Rh:88wt%, Zr:12wt%.Charcoal is rhodium enriched substance as reducing agent, the additional amount of charcoal
60wt%.Calcium oxide, calcirm-fluoride, aluminium oxide are as slag former, and calcium oxide additional amount is the 10wt% of rhodium enriched substance, and calcirm-fluoride adds
Entering the 5wt% that amount is rhodium enriched substance, the additional amount of aluminium oxide is the 5wt% of rhodium enriched substance,.Above-mentioned raw materials mixing is placed on induction furnace
In melting 5h at 1500 DEG C.Through the isolated Rh-Zr alloy of slag.Rh-Zr alloy carries out acidolysis and obtains rhodium powder, acidolysis condition
Are as follows: c (H+) be 8mol/L, 50 DEG C of acidolysis temperature.Rhodium powder obtains rhodium ingot using 2950 DEG C of smelting 30min of electric arc furnaces.Through detecting, rhodium
The rate of recovery reaches 97.1%.
Embodiment 21
Inactivation rhodium-containing homogeneous catalyst is distilled into 1h recycling organic matter at 350 DEG C and obtains rhodium enriched substance.Zirconium is as alloy member
Element, the composition proportion of Rh, Zr are Rh:74wt%, Zr:26wt%.Coke, coal, graphite, charcoal are as reducing agent, the addition of coke
Amount is the 10wt% of rhodium enriched substance, and the additional amount of charcoal is the 10wt% of rhodium enriched substance, and the additional amount of charcoal is rhodium enriched substance
10wt%, the additional amount of charcoal are the 10wt% of rhodium enriched substance.As slag former, calcirm-fluoride is added for calcirm-fluoride, aluminium oxide, magnesia
Amount is the 10wt% of rhodium enriched substance, and aluminium oxide additional amount is the 10wt% of rhodium enriched substance, and the additional amount of magnesia is rhodium enriched substance
5wt%.Above-mentioned raw materials mixing is placed in induction furnace melting 3h at 1400 DEG C.Through the isolated Rh-Zr alloy of slag.Rh-Zr is closed
Gold is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage 0.7V, 90 DEG C of electrolysis temperature, and electrolytic efficiency 80%.Rhodium powder is using electricity
3000 DEG C of smelting 30min of arc furnace obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 95.4%.
Embodiment 22
Inactivation rhodium-containing homogeneous catalyst is distilled into 5h recycling organic matter at 200 DEG C and obtains rhodium enriched substance.Iron, cobalt are as alloy
Element, the composition proportion of Rh, Fe, Co are Rh:XRh+ 4wt%, Fe:XFe- 2wt%, Co:XCo-2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 20mL/min.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, calcirm-fluoride, aluminium oxide
10wt%, the additional amount of calcirm-fluoride are the 5wt% of rhodium enriched substance, and aluminium oxide additional amount is the 5wt% of rhodium enriched substance.Above-mentioned raw materials are mixed
Conjunction is placed in induction furnace melting 2h at 1250 DEG C.Through the isolated Rh-Fe-Co alloy of slag.Rh-Fe-Co alloy carries out acid
Solution obtains rhodium powder, acidolysis condition are as follows: c (H+) be 2mol/L, 60 DEG C of acidolysis temperature.Rhodium powder is using 2000 DEG C of electric arc furnaces smeltings
20min obtains rhodium ingot.Through detecting, the rhodium rate of recovery reaches 98.1%.
Embodiment 23
Inactivation rhodium-containing homogeneous catalyst is distilled into 6h recycling organic matter at 200 DEG C and obtains rhodium enriched substance.Iron, cobalt are as alloy
Element, the composition proportion of Rh, Fe, Cr are Rh:XRh+ 6wt%, Fe:XFe- 4wt%, Cr:XCr-2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 30mL/min.As slag former, silica additional amount is rhodium enriched substance for silica, sodium carbonate, borax
5wt%, the additional amount of sodium carbonate are the 10wt% of rhodium enriched substance, and borax additional amount is the 10wt% of rhodium enriched substance.Above-mentioned raw materials mixing
Melting 4h at 1300 DEG C is placed in induction furnace.Through the isolated Rh-Fe-Cr alloy of slag.Rh-Fe-Cr alloy carries out acidolysis
Obtain rhodium powder, acidolysis condition are as follows: c (H+) be 2mol/L, 70 DEG C of acidolysis temperature.Rhodium powder uses 2000 DEG C of smelting 20min of electric arc furnaces
Obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 99.0%.
