CN105543496B - F- T synthesis dead catalyst Co Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium - Google Patents

F- T synthesis dead catalyst Co Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium Download PDF

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CN105543496B
CN105543496B CN201511017626.4A CN201511017626A CN105543496B CN 105543496 B CN105543496 B CN 105543496B CN 201511017626 A CN201511017626 A CN 201511017626A CN 105543496 B CN105543496 B CN 105543496B
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filter residue
rhodium
filtrate
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aluminium
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CN105543496A (en
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饶莎莎
宋德臣
李昌元
海国良
郑申棵
李程根
詹晓东
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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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
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • C22B21/003—Obtaining aluminium by wet processes 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
    • 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
    • C22B7/009—General processes for recovering metals or metallic compounds 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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Abstract

The invention discloses a kind of F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium.The recovery method comprises the following steps：Dead catalyst is heated into reduction treatment；With the baking mixed processing of NaOH, the leaching that adds water, filtering obtain the first filtrate and the first filter residue；First filtrate obtains the second filter residue, the second filter residue calcination process obtains Al with being filtered after sulfuric acid solution reaction2O3；First filter residue obtains the 3rd filtrate and the 3rd filter residue with being filtered after dilute nitric acid reaction again, and the evaporation of the 3rd filtrate obtains crystal Co (NO3)2·6H2O；3rd filter residue carries out chlorination processing after being mixed with potassium chloride with chlorine, and gained solid adds water leaching, refilters and obtains the 4th filtrate；4th filtrate with filtering to obtain the 5th filter residue again after potassium hydroxide reaction；5th filter residue fully reacts with concentrated nitric acid, and reactant, which is evaporated, obtains Rh (NO3)3·2H2O.Make the Al of recovery using this method2O3Carrier, active metal and precious metal additive can save catalyst cost, it is to avoid the wasting of resources and environmental pollution again as the raw material for preparing new fischer-tropsch catalysts.

Description

F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium
Technical field
The invention belongs to F- T synthesis technical field, a kind of F- T synthesis dead catalyst Co-Rh/Al is specifically referred to2O3In The recovery method of metallic cobalt, rhodium and aluminium.
Background technology
Increasingly depleted with petroleum resources and the attention to environmental protection, synthesis gas is prepared by natural gas (coal bed gas) And synthesis gas is converted into clean fuel and high-quality wax with more and more important meaning by Fischer-Tropsch (F-T) synthetic reaction.
Fischer-Tropsch catalyst generally comprises active component, the carrier for supporting active component and improves catalyst performance Auxiliary agent.Wherein, active component is based on iron, cobalt, nickel, ruthenium and rhodium.Since 1926, two German scientist Fischer With Tropsch delivered iron catalyst and Co catalysts can be with artificial oil after, up to the present this is still most study Two kinds of metal catalyst metal rutheniums and rhodium are also typical Fischer-Tropsch catalyst, for ruthenium catalyst., it, which is catalyzed, lives Property highest, remarkable activity will be shown at 150 DEG C or so, it is easy to generate high carbon chain hydrocarbon product.But its is expensive, one As be used as improver.Rhodium is similar with ruthenium, is typically used as improver.And for Raney nickel, easily formed under high pressure Carbonyl nickel；With the rise of reaction temperature, it is easier to selectively produce substantial amounts of C1, therefore be not a kind of preferably production liquid The catalyst of fluid fuel.This phenomenon can also be observed that in Co catalysts and ruthenium catalyst, but unobvious.
The water gas shift reation activity of cobalt-base catalyst is relatively low, but has high activity and high selectivity to generation long chain hydrocarbons, More suitable for the F-T synthetic reactions using natural gas base synthesis gas as raw material.Therefore it has turned into the heat that F-T synthetic catalysts are studied Point.Al2O3The cobalt group catalyst synthesized carriers of F-T are often used as, its advantage is that mechanical strength is good, are particularly suitable for slurry bed system behaviour Make.In addition, cobalt/cobalt oxide and Al2O3The catalyst for preparing high degree of dispersion is also helped in the presence of stronger interaction between carrier, But this strong interaction makes Co/Al2O3The reduction degree of catalyst is relatively low.Many studies have shown that, adding a small amount of precious metal additive can To significantly improve Co/Al2O3The reducing property of catalyst.Price of the rhodium in platinum-group noble metals is most expensive and fluctuation is big, and rhodium is in solution In chemical property it is sufficiently complex, in refining process, be normally placed at last recovery, the dissolving of rhodium is also always platinum family with refining METAL EXTRACTION is refined and the problem in chemical analysis.
