CA1210746A - Recovering metal compounds from used catalysts obtained from hydroprocessing hydrocarbon feedstocks - Google Patents
Recovering metal compounds from used catalysts obtained from hydroprocessing hydrocarbon feedstocksInfo
- Publication number
- CA1210746A CA1210746A CA000451557A CA451557A CA1210746A CA 1210746 A CA1210746 A CA 1210746A CA 000451557 A CA000451557 A CA 000451557A CA 451557 A CA451557 A CA 451557A CA 1210746 A CA1210746 A CA 1210746A
- Authority
- CA
- Canada
- Prior art keywords
- acid solution
- metal salts
- nickel
- vanadium
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
A process for recovery of valuable metals such as prin-cipally nickel and vanadium deposited on used catalyst from catalytic hydroprocessing of hydrocarbon metals-containing feedstocks. In the process, the used catalyst containing metals deposits is treated with a fresh dilute acid solution such as sulfuric acid to extract and remove the metals depo-sits without damage to the catalyst, after which the resulting spent acid solution containing metal salts is neutralized to a pH of about 3.5-12 with a hydroxide solu-tion sufficient to form a metal salts precipitate material.
The precipitate material is removed from the liquid such as by filtering, and the precipitate is then heated to evolve water vapor and the water of hydration, leaving oxides of metals such as nickel and vanadium as product. If desired to recover nickel and vanadium oxides separately, the metal oxide material can be further furnace heated with carbon to the respective melting temperatures of the metals, which are successively separately drained from the furnace.
Alternatively, to remove nickel and vanadium oxides separa-tely, the spent acid solution containing metal salts is first neutralized with hydroxide solution to a pH of about 3.5-5.0 to precipitate and recover the nickel salts. Upon further addition of hydroxide solution sufficient to neutralize the remaining spent acid solution to a pH of 7-12, vanadium and other metal salts are precipitated and recovered.
A process for recovery of valuable metals such as prin-cipally nickel and vanadium deposited on used catalyst from catalytic hydroprocessing of hydrocarbon metals-containing feedstocks. In the process, the used catalyst containing metals deposits is treated with a fresh dilute acid solution such as sulfuric acid to extract and remove the metals depo-sits without damage to the catalyst, after which the resulting spent acid solution containing metal salts is neutralized to a pH of about 3.5-12 with a hydroxide solu-tion sufficient to form a metal salts precipitate material.
The precipitate material is removed from the liquid such as by filtering, and the precipitate is then heated to evolve water vapor and the water of hydration, leaving oxides of metals such as nickel and vanadium as product. If desired to recover nickel and vanadium oxides separately, the metal oxide material can be further furnace heated with carbon to the respective melting temperatures of the metals, which are successively separately drained from the furnace.
Alternatively, to remove nickel and vanadium oxides separa-tely, the spent acid solution containing metal salts is first neutralized with hydroxide solution to a pH of about 3.5-5.0 to precipitate and recover the nickel salts. Upon further addition of hydroxide solution sufficient to neutralize the remaining spent acid solution to a pH of 7-12, vanadium and other metal salts are precipitated and recovered.
Description
-~ lZ16~
CATALYSTS OBTAINED FROM
HYDROPROCESSING HYDROCARBON FEEDSTOCKS
BACKGROUND OF INVNTION
. .
This invention pertains to recovering valuab1e metal compounds deposited on used cata1ysts. It pertains par-ticularly to a process for treating used catalysts from hydrocarbon catalytic hydroconversion processes to recover deposited nickel and vanadium compounds from the catalyst as metal oxides.
Used catalysts obtained from catalytic hydroprocessing of hydrocarbon feedstocks such as petroleum, shale oil and tar sands bitumen contain undesired nickel and vanadium com-pounds dS metdl contaminants on the catalyst. Removal of these metal contaminants is an essential part of regenera-tion of the spent catdlysts. It is known to recover such deposited metals from spent catalysts by grinding the cata-lyst to fine particle size and then recovering the metals by ch~mical processes, which thereby destroys any fur~her use-fulness of the catalyst. In my U.S. Patent No. 4,454,240, issued June 12~ 1984, it is disclosed that acid treatment of spent catalysts with dilute sulfuric acid solution can re-move most of the vanadium and nickel eompounds without ad-versely affecting the active elements of the catalyst and thereby provide a useful regenerated catalyst material. The spent acid solution contains vanadium in sulfate or oxy-sulfate form and nickel in sulfate form. However, that patent does not disclose any method for recovering the valuable metals such as vanadium and particularly nickel from the s~ent acid solution.
