CN109837393A - A kind of selective recovery is given up the method for valuable metal in hydrogenation catalyst - Google Patents
A kind of selective recovery is given up the method for valuable metal in hydrogenation catalyst Download PDFInfo
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Abstract
The present invention provides the methods of valuable metal in a kind of useless hydrogenation catalyst of selective recovery, this method will first crush after useless hydrogenation catalyst high-temperature calcination, obtain valuable metal recovery material, valuable metal recovery material is subjected to first time leaching using ammonia-ammonium salt solution again, the first leachate and the first leached mud are obtained after being separated by solid-liquid separation for the first time, the pH of the first leachate is adjusted to molybdenum precipitation value, second of separation of solid and liquid obtains molybdic acid and the second leachate, alkali is added into the second leachate, precipitating nickel precipitating, after first leached mud is carried out alkali leaching using ammonia-ammonium salt solution, third time, which is separated by solid-liquid separation, obtains oxidation aluminium slag and third leachate, the pH of third leachate is adjusted to ammonium metavanadate precipitation value.Method choice provided by the invention is high, the mass percentage content of molybdenum, nickel, vanadium in the catalyst can be made to be reduced to 0.5%, 2% and 3% respectively molybdenum, nickel, vanadium and aluminium successively selective recovery, and rate of recovery height.
Description
Technical field
The invention belongs to dead catalyst reutilization technology fields, and in particular to a kind of selective recovery is given up in hydrogenation catalyst
The method of valuable metal.
Background technique
Hydrogenation catalyst refers to the catalyst used when compound and hydrogen addition, and there are commonly the VIIIth group 4 transition metal elements
Metallic catalyst, metal oxide or sulfide catalyst, complex catalyst, generally alumina support.
As catalyst uses the extension of time, since poisoning, sintering and heat inactivation, coking and blocking are so as to cause catalysis
Agent itself component, structure are changed, and are eventually resulted in catalyst activity reduction or are failed to continue to use, it has to
The catalyst more renewed, this creates the terminal a large amount of dead catalyst.It is disposed and random heap if these dead catalyst are not added
If setting, a large amount of land resource on the one hand can be occupied, increases the management cost of enterprise；On the other hand, catalyst was using
The adsorbed some poisonous and harmful substances of Cheng Dangzhong and some metallic elements contained by itself can due to various effects and into
Enter to natural environment, brings serious pollution to environment；Furthermore it is organic that dead catalyst contains a large amount of oil, sulfide, carbon etc.
Object, such as mishandling, Yi Fasheng spontaneous combustion.
Contain a large amount of non-ferrous metal, such as W, Mo, Ni, Co, V and Al in useless hydrogenation catalyst, effectively disposition was refined oil
Useless hydrogenation catalyst in journey recycles valuable metal element therein, and it is nervous to be conducive to alleviate resource, increases economic efficiency and ring
Protect benefit, realize sustainable development, and if recycle valuable metal be directly recycled in catalyst preparation, can also reduce
Production cost.Currently, organic solvent extractionprocess technology is more mature, the advantages of method is rate of recovery height, generally be can achieve
99% or more, and the good product quality recycled, purity is high can be applied directly, however, having used in organic solvent extractionprocess
Solvent needs to recycle comprehensive use, and process flow is relative complex.In addition, there are also ion-exchange, chlorination factures etc..It is existing
Main problem existing for technology has: (1) technical process and experimental facilities are complicated, and energy consumption is high；(2) it is primarily upon single metal mostly
Recycling, residual metallic part and carrier can only be used as residue treatment, and selectivity is not strong, and there are the waste of resource and the energy.
Therefore, it in order to effectively recycle the non-ferrous metal in useless hydrogenation catalyst, still needs to develop a kind of new method.
Summary of the invention
To solve problems of the prior art, it gives up the purpose of the present invention is to provide a kind of selective recovery plus hydrogen is urged
The method of valuable metal in agent.
