CN104628035A - Resourceful utilization method of waste catalyst - Google Patents
Resourceful utilization method of waste catalyst Download PDFInfo
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- CN104628035A CN104628035A CN201510003955.7A CN201510003955A CN104628035A CN 104628035 A CN104628035 A CN 104628035A CN 201510003955 A CN201510003955 A CN 201510003955A CN 104628035 A CN104628035 A CN 104628035A
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- sodium
- solution
- molybdenum
- spent catalyst
- vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
- C22B21/003—Obtaining aluminium by wet processes from waste materials from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/026—Obtaining nickel or cobalt by dry processes 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
-
- 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
The invention relates to a resourceful utilization method of a waste catalyst. The resourceful utilization method comprises the following steps of putting the waste catalyst into a de-oiling furnace and carrying out de-oiling, decarburization and desulfurization treatment by virtue of the heat value to obtain a de-oiled material; mixing and stirring the de-oiled material and sodium salt to obtain a mixture, putting the mixture into a rotary kiln and carrying out sodium modification and roasting on the mixture at 900-1100 DEG C to obtain a sodium-modified material; carrying out multistage leaching on the sodium-modified material, recovering metallic nickel and aluminum to obtain a nickel-aluminum powder product and a leaching solution; adding a sulfate precipitating agent, precipitating to remove silicon, aluminum and phosphorus impurities to obtain a mixed solution of sodium molybdate and sodium vanadate; separating molybdenum from vanadium by virtue of an ion exchange method to obtain a sodium molybdate solution and a pure sodium vanadate solution; adding an ammonium salt precipitating agent into the pure sodium vanadate solution, precipitating to recover vanadium to obtain a high-purity ammonium metavanadate product and a sodium sulfate solution; extracting, purifying and enriching molybdenum with a solvent to obtain a pure sodium molybdate solution and a sodium sulfate solution; adding a sulfuric acid precipitating agent into the sodium molybdate solution and precipitating to recover molybdenum to obtain a high-purity molybdic acid product and a sodium sulfate solution; carrying out ion exchange on the sodium sulfate solution, recovering molybdenum and vanadium in the solution, carrying out multi-effect concentration crystallization to obtain a product anhydrous sodium sulfate, recovering sodium sulfate in the produced solution and returning condensed water.
Description
Technical field
The present invention relates to the metallurgical technologies such as oxidizing roasting, solvent extraction, ion-exchange, condensing crystal, chemical precipitation, right
spent catalystcarry out recycling, each component produces corresponding Chemicals, belongs to environment protection and comprehensive utilization of resources field.
Background technology
The capacity to reprocess of crude oil improves gradually, and the learies of oil refining catalyst is increased year by year.Oil refining catalyst is active in the process used can slowly decline in time, finally causes catalyzer to be scrapped.The major cause of catalyst deactivation: one is carbon distribution inactivation, carbon-containing sediment on catalyst surface is called coking, because carbonaceous material and other material deposit in catalyst pores, aperture is caused to reduce (or aperture reduces), reactant molecule can not be diffused in hand-hole, and cause catalyst deactivation; Two are
poison loseslive, the impurity absorption such as the heavy metal in the fluid that catalyzer contacts, in the active sites of catalyzer, make the activity of catalyzer significantly decline or disappear, in being referred to as
poison loseslive; Three is heat inactivation and sintering deactivation, and the heat inactivation of catalyzer and sintering deactivation refer to the change of catalyst structure and the performance caused by high temperature.
spent catalystin containing a large amount of useful matter, as caused the carbon distribution of catalyst deactivation, the mineral oil, molybdenum, vanadium, nickel heavy metal etc. of surface contamination, having huge recovery potentiality, secondary resource all can be it can be used as to be used.If will
spent catalystthe available stocks such as middle carbon distribution, oil, sulphur and heavy metal reclaim or directly as the raw material of other high value added product of synthesis, not only can solve
spent catalystthe environmental problem brought, and the utilization ratio that can improve resource, reduce the waste of resource, create certain economic benefit, realize Sustainable development.
Due to
spent catalystcontaining the heavy metal such as waste mineral oil and nickel, belong to the HW06 class in Hazardous Waste List and HW46 class Hazardous wastes.At present, existing
spent catalystplace
reason is mainadopt underground landfill or roasting in conjunction with heavy metals such as chemical process recovery part molybdenum vanadium.The former not only causes the pollution of underground water and soil, but also will cause the loss of the resources such as heavy metal, and the latter's metal recovery is incomplete, and ignores
spent catalystthe utilization of other component (carbon distribution, oil, sulphur, aluminum oxide/nickel), cause the wasting of resources and the secondary pollution to environment, therefore develop new
spent catalystapplication technology as the second resource, make waste resource be able to recycle and there is certain realistic meaning.
Summary of the invention
The present invention is directed to prior art Problems existing, provide easy, the easy operation of a kind of method, can oil refining be made full use of
spent catalystin a large amount of useful matter, antipollution
spent catalystresource utilization method, according to
spent catalystcompositing characteristic, adopt the metallurgical technology such as oxidizing roasting, solvent extraction, ion-exchange, condensing crystal, chemical precipitation, by rational technological design, realize
spent catalystthe recycling of each component,
spent catalystin carbon distribution, oil produce steam by desizer, for the production of; Sulphur changes into calcium sulfate (gypsum); Molybdenum, vanadium, nickel change into molybdic acid, ammonium meta-vanadate and nickel aluminium powder product; Do not have waste residue to produce in production process, water of productive use recycle, industrial residue, wastewater zero discharge, reach
spent catalystturn waste into wealth, the object of recycling.
