CN102051483B - Method for reclaiming metals from molybdenum-containing waste catalyst - Google Patents
Method for reclaiming metals from molybdenum-containing waste catalyst Download PDFInfo
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Abstract
The invention discloses a method for reclaiming metals from a molybdenum-containing waste catalyst, which comprises the following steps of: mixing the waste catalyst and a magnesium-containing compound, roasting, degreasing, removing carbon, then crushing, mixing the powder and sodium carbonate, roasting the mixture, and leaching the roasted materials by using aqueous solution, wherein ammonium salt or aqueous ammonia is added in the aqueous solution leaching step, the molybdenum in the waste catalyst enters the solution in a form of sodium molybdate or ammonium molybdate, the impurities such as silicon, phosphorus and the like entering the aqueous solution form sediment, and the sediment is kept in solid residue in a filtration step; and after the solid is separated, performing acidification, extraction, re-extraction and the like to reclaim the molybdenum and other metals. The method solves the pollution problem caused by sulfur dioxide in the discharged gas in the roasting, degreasing and carbon removal processes; and the salts formed by the reclaimed sulfur and magnesium can play a role in removing impurities in the subsequent steps so as to save the consumption of chemical reagents in the metal reclaiming process and reduce the cost. In addition, the method reduces the operation steps, reduces equipment, improves the operation effect, and also can improve the molybdenum yield.
Description
Technical field
The present invention relates to a kind of method that from molybdenum-contained waste catalyst, reclaims metal, particularly from contain the useless hydrogenation catalyst of molybdenum and nickel, reclaim the method for metal.
Background technology
Along with the development of chemical industry, particularly use the development of the chemical industry such as oil refining, chemical industry of a large amount of catalyzer, can produce a large amount of discarded catalyzer.Simultaneously, along with the increasingly stringent of environmental legislation, these spent catalyst be treated as an important topic.
Molybdenum is the important component part of hydrogenation catalyst; In petroleum refining industry and nitrogen fertilizer production industry, be widely used; Molybdenum also has a large amount of demands in fields such as national defence, iron and steel simultaneously; And molybdenum ore reserves at the earth's surface are limited, therefore, from molybdenum-contained waste catalyst, reclaim molybdenum and have important Significance for Environment and economic implications.
Most at present employing hydrometallurgic recovery methods reclaim metals such as molybdenum from molybdenum-contained waste catalyst, soon the molybdenum in the spent catalyst is dipped into and forms ionic condition in the solution, from solution, extracts then, has formed various extraction process route thus.The main technique route comprises yellow soda ash dipping-roasting method, roasting-leaching method, roasting-organic substance extraction method etc.
CN1258754A is disclosed to be the method that reclaims molybdenum the spent catalyst from molybdenum-cobalt, and step is following: the spent catalyst for sulfur compound at first carries out roasting, leaches the spent catalyst after the processing repeatedly with ammonia solution then, again with sedimentary method recovery molybdenum.This method adopts volatile ammonia solution, the harm operator, and contaminate environment, and the leaching effect of molybdenum also awaited further raising.
CN91106479.6 proposes pyrogenic process and reclaims the nickel in the spent catalyst; Do not use the conventional cost height and the chemical method of complex process; Do not use the bigger electric furnace process of current consumption to refine nickel yet; And be to use the simple pyrometallurgical smelting of common technology, and catalyzer and flux, coke are blended together place 1400～1800 ℃ of melting in the stove, temperature, can obtain yield up to the metallic nickel more than 90%.This method needs higher maturing temperature.CN87101713 proposes to be specially adapted to reclaim in the waste nickel catalyst working method of metallic nickel.This method consists predominantly of handles and extracts nickle carbonoxide to the washing of useless raw material, oven dry, reduction.This method is compared with the induction furnace melting method, and the recovery that can improve metallic nickel is about more than 2 times.It is the method that reclaims nickel and aluminium from aluminium scrap base nickel-containing catalyst that CN200310105096.X proposes, and it comprises that soda ash sintering transition-boiling water dissolving sodium aluminate separates aluminium-nickel slag reducing-matting smelting and gets nickel matte Ni
3S
2-FeS-Ni-Fe alloy or copper nickel matte Cu
2S-Ni
3S
2-FeS alloy-blow Bessemer matte Ni
3S
2Or copper Bessemer matte Cu
2S-Ni
3S
2-Cu-Ni alloy-thick NaAlO
2Solution desilicification-carbonating branch solves white lake Al
2O
33H
2The O-calcination gets anhydrous alumina α-Al
2O
3Several steps.CN1453379A proposition wet method from useless catalyst is extracted the technology of vanadium and/or molybdenum.CN1221411A proposes the recovery of molybdenum epoxidation catalyst.Above-described method is generally all mainly handled single metal recovery, and some technology is all very complicated.