Embodiment 24
Inactivation rhodium-containing homogeneous catalyst is distilled into 7h recycling organic matter at 300 DEG C and obtains rhodium enriched substance.Iron, manganese are as alloy
Element, the composition proportion of Rh, Fe, Mn are Rh:XRh+ 8wt%, Fe:XFe- 6wt%, Mn:XMn-2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 40mL/min.As slag former, silica additional amount is the 5wt% of rhodium enriched substance, borax for silica, borax
Additional amount is the 20wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 3h at 1350 DEG C.It is separated through slag
To Rh-Fe-Mn alloy.Rh-Fe-Mn alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) it is 6mol/L, acidolysis temperature
80℃.Rhodium powder obtains rhodium ingot using 3000 DEG C of smelting 20min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 97.8%.
Embodiment 25
Inactivation rhodium-containing homogeneous catalyst is distilled into 8h recycling organic matter at 300 DEG C and obtains rhodium enriched substance.Iron, zirconium are as alloy
Element, the composition proportion of Rh, Fe, Zr are Rh:XRh+ 10wt%, Fe:XFe- 8wt%, Zr:XZr-2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 50mL/min.As slag former, calcirm-fluoride additional amount is the 15wt% of rhodium enriched substance, sodium carbonate for calcirm-fluoride, sodium carbonate
Additional amount is the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 5h at 1400 DEG C.It is separated through slag
To Rh-Fe-Zr alloy.Rh-Fe-Zr alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) it is 6mol/L, acidolysis temperature
90℃.Rhodium powder obtains rhodium ingot using 3000 DEG C of smelting 20min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 98.2%.
Embodiment 26
Inactivation rhodium-containing homogeneous catalyst is distilled into 1h recycling organic matter at 350 DEG C and obtains rhodium enriched substance.Cobalt, chromium are as alloy
Element, the composition proportion of Rh, Co, Cr are Rh:XRh- 4wt%, Co:XCo+ 2wt%, Cr:XCr+2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 60mL/min.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, silica, calcirm-fluoride
20wt%, silica additional amount are the 3wt% of rhodium enriched substance, and calcirm-fluoride additional amount is the 2wt% of rhodium enriched substance.Above-mentioned raw materials are mixed
Conjunction is placed in induction furnace melting 3h at 1400 DEG C.Through the isolated Rh-Co-Cr alloy of slag.Rh-Co-Cr alloy carries out electricity
Solution obtains rhodium powder, electrolytic condition are as follows: voltage 0.7V, 90 DEG C of electrolysis temperature, and electrolytic efficiency 80%.Rhodium powder uses electric arc furnaces 3000
DEG C smelt 30min obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 95.4%.
Embodiment 27
Inactivation rhodium-containing homogeneous catalyst is distilled into 5h recycling organic matter at 200 DEG C and obtains rhodium enriched substance.Cobalt, manganese are as alloy
Element, the composition proportion of Rh, Co, Mn are Rh:XRh- 6wt%, Co:XCo+ 4wt%, Mn:XMn+2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 70mL/min.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, calcirm-fluoride, aluminium oxide, magnesia
20wt%, calcirm-fluoride additional amount be rhodium enriched substance 1wt%, aluminium oxide additional amount be rhodium enriched substance 1wt%, magnesia be added
Amount is the 3wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 2h at 1250 DEG C.Through the isolated Rh- of slag
Co-Mn alloy.Rh-Co-Mn alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage 0.6V, 80 DEG C of electrolysis temperature, and electrolysis
Efficiency is 88%.Rhodium powder obtains rhodium ingot using 2000 DEG C of smelting 20min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 98.1%.
Embodiment 28
Inactivation rhodium-containing homogeneous catalyst is distilled into 6h recycling organic matter at 200 DEG C and obtains rhodium enriched substance.Cobalt, zirconium are as alloy
Element, the composition proportion of Rh, Co, Zr are Rh:XRh- 8wt%, Co:XCo+ 6wt%, Zr:XZr+2wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 80mL/min.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, silica, magnesia, borax
17wt%, silica additional amount be rhodium enriched substance 2wt%, magnesia additional amount be rhodium enriched substance 1wt%, borax be added
Amount is the 5wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 4h at 1300 DEG C.Through the isolated Rh- of slag
Co-Zr alloy.Rh-Co-Zr alloy is electrolysed to obtain rhodium powder, electrolytic condition are as follows: voltage 0.5V, 70 DEG C of electrolysis temperature, and electrolysis
Efficiency is 92%.Rhodium powder obtains rhodium ingot using 2000 DEG C of smelting 20min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 99.0%.
