Technical background is general in the petroleum refining industry process, and to adopt aluminium sesquioxide be carrier, and the catalyzer that metal such as activeconstituents molybdenum, nickel, cobalt or its oxide compound are bonded on the alumina catalyst support carries out desulfurization or hydrogenation operation to crude oil.Catalyzer in use adsorbs impurity elements such as a large amount of vanadium, phosphorus, iron and causes poison deactivation owing to catalyzer.According to statistics, about 50~700,000 tons of the annual spent catalyst that produces in the whole world will consume a large amount of precious metals and non-ferrous metal for making these catalyzer.Only the output of the present all kinds of chemical fertilizer spent catalyst of China remains on annual about 30,000 tons.Consider from comprehensive utilization of resources and environmental protection, all must handle, reclaim valuable element, secondary resource is fully used spent catalyst.
The research of some this respects has been arranged at present, wherein Chinese patent CN1305537A " reclaims the method for molybdenum and vanadium metal " from spent catalyst by alkaline leaching, CN1321782A " technology of wet method vanadium extraction from useless catalyst ", CN1453379A " wet method is extracted the technology of vanadium and/or molybdenum from useless catalyst ", CN1557978A " extract the production technique of vanadium, molybdenum " from aluminium scrap base activator with wet method, and the technology of employing is roughly: remove oil content, sodium roasting, the water logging of roasting grog or alkali soaks, ammonium chloride precipitation, the heavy molybdenum of nitric acid acidifying or add the heavy molybdenum of calcium salt.The shortcoming of these technologies is only vanadium, molybdenum to be reclaimed, and alumina catalyst support and nickel cobalt are failed to reclaim, and vanadium molybdenum separating technology is complicated, and the soda acid consumption is big.And in leaching process, to avoid influencing the leaching yield of vanadium molybdenum because of the stripping of aluminium as far as possible.
Two patent CN1422967As approaching with the present invention are " from nickeliferous, Al in addition
2O
3Catalyst waste slag in prepare the method for nickel chemical and aluminum chemistry product ", CN1544666A " reclaims the method for nickel and aluminium " from aluminium scrap base nickel-containing catalyst; adopt yellow soda ash or sodium hydroxide and spent catalyst to react under molten state; the stripping in hot water of the sodium aluminate of generation; to adopt carbon to divide or plant point-score to prepare aluminium hydroxide from the sodium aluminate solution of stripping, the nickeliferous slag after the water logging is with acidleach or reducing-matting smelting recovery nickel.The advantage of this technology is that alumina catalyst support is reclaimed, thereby the rate of recovery of nickel is improved.But this technology only can be handled the catalyst based or only nickeliferous aluminium-based catalyst of aluminium scrap behind the recovery vanadium molybdenum.
Can find out thus, adopt prior art, all reclaim useful metals such as vanadium in the spent catalyst, molybdenum, nickel, cobalt, aluminium, need carry out in two steps: at first reclaim the vanadium molybdenum, reclaim aluminum oxide and nickel, cobalt then.Technological process need adopt two step sodium roastings, and the leaching process of vanadium molybdenum needs the stripping of inhibited oxidation aluminium, and the loss of aluminium is big and the separation of vanadium molybdenum produced adverse influence; The technology that reclaims aluminum oxide and nickel cobalt then requires to strengthen the stripping of aluminum oxide, is beneficial to the leaching of follow-up nickel cobalt.The shortcoming of this technology maximum is a complex process, long flow path, complex operation, supplies consumption height.
Summary of the invention the purpose of this invention is to provide a kind of from carrier A l
2O
3The method of effectively separating vanadium, molybdenum, nickel, cobalt, aluminium in catalyst based for the aluminium scrap that contains vanadium, molybdenum, nickel, cobalt of any crystal formation.The technical scheme principle that adopts is as follows: in aluminium scrap is catalyst based, and Al
2O
3Be major ingredient, Al
2O
3Be intermediate oxide, can react with strong acid, highly basic, but corundum type α-Al
2O
3Can not with the reaction of strong acid, highly basic, can only with the alkali reaction under the molten state, vanadium, molybdenum also can at high temperature react with alkali.The X-ray diffraction analysis revealed, after spent catalyst lost efficacy, partial oxidation aluminium was converted into corundum type α-Al
2O
3, the part of nickel cobalt also exists with the form of nickel aluminate, Leyden blue, and the nickel cobalt of this form is difficult to go out with acidleach.