CN1453379A is disclosed to be the technology that wet method is extracted vanadium and/or molybdenum from useless catalyst; It is the oil content of utilizing the useless catalyst of high temperature removal earlier; Catalyst after the de-oiling is with addition of mixing the additives of forming by single soda ash or by soda ash and salt; The material for preparing is carried out high temperature oxidation sodium roasting once more, and the grog after the roasting is sent into leaching vat, takes static water logging; Adopt extraction process to realize the recovery of molybdenum then.This method adopts twice high-temperature roasting, thereby higher to equipment requirements, and the salt that adds simultaneously can produce serious corrosion to equipment and pipeline.
In the above-mentioned method that from spent catalyst, reclaims metal; Generally need carry out spent catalyst oil removing and carbon removal earlier handles; Effectively oil removing and carbon removal method are roasting methods at present; But general also while sulfur-bearing is about 3% like sulphur content in the useless hydrogenation catalyst in the spent catalyst, contains components such as silicon, phosphorus simultaneously.Above-mentioned spent catalyst is when roasting oil removing and carbon removal, and sulphur wherein will be converted into sulfurous gas, will not produce the serious environmental pollution if do not handle.Simultaneously, in subsequent processes, need use a large amount of chemical reagent in order to remove components such as silicon, phosphorus.
Summary of the invention
To the deficiency of prior art, the present invention proposes a kind of method that from molybdenum-contained waste catalyst, reclaims molybdenum, and this method has less investment, it is little to pollute, technology simple, not high and be easy to advantage such as industriallization to equipment requirements.
The present invention reclaims metal from molybdenum-contained waste catalyst method comprises following content:
(1) spent catalyst mixes with magnesium-containing compound and carries out roasting oil removing, carbon removal, and magnesium-containing compound comprises Natural manganese dioxide, Marinco H or magnesiumcarbonate;
(2) material that obtains of step (1) is pulverized, and mixes with yellow soda ash and carries out roasting;
(3) material leaches with the aqueous solution after step (2) roasting; Aqueous solution leaching operation is 8～10 in the pH value; Aqueous solution leaching operation step adds ammonium salt or ammoniacal liquor, and the molybdenum in the spent catalyst gets in the solution to comprise Sodium orthomolybdate or ammonium molybdate form, carries out solid-liquid separation then;
(4) the isolated liquid phase of step (3) is lower than 0.5 with sulfuric acid acidation to pH value, is preferably to be lower than 0.1, extracts then;
(5) extraction liquid that obtains of step (4) is stripped with ammoniacal liquor and obtained ammonium molybdate solution, and ammonium molybdate solution is with nitre acid for adjusting pH value to 1～4, and is preferred 2～2.8, separates the ammonium molybdate deposition that obtains.
The present invention reclaims in the method for metal from molybdenum-contained waste catalyst; The temperature of roasting oil removing described in the step (1) and carbon removal process is 350～550 ℃, and roasting time is 2～10 hours, and the sulphur content that the magnesium-containing compound add-on is pressed in the spent catalyst is confirmed; Be generally 1～2 times with sulphur complete reaction requirement; Be preferably 1.1～1.5 and extraordinarily go into, in roasting oil removing and carbon removal process, the sulphur in the spent catalyst is converted into sulfurous gas; Generate magnesium sulfite and a small amount of sal epsom with the magnesium-containing compound reaction then, the content of sulfur dioxide in the torrefaction waste gas obviously reduces.
