A kind of method of multi-metal from dead catalyst synthetical recovery
The invention belongs to catalyzer secondary resource recovery technology field, be specifically related to a kind of method of multi-metal from dead catalyst comprehensive reutilization.
The metals such as vanadium, molybdenum, tungsten are normal and be called refractory metal.Have good ductility, matter is hard, the performance of resistance to hydrochloric acid and sulfuric acid, and better than most of stainless steel in the performance of gasproof-salt-aqueous corrosion, simultaneously because these metals have variable valence, is catalyzer raw material rare in chemical industry.Therefore, these elements have purposes very widely in the industry of metallurgy, chemical industry, iron and steel.Along with the high speed development of China's modernization construction, the demand of this metalloid is increasing.
Nickel has ferromagnetic metallic element, and it can high polish and anticorrosive.Be mainly used in alloy (as nickel steel and nickeline) and be used as catalyzer (as Raney nickel, being espespecially used as the catalyzer of hydrogenation), can be used to manufacture currency etc., plating can prevent from getting rusty on other metals.
Above-mentioned metal all compares dispersion in occurring in nature distribution, and raw ore ore grade is lower, and along with the continuous increase of produced quantity, minable ore grade is more and more lower, and therefore cost of winning constantly increases.And a large amount of spent catalyst becomes the rare secondary resource of these metals in petroleum industry and chemical industry.Spent catalyst has the features such as of high grade, composition is simple compared with nature ore.From spent catalyst, reclaim at present method mainly alkali roasting (or blank roasting) → water logging (alkali leaching) method of the metals such as nickel, cobalt, molybdenum, vanadium or acid, alkali two step lixiviation process, be that soluble salt enters solution by Metals from Spent Catalysts cycling of elements, solution carries out separating-purifying again and obtains metal.
Application number is the Chinese invention application of CN201110147614.9, discloses one and relates to dead catalyst containing nickel recoverying and utilizing method.Dead catalyst containing nickel is calcined by the method, temperature 300-600 DEG C, time 2-3 hour, removes the organism of catalyst residue; Then pulverized, adopt the nitric acid two-stage of concentration 1.5-4.5mol/L to leach.The nickel that the method reclaims exists with nickel nitrate solution form.
Application number is the Chinese invention application of CN200910188100.0, disclose a kind of method of Footwall drift from molybdenum-contained waste catalyst, first by spent catalyst oil removing, pulverizing, then mix with soda ash, roasting, go out with water logging after roasting, adopt organic extractant recovery molybdenum wherein, utilize the spent acid preparation mixed acid solution discharged in the method, for the treatment of the solid residue after water logging, the metal in further waste acid recovery and residue.This inventive method can improve the rate of recovery of Metals from Spent Catalysts further, and operational condition severity reduces simultaneously, and energy consumption is low, goes for the metal recovery process of molybdenum-contained waste catalyst.
Application number is the Chinese invention application of CN200910020761.2, disclose a kind of method reclaiming molybdenum from alumina base molybdenum-contained waste catalyst, carry out according to the following step successively: (1) is by alumina base molybdenum-contained waste catalyst and circulating mother liquor, NaOH solution and Na
3enter ball mill combined grinding after batching, calcine to obtain grog, stir stripping with adjustment liquid, dissolution fluid implements solid-liquid separation, obtains crude liquor of sodium aluminate; (2), after crude liquor of sodium aluminate being diluted, implement carbonation decomposition and obtain aluminum hydroxide slurry; Slurries obtain low-grade aluminium hydroxide and contain molybdenum carbon mother liquid after being separated; (3) high concentration carbon acid sodium solution is introduced carbonating tower and implement carbonation decomposition; After sodium carbonate and carbonic acid gas, water react further, separate out sodium bicarbonate crystallization, form sodium bicarbonate slurry; Sodium bicarbonate slurry is after sedimentation and thickening, and filtering separation, obtains solid sodium bicarbonate and contain molybdenum carbonization mother liquor; (4) carry out hygroscopic water solution containing molybdenum carbonization mother liquor through steam heating, evaporate after the sodium bicarbonate thermolysis in solution is converted to sodium carbonate; (5) through (1) to (4) step cycle, after adjusted to ph, molybdenum is extracted by ion exchange method.