Of the present invention
spent catalystresource utilization method, step is as follows:
(1) will
spent catalystdropping into desizer utilizes himself calorific value to carry out the process of de-oiling decarbonization, desulfuration, obtains de-oiling material;
(2), after de-oiling material step (1) obtained and sodium salt are puddled by the mass ratio of (3-5) ︰ 1, drop in rotary kiln and carry out sodium roasting at 900-1100 DEG C, obtain sodium material;
(3) sodium material step (2) obtained is at 50-90 DEG C, and sodium material and water, according to the mass ratio of 1 ︰ (2-5), carry out multistage leaching, Footwall drift nickel and aluminium, obtain nickel aluminium powder product and leach liquor;
(4) add the sulfate precipitation agent that can be settled out silicon, aluminium, phosphorus impurities in the leach liquor obtained to step (3), adopt silicon, aluminium, phosphorus impurities in chemical precipitation method removing leach liquor, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions;
(5) Sodium orthomolybdate step (4) obtained, vanadic acid sodium mixing solutions adopt ion exchange method to carry out the separation of molybdenum vanadium, obtain sodium molybdate solution and pure sodium vanadate solution respectively;
(6) add ammonium salt precipitation agent in the pure sodium vanadate solution obtained to step (5), adopt chemical precipitation method to reclaim vanadium, obtain high-purity ammonium meta-vanadate product and metabisulfite solution;
(7) by the sodium molybdate solution that step (5) obtains, by solvent extraction purification and enrichment molybdenum, pure sodium molybdate solution and metabisulfite solution is obtained;
(8) add sulfuric acid precipitation agent in the pure sodium molybdate solution obtained to step (7), regulate pH=1.0-1.5, adopt chemical precipitation method to reclaim molybdenum, obtain High-Purity Molybdenum acid product and metabisulfite solution;
(9) metabisulfite solution that step (6), (7) and (8) obtain is carried out ion-exchange, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, obtain product Sodium sulfate anhydrous.min(99), after the sodium sulfate in remanufacture solution, water of condensation returns step (3).
The temperature of described de-oiling decarbonization, desulfuration process is at least 950 DEG C, at least 1 hour residence time.
In step (1)
spent catalystde-oiling decarbonization, desulfuration contains SO 2 tail gas, after bag-type dust, Dual alkali absorb sulphur, reclaims
spent catalystmiddle sulphur, by-product gypsum.
Carry out ion-exchange to the metabisulfite solution obtained in step (6), (7) and (8), after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, obtain product Sodium sulfate anhydrous.min(99), water of condensation returns step (3).
Beneficial effect of the present invention is as follows:
This technique for
spent catalystthe compositing characteristic of raw material, by rational design, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution.
spent catalystin carbon distribution and oil firing produce steam and heat energy, for the production of; Sulphur in raw material changes into gypsum product; Molybdenum in raw material, vanadium and nickel all change into corresponding product.Nickel aluminium powder, as product, is used as the raw material producing Rhometal and aluminum oxide.In addition, in whole production process, do not have waste residue to produce, water of productive use recycle, achieve industrial residue, wastewater zero discharge,
spent catalystat utmost realize resource regeneration.
Embodiment
Of the present invention
spent catalystresource utilization method, step is as follows:
(1) will
spent catalystdropping into desizer utilizes himself calorific value to carry out the process of de-oiling decarbonization, desulfuration, obtains de-oiling material; The temperature of de-oiling decarbonization, desulfuration process is at least 950 DEG C, at least 1 hour residence time.
spent catalystde-oiling decarbonization, desulfuration contains SO 2 tail gas, after bag-type dust, Dual alkali absorb sulphur, reclaims
spent catalystmiddle sulphur, by-product gypsum.
(2), after de-oiling material step (1) obtained and sodium salt are puddled by the mass ratio of (3 or 4 or 5) ︰ 1, drop in rotary kiln and carry out sodium roasting at 900 DEG C or 1000 DEG C or 1100 DEG C, obtain sodium material;
(3) sodium material step (2) obtained is at 50 DEG C or 60 DEG C or 70 DEG C or 80 DEG C or 90 DEG C, and sodium material and water, according to the mass ratio of 1 ︰ (2 or 3 or 4 or 5), carry out multistage leaching, Footwall drift nickel and aluminium, obtain nickel aluminium powder product and leach liquor;
(4) add the sulfate precipitation agent that can be settled out silicon, aluminium, phosphorus impurities in the leach liquor obtained to step (3), adopt silicon, aluminium, phosphorus impurities in chemical precipitation method removing leach liquor, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions;
(5) Sodium orthomolybdate step (4) obtained, vanadic acid sodium mixing solutions adopt ion exchange method to carry out the separation of molybdenum vanadium, obtain sodium molybdate solution and pure sodium vanadate solution respectively;
(6) add ammonium salt precipitation agent in the pure sodium vanadate solution obtained to step (5), adopt chemical precipitation method to reclaim vanadium, obtain high-purity ammonium meta-vanadate product and metabisulfite solution;
(7) by step (5)) sodium molybdate solution that obtains, by solvent extraction purification and enrichment molybdenum, obtain pure sodium molybdate solution and metabisulfite solution;
(8) add sulfuric acid precipitation agent in the pure sodium molybdate solution obtained to step (7), regulate pH=1.0-1.5, adopt chemical precipitation method to reclaim molybdenum, obtain High-Purity Molybdenum acid product and metabisulfite solution.
(9) metabisulfite solution that step (6), (7) and (8) obtain is carried out ion-exchange, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, obtain product Sodium sulfate anhydrous.min(99), after sodium sulfate in remanufacture solution, water of condensation returns step (3), process water zero release.
The add-on of above-mentioned each precipitation agent is determined according to the sedimentable matter total amount in the solution that needs measured.
Carry out ion-exchange to the metabisulfite solution obtained in above-mentioned steps (6), (7) and (8), after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, obtain product Sodium sulfate anhydrous.min(99), water of condensation returns step (3), process water zero release.