In the inventive method; The described pulverizing of step (2) generally need be crushed to 60～120 orders; The consumption of yellow soda ash can be confirmed according to the molybdenum content in the spent catalyst, generally generates 1～2 of the theoretical requirement of Sodium orthomolybdate by the molybdenum complete reaction and extraordinarily goes into, and preferably extraordinarily goes into by 1.1～1.5; For the catalyzer that contains vanadium, need consider the amount that needs when vanadium transformed fully simultaneously.The described maturing temperature of step (2) is 550～1000 ℃, and preferred 600～800 ℃, roasting time was generally 1～12 hour.In the roasting process of step (2), molybdenum is converted into water-soluble Sodium orthomolybdate, and high-temperature calcination process is oxidized to sal epsom with the magnesium sulfite major part simultaneously.
In the inventive method, the material water leaches after step (3) roasting, and solvent and solute weight ratio is 2: 1～4: 1, and temperature is 25 ℃～85 ℃, and pH value is 8～10, and is preferred 8～9, and extraction time was generally 3～20 hours, and solid-liquid separation adopts the filtering separation mode of routine.In the solution leaching operation, add an amount of ammonium sulfate, ammonium chloride or ammoniacal liquor, molybdenum gets in the aqueous solution with the form of Sodium orthomolybdate or ammonium molybdate, impurity and magnesium and ammonium reaction generation Magnesium Silicate q-agent (MgSiO such as the silicon in the entering aqueous solution, phosphorus
3), magnesium ammonium phosphate (MgNH
4PO
4) these two kinds of materials form to be deposited in and be retained in the filtration step in the solid residue, excessive magnesium forms Marinco H and also gets in the solid residue under alkaline condition simultaneously, promptly in aqueous solution leaching, has realized the impurity separation.
In the inventive method; The leach liquor that step (4) is taken off behind the impurity adopts organic extractant to extract; Organic extractant can be selected this area extraction agent arbitrarily; Like in tributyl phosphate, two-2-ethylhexyl phosphoric acid salt, trioctylamine and the petrolenum sulfoxide etc. one or more, organic extractant generally need add thinner and auxiliary agent etc. in use, one or more in thinner such as gasoline, kerosene, diesel oil, white oil and the hexanaphthene etc.; Auxiliary agent is generally alcohol, ketone, ester etc., and the weight content of thinner in extraction agent is generally 30%～80%.The volume ratio of extraction agent and water was generally 1: 1～1: 5, and extraction temperature is generally 20 ℃～60 ℃.
In this forwarding method, to use weight concentration be that 10%～25% ammoniacal liquor is stripped to extraction liquid in the step (5), and molybdenum gets in the ammoniacal liquor with the form of ammonium molybdate, and the extraction agent after the separation recycles after regenerating with the ammoniacal liquor of weight concentration 2%～10%.It is that 98% concentrated nitric acid advances acidifying and obtains the ammonium molybdate deposition that ammonium molybdate solution adds concentrated nitric acid such as weight concentration, the further removal of impurity as required before carrying out acidifying, as add the further dephosphorization of magnesium salts, add operation such as the charcoal absorption removal of impurity.Step (5) obtains the ammonium molybdate product that ammonium molybdate deposition Hong Ganhou obtains reclaiming.
The present invention reclaims the method for metal from molybdenum-contained waste catalyst; Solved in roasting oil removing, the carbon removal process and contained the pollution problem that sulfurous gas brings in the discharging gas; The salt that sulphur that reclaims and magnesium form can play removal of impurity effect in subsequent step; Save the consumption of the chemical reagent in the metal recovery process, reduced cost.And, the leaching and the removal of impurity process of molybdenum combined, reduced operation steps, simplified equipment, improved operating effect.In addition, research shows, adds magnesium-containing compound in roasting oil removing and the carbon removal process; Can make spent catalyst in roasting process, keep loose state, and temperature distribution is more even, the local temperature of having avoided the spent catalyst direct roasting to occur is too high; Cause the molybdenum oxide distillation to run off, and cause the phenomenon that the recovery reduces, simultaneously; Prevent that other component sintering when local temperature is too high from making molybdenum be difficult for the problem that leaches, and helps improving the recovery of molybdenum.
Embodiment
Further specify the present invention program and effect through embodiment below.The per-cent that relates to is weight percentage.