~(37~
SUMMARY OF INVENTION
The present invention provides a process for recovering metals compounds deposited on used catalyst from the cataly-tic hydroprocessing of hydrooarbon feedstocks. The process comprises treating the used catalyst containing deposits of metals such as nickel and vanadium by adding a dilute fresh acid solution to the used catalyst to extract and remove the metal deposits, and then mixing the resulting spent acid solution from the acid treatment step with a hydroxide solu-tion such as ammonia, ammonium hydroxide, sodium hydroxide solution or mixtures thereof sufficient to neutralize the spent acid to a pH of between about 7 12, and forming metal salts precipitates ,uch as nickel hydroxide and hydrated vanadium trioxide. The precipitated material is then separated from the neutralized acid solution such as by a filtration step to recover useful metal salts and a filtrate liquid. The filtrate liquid can be discarded, and the metal salts are converted to metal oxides intermediate products by heating the sa-lts to about 300C. If desired, the metal salts can be mixed with granular carbon and further heated successively to their respective melting temperatures of the metals to reduce the metal oxides and recover the molten metals in substantially pure form.
Alternatively, by successively increasing the pH of the neutralized spent acid solutiolls, the nickel and v~nadium salts can be a~vantageously recovered separately from the process~ By first adding to the spent acid solution only sufficient hydroxide solution to provide a pH of about 3.5-6.0, nickel hydrox~de i5 precipitated out and removed such as by filtration~ The nickel hydroxide upon oeing heated to about 230C produces nickel oxide. Upon further ~ '~
~Zl~'7~t;
addition of a hydroxide solution to the resulting filtrate liquid sufficient to provide a pH of about 9-12, hydrated vanadium trioxide and any other metal salts present will be precipitated and can also be removed such as by filtration.
The hydrated vanadium trioxide upon being heated to about 300C produces useful vanadium oxide.
It is an important advantage of the present invention that it recovers valuable metals such as nickel and vanadium compounds deposited on used catalyst during catalytic hydroprocessing operations without damaging the catalyst, thus not only permitting the treated catalyst material to be reused but also recovers the valuable deposited meeals in relatively pure form from the spent acid solution.
BRIEF DESCRIPTION OF DRAWING
FIG~ 1 is a schematic flow diagram of a catalyst rege-neration and metals recovery process according to the inven-tion.
FIG. 2 is d schematic flow diagram showing furnace heating the recovered metal salts to produce molten metals.
DESCRIPTION OF INVENTION
As shown in FI~. 1, a hydrocarbon feedstock 10 such dS
coal, petroleum or tar sands bitumen containing metal com-pounds is catalytically hydroconverted at elevated tempera-ture and pressure in reactor 12 containing particulate cata-lyst 12a to produce a reacted effluent stream 11. IJsed catalyst particles containing metal deposits such as nickel and vanadium from the hydrocarbon hydrogenation reaction process, are withdrawn at 13 from the catalytic reactor 12, and passed to a solvent washing step 14, which uses a suit-able solvent such as naphtha or toluene to remove substan-tially all the heavy oils from the used catalyst. The re-sulting oil-free catalyst at 15 is then passed usually as d batch to catalyst treatment tank 16. A fresh dilute acid solution 17 which will extract and remove metal deposits from the catalyst, such as preferably 10-25% sulfuric acid solution, is added to the tank 16 to extract the metals deposits and thereby regenerate the used catalyst. Other dilute acids which can be used for treating the catalyst to extract deposited metals therefrom include but are not limited to citric acid, hydrochloric acid and nitric acid or mixtures thereof. The regenerated catalyst material is removed at lB and can be passed to further treatment steps, such as a wash step to remove acid and a carbon burn-off step, prior to reuse of the catalyst in reactor 12.
From the catalyst acid treatment tank 1~, the spent acid solution is withdrawn at 19 containing the dilute spent acid along with metal salts including nickel sulfate and vanadium sulfate compounds, and is passed to acid neutralizing vessel 20. Sufficient basic material such as ammonia gas, ammonium hydroxide, sodium hydroxide or mixtures thereof is added at 21 to the treating vessel 20 and mixed with the spent acid solution using mixing means 22 to neutralize the acid solu-tion therein to a pH of about 3.5-12 at a residence time of 5-30 minutes, thereby forming a precipitate material con-taining nickel and vanadium salts. The preferred basic material added at 21 for neutrali~ing the spent acid solu-tion is ammonia gas, because no water is thereby added to the solution for later removal. Ammonium hydroxide can be advantageously used for neutralizing the acid because of its ~ ~2~4~
lower costs and availability to the process, such as being a by-product from an H-Oil process for catalytic hydroconver-sion of petroleum feedstocks. Also, ammonium hydroxide addition produces ammonium sulfate precipitate, which is a desirable ~y-product as compared to sodium sulfate.
Alternatively, sodium hydroxide can also be used, as well ds mixtures of hydroxides.