Cobalt, rhodium resource heavy dependence import due to China, it is expensive, ultimately result in catalyst cost higher.From useless Call Provision and rhodium auxiliary agent in catalyst, the catalyst reproduction loaded for cobalt-based, can not only reduce dead catalyst to environment Pollution, improve cobalt, the utilization rate of rhodium resource, and the production cost of Co catalysts can be significantly reduced, with good Environment benefits and economic gains.Also, at present major part catalyst using sial as main carriers, some catalyst contain aluminum oxide into Divide very high, therefore recovery prepares active aluminum oxide carrier again, can further reduce the cost of catalyst, this is to improve oxygen The important channel of change aluminium overall economic efficiency is also China's aluminum oxide industry environmental protection in the urgent need to social environment benefit It is huge.
Before the present invention, Publication No. CN101700913A Chinese invention patent application specification describes a kind of utilization The method that alumina load cobalt-based dead catalyst used for Fischer-Tropsch synthesis prepares high-purity cobalt nitrate, this method is molten including grinding, concentrated hydrochloric acid The step such as the heavy cobalt of solution, vulcanized sodium, oxalic acid heavy cobalt, calcining, nitric acid dissolving, evaporative crystallization, finally gives high-purity Co (NO3)2· 6H2O.Publication No. CN 101270420A Chinese invention patent application specification describes a kind of co-based fischer-tropsch synthesis catalytic The recovery method of cobalt in agent, this method is that deionized water and the dead catalyst of Fischer-Tropsch containing cobalt are added into reaction for 1~5 ︰ 1 in mass ratio In kettle, CO gas is passed through in reactor, its partial pressure is between 0.5MPa~5MPa, and low whipping speed is 50~700 revs/min Under conditions of clock and 50~200 DEG C of heating, 0.5~12h of constant temperature；Cooling releases CO from reactor, arranges water from reactor After removing, lye solution is added in water, cobalt is precipitated as Co (OH)2；Nitric acid dissolving is added in precipitation, evaporative crystallization obtains nitre Sour cobalt.Publication No. CN 101260469A Chinese invention patent application specification describes a kind of from the waste material of platiniferous rhodium The method of Purification of Platinum rhodium, this method removes base metal using ion-exchange process, then solvent extraction, extration resin isolation technics It is combined together separating-purifying noble metal platinum rhodium；But this method process and complex steps, waste material Pretreatment harshness.It is open Number describe a kind of recovery method of rhodium catalyst for CN103498056A Chinese invention patent application specification, this method with Active metal is displacer, rhodium in solution is separated with precipitation form with rhodium catalyst waste liquid；But this method is applied to Rhodium exists in the form of rhodium compound in catalyst, and rhodium catalyst has been treated as liquid, in addition, this method may draw Enter active metal compound impurities.
In summary, existing patented technology has Call Provision, also has and reclaims rhodium, but these patented technologies can only be single Only Call Provision or rhodium, are not directed to the technology reclaimed together to carrier, active metal and precious metal additive, so neither It can maximize the recovery value of dead catalyst, can also generate detrimental effect to environment.How in same technological process Reclaim effectively and synchronously F- T synthesis dead catalyst Co-Rh/Al2O3In metallic cobalt, rhodium and aluminium, be always people in the art The problem that member faces.
The content of the invention
Present invention aim to provide a kind of F- T synthesis dead catalyst Co-Rh/Al2O3Middle metallic cobalt, rhodium and aluminium Recovery method, and make the Al of recovery2O3Carrier, active metal and precious metal additive can again be used as and prepare new fischer-tropsch catalysts Raw material, to save catalyst cost, it is to avoid the wasting of resources and environmental pollution.