To achieve the above object, the invention adopts the following technical scheme:
A kind of selective recovery is given up the method for valuable metal in hydrogenation catalyst, and step includes:
(1) it will be crushed after useless hydrogenation catalyst high-temperature calcination, obtain valuable metal recovery material；
(2) the valuable metal recovery material for obtaining step (1) carries out first time leaching using ammonia-ammonium salt solution, for the first time
The first leachate and the first leached mud are obtained after separation of solid and liquid；
(3) to molybdenum precipitation value, second of separation of solid and liquid obtains molybdic acid and second and soaks the pH of (2) first leachate of regulating step
Liquid out；
(4) alkali, precipitating nickel precipitating are added in the second leachate obtained to step (3)；
(5) after the first leached mud of step (2) being carried out alkali leaching using ammonia-ammonium salt solution, third time is separated by solid-liquid separation and obtains
Aluminium slag and third leachate are aoxidized, adjusts the pH of third leachate to ammonium metavanadate precipitation value.
Preferably, the temperature of step (1) described high-temperature calcination is 400~700 DEG C, and the time is 1~4h.
High-temperature burning process can remove the most sulphur and carbon contained in dead catalyst.
Under normal conditions, for sulphur, 150~200 DEG C start burn sulphur, 200~250 DEG C of burning sulphur are most, then with
The raising burning sulphur of temperature is slack-off, could burn out when 650~700 DEG C.
For charcoal, 300~350 DEG C start to make charcoal, 450 DEG C of basic burning-ups.
Catalyst color under high-temperature calcination is gradually turned yellow by black or light green color as the temperature rises, sulphur
Content is dropped to from being greater than 5.3% less than 0.5%.It is big from increasing to less than 24.71% with calcined rate of mass reduction before calcining
In 39.15%.
When calcining heating, due to containing carbon and sulphur in useless hydrogenation catalyst, liter should be controlled according to conventional methods in the art
Warm speed prevents from causing temperature runaway.
The smashed partial size of dead catalyst is less than 100 mesh.
Preferably, total ammonia density of step (2) ammonia-ammonium salt solution is 2~8mol/L.
In ammonia-ammonium salt solution, ammonium salt is one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate.
Preferably, the pH that step (2) first time leaches is 8~11.
Preferably, step (2) the valuable metal recovery material and ammonia-ammonium salt solution solid-to-liquid ratio are 1:(5~40).
Preferably, the temperature that step (2) first time leaches is 25~75 DEG C, the time leached for the first time is 20~
200 min。
It is more abundant in order to make to leach when leach for the first time in step (2), it can be with the speed of 200~600rpm
It is stirred.
Preferably, step (3) the molybdenum precipitation value is 1.5~3.
In step (3), after pH is adjusted to 1.5~3, molybdenum is precipitated in the form of molybdic acid, is separated by solid-liquid separation obtained molybdenum for the second time
Acid calcines 1~3h at 300~700 DEG C, and molybdic acid is decomposed into the oxide of molybdenum.
In step (3), being separated by solid-liquid separation obtained molybdic acid for the second time can first be washed with alcohol reagent, use alcohol reagent
Washed, thus it is possible to vary the pattern of oxide, conducive to the formation of porous oxides material, purity can maintain 95% with
On.
In step (4), alkali is added in the second leachate for obtaining to step (3), nickel is with nickel hydroxide or basic nickel carbonate
Form as Precipitation, recycled.
The alkali added in step (4) includes the mixture of sodium hydroxide, potassium hydroxide, sodium carbonate or in which the two.
Preferably, the pH range of step (5) alkali leaching is 10~12, total 4~8mol/L of ammonia density, by adjust ammonia and
The proportion of ammonium salt adjusts pH.
It is further preferred that oxidant can be added when soaking in alkali, the leaching rate of subsequent vanadium is can be improved in the addition of oxidant.
It is further preferred that oxidant includes in sodium chlorate, sodium hypochlorite, iron chloride, potassium permanganate and hydrogen peroxide
At least one.
Preferably, step (5) the vanadium precipitation value is 7.5~9.
In step (5), can first the first leached mud of step (2) be washed and be dried, then use ammonia-ammonium salt solution
Carry out alkali leaching.Drying condition is 60~100 DEG C, and drying time is 2~20h.
Preferably, in the useless hydrogenation catalyst, molybdenum content is greater than 15wt%, and nickel content is greater than 6wt%, and content of vanadium is greater than
11wt%, aluminium content are 24~32wt%.
In step (5), there are two ways to pH of third leachate is to ammonium metavanadate precipitation value is adjusted, a kind of method is logical
The mode of pervaporation ammonia makes the pH of third leachate be adjusted to ammonium metavanadate precipitation value, and the temperature for evaporating ammonia is 90~200
DEG C, the ammonia being evaporated can recycle；Another method is acid to be added into third leachate to adjust, and can be added
Acid include nitric acid, hydrochloric acid and sulfuric acid.