For
spent catalystthe compositing characteristic of raw material, by rational design, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution,
spent catalystin carbon distribution and oil firing produce steam and heat energy, for the production of; Sulphur in raw material changes into gypsum product; Molybdenum in raw material, vanadium, nickel and aluminium all change into corresponding product, do not have waste residue to produce in whole production process, water of productive use recycle, industrial residue, wastewater zero discharge,
spent catalystrealize at utmost resource regeneration.
State technical characteristic of the present invention further below by specific embodiment, but be not limited to embodiment, relating to per-cent is mass percent.
Embodiment 1
Get oil refining
spent catalyst500t,
spent catalystoutward appearance is black, trifolium-shaped, particle diameter φ 1.3 × (3 ~ 5) mm,
spent catalystcontaining porcelain ball 4.6%, carbon distribution 7.4%, oil 12.2%, sulphur 5.4%, molybdenum 5.3%, vanadium 7.5%, nickel 5.2%, aluminium 11.9%, wherein molybdenum, vanadium, nickel exist with metallic sulfide form, and aluminium exists with metal oxide form.
(1) adopt 10 × 10mm sieve, sift out
spent catalystmiddle porcelain ball, after screening
spent catalyst, drop into desizer and carry out the process of de-oiling decarbonization, desulfuration, residence time 70min, temperature 960 DEG C, the steam of output pressure 0.3Mpa, the steam of generation is for production and applications such as the water temp. heating leached and pipeline tracings.
(2) by the de-oiling material after step (1) de-oiling, with sodium salt in 3.4:1 ratio, add water after Mix and dosing with stirrer, in feeding rotary kiln, at 950 DEG C, carry out sodium roasting, residence time 70min, discharging, through cooling rapidly, controls drop temperature at 550 DEG C, makes
spent catalystin the convert metals such as molybdenum vanadium be water-soluble sodium material.
(3) tail gas that step (1) and step (2) produce is sent into exhaust treatment system, tail gas is first after cooling dedusting, enter thionizer, desulfurization absorption is carried out by lime slurry, be calcium sulfate by the sulfurous gas conversion in tail gas, after plate-and-frame filter press filters, obtain gypsum product, tail gas rear discharge up to standard, remaining liquid recovery.
(4) sodium material step (2) roasting obtained drops in Leaching reaction still, by 1:4 solid-to-liquid ratio, keeps 80 DEG C of temperature, stirs 50min, carries out multistage leaching.Obtaining filtrate through plate-and-frame filter press separation is leach liquor, and squeeze in immersion liquid tank, filter residue, through repetitive scrubbing, obtains nickel aluminium powder product, and wherein containing molybdenum 0.3%, vanadium 0.55%, washings is recovery repeatedly.
(5) molybdenum 12.75g/L, vanadium 17.83g/L is contained in the leach liquor that step (4) obtains, regulate pH=5.5, control temperature is at 50 DEG C, sulfate precipitation agent is added according to calculating ratio, stirring reaction 30min in a kettle., the impurity such as removing silicon, aluminium, phosphorus, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions, wherein silicon, aluminium, phosphorus impurities concentration are all less than 0.01g/L, and after removal of impurities, Molybdenum in Solution vanadium concentration is respectively 11.2g/L and 15.66g/L.
(6) by the Sodium orthomolybdate after step (5) removal of impurities, vanadic acid sodium mixing solutions, ion exchange method is adopted to carry out the separation of molybdenum vanadium, mixing solutions regulates pH=7, by three group of four row ion exchange column, utilize specific ion exchange resin to adsorb, adsorb saturated after, with 19% sodium hydroxide solution resolve, obtain pure sodium molybdate solution and pure sodium vanadate solution, wherein
Molybdenum concentration 10.89g/L in sodium molybdate solution, vanadium is not more than 0.01g/L;
Vanadium concentration 60.6g/L in sodium vanadate solution, molybdenum is not more than 0.01g/L.
(7) sodium vanadate solution of step (6) 60.6g/L is diluted with water to 25g/L, regulate pH=8, the weight of the ammonium salt precipitation agent needed for calculating by 3:1 weight ratio, ammonium salt precipitation agent is at the uniform velocity added in whipping process, control temperature 45 DEG C, stirring reaction, after 1 hour, filters immediately, after being separated by filter press, obtain high-purity ammonium meta-vanadate product and metabisulfite solution.
(8) sodium molybdate solution that step (6) obtains is pumped into acid adjustment reactor, add sulfuric acid acidation, adopt specific extraction agent, by multi-stage continuous extraction technique, purify molybdenum ion, obtains pure rich molybdenum liquid and metabisulfite solution.Wherein the concentration of molybdenum is 126.4g/L.
(9) pure for step (8) rich molybdenum liquid is added sulfuric acid precipitation agent, regulate pH=1.5, slowly add sulfuric acid in whipping process, control temperature 50 DEG C, after stirring reaction 60min, is separated by plate-and-frame filter press, obtains High-Purity Molybdenum acid product and metabisulfite solution.
(10) ion-exchange is carried out after being collected by the metabisulfite solution that step (7), (8) and (9) obtain, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, control vapor pressure is 0.3Mpa, vacuum tightness 0.05Mpa, temperature 75-105 DEG C, evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product, the water of condensation that concentration and evaporation is regained returns leaching operation and recycles, process water zero release.
This 500t
spent catalystcommerical test, for
spent catalystthe compositing characteristic of raw material, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution,
spent catalystin carbon distribution and oil firing produce steam 1500t, for the production of; Sulphur in raw material is converted into gypsum product 145t; Molybdenum in raw material, vanadium and nickel aluminium are separately converted to product molybdic acid 42.49t, ammonium meta-vanadate 77.43t, nickel aluminium powder 324t, and evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product 139t, and wherein nickel, aluminium can reclaim completely, molybdenum recovery 95.02%, vanadium recovery 90%.Waste residue is not had to produce in whole production process, water of productive use recycle, industrial residue, wastewater zero discharge,
spent catalystrealize at utmost resource regeneration.