Embodiment 29
Inactivation rhodium-containing homogeneous catalyst is distilled into 7h recycling organic matter at 300 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Cr, Mn are Rh:XRh- 10wt%, Cr:XCr+ 6wt%, Mn:XMn+4wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 90mL/min.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, calcirm-fluoride, magnesia
19wt%, calcirm-fluoride additional amount are the 3wt% of rhodium enriched substance, and magnesia additional amount is the 2wt% of rhodium enriched substance.Above-mentioned raw materials mixing
Melting 3h at 1350 DEG C is placed in induction furnace.Through the isolated Rh-Cr-Mn alloy of slag.Rh-Cr-Mn alloy is electrolysed
Obtain rhodium powder, electrolytic condition are as follows: voltage 0.4V, 60 DEG C of electrolysis temperature, electrolytic efficiency 93%.Rhodium powder uses 3000 DEG C of electric arc furnaces
It smelts 20min and obtains rhodium ingot.Through detecting, the rhodium rate of recovery reaches 97.8%.
Embodiment 30
Inactivation rhodium-containing homogeneous catalyst is distilled into 8h recycling organic matter at 300 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Fe, Co are Rh:XRh+ 2wt%, Fe:XFe+ 2wt%, Co:XCo-4wt%.Hydrogen is as reducing agent, hydrogen
Gas velocity is 100mL/min.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, aluminium oxide, sodium carbonate
21wt%, aluminium oxide additional amount are the 1wt% of rhodium enriched substance, and sodium carbonate additional amount is the 3wt% of rhodium enriched substance.Above-mentioned raw materials mixing
Melting 5h at 1400 DEG C is placed in induction furnace.Through the isolated Rh-Fe-Co alloy of slag.Rh-Fe-Co alloy is electrolysed
Obtain rhodium powder, electrolytic condition are as follows: voltage 0.3V, 40 DEG C of electrolysis temperature, electrolytic efficiency 94%.Rhodium powder uses 3000 DEG C of electric arc furnaces
It smelts 20min and obtains rhodium ingot.Through detecting, the rhodium rate of recovery reaches 98.2%.
Embodiment 31
Inactivation rhodium-containing homogeneous catalyst is distilled into 1h recycling organic matter at 200 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Fe, Co are Rh:XRh+ 3wt%, Mn:XMn- 1wt%, Zr:XZr-2wt%.Coke, graphite are as reduction
Agent, coke additional amount are the 30wt% of rhodium enriched substance, and the additional amount of graphite is the 10wt% of rhodium enriched substance.Silica, calcirm-fluoride,
As slag former, silica additional amount is the 5wt% of rhodium enriched substance for aluminium oxide, sodium carbonate, borax, and calcirm-fluoride additional amount is rhodium
The 12wt% of enriched substance, sodium carbonate additional amount are the 3wt% of rhodium enriched substance, and borax additional amount is the 2wt% of rhodium enriched substance.Above-mentioned original
Material mixing is placed in induction furnace melting 5h at 1200 DEG C.Through the isolated Rh-Mn-Zr alloy of slag.Rh-Mn-Zr alloy into
Row electrolysis obtains rhodium powder, electrolytic condition are as follows: voltage 0.1V, 90 DEG C of electrolysis temperature, and electrolytic efficiency 91%.Rhodium powder uses electric arc furnaces
2600 DEG C of smelting 15min obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 99.1%.
Embodiment 32
Inactivation rhodium-containing homogeneous catalyst is distilled into 5h recycling organic matter at 220 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Co, Mn are Rh:XRh+ 5wt%, Co:XCo- 1wt%, Mn:XMn-4wt%,.Coke, charcoal are as reduction
Agent, coke additional amount are the 10wt% of rhodium enriched substance, and the additional amount of charcoal is the 30wt% of rhodium enriched substance.Calcium oxide, silica,
As slag former, calcium oxide additional amount is the 8wt% of rhodium enriched substance for magnesia, sodium carbonate, and silica additional amount is rhodium enriched substance
10wt%, magnesia additional amount be rhodium enriched substance 2wt%, sodium carbonate additional amount be rhodium enriched substance 5wt%.Above-mentioned raw materials are mixed
Conjunction is placed in induction furnace melting 4.5h at 1300 DEG C.Through the isolated Rh-Co-Mn alloy of slag.Rh-Co-Mn alloy carries out
Electrolysis obtains rhodium powder, electrolytic condition are as follows: voltage 0.2V, 80 DEG C of electrolysis temperature, and electrolytic efficiency 90%.Rhodium powder uses electric arc furnaces