To achieve the above object, the F- T synthesis dead catalyst Co-Rh/Al designed by the present invention2O3Middle metallic cobalt, rhodium and The recovery method of aluminium, comprises the following steps：
1) by dead catalyst Co-Rh/Al2O3Heating reduction treatment is carried out after fired removal of impurities；
2) dead catalyst after reduction treatment is well mixed and the calcination process at 750~900 DEG C with appropriate NaOH, so After add water leaching, filtering, respectively obtain the first filtrate and the first filter residue；
3) to step 2) gained the first filtrate in be added dropwise sulfuric acid solution to pH=6~7, fully reaction after refilter, obtain Second filtrate and the second filter residue, then gained the second filter residue calcination process is obtained into solids, it is Al2O3；
4) to step 2) gained the first filter residue in enough dust technologies are added dropwise, fully reaction after again filter, obtain the 3rd filtrate With the 3rd filter residue, by the 3rd filtrate evaporative crystallization, crystal thing is obtained, is Co (NO3)2·6H2O；
5) by step 4) gained the 3rd filter residue and drying processing after be well mixed with potassium chloride, in 500~700 DEG C of conditions and chlorine Gas carry out chlorination processing, chlorination processing after solid be added to the water leaching processing, then filter again, obtain the 4th filter residue With the 4th filtrate；
6) to step 5) obtained by the 4th filtrate in add potassium hydroxide to pH value of solution=7~9, fully reaction after carry out again Secondary filtering, obtains the 5th filtrate and the 5th filter residue；
7) to step 6) obtained by add excessive concentrated nitric acid in the 5th filter residue and fully react, then reactant is evaporated It is Rh (NO to solid3)3·2H2O。
Any of following scheme can be used as further preferred scheme：
Step 1) in, the roasting removal of impurities is by dead catalyst Co-Rh/Al2O3It is placed in Muffle furnace, at 400~600 DEG C 2~5h of lower roasting.
Step 1) in, the reduction treatment gas used during the heating reduction treatment is H2、N2Gaseous mixture.
Step 1) in, the heating reduction treatment is to carry out in a fluidized bed reactor, H in reducing gas2︰ N2Volume ratio For 1~3 ︰ 1, air speed is 1500~3500h-1, temperature is 350~750 DEG C, and the recovery time is 2~10h.
Step 2) in, the NaOH and dead catalyst Co-Rh/Al2O3Mass ratio be 0.8~2 ︰ 1.
Step 2) in, the leaching that adds water uses temperature for 90~110 DEG C of distillation water extraction.
Step 2) in, it is described add water leaching when water and dead catalyst mass ratio be 1~3 ︰ 1, leaching time be 5~ 60min。
Step 3) in, the concentration of the sulfuric acid solution is 0.5~2mol/L.
Step 3) in, the calcination process of second filter residue is in 4~8h of roasting at 500~700 DEG C in Muffle furnace.
Step 4) in, the dust technology concentration is 0.5~2mol/L.
Step 5) in, when being mixed after the 3rd filter residue and drying processing with potassium chloride, the potassium chloride and the 3rd filter residue Mass ratio is 2~3 ︰ 1.
Step 5) in, the chlorination processing time is 30~100min.
Step 5) in, the solid after chlorination processing be added to the water leaching processing when, the mass ratio of water and solid is 1 ~3 ︰ 1, leach 10~60min.