From acid neutralizing vessel 20, the resulting neutra-lized liquid and precipitate material is wi~hdrawn at 24, and the precipitated hydroxide salts are separated from the liquid sulfate solution and removed by suitable means 26, such as by a filtration step or by centrifuging, after which the sulfate filtrate solution at 27 can be discarded, if desired.
From filtration at 26 the filtered precipitate solids are removed at 28 and are water washed at 29 to remove any remaining sulfates at 29~. The washed solids material is then heated in tank 30 to d temperature of about 230C so as to drive off water vapor at 31, such as by passing a hot gas 32 upwardly through the solids to heat the solids. Useful heating gases at 32 can include air, carbon dioxide and nitrogen. The resulting metal oxides are recovered at 34 as productO These metal oxides recovered at 34 can be advan-tageously reused either in the manufacture of fresh cata-lyst, or for other appropriate uses.
Alternatively, if it is desired to recover nickel oxide and vanadium oxide separately from the spent acid solution, the metal salts precipitate removed at 28 as a filter cake material is mixed with gran~ldr carbon at SO~as shown in FIG. 2~ The moist filter cake mdterial is usually mechani~
cally mixed by mixer 53 with charcoal powder in a weight *~a~rk :~ILZ~L~74~ `
ra~io of metal salts to carbon in a range of 2/I 4/1. The resulting filter cake and carbon mixture at 52 is then introduced into a furnace 54, in which a suitable inert gas atmosphere is maintained, such as by nitrogen or C02. The furnace ~4 is usually heated electrically such as by resistance wire coils 55. The filter ~ake~carbon mixture is then heated therein to first evolve water vapor and the water of hydration, and then further heated successively to the melting temperature of the various metals contained in the filter cake material. Such heatins of the metal salts with carbon converts the metal salts to oxides and reduces the metal oxides to their respective metals and evolves C0 and C02 gases at 57, generally according to the following principal reaction equations:
V23 ~zC -~2V~ C02 + C0 NiO + C - ~ Ni + C0 The filter cake material is heated to temperatures corresponding to the melting temperature of the respective metals and held at each temperature for sufficient time to allow each ~olten metal to drain from the furnace at 58 in substantially pure metdl forms. The appropriate furnace temperature for the various metals in the filter cake materiat are listed below:
ME~AL MELTING TEMPERATURE, C
_ Aluminum 660 Nickel 1455 Iron 1530 Yanadium 1710 Molybderlum 2620 As another alternative embod~nent of the invention for remo~ing the nicXe1 and vanadium separately in relatively pure forms, only sufficient hydroxide solution is added at 21 to neutralize the spent acid in treating vessel 20 to provide a pH of about 3.5-5Ø Under these conditions, nic-kel hydroxide is precipitated, separated at filter 26 and removed at 28. The nickel hydroxide is water washed at 29 to remove any remaining sulfates at 29~, and heated at 30 to 230-300C by upflowing hot gas 32, and converted to nicke1 oxide product at 34. Furthermore, additiona1 hydroxide solution is added at 35 to first filtrate solution 27 in mixing tank 36 and mixed using mixing means 37 to produce a pH therein of at least about 9.0 and preferably 9.5-12.0, the salts of vanadium and other metals such as aluminum, iron and molybdenum are then also precipitated and withdrawn at 38. The precipitated solids are separated at 40 by suit-able means such as filtration as generally disclosed above to produce second filtrate liquid stream 41. The filtered precipitate solids material is removed at 423 and water washed at 43 to remove any remaining .sulfates at 43l3. The washed material is then heated in tank 44 by an upflowing gas such as air to a temperature of about 240-300F to drive off all water vapor at 45 by hot gases 46 passed upwardly through the bed to produce oxides of vanadium and other metals, which are recovered at 48.
This invention will be further described by reference to the following example, which should not be construed as limiting the scope of the invention.
Used particulate catalyst removed from a petroleum cata-lytic hydroconversion process and containing metals deposits including nickel and vanadium was treated with a 15~ solu-tion of sulfuric acid at 180F temperature for 10 minutes to
CATALYSTS OBTAINED FROM
HYDROPROCESSING HYDROCARBON FEEDSTOCKS
BACKGROUND OF INVNTION
. .
This invention pertains to recovering valuab1e metal compounds deposited on used cata1ysts. It pertains par-ticularly to a process for treating used catalysts from hydrocarbon catalytic hydroconversion processes to recover deposited nickel and vanadium compounds from the catalyst as metal oxides.