Embodiment 2
Get oil refining
spent catalyst1000t,
spent catalystoutward appearance is black, trifolium-shaped, particle diameter φ 1.3 × (3 ~ 5) mm,
spent catalystcontaining porcelain ball 4.3%, carbon distribution 8.2%, oil 10.7%, sulphur 4.8%, molybdenum 4.6%, vanadium 6.7%, nickel 5.4%, aluminium 12.3%, wherein molybdenum, vanadium, nickel exist with metallic sulfide form, and aluminium exists with metal oxide form.
(1) adopt 10 × 10mm sieve, sift out
spent catalystmiddle porcelain ball, after screening
spent catalyst, drop into desizer and carry out the process of de-oiling decarbonization, desulfuration, residence time 60min, temperature 970 DEG C, the steam of output pressure 0.3Mpa, the steam of generation is for production and applications such as the water temp. heating leached and pipeline tracings.
(2) by the de-oiling material after step (1) de-oiling, with sodium salt in 3.8:1 ratio, add water after Mix and dosing with stirrer, in feeding rotary kiln, at 970 DEG C, carry out sodium roasting, residence time 65min, discharging, through cooling rapidly, controls drop temperature at 550 DEG C, makes
spent catalystin the convert metals such as molybdenum vanadium be water-soluble sodium material.
(3) tail gas that step (1) and step (2) produce is sent into exhaust treatment system, tail gas is first after cooling dedusting, enter thionizer, desulfurization absorption is carried out by lime slurry, be calcium sulfate by the sulfurous gas conversion in tail gas, after plate-and-frame filter press filters, obtain gypsum product, tail gas rear discharge up to standard, remaining liquid recovery.
(4) sodium material step (2) roasting obtained drops in Leaching reaction still, by 1:3.5 solid-to-liquid ratio, keeps 70 DEG C of temperature, stirs 50min, carries out multistage leaching.Obtaining filtrate through plate-and-frame filter press separation is leach liquor, and squeeze in immersion liquid tank, filter residue, through repetitive scrubbing, obtains nickel aluminium powder product, and wherein containing molybdenum 0.21%, vanadium 0.52%, washings is recovery repeatedly.
(5) molybdenum 12.74g/L, vanadium 18.18g/L is contained in the leach liquor that step (4) obtains, regulate pH=5.8, control temperature is at 60 DEG C, sulfate precipitation agent is added according to calculating ratio, stirring reaction 40min in a kettle., the impurity such as removing silicon, aluminium, phosphorus, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions, wherein silicon, aluminium, phosphorus impurities concentration are all less than 0.01g/L, and after removal of impurities, Molybdenum in Solution vanadium concentration is respectively 10.96g/L and 15.64g/L.
(6) by the Sodium orthomolybdate after step (5) removal of impurities, vanadic acid sodium mixing solutions, ion exchange method is adopted to carry out the separation of molybdenum vanadium, mixing solutions regulates pH=7.2, by three group of four row ion exchange column, utilize specific ion exchange resin to adsorb, adsorb saturated after, with 15% sodium hydroxide solution resolve, obtain pure sodium molybdate solution and pure sodium vanadate solution, wherein
Molybdenum concentration 10.46g/L in sodium molybdate solution, vanadium is not more than 0.01g/L;
Vanadium concentration 62.15g/L in sodium vanadate solution, molybdenum is not more than 0.01g/L.
(7) sodium vanadate solution of step (6) 62.15g/L is diluted with water to 25g/L, regulate pH=8, the weight of the ammonium salt precipitation agent needed for calculating according to 3.4:1 weight ratio, ammonium salt precipitation agent is at the uniform velocity added in whipping process, control temperature 45 DEG C, stirring reaction, after 1 hour, filters immediately, after being separated by filter press, obtain high-purity ammonium meta-vanadate product and metabisulfite solution.
(8) sodium molybdate solution that step (6) obtains is pumped into acid adjustment reactor, add sulfuric acid acidation, adopt specific extraction agent, by multi-stage continuous extraction technique, purify molybdenum ion, obtains pure rich molybdenum liquid and metabisulfite solution.Wherein the concentration of molybdenum is 121.7g/L.
(9) pure for step (8) rich molybdenum liquid is added sulfuric acid precipitation agent, regulate pH=1.3, slowly add sulfuric acid in whipping process, control temperature 50 DEG C, after stirring reaction 50min, is separated by plate-and-frame filter press, obtains High-Purity Molybdenum acid product and metabisulfite solution.
(10) ion-exchange is carried out after being collected by the metabisulfite solution that step (7), (8) and (9) obtain, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, control vapor pressure is 0.3Mpa, vacuum tightness 0.05Mpa, temperature 75-105 DEG C, evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product, the water of condensation that concentration and evaporation is regained returns leaching operation and recycles, process water zero release.
This 1000t
spent catalystcommerical test, for
spent catalystthe compositing characteristic of raw material, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution,
spent catalystin carbon distribution and oil firing produce steam 3000t, for the production of; Sulphur in raw material is converted into gypsum product 259t; Molybdenum in raw material, vanadium and nickel aluminium are separately converted to molybdic acid 74.52t, ammonium meta-vanadate 144.4t, nickel aluminium powder 650t, and evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product 255t, and wherein nickel, aluminium can reclaim completely, molybdenum recovery 96%, vanadium recovery 93.9%.Waste residue is not had to produce in whole production process, water of productive use recycle, industrial residue, wastewater zero discharge,
spent catalystrealize at utmost resource regeneration.