In step (5), after ammonium metavanadate is precipitated to ammonium metavanadate precipitation value in the pH of adjusting third leachate, by metavanadic acid
Ammonium calcines 1~3h at 300~700 DEG C and obtains the oxide of vanadium.
It is 4~8mol/L that first time leaching in step (2) and the alkali leaching in step (5), which are using total ammonia density,
Ammonia-ammonium salt solution leaches, the difference is that, when being leached for the first time in step (2) ammonia-ammonium salt solution pH be 8~
10, and ammonia-ammonium salt solution pH is 10~12 when alkali leaching in step (5).
The useless hydrogenation catalyst handled through the method for the present invention, can be such that the mass percent of molybdenum, nickel, vanadium in the catalyst contains
Amount is reduced to 0.5%, 2%, 3% respectively, and the content enrichment of aluminium in the catalyst is made to be promoted to 74%.
Useless hydrogenation catalyst of the present invention is referred to since poisoning, sintering and heat inactivation, coking and blocking are to draw
Play that itself component, structure are changed and to eventually lead to catalyst activity reduction or fail to continues to use plus hydrogen de-
Sulphur or hydrodenitrogeneration dead catalyst, which is mainly Ni, Mo, V, and other than active metal, there are also few
Measure the impurity such as heavy metals and carbon distribution such as silicon, phosphorus, sulphur, calcium, iron, copper.Generally in 5-40%, shape is usually the content of valuable metal
Cylinder, it is spherical or multi-leaf-shaped.
Beneficial effects of the present invention
1, compared with prior art, present invention uses ammonia-ammonium salt solution, the solution is very low for the leaching rate of aluminium, and
The value of aluminium is relatively cheap for other three kinds of metals, it is ensured that aluminium stays in slag, and ammonia can with other three
Kind metal forms complex and leaches into solution；
It 2, directly can be by nickel, molybdenum, vanadium selectivity by changing the pH of leachate using method provided by the present invention
Carry out precipitate, process is simple；
3, ammonia used is leached, can be entered in the leaching experiment of next round and be continued with by way of evaporation, more
Add economy, not having to ammonium salt is additionally added again in the forming process of subsequent ammonium molybdate and ammonium metavanadate makes its precipitating, also embodies letter
Single economic principle；
4, in the prior art, conventional useless hydrogenation catalyst usually have high pollution, high energy consumption, the rate of recovery low and selectivity not
Strong feature, and method choice provided by the invention is high, it can be by molybdenum, nickel, vanadium and aluminium successively selective recovery, and recycling
Rate is high, and the mass percentage content of molybdenum, nickel, vanadium in the catalyst can be made to be reduced to 0.5%, 2% and 3% respectively, urging aluminium
Content enrichment in agent slag is promoted to 74%；
5, calcination temperature required for method provided by the present invention is lower than the prior art, saves energy consumption；
6, method provided by the present invention, unharmful substance discharges during processing, environmentally protective, and useless add may be implemented
The environmentally protective sustainable utilization of hydrogen catalyst meets future social development requirement.
Detailed description of the invention
Fig. 1 is the flow chart of the method for the present invention.
Specific embodiment
The following is specific embodiments of the present invention, and further retouches to technical solution of the present invention work in conjunction with the embodiments
It states, however, the present invention is not limited to these examples.
Embodiment
A kind of selective recovery is given up the method for valuable metal in hydrogenation catalyst, and process is as shown in Figure 1, step is specifically wrapped
It includes:
(1) it will be crushed after useless hydrogenation catalyst high-temperature calcination, obtain valuable metal recovery material；
(2) the valuable metal recovery material for obtaining step (1) carries out first time leaching using ammonia-ammonium salt solution, for the first time
The first leachate and the first leached mud are obtained after separation of solid and liquid；
(3) to molybdenum precipitation value, second of separation of solid and liquid obtains molybdic acid and second and soaks the pH of (2) first leachate of regulating step
Liquid out；
(4) alkali, precipitating nickel precipitating are added in the second leachate obtained to step (3)；
(5) after the first leached mud of step (2) being carried out secondary alkali leaching using ammonia-ammonium salt solution, third time is separated by solid-liquid separation
Oxidation aluminium slag and third leachate is obtained, adjusts the pH of third leachate to ammonium metavanadate precipitation value.