Embodiment 1
(3996 is the heavy distillate hydrogen cracking pretreatment catalyst of Fushun Petrochemical Research Institute's development and production to 3996 useless hydrogenation catalysts; Carrier is siliceous aluminum oxide, and active ingredient contains auxiliary agent phosphorus simultaneously for containing molybdenum and nickel; Spent catalyst after the use contains charcoal and sulphur etc.) 100g all is being converted into 1.2 of magnesium sulfite requirement and extraordinarily going into Natural manganese dioxide by changeing sulphur; 450 ℃ were carried out roasting 3 hours, will be crushed to 120 orders again after the cooling, mixed with yellow soda ash then; When sodium carbonate amount transforms by molybdenum fully 1.1 times of requirement, with mixed powder 700 ℃ of roastings 10 hours.
The material water leaches after the roasting, presses the complete sedimentary amount adding ammoniacal liquor of phosphorus in the spent catalyst, and solvent and solute weight ratio is 2: 1,55 ℃ of temperature, and 10 hours time, the pH value is 9.5, adopts filter method to carry out solid-liquid separation then.Liquid after the separation adds 98% vitriol oil adjusting pH value to 0.01 and extracts.It is tributyl phosphate 10% that extraction agent adopts volume ratio, trioctylamine 10% and kerosene 80%.Extraction agent consumption and water consumption volume ratio 1: 2, extraction temperature is 25 ℃.
The collection fluid is stripped with the ammoniacal liquor of concentration 18% and is obtained ammonium molybdate solution; Using and using the nitre acid for adjusting pH value behind the remaining organism of charcoal absorption is 2 to obtain the ammonium molybdate deposition; Ammonium molybdate forms sediment to dry and obtains final ammonium molybdate product, and the mother liquor behind the deposition ammonium molybdate extracts further recovery molybdenum wherein again.The recovery of molybdenum is 95.2% in the present embodiment spent catalyst.
Comparative example 1
According to embodiment 1 described method, in roasting oil removing and carbon removal process, do not add Natural manganese dioxide, be increased in the aqueous solution and leach back sal epsom and ammonia removal of impurity step, other operational condition is constant, the ult rec 82.4% of molybdenum.
Embodiment 2
3996 useless hydrogenation catalyst 100g of Fushun Petrochemical Research Institute's development and production all are being converted into 1.2 of magnesium sulfite requirement and are extraordinarily going into oxidation by changeing sulphur; 450 ℃ were carried out roasting 3 hours; To be crushed to 120 orders again after the cooling; Mix with yellow soda ash then, when sodium carbonate amount transforms by molybdenum fully 1.1 times of requirement, with mixed powder 700 ℃ of roastings 10 hours.
The material water leaches after the roasting, presses the complete sedimentary amount adding ammoniacal liquor of phosphorus in the spent catalyst, and solvent and solute weight ratio is 2: 1,55 ℃ of temperature, and 10 hours time, the pH value is 9.5, adopts filter method to carry out solid-liquid separation then.Liquid after the separation adds 98% vitriol oil adjusting pH value to 0.01 and extracts.Extraction agent adopts the mixture of 15% trioctylamine, 15% tributyl phosphate and 70% kerosene.Extraction agent consumption and water consumption volume ratio 1: 2, extraction temperature is 25 ℃.
The collection fluid is stripped with the ammoniacal liquor of concentration 21% and is obtained ammonium molybdate solution; Using and using the nitre acid for adjusting pH value behind the remaining organism of charcoal absorption is 2 to obtain the ammonium molybdate deposition; Ammonium molybdate forms sediment to dry and obtains final ammonium molybdate product, and the mother liquor behind the deposition ammonium molybdate extracts further recovery molybdenum wherein again.The recovery of molybdenum is 97.2% in the present embodiment spent catalyst.
Embodiment 3
According to the method for embodiment 1, Natural manganese dioxide changes magnesiumcarbonate into, and the magnesiumcarbonate consumption increases to 1.5 times of theoretical requirement, and oil removing and carbon removal maturing temperature are 550 ℃, and roasting time is 5 hours.Other is identical with embodiment 1, and molybdenum recovery is 95.7%.