Embodiment 3
Get
spent catalyst1500t,
spent catalystoutward appearance is black, trifolium-shaped, particle diameter φ 1.3 × (3 ~ 5) mm,
spent catalystcontaining porcelain ball 4.9%, carbon distribution 9.3%, oil 11.2%, sulphur 5.8%, molybdenum 6.2%, vanadium 7.8%, nickel 5.3%, aluminium 10.6%, wherein molybdenum, vanadium, nickel exist with metallic sulfide form, and aluminium exists with metal oxide form.
(1) adopt 10 × 10mm sieve, sift out
spent catalystmiddle porcelain ball, after screening
spent catalyst, drop into desizer and carry out the process of de-oiling decarbonization, desulfuration, residence time 60min, temperature 980 DEG C, the steam of output pressure 0.3Mpa, the steam of generation is for production and applications such as the water temp. heating leached and pipeline tracings.
(2) by the de-oiling material after step (1) de-oiling, with sodium salt in 4:1 ratio, add water after Mix and dosing with stirrer, send in rotary kiln, carry out sodium roasting, residence time 60min at 1000 DEG C, discharging, through cooling rapidly, controls drop temperature at 550 DEG C, makes
spent catalystin the convert metals such as molybdenum vanadium be water-soluble sodium material.
(3) tail gas that step (1) and step (2) produce is sent into exhaust treatment system, tail gas is first after cooling dedusting, enter thionizer, desulfurization absorption is carried out by lime slurry, be calcium sulfate by the sulfurous gas conversion in tail gas, after plate-and-frame filter press filters, obtain gypsum product, tail gas rear discharge up to standard, remaining liquid recovery.
(4) sodium material step (2) roasting obtained drops in Leaching reaction still, by 1:3.2 solid-to-liquid ratio, keeps 65 DEG C of temperature, stirs 60min, carries out multistage leaching.Obtaining filtrate through plate-and-frame filter press separation is leach liquor, and squeeze in immersion liquid tank, filter residue, through repetitive scrubbing, obtains nickel aluminium powder product, and wherein containing molybdenum 0.19%, vanadium 0.48%, washings is recovery repeatedly.
(5) molybdenum 18.99g/L, vanadium 23.4g/L is contained in the leach liquor that step (4) obtains, regulate pH=6, control temperature is at 65 DEG C, sulfate precipitation agent is added according to calculating ratio, stirring reaction 50min in a kettle., the impurity such as removing silicon, aluminium, phosphorus, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions, wherein silicon, aluminium, phosphorus impurities concentration are all less than 0.01g/L, and after removal of impurities, Molybdenum in Solution vanadium concentration is respectively 16.5g/L and 20.33g/L.
(6) by the Sodium orthomolybdate after step (5) removal of impurities, vanadic acid sodium mixing solutions, ion exchange method is adopted to carry out the separation of molybdenum vanadium, mixing solutions regulates pH=7.5, by three group of four row ion exchange column, utilize specific ion exchange resin to adsorb, adsorb saturated after, with 12% sodium hydroxide solution resolve, obtain pure sodium molybdate solution and pure sodium vanadate solution, wherein
Molybdenum concentration 15.6g/L in sodium molybdate solution, vanadium is not more than 0.01g/L;
Vanadium concentration 65.42g/L in sodium vanadate solution, molybdenum is not more than 0.01g/L.
(7) sodium vanadate solution of step (6) 65.42g/L is diluted with water to 25g/L, regulate pH=8.4, the weight of the ammonium salt precipitation agent needed for calculating according to 3.6:1 weight ratio, ammonium salt precipitation agent is at the uniform velocity added in whipping process, control temperature 45 DEG C, stirring reaction, after 1 hour, filters immediately, after being separated by filter press, obtain high-purity ammonium meta-vanadate product and metabisulfite solution.
(8) sodium molybdate solution that step (6) obtains is pumped into acid adjustment reactor, add sulfuric acid acidation, adopt specific extraction agent, by multi-stage continuous extraction technique, purify molybdenum ion, obtains pure rich molybdenum liquid and metabisulfite solution.Wherein the concentration of molybdenum is 130.4g/L.
(9) pure for step (8) rich molybdenum liquid is added sulfuric acid precipitation agent, regulate pH=1.3, slowly add sulfuric acid in whipping process, control temperature 50 DEG C, after stirring reaction 45min, is separated by plate-and-frame filter press, obtains High-Purity Molybdenum acid product and metabisulfite solution.
(10) ion-exchange is carried out after being collected by the metabisulfite solution that step (7), (8) and (9) obtain, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, control vapor pressure is 0.3Mpa, vacuum tightness 0.05Mpa, temperature 75-105 DEG C, evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product, the water of condensation that concentration and evaporation is regained returns leaching operation and recycles, process water zero release.
This 1500t
spent catalystcommerical test, for
spent catalystthe compositing characteristic of raw material, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution,
spent catalystin carbon distribution and oil firing produce steam 4500t, for the production of; Sulphur in raw material is converted into gypsum product 467t; Molybdenum in raw material, vanadium and nickel aluminium are separately converted to molybdic acid 152.2t, ammonium meta-vanadate 255t, nickel aluminium powder 973t, and evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product 347t, and wherein nickel, aluminium can reclaim completely, molybdenum recovery 96.98%, vanadium recovery 95%.Waste residue is not had to produce in whole production process, water of productive use recycle, industrial residue, wastewater zero discharge,
spent catalystrealize at utmost resource regeneration.
Embodiment 4
Get catalyzer 2500t,
spent catalystoutward appearance is black, trifolium-shaped, particle diameter φ 1.3 × (3 ~ 5) mm,
spent catalystcontaining porcelain ball 5.1%, carbon distribution 7.8%, oil 13.1%, sulphur 5.3%, molybdenum 5.1%, vanadium 6.2%, nickel 5.2%, aluminium 11.6%, wherein molybdenum, vanadium, nickel exist with metallic sulfide form, and aluminium exists with metal oxide form.