Step 7) in, the mass percent concentration of the concentrated nitric acid is 35~65%
The F- T synthesis dead catalyst Co-Rh/Al of the present invention2O3Each step reaction of recovery method of middle metallic cobalt, rhodium and aluminium Principle is as follows：
Step 2) in, the NaOH is with the dead catalyst reaction equation after reduction treatment：
2NaOH+Al2O3=Na2O·Al2O3+H2O；
Add water leaching when water and the key reaction of dead catalyst be：
Na2O·Al2O3+ aq=2NaAl (OH)4+aq；
Step 3) in, the reaction equation of sulfuric acid and sodium metaaluminate is：
2NaAl(OH)4+H2SO4=Na2SO4+2Al(OH)3↓+2H2O；
Step 4) in, the reaction equation of generation is：
Co+HNO3=Co (NO3)2+H2↑。
Step 5) in, the reaction equation of chlorination processing is：
2Rh+4KCl+3Cl2=2K2RhCl5；
Chlorination processing after solid be with water reaction equation：
K2RhCl5+H2O=K2[Rh(H2O)Cl5]。
Step 6) in, the reaction equation occurred after hydrogenation sodium oxide molybdena is：
K2[Rh(H2O)Cl5]+3KOH=Rh (OH)3↓+5KCl+H2O。
Step 7) in, the concentrated nitric acid and Rh (OH)3The key reaction equation of filter residue is
Rh(OH)3+3HNO3=Rh (NO3)3+H2O。
The advantageous effects of the present invention are：
1) present invention firstly provides the method for synthetical recovery Call Provision, rhodium and aluminium from dead catalyst, technique is simple, operation Safety, cost are low, suitable for industrialized production.2) method of Call Provision, rhodium and aluminium, metal from dead catalyst that the present invention is provided The rate of recovery it is high, wherein cobalt maximum recovery is 98.53%, and rhodium maximum recovery is 98.41%, and aluminium maximum recovery is 95.19%.3) method of Call Provision, rhodium and aluminium from dead catalyst that the present invention is provided, the Co (NO of recovery3)2·6H2O purity Close to 99%, the aluminum oxide of recovery has reached the quality requirement of national standard stair oxidation aluminium, the rhodium nitrate purity of recovery for 95% with On.These raw materials reclaimed can be directly used for preparing catalyst, dead catalyst has been obtained effective utilization.It was verified that The present invention will be to Fischer-Tropsch dead catalyst Co-Rh/Al2O3Carrier, active metal and precious metal additive carry out synthetical recovery, and make Carrier, active metal and the precious metal additive of recovery could act as preparing the raw material of fischer-tropsch catalysts, save cost, it is to avoid The wasting of resources and environmental pollution.
Brief description of the drawings
Fig. 1 is a kind of F- T synthesis dead catalyst Co-Rh/Al2O3The technique stream of the recovery method of middle metallic cobalt, rhodium and aluminium Cheng Tu.
Embodiment
Below in conjunction with the accompanying drawings with specific embodiment to F- T synthesis dead catalyst Co-Rh/Al of the present invention2O3Middle metallic cobalt, rhodium It is described in further detail with the recovery method of aluminium.
Embodiment 1
A kind of F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium, operating process is for example attached Shown in Fig. 1, comprise the following steps：
1) dead catalyst pre-treatment：Weigh 60g dead catalyst Co-Rh/Al2O3(wherein mass content is cobalt：19.88%, Rhodium：1.1%, aluminium：40.11%) it is placed in Muffle furnace, roasting removal of impurities processing 2h is carried out at 600 DEG C, then by obtained useless catalysis Agent is ground to after 100~300 mesh, is transferred in fluidized-bed reactor, and dead catalyst is carried out into reduction treatment, its reduction treatment gas Body is H2︰ N2Volume ratio is 1 ︰ 1 mixed gas, and air speed is 1500h-1, temperature is 350 DEG C, and the recovery time is 10h；
2) a certain amount of NaOH will be added in the dead catalyst after reduction treatment to mix, wherein NaOH and catalysis of giving up after reduction The mass ratio of agent is 0.8 ︰ 1, and mixed material is placed in Muffle furnace, in calcination process 4h at 750 DEG C, room temperature is cooled to Afterwards, the quality, temperature such as add it to in 90 DEG C of distilled water, after leaching 60min, suction filtration obtains the first filtrate and the One filter residue；
3) aluminum oxide is reclaimed：Be added dropwise concentration for 0.5mol/L sulfuric acid in above-mentioned steps 2) gained the first filtrate in, regulation PH=6~7, filter after reaction, obtain the second filtrate and the second filter residue, will dry 3h at 90 DEG C after the residue washing of gained second, In being calcined at 550 DEG C after 8h in Muffle furnace, 43.55g solid is obtained, main component is Al2O3, wherein measuring aluminum oxide Weight/mass percentage composition is 99.02%, and the rate of recovery of aluminium is 94.88%；