Application number is the Chinese invention application of CN200710303806.8, disclose a kind of dissolution processing method of nickelous oxide dead catalyst, it is characterized in that its dissolution process process sieve is removed the nickelous oxide dead catalyst of the lumpy material such as handstone, slag, adding concentration is in the hydrochloric acid soln of more than 5N/L, under the condition of 85 DEG C of-100 DEG C of temperature, stirring, add oxygenant sodium chlorate or pass into chlorine, controlled oxidization current potential is 0.5-1.0V; Carry out solubilizing reaction 1-5 hour, obtain green nickel chloride solution.The method of this invention, leach and dissolution rate high, do not need to carry out pyroprocessing and pressure treatment reduces cost, solve a production technology difficult problem.In conjunction with existing nickel electrowinning technique, can nickel in efficient recovery spent catalyst.
Application number is the Chinese invention application of CN200410050503.6, disclose a kind of method utilizing vanadium-containing wasting catalyst to produce Vanadium Pentoxide in FLAKES, the method is: a certain amount of deposition oil in first Removal of catalyst, then put in water after being pulverized and leach, by being oxidized and adding alkali adjust ph 8.5-9.5, extraction time 1-2 hour at 50-60 DEG C, reclaims vanadic acid sodium after solid-liquid separation and sodium molybdate solution is a leach liquor; Filter residue after washing is calcined in rotary kiln, temperature of kiln head 850 ~ 900 DEG C, and 350 ~ 400 DEG C, kiln tail makes vanadium transformation efficiency be greater than 96%; Material after calcining is soluble in water, and leaching under stirring, reclaims vanadic acid sodium after solid-liquid separation and sodium molybdate solution is secondary leach liquor; Merge leach liquor, remove foreign matter of phosphor again, excessive ammonium chloride is added by the leach liquor after purification under normal temperature, vanadic acid sodium is made to generate ammonium metavanadate precipitate, ammonium meta-vanadate after solid-liquid separation is put in film-making stove, at 800 ~ 850 DEG C, ammonium vanadate decomposes the V2O5 of obtained melting, makes sheet be finished product through film-making stove.This invention feature is deviate from the method for the sulphur in spent catalyst by oxidation dipping, by deviating from the part oil composition in spent catalyst, reduces the flue-gas temperature of calcining kiln kiln tail.
Aforesaid method is said on the whole, and resource recovery is low, and it is serious that not easy to be recycled or that economic worth is low renewable resource abandon phenomenon.
Summary of the invention
The object of the invention is the deficiency for previous process, a kind of wide adaptability is provided, save leaching agent, the spent catalyst treatment technology of comprehensive energy utilization.
Object of the present invention is achieved through the following technical solutions:
A method for multi-metal from dead catalyst synthetical recovery, is characterized in that,
A: when the content of vanadium in spent catalyst is more than 0.5%, comprise the following steps:
(1) dilute sulphuric acid preimpregnation: spent catalyst is placed in Ball-stirring mill, adds dilute sulphuric acid, levigate, preimpregnation;
(2) slaking water logging: by preimpregnation slag vitriol oil slaking in step (1), add fluorochemical in maturing process as additive, promote dissociating between element, after slaking, the vanadium extraction of water logging selectivity, obtains Vanadium Pentoxide in FLAKES product;
(3) pyrometallurgical smelting: vanadium making slag in step (2) is carried out pyrometallurgical smelting, reclaim nickel, cobalt, molybdenum, nickel, cobalt, molybdenum enter sulfonium, and the impurity such as aluminium, silicon enters slag;
(4) pressure leaching: the sulfonium phase pressurized acid leaching obtained in step (3), reclaims nickel, cobalt, obtains single nickel salt, rose vitriol product;
(5) ammonia lixiviate molybdenum: adopt ammonia leaching to reclaim molybdenum the leached mud obtained in step (4), obtain ammonium molybdate product;
B: when vanadium in spent catalyst content lower than 0.5% time, spent catalyst directly enters step (3) pyrometallurgical smelting, (4) pressure leaching and (5) ammonia lixiviate molybdenum successively.
The content ratio (per-cent) related in the present invention, unless otherwise indicated, is mass ratio.
Further, in step (1) spent catalyst preimpregnation and levigate while carry out in Ball-stirring mill, preimpregnation liquid-solid ratio is 2-10:1, and preimpregnation temperature is normal temperature-90 DEG C, and preimpregnation acidity is 20g/L-150g/L.
Further, step (2) maturing process fluoride additive is CaF
Further, in step (2), slaking acid amount is the 15-30% of weight of material, and curing temperature 80-150 DEG C, the curing time is 12h-48h, addition of C aF in maturing process
2add-on be the 1-10% of raw catalyst quality.
Further, step (3), before pyrometallurgical smelting, allocates silicon-dioxide and reduced iron powder in vanadium making slag.
Further, melting temperature range 1200-1500 DEG C in step (3), smelting time is 0.5h-2h.