Claims (15)
1. method that from molybdenum-contained waste catalyst, reclaims metal comprises following process:
(1) spent catalyst mixes with magnesium-containing compound and carries out roasting oil removing, carbon removal;
(2) material that obtains of step (1) is pulverized, and mixes with yellow soda ash and carries out roasting;
(3) material leaches with the aqueous solution after step (2) roasting, and aqueous solution leaching operation step adds ammonium salt or ammoniacal liquor, and the molybdenum in the spent catalyst gets in the solution to comprise Sodium orthomolybdate or ammonium molybdate form, carries out solid-liquid separation then;
(4) the isolated liquid phase of step (3) is lower than 0.5 with sulfuric acid acidation to pH value, extracts then;
(5) extraction liquid that obtains of step (4) is stripped with ammoniacal liquor and is obtained ammonium molybdate solution, and ammonium molybdate solution separates the ammonium molybdate deposition that obtains with nitre acid for adjusting pH value to 1～4;
The described magnesium-containing compound of step (1) comprises Natural manganese dioxide, Marinco H or magnesiumcarbonate.
2. according to the described method of claim 1, it is characterized in that: the temperature of roasting oil removing described in the step (1) and carbon removal process is 350～550 ℃, and roasting time is 2～10 hours.
3. according to the described method of claim 1, it is characterized in that: step (1) magnesium-containing compound add-on for 1～2 times of sulphur complete reaction requirement.
4. according to the described method of claim 1, it is characterized in that: step (1) magnesium-containing compound add-on is and 1.1～1.5 of sulphur complete reaction requirement.
5. according to the described method of claim 1, it is characterized in that: the described pulverizing of step (2) is for being crushed to 60～120 orders, and the consumption of yellow soda ash is pressed 1～2 times of the theoretical requirement of molybdenum complete reaction generation Sodium orthomolybdate.
6. according to the described method of claim 1, it is characterized in that: the consumption of step (2) yellow soda ash is pressed the molybdenum complete reaction and is generated 1.1～1.5 of the theoretical requirement of Sodium orthomolybdate.
7. according to claim 1 or 5 described methods, it is characterized in that: the described maturing temperature of step (2) is 550～1000 ℃, and roasting time is 1～12 hour.
8. according to claim 1 or 5 described methods, it is characterized in that: the described maturing temperature of step (2) is 600～800 ℃.
9. according to the described method of claim 1, it is characterized in that: the material water leaches after step (3) roasting, and solvent and solute weight ratio is 2: 1～4: 1; Temperature is 25 ℃～85 ℃; The pH value is 8～10, and extraction time is 3～20 hours, and solid-liquid separation adopts conventional filtering separation mode.
10. according to claim 1 or 9 described methods; It is characterized in that: step (3) in the solution leaching operation; Add an amount of ammonium sulfate, ammonium chloride or ammoniacal liquor; Get into silicon or phosphorus impurities and magnesium and ammonium reaction generation Magnesium Silicate q-agent and magnesium ammonium phosphate in the aqueous solution, these two kinds of materials form to be deposited in the filtration step and are retained in the solid residue.
11. according to the described method of claim 1, it is characterized in that: the isolated liquid phase of step (3) is lower than 0.1 with sulfuric acid acidation to pH value, extracts then.
12. according to the described method of claim 1; It is characterized in that: the leach liquor that step (4) is taken off behind the impurity adopts organic extractant to extract; The active principle of organic extractant is selected one or more in tributyl phosphate, trioctylamine and the petrolenum sulfoxide, and thinner is one or more in gasoline, kerosene, diesel oil, white oil and the hexanaphthene.
13. according to claim 1 or 12 described methods, it is characterized in that: in the described extracting operation of step (4), the volume ratio of extraction agent and water is 1: 1～1: 5, and extraction temperature is 20 ℃～60 ℃.
14. according to the described method of claim 1, it is characterized in that: step (5) ammonium molybdate solution separates the ammonium molybdate deposition that obtains with nitre acid for adjusting pH value to 2～2.8.
15. according to the described method of claim 1; It is characterized in that: to use weight concentration be that 10%～25% ammoniacal liquor is stripped to extraction liquid in the step (5); Molybdenum gets in the ammoniacal liquor with the form of ammonium molybdate, recycles after the ammoniacal liquor regeneration of the extraction agent after the separation with weight concentration 2%～10%.
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