(1) adopt 10 × 10mm sieve, sift out
spent catalystmiddle porcelain ball, after screening
spent catalyst, drop into desizer and carry out the process of de-oiling decarbonization, desulfuration, residence time 55min, temperature 990 DEG C, the steam of output pressure 0.3Mpa, the steam of generation is for production and applications such as the water temp. heating leached and pipeline tracings.
(2) by the de-oiling material after step (1) de-oiling, with sodium salt in 4.5:1 ratio, add water after Mix and dosing with stirrer, in feeding rotary kiln, at 1050 DEG C, carry out sodium roasting, residence time 55min, discharging, through cooling rapidly, controls drop temperature at 550 DEG C, makes
spent catalystin the convert metals such as molybdenum vanadium be water-soluble sodium material.
(3) tail gas that step (1) and step (2) produce is sent into exhaust treatment system, tail gas is first after cooling dedusting, enter thionizer, desulfurization absorption is carried out by lime slurry, be calcium sulfate by the sulfurous gas conversion in tail gas, after plate-and-frame filter press filters, obtain gypsum product, tail gas rear discharge up to standard, remaining liquid recovery.
(4) sodium material step (2) roasting obtained drops in Leaching reaction still, by 1:4.5 solid-to-liquid ratio, keeps 60 DEG C of temperature, stirs 40min, carries out multistage leaching.Obtaining filtrate through plate-and-frame filter press separation is leach liquor, and squeeze in immersion liquid tank, filter residue, through repetitive scrubbing, obtains nickel aluminium powder product, and wherein containing molybdenum 0.08%, vanadium 0.29%, washings is recovery repeatedly.
(5) molybdenum 11.2g/L, vanadium 13.36g/L is contained in the leach liquor that step (4) obtains, regulate pH=6.5, control temperature is at 70 DEG C, sulfate precipitation agent is added according to calculating ratio, stir 60min in a kettle., the impurity such as removing silicon, aluminium, phosphorus, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions, wherein silicon, aluminium, phosphorus impurities concentration are all less than 0.01g/L, and after removal of impurities, Molybdenum in Solution vanadium concentration is respectively 10.6g/L and 12.64g/L.
(6) by the Sodium orthomolybdate after step (5) removal of impurities, vanadic acid sodium mixing solutions, ion exchange method is adopted to carry out the separation of molybdenum vanadium, mixing solutions regulates pH=7.7, by three group of four row ion exchange column, utilize specific ion exchange resin to adsorb, adsorb saturated after, with 10% sodium hydroxide solution resolve, obtain pure sodium molybdate solution and pure sodium vanadate solution, wherein
Molybdenum concentration 10.14g/L in sodium molybdate solution, vanadium is not more than 0.01g/L;
Vanadium concentration 58.79g/L in sodium vanadate solution, molybdenum is not more than 0.01g/L.
(7) sodium vanadate solution of step (6) 58.79g/L is diluted with water to 25g/L, regulate pH=8.6, the weight of the ammonium salt precipitation agent needed for calculating according to 3.8:1 weight ratio, ammonium salt precipitation agent is at the uniform velocity added in whipping process, control temperature 45 DEG C, stirring reaction, after 1 hour, filters immediately, after being separated by filter press, obtain high-purity ammonium meta-vanadate product and metabisulfite solution.
(8) sodium molybdate solution that step (6) obtains is pumped into acid adjustment reactor, add sulfuric acid acidation, adopt specific extraction agent, by multi-stage continuous extraction technique, purify molybdenum ion, obtains pure rich molybdenum liquid and metabisulfite solution.Wherein the concentration of molybdenum is 122.4g/L.
(9) pure for step (8) rich molybdenum liquid is added sulfuric acid precipitation agent, regulate pH=1.2, slowly add sulfuric acid in whipping process, control temperature 50 DEG C, after stirring reaction 40min, is separated by plate-and-frame filter press, obtains High-Purity Molybdenum acid product and metabisulfite solution.
(10) ion-exchange is carried out after being collected by the metabisulfite solution that step (7), (8) and (9) obtain, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, control vapor pressure is 0.3Mpa, vacuum tightness 0.05Mpa, temperature 75-105 DEG C, evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product, the water of condensation that concentration and evaporation is regained returns leaching operation and recycles, process water zero release.
This 2500t
spent catalystcommerical test, for
spent catalystthe compositing characteristic of raw material, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution,
spent catalystin carbon distribution and oil firing produce steam 7500t, for the production of; Sulphur in raw material is converted into gypsum product 712t; Molybdenum in raw material, vanadium and nickel aluminium are separately converted to product molybdic acid 210.86t, ammonium meta-vanadate 342.3t, nickel aluminium powder 1626t, and evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product 465t, and wherein nickel, aluminium can reclaim completely, molybdenum recovery 98%, vanadium recovery 96.26%.Waste residue is not had to produce in whole production process, water of productive use recycle, industrial residue, wastewater zero discharge,
spent catalystrealize at utmost resource regeneration.
Embodiment 5
Get
spent catalyst3500t,
spent catalystoutward appearance is black, trifolium-shaped, particle diameter φ 1.3 × (3 ~ 5) mm,
spent catalystcontaining porcelain ball 4.5%, carbon distribution 10.4%, oil 9.3%, sulphur 5.6%, molybdenum 5.7%, vanadium 6.5%, nickel 5.6%, aluminium 13.3%, wherein molybdenum, vanadium, nickel exist with metallic sulfide form, and aluminium exists with metal oxide form.
(1) adopt 10 × 10mm sieve, sift out
spent catalystmiddle porcelain ball, after screening
spent catalyst, drop into desizer and carry out the process of de-oiling decarbonization, desulfuration, residence time 50min, temperature 1000 DEG C, the steam of output pressure 0.3Mpa, the steam of generation is for production and applications such as the water temp. heating leached and pipeline tracings.