2650 DEG C of smelting 20min obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 96.6%.
Embodiment 33
Inactivation rhodium-containing homogeneous catalyst is distilled into 6h recycling organic matter at 230 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Cr, Mn are Rh:XRh+ 7wt%, Cr:XCr- 5wt%, Mn:XMn-2wt%,.Coal, charcoal are as reduction
Agent, the additional amount of coal are the 50wt% of rhodium enriched substance, and the additional amount of charcoal is the 10wt% of rhodium enriched substance.Silica, calcirm-fluoride,
As slag former, silica additional amount is the 3wt% of rhodium enriched substance for aluminium oxide, sodium carbonate, and calcirm-fluoride additional amount is rhodium enriched substance
7wt%, aluminium oxide additional amount be rhodium enriched substance 10wt%, sodium carbonate additional amount be rhodium enriched substance 5wt%.Above-mentioned raw materials are mixed
Conjunction is placed in induction furnace melting 4.5h at 1300 DEG C.Through the isolated Rh-Cr-Mn alloy of slag.Rh-Cr-Mn alloy carries out
Electrolysis obtains rhodium powder, electrolytic condition are as follows: voltage 0.3V, 70 DEG C of electrolysis temperature, and electrolytic efficiency 89%.Rhodium powder uses electric arc furnaces
2700 DEG C of smelting 20min obtain rhodium ingot.Through detecting, the rhodium rate of recovery reaches 99.1%.
Embodiment 34
Inactivation rhodium-containing homogeneous catalyst is distilled into 7h recycling organic matter at 240 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Fe, Cr are Rh:XRh- 3wt%, Fe:XFe+ 4wt%, Cr:XCr-1wt%,.Coke, graphite, charcoal are made
For reducing agent, the additional amount of coke is the 20wt% of rhodium enriched substance, and the additional amount of graphite is the 10wt% of rhodium enriched substance, and charcoal adds
Enter the 10wt% that amount is rhodium enriched substance.As slag former, calcium oxide additional amount is rhodium enriched substance for calcium oxide, silica, magnesia
18wt%, silica additional amount be rhodium enriched substance 2wt%, magnesia additional amount be rhodium enriched substance 5wt%.Above-mentioned raw materials
Mixing is placed in induction furnace melting 4.5h at 1350 DEG C.Through the isolated Rh-Cr-Mn alloy of slag.Rh-Cr-Mn alloy into
Row acidolysis obtains rhodium powder, acidolysis condition are as follows: c (H+) be 1mol/L, 20 DEG C of acidolysis temperature.Rhodium powder is using 2750 DEG C of electric arc furnaces smeltings
20min obtains rhodium ingot.Through detecting, the rhodium rate of recovery reaches 97.2%.
Embodiment 35
Inactivation rhodium-containing homogeneous catalyst is distilled into 8h recycling organic matter at 250 DEG C and obtains rhodium enriched substance.Chromium, manganese are as alloy
Element, the composition proportion of Rh, Mn, Cr are Rh:XRh- 9wt%, Mn:XMn+ 7wt%, Zr:XZr+2wt%,.Coal, graphite, charcoal conduct
Reducing agent, the additional amount of coal are the 30wt% of rhodium enriched substance, and the additional amount of graphite is the 10wt% of rhodium enriched substance, the additional amount of charcoal
For the 20wt% of rhodium enriched substance.As slag former, calcirm-fluoride additional amount is rhodium enriched substance for calcirm-fluoride, aluminium oxide, magnesia, borax
13wt%, aluminium oxide additional amount be rhodium enriched substance 2wt%, magnesia additional amount be rhodium enriched substance 4wt%, borax additional amount
For the 1wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 4h at 1400 DEG C.Through the isolated Rh- of slag
Mn-Zr alloy.Rh-Mn-Zr alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) be 2mol/L, 25 DEG C of acidolysis temperature.
Rhodium powder obtains rhodium ingot using 2800 DEG C of smelting 20min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 98.3%.
Embodiment 36
Inactivation rhodium-containing homogeneous catalyst is distilled into 6.5h recycling organic matter at 260 DEG C and obtains rhodium enriched substance.Chromium, manganese are as conjunction
Gold element, the composition proportion of Rh, Fe, Mn are Rh:XRh- 1wt%, Fe:XFe+ 5wt%, Mn:XMn-4wt%,.Coal, graphite are as reduction
Agent, the additional amount of coal are the 50wt% of rhodium enriched substance, and the additional amount of graphite is the 10wt% of rhodium enriched substance.Silica, calcirm-fluoride,
For aluminium oxide as slag former, silica additional amount is the 2wt% of rhodium enriched substance, and calcirm-fluoride additional amount is the 8wt% of rhodium enriched substance,
Magnesia additional amount is the 10wt% of rhodium enriched substance.Above-mentioned raw materials mixing is placed in induction furnace melting 3.5h at 1450 DEG C.Through molten
The isolated Rh-Fe-Mn alloy of slag.Rh-Fe-Mn alloy carries out acidolysis and obtains rhodium powder, acidolysis condition are as follows: c (H+) it is 3mol/L,
30 DEG C of acidolysis temperature.Rhodium powder obtains rhodium ingot using 2600 DEG C of smelting 20min of electric arc furnaces.Through detecting, the rhodium rate of recovery reaches 99.1%.