Wherein, in step (1), the temperature of high-temperature calcination is 400~700 DEG C, and the time is 1~4h.High-temperature burning process can
To remove the sulphur and carbon that contain in dead catalyst.Under normal conditions, start to burn sulphur for 150~200 DEG C, 200~250 DEG C of burning sulphur are most
More, then burning sulphur is slack-off as the temperature rises, could burn out when 650~700 DEG C；300~350 DEG C start to make charcoal, and 450
It is DEG C basic to burn out.Catalyst color under high-temperature calcination is gradually turned yellow by black or light green as the temperature rises
Color, sulfur content are dropped to from being greater than 5.3% less than 0.5%.Increase with calcined rate of mass reduction from less than 24.71% before calcining
To greater than 39.15%.It, should be according to conventional methods in the art due to containing carbon and sulphur in useless hydrogenation catalyst when calcining heating
Heating rate is controlled, prevents from causing temperature runaway.The smashed partial size of dead catalyst is less than 100 mesh.
In step (2), the total ammonia density of ammonia-ammonium salt solution is 4-8mol/L.In ammonia-ammonium salt solution, ammonium salt be ammonium sulfate,
One of ammonium chloride, ammonium nitrate, ammonium carbonate.
The pH leached for the first time is 8~10.Valuable metal recovery material and ammonia-ammonium salt solution solid-to-liquid ratio be 1:(10~
40).The temperature leached for the first time is 30~75 DEG C, and the time leached for the first time is 20~200min.When leach for the first time,
It is more abundant in order to make to leach, it can be stirred with the speed of 200~600rpm.
In step (3), molybdenum precipitation value is 1.5~3.After pH is adjusted to 1.5~3, molybdenum is precipitated in the form of molybdic acid, and second
It is separated by solid-liquid separation obtained molybdic acid and calcines 1~3h at 300~700 DEG C, molybdic acid is decomposed into the oxide of molybdenum.Second of separation of solid and liquid
Obtained molybdic acid can be washed first with alcohol reagent, be washed with alcohol reagent, thus it is possible to vary the pattern of oxide, benefit
In the formation of porous oxides material, purity can maintain 95% or more.
In step (4), alkali is added in the second leachate for obtaining to step (3), nickel is with nickel hydroxide or basic nickel carbonate
Form as Precipitation, recycled, the alkali that can be added includes sodium hydroxide, potassium hydroxide, sodium carbonate or in which two
The mixture of person.
In step (5), the pH range of alkali leaching is 10~12, and the method for alkali leaching is to maintain total ammonia density in 4-8mol/L, is changed
Become the ratio of ammonia and ammonium salt to adjust the pH of solution, oxidant can be added when soaking in alkali, and the addition of oxidant can be improved subsequent
The leaching rate of vanadium, oxidant include at least one of sodium chlorate, sodium hypochlorite, iron chloride, potassium permanganate and hydrogen peroxide.
In step (5), vanadium precipitation value is 7.5~9, can first the first leached mud of step (2) be washed and be dried,
Alkali leaching is carried out using ammonia-ammonium salt solution again, drying condition is 60~100 DEG C, and drying time is 2~20h.Adjust third leachate
PH to ammonium metavanadate precipitation value there are two ways to, a kind of method is the pH quilt for making third leachate by way of evaporating ammonia
It is adjusted to ammonium metavanadate precipitation value, the temperature for evaporating ammonia is 90~200 DEG C, and the ammonia being evaporated can recycle；It is another
Kind method is acid to be added into third leachate to adjust, and the acid that can be added includes nitric acid, hydrochloric acid and sulfuric acid.Adjust third leaching
After ammonium metavanadate is precipitated to ammonium metavanadate precipitation value in the pH of liquid out, ammonium metavanadate is calcined to 1~3h at 300~700 DEG C and is obtained
To the oxide of vanadium.
In useless hydrogenation catalyst, molybdenum content is greater than 15wt%, and nickel content is greater than 6wt%, and content of vanadium is greater than 11wt%, and aluminium contains
Amount is 24~32wt%.
The useless hydrogenation catalyst handled through the method for the present invention can be such that molybdenum, nickel, vanadium, the mass percent in catalyst contains
Amount is reduced to 0.5%, 2%, 3% respectively, and the quality of aluminium is made to be increased to 74%.