Used catalysts obtained from catalytic hydroprocessing of hydrocarbon feedstocks such as petroleum, shale oil and tar sands bitumen contain undesired nickel and vanadium com-pounds dS metdl contaminants on the catalyst. Removal of these metal contaminants is an essential part of regenera-tion of the spent catdlysts. It is known to recover such deposited metals from spent catalysts by grinding the cata-lyst to fine particle size and then recovering the metals by ch~mical processes, which thereby destroys any fur~her use-fulness of the catalyst. In my U.S. Patent No. 4,454,240, issued June 12~ 1984, it is disclosed that acid treatment of spent catalysts with dilute sulfuric acid solution can re-move most of the vanadium and nickel eompounds without ad-versely affecting the active elements of the catalyst and thereby provide a useful regenerated catalyst material. The spent acid solution contains vanadium in sulfate or oxy-sulfate form and nickel in sulfate form. However, that patent does not disclose any method for recovering the valuable metals such as vanadium and particularly nickel from the s~ent acid solution.
~(37~
SUMMARY OF INVENTION
The present invention provides a process for recovering metals compounds deposited on used catalyst from the cataly-tic hydroprocessing of hydrooarbon feedstocks. The process comprises treating the used catalyst containing deposits of metals such as nickel and vanadium by adding a dilute fresh acid solution to the used catalyst to extract and remove the metal deposits, and then mixing the resulting spent acid solution from the acid treatment step with a hydroxide solu-tion such as ammonia, ammonium hydroxide, sodium hydroxide solution or mixtures thereof sufficient to neutralize the spent acid to a pH of between about 7 12, and forming metal salts precipitates ,uch as nickel hydroxide and hydrated vanadium trioxide. The precipitated material is then separated from the neutralized acid solution such as by a filtration step to recover useful metal salts and a filtrate liquid. The filtrate liquid can be discarded, and the metal salts are converted to metal oxides intermediate products by heating the sa-lts to about 300C. If desired, the metal salts can be mixed with granular carbon and further heated successively to their respective melting temperatures of the metals to reduce the metal oxides and recover the molten metals in substantially pure form.
Alternatively, by successively increasing the pH of the neutralized spent acid solutiolls, the nickel and v~nadium salts can be a~vantageously recovered separately from the process~ By first adding to the spent acid solution only sufficient hydroxide solution to provide a pH of about 3.5-6.0, nickel hydrox~de i5 precipitated out and removed such as by filtration~ The nickel hydroxide upon oeing heated to about 230C produces nickel oxide. Upon further ~ '~
~Zl~'7~t;
addition of a hydroxide solution to the resulting filtrate liquid sufficient to provide a pH of about 9-12, hydrated vanadium trioxide and any other metal salts present will be precipitated and can also be removed such as by filtration.
The hydrated vanadium trioxide upon being heated to about 300C produces useful vanadium oxide.
It is an important advantage of the present invention that it recovers valuable metals such as nickel and vanadium compounds deposited on used catalyst during catalytic hydroprocessing operations without damaging the catalyst, thus not only permitting the treated catalyst material to be reused but also recovers the valuable deposited meeals in relatively pure form from the spent acid solution.
BRIEF DESCRIPTION OF DRAWING
FIG~ 1 is a schematic flow diagram of a catalyst rege-neration and metals recovery process according to the inven-tion.
FIG. 2 is d schematic flow diagram showing furnace heating the recovered metal salts to produce molten metals.
DESCRIPTION OF INVENTION
As shown in FI~. 1, a hydrocarbon feedstock 10 such dS
coal, petroleum or tar sands bitumen containing metal com-pounds is catalytically hydroconverted at elevated tempera-ture and pressure in reactor 12 containing particulate cata-lyst 12a to produce a reacted effluent stream 11. IJsed catalyst particles containing metal deposits such as nickel and vanadium from the hydrocarbon hydrogenation reaction process, are withdrawn at 13 from the catalytic reactor 12, and passed to a solvent washing step 14, which uses a suit-able solvent such as naphtha or toluene to remove substan-tially all the heavy oils from the used catalyst. The re-sulting oil-free catalyst at 15 is then passed usually as d batch to catalyst treatment tank 16. A fresh dilute acid solution 17 which will extract and remove metal deposits from the catalyst, such as preferably 10-25% sulfuric acid solution, is added to the tank 16 to extract the metals deposits and thereby regenerate the used catalyst. Other dilute acids which can be used for treating the catalyst to extract deposited metals therefrom include but are not limited to citric acid, hydrochloric acid and nitric acid or mixtures thereof. The regenerated catalyst material is removed at lB and can be passed to further treatment steps, such as a wash step to remove acid and a carbon burn-off step, prior to reuse of the catalyst in reactor 12.