4) cobalt nitrate is reclaimed：Quality is weighed for step 2) dust technology of 6 times of the first filter residue quality of gained, it is added drop-wise to the first filter In slag, during wherein the concentration of nitric acid is 0.5mol/L, react after 120min, but suction filtration, the 3rd filtrate and the 3rd filter residue are obtained, will The filtrate evaporative crystallization of gained the 3rd, obtains 58.35g solid, and main component is Co (NO3)2·6H2O, wherein measuring six water nitre Sour cobalt weight/mass percentage composition is 99.10%, and the rate of recovery of cobalt is 98.12%；
5) rhodium nitrate is reclaimed：Quality is weighed for step 4) potassium chloride of 2 times of the 3rd filter residue quality of gained, it is mixed with the 3rd filter residue Close, be ground to 150~300 mesh, mixture is placed in chlorination furnace and is passed through chlorine progress chlorination processing, temperature is 500 DEG C, time For 100min, in the distilled water of quality such as the solid after chlorination is handled is added to, 60min is leached；Then filter, obtain again To the 4th filtrate and the 4th filter residue；
6) to step 5) potassium hydroxide is added in the 4th filtrate of gained, adjust pH value of solution=7, fully filtration washing after reaction Into filtrate without potassium ion, this step is filtrated to get the 5th filtrate and the 5th filter residue；
7) to step 6) gained the 5th filter residue in add excessive mass percent concentration be 35% concentrated nitric acid, 120 Flowed back 3h at DEG C, and solution is evaporated at 70 DEG C and can obtain 2.1g solid Rh (NO3)3·2H2O, wherein measuring two water nitric acid The weight/mass percentage composition of rhodium is 95.1%, and the yield of rhodium is 95.88%.
Embodiment 2
A kind of F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method method of middle metallic cobalt, rhodium and aluminium, operating process As shown in Figure 1, comprise the following steps：
1) dead catalyst pre-treatment：Weigh 60g dead catalyst Co-Rh/Al2O3(wherein mass content is cobalt：25.03%, Rhodium：1.6%, aluminium：42.56%) it is placed in Muffle furnace, roasting removal of impurities processing 6h is carried out at 400 DEG C, then by obtained useless catalysis Agent is ground to after 100~300 mesh, is transferred in fluidized-bed reactor, and dead catalyst is reduced, its reduction treatment gas be for H2︰ N2Volume ratio is 2 ︰ 1 mixed gas, and air speed is 3500h-1, temperature is 750 DEG C, and the recovery time is 2h；
2) a certain amount of NaOH will be added in the dead catalyst after reduction treatment to mix, wherein NaOH and catalysis of giving up after reduction The mass ratio of agent is 2 ︰ 1, and mixed material is placed in Muffle furnace, in calcination process 1h at 900 DEG C, is cooled to after room temperature, Add it in distilled water that quality is 3 times of solid masses, that temperature is 110 DEG C, after leaching 5min, suction filtration obtains first Filtrate and the first filter residue；
3) aluminum oxide is reclaimed：Be added dropwise concentration for 1mol/L sulfuric acid in above-mentioned steps 2) gained the first filtrate in, adjust pH =6~7, filtered after reaction, obtain the second filtrate and the second filter residue, 1h will be dried at 120 DEG C after the residue washing of gained second, then In being calcined at 650 DEG C after 6h in Muffle furnace, 46.21g solid is obtained, main component is Al2O3, wherein measuring aluminum oxide It is 99.15% to measure percentage composition, and the rate of recovery of aluminium is 94.99%；
4) cobalt nitrate is reclaimed：Quality is weighed for step 2) dust technology of 6 times of the first filter residue quality of gained, it is added drop-wise to the first filter In slag, during wherein the concentration of nitric acid is 1mol/L, react after 30min, and suction filtration, the 3rd filtrate and the 3rd filter residue are obtained, by institute The 3rd filtrate evaporative crystallization is obtained, 73.52g solids are obtained, main component is Co (NO3)2·6H2O, wherein measuring cobalt nitrate hexahydrate Weight/mass percentage composition is 99.25%, and the rate of recovery of cobalt is 98.33%；