Claims (10)
1. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst, which is characterized in that the described method comprises the following steps:
(1) organic matter in inactivation rhodium-containing homogeneous catalyst is recycled by the way of distillation, obtains rhodium enriched substance；
(2) transition metal M is mixed with rhodium enriched substance, reducing agent, slag former, obtains mixture；
(3) mixture for obtaining step (2) carries out melting, obtains Rh-M alloy and metallurgical slag；
(4) separation that Rh-M alloy is realized to rhodium and transition metal M by electrolysis or acidolysis, is obtained by filtration rhodium powder.
2. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that described
Inactivation rhodium-containing homogeneous catalyst is carbonylation synthesis rhodium-containing dead catalyst, hydroformylation reaction rhodium-containing dead catalyst, Cyclopropanated contains
One of rhodium dead catalyst and rhodium caprylate organic liquid waste or more than one.
3. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that step
It (1) include triphenylphosphine, triphenylphosphine oxide, acetylacetone,2,4-pentanedione, alcohol, acetic acid second by the organic matter that the way of distillation removes in
Ester, acetonitrile, methylene chloride, toluene and aldehyde one of condensation polymer or more than one；The condition of the way of distillation specifically: steam
Evaporating temperature is 100-350 DEG C, distillation time 1-10h.
4. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that step
(2) transition metal M described in be one of Fe, Co, Cr, Mn, Zr or more than one, the transition metal M and the rhodium are rich
The Rh mass for collecting object is respectively XM± 10% and XRh± 10%, XM、XRhThe respectively eutectic composition of Rh-M alloy.
5. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that described
Reducing agent is hydrogen or carbonizable substance, the carbonizable substance be one of coke, coal, graphite and charcoal or more than one；
When using hydrogen as reducing agent, control hydrogen flow rate is 10~100mL/min；When using carbonizable substance as reducing agent, control
The additional amount of carbonizable substance is 10 ~ 60wt.% of the rhodium enriched substance.
6. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that described
Slag former be one of calcium oxide, silica, calcirm-fluoride, aluminium oxide, magnesia, sodium carbonate and borax or more than one,
The additional amount of the slag former is 5 ~ 25wt.% of rhodium enriched substance.
7. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that step
(3) in, the condition of the melting is controlled are as follows: 800 ~ 1600 DEG C of smelting temperature, 1 ~ 6h of smelting time.
8. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that step
(4) in:
The isolated actual conditions of rhodium and transition metal M are realized using electrolysis are as follows: using Rh-M alloying substance as anode, with platinized platinum or
Titanium plate is cathode；Electrolytic condition are as follows: voltage -0.4 ~ 0.7V, electrolytic efficiency 80-98%, electrolysis temperature are 25 ~ 90 DEG C；
Using acidolysis realize rhodium and transition metal M isolated actual conditions are as follows: acid hydrolysis solution used in acidolysis be sulfuric acid, hydrochloric acid,
One of nitric acid, hydrofluoric acid or more than one, acidolysis condition are as follows: in acid hydrolysis solution hydrogen ion concentration be 1 ~ 8.0mol/L, acidolysis
20 ~ 90 DEG C of temperature.
9. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 1, which is characterized in that described
Method further includes step (5): obtaining rhodium ingot using rhodium powder described in electric arc furnace smelting.
10. a kind of method for recycling rhodium from inactivation rhodium-containing homogeneous catalyst according to claim 9, which is characterized in that institute
It states in step (5), electric arc furnace smelting condition are as follows: temperature is 2000-3000 DEG C, and the duration of heat is 5~30min.
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| CN111996387A (en) * | 2020-08-28 | 2020-11-27 | 昆明铂锐金属材料有限公司 | Enrichment and separation method of rhodium element in waste liquid containing low-concentration organic rhodium |
| CN113462900A (en) * | 2021-07-04 | 2021-10-01 | 贵研资源（易门）有限公司 | Method for recovering rhodium from waste rhodium park catalyst |
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