The present invention is by reacting spent catalyst and alkali under molten state, after reaction product was water-soluble, the aluminum oxide of various crystal formations, vanadium, molybdenum all changed liquid phase over to; Add suitable precipitation agent, substep separates vanadium, molybdenum from sodium aluminate solution, preparation vanadium, molybdenum Chemicals; Prepare aluminium hydroxide with carbon method from sodium aluminate solution again.The stripping of aluminum oxide is that condition has been created in the leaching of follow-up nickel cobalt slag in the spent catalyst, adopts conventional acidleach the nickel cobalt all can be leached.
Concrete processing step is as follows:
1. utilize the oil content on the catalyst based surface of high temperature removal aluminium scrap, processing condition are 500~1000 ℃ of temperature, and the time is 3~5 hours, and top condition is 700~800 ℃, 3 hours time.The oily waste water aluminium-based catalyst of natural particle size is sent into rotary kiln high temperature removal surface oil content, and the material downbeam feeds in air-flow and the kiln; Also can place the de-oiling of Reaktionsofen high temperature with aluminium scrap is catalyst based.
2. remove spent catalyst after the oil content with addition of a certain amount of sodium hydroxide, sodium hydroxide and spent catalyst (are pressed Al
2O
3Meter) mol ratio is 2~4: 1, with spent catalyst and the abundant mixing of sodium hydroxide;
3. the material for preparing is carried out high-temperature roasting in rotary kiln or Reaktionsofen, temperature is 600~900 ℃, time is 0.5~2 hour, part is oxidized with the nickel cobalt that sulphided form exists in the spent catalyst, vanadium, molybdenum are oxidized to high valence state at a low price, and forming water-soluble vanadic acid sodium and Sodium orthomolybdate with sodium hydroxide reaction, the transformation efficiency of vanadium molybdenum is greater than 95%; Aluminum oxide then generates sodium aluminate with alkali reaction, and the transformation efficiency of aluminum oxide is greater than 98%.The principal reaction equation is as follows:
Al
2O
3+2NaOH=2NaAlO
2+H
2O
V
2O
5+6NaOH=2Na
3VO
4+3H
2O
MoO
3+2NaOH=Na
2MoO4+H
2O
4. the grog after the roasting is leached in 80~90 ℃ hot water, solvent and solute weight ratio is 1~3: 1, and the time is 0.5~2 hour, and sodium aluminate, vanadic acid sodium, Sodium orthomolybdate all change liquid phase over to, the further enrichment of nickel cobalt in the water logging slag;
5. be that 20% sulfuric acid leaches the water logging slag with volume ratio, the nickel cobalt is reclaimed in acidleach, and service temperature is 80~100 ℃, liquid-solid ratio L/S=4~8: 1, extraction time 4~8 hours.The equation of reaction is respectively:
Ni+H
2SO4=NiSO
4+H
2?↑
NiO+H
2SO4=NiSO
4+H
2O
Co+H
2SO
4=CoSO
4+H
2?↑
CoO+H
2SO
4=CoSO
4+H
2O
6. add hydrated barta or barium aluminate in infusion, because barium aluminate is dissolved in alkaline solution, vanadic acid barium, barium molybdate then are precipitation, and hydrated barta and VO
4 3-Speed of response much larger than with MoO
4 2-Speed of response.Therefore, control adds the amount of hydrated barta, can isolate vanadium, molybdenum from sodium aluminate solution successively.At 40 ℃~60 ℃, adding mol ratio is 1~1.2: 1 (press the metering of vanadic acid sodium and hydrated barta reactive chemistry), reacts 15~30 minutes, and filtration can be with 95% vanadium separation in the solution; Solution is heated to 80~90 ℃, and continue adding mol ratio is 1~1.5: 1 (press the metering of Sodium orthomolybdate and hydrated barta reactive chemistry), reacts 30~50 minutes, and filtration can be with 92%~93% molybdenum separation in the solution.The principal reaction equation is as follows:
2Na
3VO
4+3Ba(OH)
2=6NaOH+Ba
3(VO
4)
2?↓
Na
2MoO
4+Ba(OH)
2=2NaOH+BaMoO
4?↓
7. will separate the sodium aluminate solution Al behind vanadium, the molybdenum
2O
3Concentration be adjusted to 100g/l~140g/l, and be heated to 65~85 ℃, in the carbonating groove, stir, to wherein feeding carbonic acid gas, CO
2Gas contacts with solution carbonation reaction takes place, and 8~16 hours resolving times, it is neutral that aluminum hydroxide crystals is washed to washing lotion with tap water, in 100~170 ℃ of oven dry.Decomposition nut liquid contains Al
2O
34~6g/l carries out causticizing reaction to wherein adding lime, and the sodium hydroxide of causticizing reaction returns burden process and does the use of sodium roasting raw material.The principal reaction equation is:
2NaAlO
2+CO
2+3H
2O=Na
2CO
3+2Al(OH)
3?↓
Na
2CO
3+Ca(OH)
2=2NaOH+CaCO
3↓
8. aluminium hydroxide is carried out high-temperature calcination under 1100~1300 ℃, the preparation alumina product, reaction equation is:
2Al(OH)
3=Al
2O
3+3H
2O
Advantage of the present invention and positively effect:
1. this technology can realize the effective separation and comprehensive recovery of vanadium, molybdenum, al and ni cobalt.Alumina product reaches the specification of quality of GB stair oxidation aluminium, and the rate of recovery of aluminium (is pressed Al
2O
3Meter) can reach 92%; Vanadic acid barium, barium molybdate meet the requirement of vanadium molybdenum quality of chemical products, also it can be reprocessed, and preparation vanadium, molybdenum product, the rate of recovery of vanadium, molybdenum can reach 90%.