From the catalyst acid treatment tank 1~, the spent acid solution is withdrawn at 19 containing the dilute spent acid along with metal salts including nickel sulfate and vanadium sulfate compounds, and is passed to acid neutralizing vessel 20. Sufficient basic material such as ammonia gas, ammonium hydroxide, sodium hydroxide or mixtures thereof is added at 21 to the treating vessel 20 and mixed with the spent acid solution using mixing means 22 to neutralize the acid solu-tion therein to a pH of about 3.5-12 at a residence time of 5-30 minutes, thereby forming a precipitate material con-taining nickel and vanadium salts. The preferred basic material added at 21 for neutrali~ing the spent acid solu-tion is ammonia gas, because no water is thereby added to the solution for later removal. Ammonium hydroxide can be advantageously used for neutralizing the acid because of its ~ ~2~4~
lower costs and availability to the process, such as being a by-product from an H-Oil process for catalytic hydroconver-sion of petroleum feedstocks. Also, ammonium hydroxide addition produces ammonium sulfate precipitate, which is a desirable ~y-product as compared to sodium sulfate.
Alternatively, sodium hydroxide can also be used, as well ds mixtures of hydroxides.
From acid neutralizing vessel 20, the resulting neutra-lized liquid and precipitate material is wi~hdrawn at 24, and the precipitated hydroxide salts are separated from the liquid sulfate solution and removed by suitable means 26, such as by a filtration step or by centrifuging, after which the sulfate filtrate solution at 27 can be discarded, if desired.
From filtration at 26 the filtered precipitate solids are removed at 28 and are water washed at 29 to remove any remaining sulfates at 29~. The washed solids material is then heated in tank 30 to d temperature of about 230C so as to drive off water vapor at 31, such as by passing a hot gas 32 upwardly through the solids to heat the solids. Useful heating gases at 32 can include air, carbon dioxide and nitrogen. The resulting metal oxides are recovered at 34 as productO These metal oxides recovered at 34 can be advan-tageously reused either in the manufacture of fresh cata-lyst, or for other appropriate uses.
Alternatively, if it is desired to recover nickel oxide and vanadium oxide separately from the spent acid solution, the metal salts precipitate removed at 28 as a filter cake material is mixed with gran~ldr carbon at SO~as shown in FIG. 2~ The moist filter cake mdterial is usually mechani~
cally mixed by mixer 53 with charcoal powder in a weight *~a~rk :~ILZ~L~74~ `
ra~io of metal salts to carbon in a range of 2/I 4/1. The resulting filter cake and carbon mixture at 52 is then introduced into a furnace 54, in which a suitable inert gas atmosphere is maintained, such as by nitrogen or C02. The furnace ~4 is usually heated electrically such as by resistance wire coils 55. The filter ~ake~carbon mixture is then heated therein to first evolve water vapor and the water of hydration, and then further heated successively to the melting temperature of the various metals contained in the filter cake material. Such heatins of the metal salts with carbon converts the metal salts to oxides and reduces the metal oxides to their respective metals and evolves C0 and C02 gases at 57, generally according to the following principal reaction equations:
V23 ~zC -~2V~ C02 + C0 NiO + C - ~ Ni + C0 The filter cake material is heated to temperatures corresponding to the melting temperature of the respective metals and held at each temperature for sufficient time to allow each ~olten metal to drain from the furnace at 58 in substantially pure metdl forms. The appropriate furnace temperature for the various metals in the filter cake materiat are listed below:
ME~AL MELTING TEMPERATURE, C
_ Aluminum 660 Nickel 1455 Iron 1530 Yanadium 1710 Molybderlum 2620 As another alternative embod~nent of the invention for remo~ing the nicXe1 and vanadium separately in relatively pure forms, only sufficient hydroxide solution is added at 21 to neutralize the spent acid in treating vessel 20 to provide a pH of about 3.5-5Ø Under these conditions, nic-kel hydroxide is precipitated, separated at filter 26 and removed at 28. The nickel hydroxide is water washed at 29 to remove any remaining sulfates at 29~, and heated at 30 to 230-300C by upflowing hot gas 32, and converted to nicke1 oxide product at 34. Furthermore, additiona1 hydroxide solution is added at 35 to first filtrate solution 27 in mixing tank 36 and mixed using mixing means 37 to produce a pH therein of at least about 9.0 and preferably 9.5-12.0, the salts of vanadium and other metals such as aluminum, iron and molybdenum are then also precipitated and withdrawn at 38. The precipitated solids are separated at 40 by suit-able means such as filtration as generally disclosed above to produce second filtrate liquid stream 41. The filtered precipitate solids material is removed at 423 and water washed at 43 to remove any remaining .sulfates at 43l3. The washed material is then heated in tank 44 by an upflowing gas such as air to a temperature of about 240-300F to drive off all water vapor at 45 by hot gases 46 passed upwardly through the bed to produce oxides of vanadium and other metals, which are recovered at 48.
This invention will be further described by reference to the following example, which should not be construed as limiting the scope of the invention.