(2) by the de-oiling material after step (1) de-oiling, with sodium salt in 5:1 ratio, add water after Mix and dosing with stirrer, send in rotary kiln, carry out sodium roasting, residence time 50min at 1100 DEG C, discharging, through cooling rapidly, controls drop temperature at 550 DEG C, makes
spent catalystin the convert metals such as molybdenum vanadium be water-soluble sodium material.
(3) tail gas that step (1) and step (2) produce is sent into exhaust treatment system, tail gas is first after cooling dedusting, enter thionizer, desulfurization absorption is carried out by lime slurry, be calcium sulfate by the sulfurous gas conversion in tail gas, after plate-and-frame filter press filters, obtain gypsum product, tail gas rear discharge up to standard, remaining liquid recovery.
(4) sodium material step (2) roasting obtained drops in Leaching reaction still, by 1:5 solid-to-liquid ratio, keeps 55 DEG C of temperature, stirs 40min, carries out multistage leaching.Obtaining filtrate through plate-and-frame filter press separation is leach liquor, and squeeze in immersion liquid tank, filter residue, through repetitive scrubbing, obtains nickel aluminium powder product, and wherein containing molybdenum 0.04%, vanadium 0.2%, washings is recovery repeatedly.
(5) molybdenum 11.35g/L, vanadium 12.74g/L is contained in the leach liquor that step (4) obtains, regulate pH=6.8, control temperature is at 75 DEG C, sulfate precipitation agent is added according to calculating ratio, stirring reaction 70 minutes in a kettle., the impurity such as removing silicon, aluminium, phosphorus, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions, wherein silicon, aluminium, phosphorus impurities concentration are all less than 0.01g/L, and after removal of impurities, Molybdenum in Solution vanadium concentration is respectively 10.17g/L and 11.41g/L.
(6) by the Sodium orthomolybdate after step (5) removal of impurities, vanadic acid sodium mixing solutions, ion exchange method is adopted to carry out the separation of molybdenum vanadium, mixing solutions regulates pH=8, by three group of four row ion exchange column, utilize specific ion exchange resin to adsorb, adsorb saturated after, with 8% sodium hydroxide solution resolve, obtain pure sodium molybdate solution and pure sodium vanadate solution, wherein
Molybdenum concentration 9.92g/L in sodium molybdate solution, vanadium is not more than 0.01g/L;
Vanadium concentration 63.35g/L in sodium vanadate solution, molybdenum is not more than 0.01g/L.
(7) sodium vanadate solution of step (6) 63.35g/L is diluted with water to 25g/L, regulate pH=9, the weight of the ammonium salt precipitation agent needed for calculating according to 4:1 weight ratio, ammonium salt precipitation agent is at the uniform velocity added in whipping process, control temperature 45 DEG C, stirring reaction, after 1 hour, filters immediately, after being separated by filter press, obtain high-purity ammonium meta-vanadate product and metabisulfite solution.
(8) sodium molybdate solution that step (6) obtains is pumped into acid adjustment reactor, add sulfuric acid acidation, adopt specific extraction agent, by multi-stage continuous extraction technique, purify molybdenum ion, obtains pure rich molybdenum liquid and metabisulfite solution.Wherein the concentration of molybdenum is 125.65g/L.
(9) pure for step (8) rich molybdenum liquid is added sulfuric acid precipitation agent, regulate pH=1, slowly add sulfuric acid in whipping process, control temperature 50 DEG C, after stirring reaction 30min, is separated by plate-and-frame filter press, obtains High-Purity Molybdenum acid product and metabisulfite solution.
(10) ion-exchange is carried out after being collected by the metabisulfite solution that step (7), (8) and (9) obtain, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, control vapor pressure is 0.3Mpa, vacuum tightness 0.05Mpa, temperature 75-105 DEG C, evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product, the water of condensation that concentration and evaporation is regained returns leaching operation and recycles, process water zero release.
This 3500t
spent catalystcommerical test, for
spent catalystthe compositing characteristic of raw material, will
spent catalystthe abundant recycling of middle useful matter, has accomplished to make the best use of everything, and in harmless treatment
spent catalystwhile, do not produce secondary pollution,
spent catalystin carbon distribution and oil firing produce steam 10500t, for the production of; Sulphur in raw material is converted into gypsum product 1054t; Molybdenum in raw material, vanadium and nickel aluminium are separately converted to product molybdic acid 333.9t, ammonium meta-vanadate 509.9t, nickel aluminium powder 2274t, and evaporative crystallization obtains Sodium sulfate anhydrous.min(99) product 660t, and wherein nickel, aluminium can reclaim completely, molybdenum recovery 99.18%, vanadium recovery 97.7%.Waste residue is not had to produce in whole production process, water of productive use recycle, industrial residue, wastewater zero discharge,
spent catalystrealize at utmost resource regeneration.
Claims (4)
1. a spent catalyst resource utilization method, is characterized in that: step is as follows:
(1) spent catalyst being dropped into desizer utilizes himself calorific value to carry out the process of de-oiling decarbonization, desulfuration, obtains de-oiling material;
(2), after de-oiling material step (1) obtained and sodium salt are puddled by the mass ratio of (3-5) ︰ 1, drop in rotary kiln and carry out sodium roasting at 900-1100 DEG C, obtain sodium material;
(3) sodium material step (2) obtained is at 50-90 DEG C, and sodium material and water, according to the mass ratio of 1 ︰ (2-5), carry out multistage leaching, Footwall drift nickel and aluminium, obtain nickel aluminium powder product and leach liquor;
(4) add sulfate precipitation agent in the leach liquor obtained to step (3), adopt silicon, aluminium, phosphorus impurities in chemical precipitation method removing leach liquor, obtain Sodium orthomolybdate, vanadic acid sodium mixing solutions;
(5) Sodium orthomolybdate step (4) obtained, vanadic acid sodium mixing solutions adopt ion exchange method to carry out the separation of molybdenum vanadium, obtain sodium molybdate solution and pure sodium vanadate solution respectively;
(6) add ammonium salt precipitation agent in the pure sodium vanadate solution obtained to step (5), adopt chemical precipitation method to reclaim vanadium, obtain high-purity ammonium meta-vanadate product and metabisulfite solution;
(7) by the sodium molybdate solution that step (5) obtains, by solvent extraction purification and enrichment molybdenum, pure sodium molybdate solution and metabisulfite solution is obtained;
(8) add sulfuric acid precipitation agent in the pure sodium molybdate solution obtained to step (7), regulate pH=1.0-1.5, adopt chemical precipitation method to reclaim molybdenum, obtain High-Purity Molybdenum acid product and metabisulfite solution;
(9) metabisulfite solution that step (6), (7) and (8) obtain is carried out ion-exchange, after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, obtain product Sodium sulfate anhydrous.min(99), after the sodium sulfate in remanufacture solution, water of condensation returns step (3).