Test example 1
1. 2.0772g dead catalyst is calcined 2h at 400 DEG C, quality 1.4297g after calcining, reduction amount 0.6475g subtract
Few rate is 31.17%.The black greasy dirt of catalyst surface disappears, and catalyst color becomes light yellow, grinds in quartzy mortar.
The content of the essential element in useless hydrogenation catalyst after roasting at 400 DEG C is respectively Ni:8.794%, Mo:
4.125%, V:10.637%, Al2O3: 28.013%.
2. weighing dead catalyst 0.5g, leached under conditions of pH=9.Leaching condition: with ammonia-ammonium chloride body of 6mol/L
System leaches, extraction time 2h, and 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20, mixing speed 200r/min.In pH=9, nickel, molybdenum,
Vanadium, aluminium leaching rate be respectively 68%, 78%, 2.0%, 0.8%.Leachate and leached mud separation, leached mud (V-Al) are used for
Second of alkali leaches.
3. concentrated nitric acid is added in the leachate of step 2, the pH of solution is adjusted between 1.5-3, precipitate molybdic acid goes out at this time
It is existing.Molybdic acid is separated, continues that concentrated sodium hydroxide is added into leachate, until there is the nickel hydroxide precipitate of green.Filtering, will
Nickel hydroxide is separated.
4. the leached mud (V-Al) in step 2 is leached with the ammonia-ammonium chloride system of the 6mol/L of pH=12, extraction time
2h, 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20, mixing speed 200r/min.In pH=12, the leaching rate difference of nickel, molybdenum, vanadium, aluminium
It is 0.7%, 3%, 50%, 0.86%.Leachate and leached mud separation, leached mud (Al) are used for carrier when waste catalyst recovery
Preparation.
5. the vanadium leachate in step 4 adjusts pH to 7.5-9 with concentrated nitric acid, there is faint yellow ammonium metavanadate precipitate to be precipitated.Gu
Liquid separation, after ammonium metavanadate is washed with water, roasts 1h at 500 DEG C, generates the vanadic anhydride oxide of brown.
Test example 2
1. weighing the useless hydrogenation catalyst 2.0401g not calcined, 2h, quality after calcining are calcined at 600 DEG C
1.2865g, reduction amount 0.7536, slip 36.94%.The black greasy dirt of catalyst surface disappears, and catalyst color becomes
Yellow is ground in quartzy mortar, and the content of essential element is respectively Ni:9.927%, Mo:6.379%, V:12.043%,
Al2O3: 32.141%.
2. weighing dead catalyst 0.5g, leached under conditions of pH=9.Leaching condition: with ammonia-ammonium chloride body of 6mol/L
System leaches, extraction time 2h, and 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20, mixing speed 200r/min, the leaching of nickel, molybdenum, vanadium, aluminium
Extracting rate is respectively 39%, 77%, 2.4%, 0.8%.Leachate and leached mud separation, leached mud (V-Al) is for second of alkali leaching
Out.
3. concentrated nitric acid is added in the leachate of step 2, the pH of solution is adjusted between 1.5-3, precipitate molybdic acid goes out at this time
It is existing.Molybdic acid is separated, continues that concentrated sodium hydroxide is added into leachate, until there is the nickel hydroxide precipitate of green.Filtering, will
Nickel hydroxide is separated.
4. the leached mud (V-Al) in step 2 is leached with the ammonia-ammonium chloride system of the 6mol/L of pH=12, extraction time
2h, 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20, mixing speed 200r/min.In pH=12, the leaching rate difference of nickel, molybdenum, vanadium, aluminium
It is 2.3%, 8.4%, 28.33%, 0.5%.Leachate and leached mud separation, when leached mud (Al) is used for waste catalyst recovery
The preparation of carrier.
5. the vanadium leachate in step 4 adjusts pH to 7.5-9 with concentrated nitric acid, there is faint yellow ammonium metavanadate precipitate to be precipitated.Gu
Liquid separation, after ammonium metavanadate is washed with water, roasts 1h at 500 DEG C, generates the vanadic anhydride oxide of brown.
6. surveying EDS content of vanadium in 90~97% ranges.The content of aluminium is 74% in phase analysis.
Test example 3
1. dead catalyst is calcined 2h at 400 DEG C, soaked after being ground with quartzy mortar with the ammonia-ammonium chloride system of 6mol/L
Out.