Used particulate catalyst removed from a petroleum cata-lytic hydroconversion process and containing metals deposits including nickel and vanadium was treated with a 15~ solu-tion of sulfuric acid at 180F temperature for 10 minutes to
2~t~7~
extract and remove the metal deposits including nickel and vanadium in the form of sulfates and oxysulfates. The resulting spent acid solution was treated with ammonia gas, ammonium hydroxide, and sodium hydroxide in a mixing tank for 10 minutes residence time to neutralize the acid to pH
of 9.0 and form a precipitate metal salts material. The liquid and precipitate material was filtered, and the resulting filter cake material ~as water washed and heated to 300C (572F) to produce oxides of nickel and vanadium.
Results are summarized in Table 1..
METALS COMPOUNDS RECOVERY FROM SPENT ACID SOLUTIONS
CONTAINING METALS SALTS
Used Catalyst Treated, lb l.~ 1.0 ~, Metals Deposits on Used Catalyst, W %
Nickel 1 1 2 Vanadium 10 10 8 Fresh Acid 15% 15~ 15~
Used for TreatmentSulfuricSulfuricSulfuric Spent Acid Solution Containing Metals, lb 2. 5 2. 5 3.0 Neutralizing Agent Ammonia AmmoniumSodium Added to Spent Acid Gas HydroxideHydroxide pH of Neutralized Acid Solution 9 9 g Metal Salts Precipitate Material Recovered, lb. 0.10 0.10 0.12 Metal Oxides Recovered from Fi~lter Cake:
NiO~ % 6.1 6 20 V2 3~ % 89 89 62 Others, ~ 4.9 5 18 Metal Salts Contained in Filtrate Liquid, lb0.37 0.87 0.74 Analysis of Salts in Filtrate Liquid Nickel 0.02 0.03 0.01 Vanadium 0.01 0.01 0.01 7~
From the above results, it is seen that substantially all the metal salts including nickel and vanadium contained in the spent acid solution were recovered from the precipi-tate in the form of metal salts or oxides, and negligible metals remained in the acid solution. These metal salts can be converted by heating to metal oxides product at high recovery.
Although this invention has been described broadly and in terms of certain preferred embodiments, it will be understood that modifications and variations to the process can be made within the spirit and scope of the invention, which is defined by the following claims.
extract and remove the metal deposits including nickel and vanadium in the form of sulfates and oxysulfates. The resulting spent acid solution was treated with ammonia gas, ammonium hydroxide, and sodium hydroxide in a mixing tank for 10 minutes residence time to neutralize the acid to pH
of 9.0 and form a precipitate metal salts material. The liquid and precipitate material was filtered, and the resulting filter cake material ~as water washed and heated to 300C (572F) to produce oxides of nickel and vanadium.
Results are summarized in Table 1..
METALS COMPOUNDS RECOVERY FROM SPENT ACID SOLUTIONS
CONTAINING METALS SALTS
Used Catalyst Treated, lb l.~ 1.0 ~, Metals Deposits on Used Catalyst, W %
Nickel 1 1 2 Vanadium 10 10 8 Fresh Acid 15% 15~ 15~
Used for TreatmentSulfuricSulfuricSulfuric Spent Acid Solution Containing Metals, lb 2. 5 2. 5 3.0 Neutralizing Agent Ammonia AmmoniumSodium Added to Spent Acid Gas HydroxideHydroxide pH of Neutralized Acid Solution 9 9 g Metal Salts Precipitate Material Recovered, lb. 0.10 0.10 0.12 Metal Oxides Recovered from Fi~lter Cake:
NiO~ % 6.1 6 20 V2 3~ % 89 89 62 Others, ~ 4.9 5 18 Metal Salts Contained in Filtrate Liquid, lb0.37 0.87 0.74 Analysis of Salts in Filtrate Liquid Nickel 0.02 0.03 0.01 Vanadium 0.01 0.01 0.01 7~
From the above results, it is seen that substantially all the metal salts including nickel and vanadium contained in the spent acid solution were recovered from the precipi-tate in the form of metal salts or oxides, and negligible metals remained in the acid solution. These metal salts can be converted by heating to metal oxides product at high recovery.
Although this invention has been described broadly and in terms of certain preferred embodiments, it will be understood that modifications and variations to the process can be made within the spirit and scope of the invention, which is defined by the following claims.
Claims (18)
1. A process for recovering metal compounds deposited on used catalyst from catalytic hydroprocessing of hydrocar-bon metals-containing feedstocks, comprising:
(a) treating used catalyst containing metal deposits with a fresh dilute acid solution to remove the metal deposits from the catalyst and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a hydroxide solution sufficient to neutralize the acid to a pH
between about 7 and 12, and forming a metal salts precipitate material;
(c) separating said precipitate material from the neutralized spent acid liquid solution and removing the metal salts from the solution; and (d) heating the metal salts to remove water and provide metal oxides products.
(a) treating used catalyst containing metal deposits with a fresh dilute acid solution to remove the metal deposits from the catalyst and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a hydroxide solution sufficient to neutralize the acid to a pH
between about 7 and 12, and forming a metal salts precipitate material;
(c) separating said precipitate material from the neutralized spent acid liquid solution and removing the metal salts from the solution; and (d) heating the metal salts to remove water and provide metal oxides products.