2. spent catalyst resource utilization method as claimed in claim 1, is characterized in that: the temperature of described de-oiling decarbonization, desulfuration process is at least 950 DEG C, at least 1 hour residence time.
3. spent catalyst resource utilization method as claimed in claim 1, it is characterized in that: the spent catalyst de-oiling decarbonization, desulfuration in step (1) contains SO 2 tail gas, after bag-type dust, Dual alkali absorb sulphur, reclaim sulphur in spent catalyst, by-product gypsum.
4. spent catalyst resource utilization method as claimed in claim 1, it is characterized in that: ion-exchange is carried out to the metabisulfite solution obtained in step (6), (7) and (8), after reclaiming molybdenum in solution and vanadium, carry out Multi-effect concentration crystallization, obtain product Sodium sulfate anhydrous.min(99), water of condensation returns step (3).
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| CN106521140A (en) * | 2016-11-06 | 2017-03-22 | 陈礼华 | Oil-carbon-sulfur removing high-alkali sodium roasting process |
| CN106521141A (en) * | 2016-11-06 | 2017-03-22 | 陈礼华 | Deoiling, decarbonizing and desulfuration low-alkaline sodium salt roasting process |
| CN107723468A (en) * | 2017-11-08 | 2018-02-23 | 大连东泰资源再生有限公司 | A kind of dead catalyst utilization system |
| CN107805716A (en) * | 2017-11-08 | 2018-03-16 | 大连东泰资源再生有限公司 | A kind of nickel aluminium powder recovery method |
| CN107915256A (en) * | 2017-11-08 | 2018-04-17 | 大连东泰资源再生有限公司 | Dead catalyst prepares high-purity molybdic acid method |
| CN108467939A (en) * | 2018-06-11 | 2018-08-31 | 江苏北矿金属循环利用科技有限公司 | A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst |
| CN108728653A (en) * | 2018-06-11 | 2018-11-02 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN109628765A (en) * | 2018-12-27 | 2019-04-16 | 大连博融新材料有限公司 | A kind of recovery method of vpo catalyst |
| CN111455172A (en) * | 2020-04-15 | 2020-07-28 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN112301227A (en) * | 2020-10-30 | 2021-02-02 | 岳阳鼎格云天环保科技有限公司 | Recycling method of hydrogenation type waste catalyst |
| CN112646977A (en) * | 2020-12-18 | 2021-04-13 | 北京普能世纪科技有限公司 | Method for recovering vanadium, molybdenum, nickel and aluminum from petroleum refining waste catalyst |
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| CN106521140A (en) * | 2016-11-06 | 2017-03-22 | 陈礼华 | Oil-carbon-sulfur removing high-alkali sodium roasting process |
| CN106521141A (en) * | 2016-11-06 | 2017-03-22 | 陈礼华 | Deoiling, decarbonizing and desulfuration low-alkaline sodium salt roasting process |
| CN107723468A (en) * | 2017-11-08 | 2018-02-23 | 大连东泰资源再生有限公司 | A kind of dead catalyst utilization system |
| CN107805716A (en) * | 2017-11-08 | 2018-03-16 | 大连东泰资源再生有限公司 | A kind of nickel aluminium powder recovery method |
| CN107915256A (en) * | 2017-11-08 | 2018-04-17 | 大连东泰资源再生有限公司 | Dead catalyst prepares high-purity molybdic acid method |
| CN107805716B (en) * | 2017-11-08 | 2019-07-23 | 大连东泰资源再生有限公司 | A kind of nickel aluminium powder recovery method |
| CN108728653A (en) * | 2018-06-11 | 2018-11-02 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN108467939A (en) * | 2018-06-11 | 2018-08-31 | 江苏北矿金属循环利用科技有限公司 | A method of recycling nickel, molybdenum from useless nickel molybdenum catalyst |
| CN108728653B (en) * | 2018-06-11 | 2019-11-22 | 江苏北矿金属循环利用科技有限公司 | A method of extracting molybdenum from useless nickel molybdenum catalyst |
| CN109628765A (en) * | 2018-12-27 | 2019-04-16 | 大连博融新材料有限公司 | A kind of recovery method of vpo catalyst |
| CN109628765B (en) * | 2018-12-27 | 2021-06-15 | 大连博融新材料有限公司 | Method for recovering VPO catalyst |
| CN111455172A (en) * | 2020-04-15 | 2020-07-28 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN111455172B (en) * | 2020-04-15 | 2022-05-06 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN112301227A (en) * | 2020-10-30 | 2021-02-02 | 岳阳鼎格云天环保科技有限公司 | Recycling method of hydrogenation type waste catalyst |
| CN112646977A (en) * | 2020-12-18 | 2021-04-13 | 北京普能世纪科技有限公司 | Method for recovering vanadium, molybdenum, nickel and aluminum from petroleum refining waste catalyst |
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Application publication date: 20150520 |