2. leach at pH=9, extraction time 1h, 75 DEG C of extraction temperature, solid-to-liquid ratio 1:15, blue leachate is obtained, nickel,
Molybdenum, vanadium, aluminium leaching rate be respectively 84%, 90%, 0.6%, 0.6%.Leachate and leached mud separation, leached mud (V-Al) are used
It is leached in second of alkali.
3. using acidic extractant V-10, the extraction yield 95% of the leachate at pH=6.86 in extraction step 2, nickel is left
The right side, the extraction yield of molybdenum for several times through water washing are dried for 24 hours in an oven using alkali back extraction nickel 6% or so, obtain light green hydrogen-oxygen
Change nickel by powder.Water phase containing molybdenum has precipitate molybdic acid to come out, roasts 1h at 500 DEG C, obtain molybdenum oxide through adjusting pH=1.5-3.
4. the ammonia-ammonium chloride system that the leached mud (V-Al) in step 2 is added to the 6mol/L of pH=12 with 6% hydrogen peroxide
It leaches, extraction time 2h, 75 DEG C of extraction temperature, solid-to-liquid ratio 1:20, mixing speed 200r/min.In pH=12, nickel, molybdenum, vanadium, aluminium
Leaching rate be respectively 0.52%, 2.43%, 65%, 0.47%.Leachate and leached mud separation, leached mud (Al) are urged for useless
The preparation of carrier when agent recycles.
5. the vanadium leachate in step 4 adjusts pH to 7.5-9 with concentrated nitric acid, there is faint yellow ammonium metavanadate precipitate to be precipitated.Gu
Liquid separation, after ammonium metavanadate is washed with ethyl alcohol, roasts 1h at 500 DEG C, generates the vanadic anhydride oxide of brown color.
6. surveying the content of EDS content of vanadium aluminium in 88-95%, phase analysis 71%.
Comparative example 1
1. 2.0772g dead catalyst is calcined 2h at 400 DEG C, quality 1.4297g after calcining, reduction amount 0.6475g subtract
Few rate is 31.17%.The black greasy dirt of catalyst surface disappears, and catalyst color becomes light yellow, grinds in quartzy mortar.
The content of the essential element in useless hydrogenation catalyst after roasting at 400 DEG C is respectively Ni:8.794%, Mo:4.125%, V:
10.637%, Al2O3: 28.013%.
2. weighing dead catalyst 0.5g, leached under conditions of pH=12.Leaching condition: with ammonia-ammonium chloride of 6mol/L
System leaches, extraction time 2h, and 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20.Nickel, molybdenum, vanadium, aluminium leaching rate be respectively
51.36%, 69.66%, 58.7%, 3.9%.
It can be seen that vanadium will leach, and cannot reach the first step and extract nickel molybdenum, vanadium stays in slag when the value of pH is higher than 9
Purpose.
Comparative example 2
Dead catalyst is roasted at 300 DEG C, catalyst color has not been changed, and the oil and carbon on surface burn incompletely.
It can be seen that temperature lower than 400 DEG C catalyst surface substance cannot be dryouied it is net.
Comparative example 3
1. weighing the useless hydrogenation catalyst 2.0401g not calcined, 2h, quality after calcining are calcined at 600 DEG C
1.2865g, reduction amount 0.7536, slip 36.94%.The black greasy dirt of catalyst surface disappears, and catalyst color becomes
Yellow is ground in quartzy mortar, and the content of essential element is respectively Ni:9.927%, Mo:6.379%, V:12.043%,
Al2O3: 32.141%.
2. weighing dead catalyst 0.5g, leached under conditions of pH=12.Leaching condition: with ammonia-ammonium chloride of 6mol/L
System leaches, extraction time 2h, and 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20.Under, nickel, molybdenum, vanadium, aluminium leaching rate be respectively
35%, 76%, 68%, 3.69%.
It can be seen that vanadium will leach, and cannot reach the first step and extract nickel molybdenum, vanadium stays in slag when the value of pH is higher than 9
Purpose.
Comparative example 4
1. existing calcine 2h at 600 DEG C for dead catalyst, after being ground with quartzy mortar, dead catalyst 0.5g is weighed, total
It leaches, extraction time 1h, 60 DEG C of extraction temperature, solid-to-liquid ratio 1:20, leaches in the ammonia-ammonium chloride system that ammonia density is 1mol/L
The pH=12 of liquid.