2. The process of claim 19 wherein the metal deposits on said used catalyst are principally nickel and vanadium compounds.
3. The process of claim 1, wherein said used catalyst is withdrawn from a catalytic hydroprocessing reaction and washed with a solvent to remove heavy oils before said acid treating step.
4. The process of claim 1, wherein said used catalyst is treated with a fresh dilute sulfuric acid solution at 150-250°F temperature to form a spent acid solution con-taining metal sulfates and oxysulfates.
5. The process of claim 1, wherein said spent acid solution is mixed with ammonia gas to neutralize the acid.
6. The process of claim 1, wherein said spent acid solution is mixed with an ammonium hydroxide solution to neutralize the acid.
7. The process of claim 1, wherein said spent acid solution is mixed with sodium hydroxide solution to neutra-lize the acid.
8. The process of claim 1, wherein said metal salts precipitate material is separated from the neutralized spent acid solution by filtration.
9. The process of claim 1, wherein said metal salts precipitate material removed is water washed to remove any remaining sulfates.
10. The process of claim 1, wherein said metal salts removed are mixed with carbon and furnace heated to suc-cessively higher temperatures to first produce metal oxides and then reduce the metal oxides to produce substantially pure metals.
11. The process of claim 2, wherein said spent acid solution is mixed with a hydroxide solution sufficient to neutralize the acid to a pH between about 3.5 and 7 to first precipitate and remove nickel salts, and then mixing addi-tional hydroxide solution with the remaining spent acid solution sufficient to increase the pH to between about 7 and 12 and precipitate and remove vanadium and other metal salts.
12. The process of claim 11, wherein said nickel salts are heated to 250-300°C to remove water vapor and water of hydration and produce nickel oxide product.
13. The process of claim 11, wherein said vanadium and other metal salts are heated to 250-300°C to remove water vapor and water of hydration and produce principally vanadium oxide product.
14. A process for recovering metal compounds deposited on used catalyst from the catalytic hydroprocessing of hydrocarbon metals-containing feedstocks, comprising:
(a) treating used oil-free catalyst containing deposits of nickel and vanadium with a fresh dilute sulfuric acid solution to extract and remove the metal depo-sits from the catalyst without damaging the cata-lyst, and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a ammonium hydroxide solution sufficient to neutralize the acid and provide a pH between about 7.0 and 12, and forming a precipitate material containing nickel and vanadium salts;
(c) filtering said neutralized spent acid solution and removing the metal salts precipitate material therefrom, and withdrawing a filtrate liquid stream; and (d) heating the resulting metal salts to remove water vapor and water of hydration and provide a nickel and vanadium oxides product.
(a) treating used oil-free catalyst containing deposits of nickel and vanadium with a fresh dilute sulfuric acid solution to extract and remove the metal depo-sits from the catalyst without damaging the cata-lyst, and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a ammonium hydroxide solution sufficient to neutralize the acid and provide a pH between about 7.0 and 12, and forming a precipitate material containing nickel and vanadium salts;
(c) filtering said neutralized spent acid solution and removing the metal salts precipitate material therefrom, and withdrawing a filtrate liquid stream; and (d) heating the resulting metal salts to remove water vapor and water of hydration and provide a nickel and vanadium oxides product.
15. A process for recovering metal compounds deposited on used catalyst from catalytic hydroprocessing of hydrocar-bon metals-containing feedstocks, comprising:
(a) treating used catalyst containing metal deposits with a fresh dilute acid solution to remove the metal deposits from the catalyst and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a hydroxide solution sufficient to neutralize the acid to a pH
between about 7 and 12, and forming a metal salts precipitate material;
(c) separating said precipitate material from the neutralized spent acid liquid solution and removing the metal salts from the solution;
(d) mixing said metal salts with granular carbon; and (e) furnace heating the metal salts to remove water and first produce metal oxides and then reduce the metal oxides to produce substantially pure metals.
(a) treating used catalyst containing metal deposits with a fresh dilute acid solution to remove the metal deposits from the catalyst and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a hydroxide solution sufficient to neutralize the acid to a pH
between about 7 and 12, and forming a metal salts precipitate material;
(c) separating said precipitate material from the neutralized spent acid liquid solution and removing the metal salts from the solution;
(d) mixing said metal salts with granular carbon; and (e) furnace heating the metal salts to remove water and first produce metal oxides and then reduce the metal oxides to produce substantially pure metals.
16. The process of claim 15, wherein said metal salts to carbon ratio is from about 2/1 to about 4/1.
17. The process of claim 15, wherein the metal salts removed are principally nickel and vanadium, and the metal salts and carbon mixture is first heated to about 1400-1500°F to drain molten nickel, then heated to 1700-1730°C to drain molten vanadium from the furnace.