The present invention has the following advantages and effect compared with existing technology:
1. selectivity vanadium extraction, by adding additive in maturing process, achieves the object that single stage method is separated the metal such as vanadium and aluminium, molybdenum, nickel, cobalt.In whole selectivity vanadium extracting process, the leaching yield of vanadium is greater than 85%, and the leaching yield of aluminium is lower than 10%, avoids aluminium vanadium separation problem in prior art, saves corresponding flow process and cost.
If the content of vanadium 2. in former spent catalyst is lower, be worth without recycling, then in this technique, selectivity vanadium extraction link can be omitted, and directly enters subsequent technique, and therefore present invention process has adaptability widely.
3. pyrometallurgical smelting, makes full use of the thermal value of the residual organic matter in spent catalyst, has saved the energy, and owing to being separated aluminium and nickel, cobalt, molybdenum by the method for pyrometallurgical smelting, compared with traditional technology, the leaching agent avoided when aluminium is leached consumes.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Below in conjunction with accompanying drawing, the present invention is further described.
Determine whether to carry out Selectively leaching vanadium process according to the content of vanadium in spent catalyst: if content of vanadium is more than 0.5% in spent catalyst, then carry out Selectively leaching vanadium process, otherwise spent catalyst directly enters pyrometallurgical smelting process.
If the content of vanadium is more than 0.5% in spent catalyst, comprise the following steps:
(1) dilute sulphuric acid preimpregnation: spent catalyst is placed in Ball-stirring mill, adds dilute sulphuric acid, levigate, preimpregnation.
(2) slaking water logging: by preimpregnation slag vitriol oil slaking in step (1), adding fluorochemical in maturing process (can be NaF, KF, CaF
2, preferred CaF
2) as additive, promote dissociating between element.Slaking acid amount is the 15-30% of weight of material, and curing temperature 80-150 DEG C, the curing time is 12h-48h, addition of C aF in maturing process
2add-on be the 1-10% of raw catalyst quality.Water logging selectivity vanadium extraction after slaking, leach liquor obtains Vanadium Pentoxide in FLAKES product after conventional Metallurgical Means purification and impurity removal, separation.In whole selectivity vanadium extracting process, the leaching yield of vanadium is greater than 85%, and the leaching yield of aluminium is lower than 10%.
(3) pyrometallurgical smelting: vanadium making slag in step (2) is carried out pyrometallurgical smelting, reclaim nickel, cobalt, molybdenum, nickel, cobalt, molybdenum enter sulfonium, and the impurity such as aluminium, silicon enters slag.
(4) pressure leaching: the sulfonium phase pressurized acid leaching obtained in step (3), reclaims nickel, cobalt, obtains single nickel salt, rose vitriol product.
(5) ammonia lixiviate molybdenum: adopt ammonia leaching to reclaim molybdenum the leached mud obtained in step (4), obtain ammonium molybdate product.
If the content of vanadium is lower than 0.5% in spent catalyst, then spent catalyst directly enters step (3) pyrometallurgical smelting, then carries out subsequent step (4) pressure leaching and step (5) ammonia lixiviate molybdenum.
Fetch the high-nickel catalyst 1000g from certain petrochemical plant, adopt the sulfuric acid preimpregnation of liquid-solid ratio 5:1,100g/L in Ball-stirring mill, the employing of preimpregnation slag adds the vitriol oil and carries out slaking, slag acid mass ratio 4:1, curing temperature 106 DEG C, curing time 48h.Slaking slag presoak leaches, and extraction temperature is 80 DEG C, extraction time 4h.After preimpregnation, slaking water logging, the leaching yield of vanadium is 88.0%, and the leaching yield of aluminium is 9.3%.The leached mud obtained allocates silicon-dioxide and reduced iron powder into, melting 2h at 1350 DEG C, obtains sulfonium phase and slag item, and the sulfonium rate that enters of nickel, cobalt, molybdenum is respectively 90%, 89%, 82%.Sulfonium phase conveniently Metallurgical Means obtains nickel, cobalt, molybdenum product.
Fetch the high cobalt spent catalyst 1000g from certain petroleum chemical enterprise, in this catalyzer, content of vanadium is very low, being worth, therefore directly carrying out pyrometallurgical smelting without recycling, according to the concrete composition of catalyzer, allocate 280g silicon-dioxide into, 420g reduced iron powder, melting 2h at 1350 DEG C, obtain sulfonium phase and slag phase, the sulfonium rate that enters of nickel, cobalt, molybdenum is respectively 94%, 95%, 79%.Sulfonium phase conveniently Metallurgical Means obtains nickel, cobalt, molybdenum product.