5) rhodium nitrate is reclaimed：Quality is weighed for step 4) potassium chloride of 2 times of the 3rd filter residue quality of gained, it is mixed with the 3rd filter residue Close, be ground to 150~300 mesh, mixture is placed in chlorination furnace and is passed through chlorine progress chlorination processing, temperature is 700 DEG C, time For 30min, the solid after chlorination is handled is added in distilled water, and wherein the mass ratio of distilled water and solid is 3 ︰ 1, leaching 10min；Then filter again, obtain the 4th filtrate and the 4th filter residue；
6) to step 5) potassium hydroxide is added in the 4th filtrate of gained, adjust pH value of solution=8, fully filtration washing after reaction Into filtrate without potassium ion, this step is filtrated to get the 5th filtrate and the 5th filter residue；
7) to step 6) gained the 5th filter residue in add excessive mass percent concentration be 50% concentrated nitric acid, 120 Flowed back 1h at DEG C, and solution is evaporated at 100 DEG C, obtains 3.05g solid Rh (NO3)3·2H2O, wherein measuring two water nitric acid The weight/mass percentage composition of rhodium is 96.03%, and the yield of rhodium is 96.65%.
Embodiment 3
A kind of F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method method of middle metallic cobalt, rhodium and aluminium, operating process As shown in Figure 1, comprise the following steps：
1) dead catalyst pre-treatment：Weigh 60g dead catalyst Co-Rh/Al2O3(wherein mass content is cobalt：15.88%, Rhodium：0.5%, aluminium：44.35%) it is placed in Muffle furnace, roasting removal of impurities processing 4h is carried out at 500 DEG C, then by obtained useless catalysis Agent is ground to after 100~300 mesh, is transferred in fluidized-bed reactor, and dead catalyst is reduced, and its reduction treatment gas is H2︰ N2 Volume ratio is 3 ︰ 1 mixed gas, and air speed is 3500h-1, temperature is 600 DEG C, and the recovery time is 5h；
2) a certain amount of NaOH will be added in the dead catalyst after reduction treatment to mix, wherein NaOH and catalysis of giving up after reduction The mass ratio of agent is 1.3 ︰ 1, and mixed material is placed in Muffle furnace, in calcination process 2h at 850 DEG C, room temperature is cooled to Afterwards, add it in distilled water that quality is 2 times of solid masses, that temperature is 100 DEG C, after leaching 30min, suction filtration is obtained First filtrate and the first filter residue；
3) aluminum oxide is reclaimed：Be added dropwise concentration for 2mol/L sulfuric acid in above-mentioned steps 2) gained the first filtrate in, adjust pH =6~7, filtered after reaction, obtain the second filtrate and the second filter residue, 2h will be dried at 100 DEG C after the residue washing of gained second, then In being calcined at 700 DEG C after 4h in Muffle furnace, 48.23g solid is obtained, main component is Al2O3, wherein measuring aluminum oxide It is 99.20% to measure percentage composition, and the rate of recovery of aluminium is 95.18%；
4) cobalt nitrate is reclaimed：Quality is weighed for step 2) dust technology of 4 times of the first filter residue quality of gained, it is added drop-wise to the first filter In slag, during wherein the concentration of nitric acid is 2mol/L, react after 80min, and suction filtration, the 3rd filtrate and the 3rd filter residue are obtained, by institute The 3rd filtrate evaporative crystallization is obtained, 46.66g solid, main component Co (NO is obtained3)2·6H2O, wherein measuring cobalt nitrate hexahydrate Weight/mass percentage composition is 99.23%, and the rate of recovery of cobalt is 98.35%；
5) rhodium nitrate is reclaimed：Quality is weighed for step 4) 2 times of potassium chloride of the 3rd filter residue quality of gained, by itself and the 3rd Filter residue is mixed, and is ground to 150~300 mesh, and mixture is placed in chlorination furnace and is passed through chlorine progress chlorination processing, temperature is 600 DEG C, the time is 70min, and the solid after chlorination is handled is added in distilled water, and wherein the mass ratio of distilled water and solid is 2 ︰ 1, leach 40min；Then filter again, obtain the 4th filtrate and the 4th filter residue；
6) to step 5) potassium hydroxide is added in the 4th filtrate of gained, adjust pH value of solution=9, fully filtration washing after reaction Into filtrate without potassium ion, this step is filtrated to get the 5th filtrate and the 5th filter residue；
7) to step 6) gained the 5th filter residue in add excessive mass percent concentration be 65% concentrated nitric acid, 100 Flowed back 2h at DEG C, and solution is evaporated at 90 DEG C, obtains 0.96g solid Rh (NO3)3·2H2O, wherein measuring two water nitric acid The weight/mass percentage composition of rhodium is 96.38%, and the yield of rhodium is 97.64%.