18. A process for recovering metal compounds deposited on used catalyst from the catalytic hydroprocessing of hydrocarbon feedstocks containing metals compounds, said process comprising:
(a) treating used oil-free catalyst containing deposits of nickel and vanadium with a fresh dilute sulfuric acid solution to extract and remove the metal depo-sits from the catalyst without damaging the cata-lyst, and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a ammonium hydroxide solution sufficient to neutralize the acid and provide a pH between about 3.5 and 7.0, and forming a precipitate material containing nickel sulfate salts;
(c) filtering said neutralized spent acid solution and removing the nickel salts precipitate material therefrom, and withdrawing a first filtrate liquid stream;
(d) mixing said filtrate liquid stream with additional ammonium hydroxide solution sufficient to further neutralize the acid to a pH between about 7 and 12 and precipitate vanadium and other metal salts;
(e) filtering said further neutralized acid solution and removing vanadium salts therefrom, and withdrawing a second filtrate liquid stream; and (f) heating the resulting nickel and vanadium salts separately to remove water vapor and water of hydration and provide separate nickel and vanadium oxide products.
(a) treating used oil-free catalyst containing deposits of nickel and vanadium with a fresh dilute sulfuric acid solution to extract and remove the metal depo-sits from the catalyst without damaging the cata-lyst, and forming a spent acid solution containing metal salts;
(b) mixing said spent acid solution with a ammonium hydroxide solution sufficient to neutralize the acid and provide a pH between about 3.5 and 7.0, and forming a precipitate material containing nickel sulfate salts;
(c) filtering said neutralized spent acid solution and removing the nickel salts precipitate material therefrom, and withdrawing a first filtrate liquid stream;
(d) mixing said filtrate liquid stream with additional ammonium hydroxide solution sufficient to further neutralize the acid to a pH between about 7 and 12 and precipitate vanadium and other metal salts;
(e) filtering said further neutralized acid solution and removing vanadium salts therefrom, and withdrawing a second filtrate liquid stream; and (f) heating the resulting nickel and vanadium salts separately to remove water vapor and water of hydration and provide separate nickel and vanadium oxide products.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49521883A | 1983-05-16 | 1983-05-16 | |
| US495,218 | 1983-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1210746A true CA1210746A (en) | 1986-09-02 |
Family
ID=23967752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451557A Expired CA1210746A (en) | 1983-05-16 | 1984-04-09 | Recovering metal compounds from used catalysts obtained from hydroprocessing hydrocarbon feedstocks |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS6121902A (en) |
| CA (1) | CA1210746A (en) |
| DE (1) | DE3413801A1 (en) |
| MX (1) | MX174038B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1034329C2 (en) * | 2007-09-04 | 2009-03-27 | Greenshores Patent B V | Deposition formation preventing method for liquid food treating device, involves separating stream of liquid food from mainstream, adding calcium salt to stream of liquid food, and re-introducing stream of liquid food into mainstream |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD239348A5 (en) * | 1985-07-19 | 1986-09-24 | ��������@�����������@�@������������@���������@����@����������@���k�� | PROCESS FOR PROCESSING VANADIN-CONTAINING ALTAT CATALYSTS |
| DE4205980C2 (en) * | 1992-02-27 | 1999-02-11 | Huels Silicone Gmbh | Process for working up solid, metal - containing residues from the direct synthesis of organochlorosilanes and / or chlorosilanes |
| JP4992003B2 (en) * | 2000-12-27 | 2012-08-08 | 独立行政法人産業技術総合研究所 | Method for producing metal oxide fine particles |
| JP5867015B2 (en) * | 2011-11-24 | 2016-02-24 | 住友金属鉱山株式会社 | Manufacturing method of high purity nickel sulfate |
| CN116144950B (en) * | 2023-04-21 | 2023-07-14 | 国能龙源环保有限公司 | Method for leaching vanadium in waste denitration catalyst |
-
1984
- 1984-04-09 CA CA000451557A patent/CA1210746A/en not_active Expired
- 1984-04-12 DE DE19843413801 patent/DE3413801A1/en not_active Withdrawn
- 1984-05-15 MX MX20134584A patent/MX174038B/en unknown
- 1984-05-16 JP JP59098454A patent/JPS6121902A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1034329C2 (en) * | 2007-09-04 | 2009-03-27 | Greenshores Patent B V | Deposition formation preventing method for liquid food treating device, involves separating stream of liquid food from mainstream, adding calcium salt to stream of liquid food, and re-introducing stream of liquid food into mainstream |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3413801A1 (en) | 1984-11-22 |
| MX174038B (en) | 1994-04-15 |
| JPS6121902A (en) | 1986-01-30 |
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