2. in the ammonia-ammonium chloride system of 1mol/L, nickel, molybdenum, vanadium, aluminium leaching rate be respectively 3.6%, 75%,
43%, 1.7%.
As it can be seen that the leaching rate of nickel is lower when the concentration of total ammonia is lower than 4mol/L.
Comparative example 5
1. 2.0772g dead catalyst is calcined 2h at 400 DEG C, quality 1.4297g after calcining, reduction amount 0.6475g subtract
Few rate is 31.17%.The black greasy dirt of catalyst surface disappears, and catalyst color becomes light yellow, grinds in quartzy mortar.
The content of the essential element in useless hydrogenation catalyst after roasting at 400 DEG C is respectively Ni:8.794%, Mo:4.125%, V:
10.637%, Al2O3: 28.013%.
2. weighing dead catalyst 0.5g, under conditions of pH=12,6% hydrogen peroxide is added and leaches.Leaching condition: with 6
The ammonia-ammonium chloride system of mol/L leaches, extraction time 2h, and 60 DEG C of extraction temperature, solid-to-liquid ratio 1:5, mixing speed 200r/
min.In pH=12, nickel, molybdenum, vanadium, aluminium leaching rate be respectively 68%, 82%, 5%, 0.8%.
When solid-to-liquid ratio is lower than 10, even if oxidant is added, the leaching rate of vanadium remains unchanged very low, it is seen that solid-to-liquid ratio will be in 10-
Between 40.
Comparative example 6
1. weighing the useless hydrogenation catalyst 2.0044g not calcined, 2h, quality after calcining are calcined at 800 DEG C
1.2196g, reduction amount 0.7848g, slip 39.15%.The black greasy dirt of catalyst surface disappears, and catalyst color becomes
Light green is ground in quartzy mortar.
2. in the ammonia-ammonium chloride system of 6mol/L, when pH=9, solid-to-liquid ratio 1:20,60 DEG C of extraction temperature, 2h is leached,
Nickel, molybdenum, vanadium, aluminium leaching rate be respectively 15%, 85%, 45%, 3.02%.
As it can be seen that nickel can not leach in first step leaching, and leaching rate is very low, can not be by nickel molybdenum when maturing temperature is too high
It leaches into solution.
Claims (10)
1. a kind of selective recovery is given up in hydrogenation catalyst valuable metal method, which is characterized in that step includes:
(1) it will be crushed after useless hydrogenation catalyst high-temperature calcination, obtain valuable metal recovery material；
(2) the valuable metal recovery material for obtaining step (1) carries out first time leaching, first time solid-liquid using ammonia-ammonium salt solution
The first leachate and the first leached mud are obtained after separation；
(3) to molybdenum precipitation value, second of separation of solid and liquid obtains molybdic acid and second and leaches the pH of (2) first leachate of regulating step
Liquid；
(4) alkali, precipitating nickel precipitating are added in the second leachate obtained to step (3)；
(5) after the first leached mud of step (2) being carried out alkali leaching using ammonia-ammonium salt solution, third time is separated by solid-liquid separation and is aoxidized
Aluminium slag and third leachate adjust the pH of third leachate to ammonium metavanadate precipitation value.
2. the method according to claim 1, wherein the temperature of step (1) described high-temperature calcination is 400~700
DEG C, the time is 1~4h.
3. the method according to claim 1, wherein total ammonia density of step (2) ammonia-ammonium salt solution is 2-
8mol/L。
4. the method according to claim 1, wherein the pH that step (2) first time leaches is 8~11.
5. the method according to claim 1, wherein step (2) the valuable metal recovery material and ammonia-ammonium salt are molten
The solid-to-liquid ratio of liquid is 1:(5~40).
6. the method according to claim 1, wherein the temperature that step (2) first time leaches is 25~75
DEG C, the time leached for the first time is 20~200min.
7. the method according to claim 1, wherein step (3) the molybdenum precipitation value is 1.5~3.
8. the method according to claim 1, wherein the pH range of step (5) the alkali leaching is 10~12.
9. the method according to claim 1, wherein step (5) the vanadium precipitation value is 7.5~9.
10. described in any item methods according to claim 1~9, which is characterized in that in the useless hydrogenation catalyst, molybdenum content
Greater than 15wt%, nickel content is greater than 6wt%, and content of vanadium is greater than 11wt%, aluminium content 24-32wt%.
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