Embodiment 4
A kind of F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method method of middle metallic cobalt, rhodium and aluminium, operating process As shown in Figure 1, comprise the following steps：
1) dead catalyst pre-treatment：Weigh 60g dead catalyst Co-Rh/Al2O3(wherein mass content is cobalt：20.13%, Rhodium：1.15%, aluminium：42.55%) it is placed in Muffle furnace, removal of impurities processing 2h is calcined at 600 DEG C, then by obtained dead catalyst It is ground to after 100~300 mesh, is transferred in fluidized-bed reactor, dead catalyst is reduced, its reduction treatment gas is H2︰ N2Body Product is than the mixed gas for 2 ︰ 1, and air speed is 3500h-1, temperature is 750 DEG C, and the recovery time is 2h；
2) a certain amount of NaOH will be added in the dead catalyst after reduction treatment to mix, wherein NaOH and catalysis of giving up after reduction The mass ratio of agent is 1 ︰ 1, and mixed material is placed in Muffle furnace, in calcination process 2h at 800 DEG C, is cooled to after room temperature, Add it in distilled water that quality is 1.8 times of solid masses, that temperature is 95 DEG C, after leaching 25min, suction filtration obtains the One filtrate and the first filter residue；
3) aluminum oxide is reclaimed：Be added dropwise concentration for 2mol/L sulfuric acid in above-mentioned steps 2) gained the first filtrate in, adjust pH =6~7, filtered after reaction, obtain the second filtrate and the second filter residue, 2h will be dried at 100 DEG C after the residue washing of gained second, then In being calcined at 700 DEG C after 4h in Muffle furnace, 46.13g solid is obtained, main component is Al2O3, wherein measuring aluminum oxide It is 99.50% to measure degree, and the rate of recovery of aluminium is 95.19%；
4) cobalt nitrate is reclaimed：Quality is weighed for step 2) 6 times of dust technology of the first filter residue quality of gained, it is added drop-wise to first In filter residue, during wherein the concentration of nitric acid is 2mol/L, react after 80min, but suction filtration, the 3rd filtrate and the 3rd filter residue are obtained, will The filtrate evaporative crystallization of gained the 3rd, obtains 59.23g solid, and main component is Co (NO3)2·6H2O, wherein measuring six water nitre Sour cobalt weight/mass percentage composition is 99.28%, and the rate of recovery of cobalt is 98.53%；
5) rhodium nitrate is reclaimed：Quality is weighed for step 4) potassium chloride of 2 times of the 3rd filter residue quality of gained, it is mixed with the 3rd filter residue Close, be ground to 150~300 mesh, mixture is placed in chlorination furnace and is passed through chlorine progress chlorination processing, temperature is 550 DEG C, time For 60min, the solid after chlorination is handled is added in distilled water, and wherein the mass ratio of distilled water and solid is 2 ︰ 1, leaching 60min；Then refilter once, obtain the 4th filtrate and the 4th filter residue；
6) to step 5) potassium hydroxide is added in the 4th filtrate of gained, adjust pH value of solution=9, fully filtration washing after reaction Into filtrate without potassium ion, this step is filtrated to get the 5th filtrate and the 5th filter residue；
7) to step 6) gained the 5th filter residue in add excessive mass percent concentration be 65% concentrated nitric acid, at 90 DEG C Lower backflow 2h, solution is evaporated at 75 DEG C, obtains 2.21g solids Rh (NO3)3·2H2O, wherein measuring two water rhodium nitrates Mass percentage content be 96.88%, the yield of rhodium is 98.41%.

Claims (11)

1. a kind of F- T synthesis dead catalyst Co-Rh/Al2O3The recovery method of middle metallic cobalt, rhodium and aluminium, it is characterised in that：Including Following steps：
1) by dead catalyst Co-Rh/Al2O3Heating reduction treatment is carried out after fired removal of impurities；
2) dead catalyst after reduction treatment is well mixed and the calcination process at 750~900 DEG C with appropriate NaOH, Ran Houjia Water extraction, filtering, obtain the first filtrate and the first filter residue；The NaOH and dead catalyst Co-Rh/Al2O3Mass ratio be 0.8 ~2 ︰ 1；
3) to step 2) gained the first filtrate in be added dropwise sulfuric acid solution to pH=6~7, fully reaction after refilter, obtain second Filtrate and the second filter residue, obtain solids by gained the second filter residue calcination process, are Al2O3；
4) to step 2) enough dust technologies are added dropwise in the first filter residue of gained, fully filtered again after reaction, obtain the 3rd filtrate and the Three filter residues, by the filtrate evaporative crystallization of gained the 3rd, obtain crystal thing, are Co (NO3)2·6H2O；
5) by step 4) gained the 3rd filter residue and drying processing after be well mixed with potassium chloride, enter in 500~700 DEG C of conditions with chlorine Row chlorination handle, the chlorination processing time be 30~100min, chlorination processing after solid be added to the water leaching processing, so Filter again afterwards, obtain the 4th filtrate and the 4th filter residue, when the 3rd filter residue is mixed with potassium chloride, the potassium chloride and The mass ratio of three filter residues is 2~3 ︰ 1；
6) to step 5) gained the 4th filtrate in add potassium hydroxide to pH value of solution=7~9, fully reaction after carry out mistake again Filter, obtains the 5th filtrate and the 5th filter residue；
7) to step 6) add excessive concentrated nitric acid and fully react in the 5th filter residue of gained, then reactant is evaporated and consolidated Body, is Rh (NO3)3·2H2O。
2. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 1) in, the roasting removal of impurities is by dead catalyst Co-Rh/Al2O3It is placed in Muffle furnace, at 400~600 DEG C 2~5h of lower roasting.
3. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 1) in, the reducing gas that the heating reduction treatment is used is H2、N2Gaseous mixture.
4. F- T synthesis dead catalyst Co-Rh/Al according to claim 32O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 1) in, the heating reduction treatment is to carry out in a fluidized bed reactor, H in reducing gas2︰ N2Volume ratio For 1~3 ︰ 1, air speed is 1500~3500h-1, temperature is 350~750 DEG C, and the recovery time is 2~10h.
5. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 2) in, the leaching that adds water uses temperature for 90~110 DEG C of distillation water extraction.
6. F- T synthesis dead catalyst Co-Rh/Al according to claim 52O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 2) in, it is described add water leaching when water and dead catalyst mass ratio be 1~3 ︰ 1, leaching time be 5~ 60min。
7. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 3) in, the concentration of the sulfuric acid solution is 0.5~2mol/L.
8. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 3) in, the calcination process of second filter residue is in 4~8h of roasting at 500~700 DEG C in Muffle furnace.
9. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, its It is characterised by：Step 4) in, the dust technology concentration is 0.5~2mol/L.
10. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, It is characterized in that：Step 5) in, the solid after chlorination processing be added to the water leaching processing when, the mass ratio of water and solid For 1~3 ︰ 1,10~60min is leached.
11. F- T synthesis dead catalyst Co-Rh/Al according to claim 12O3The recovery method of middle metallic cobalt, rhodium and aluminium, It is characterized in that：Step 7) in, the mass percent concentration of the concentrated nitric acid is 35~65%.
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