2. the present invention is owing to change aluminium, vanadium, molybdenum over to liquid phase, Al earlier
2O
3A large amount of strippings, for favourable condition has been created in the recovery of follow-up nickel cobalt, in the water logging slag content enrichment of nickel cobalt 5~7 times, adopt sulfuric acid to leach, the leaching yield of nickel cobalt can reach 97%~99%.Nickel cobalt leach liquor can adopt conventional solvent extraction and separation, preparation nickel cobalt Chemicals.
3. strong to adaptability to raw material, good market outlook and application value are arranged.Applicable to the processing of catalyst based (comprising one or more compositions such as vanadium, molybdenum, nickel, cobalt) of various aluminium scraps.
4. sodium hydroxide and spent catalyst high temperature sintering instead would not produce obnoxious flavour, the CaCO that causticizing reaction generates
3Can be used for preparing CO
2, the CaO of generation can be used for causticizing reaction again, thereby carbon method prepares the technology reusable edible CO of aluminium hydroxide
2Gas, whole technological process can not produce harmful solid waste yet, helps environmental protection.
Embodiment is further described concrete enforcement of the present invention below in conjunction with accompanying drawing:
Embodiment 1 is extracted the method for vanadium, molybdenum, nickel, cobalt, aluminium from aluminium scrap is catalyst based, carry out according to the following steps:
1, the oily waste water aluminium-based catalyst of natural particle size is sent into rotary kiln high temperature removal surface oil content, the material downbeam feeds in air-flow and the kiln, and controlled temperature is 700 ℃, and the time is 4 hours;
2, remove oil content after spent catalyst with addition of a certain amount of sodium hydroxide, sodium hydroxide and spent catalyst (are pressed Al
2O
3Meter) mol ratio is 2.4: 1, with spent catalyst and the abundant mixing of sodium hydroxide;
3, the material for preparing is carried out high-temperature roasting in Reaktionsofen, temperature is 750 ℃, and the time is 1 hour, and the transformation efficiency of vanadium molybdenum is respectively 96.1% and 97.3%, and the transformation efficiency of aluminum oxide is 97.0%.The principal reaction equation is as follows:
Al
2O
3+2NaOH=2NaAlO
2+H
2O
V
2O
5+6NaOH=2Na
3VO
4+3H
2O
MoO
3+2NaOH=Na
2MoO
4+H
2O
4, the grog after the roasting is leached in 80 ℃ hot water, solvent and solute weight ratio is 2: 1, and the time is 0.5 hour, and sodium aluminate, vanadic acid sodium, Sodium orthomolybdate all change liquid phase over to, and the nickel cobalt concentration ratio in the water logging slag is 5.1;
5, be that 20% the sulfuric acid nickel cobalt slag after to water logging leaches with volume ratio, the nickel cobalt is reclaimed in acidleach, and temperature of reaction is 85 ℃, liquid-solid ratio L/S=6: 1, and extraction time 6 hours, the leaching yield of nickel, cobalt is respectively 98.6%, 97.3%.The principal reaction equation is respectively:
Ni+H
2SO
4=NiSO
4+H
2↑
NiO+H
2SO
4=NiSO
4+H
2O
Co+H
2SO
4=CoSO
4+H
2↑
CoO+H
2SO
4=CoSO
4+H
2O
6, add hydrated barta in infusion, solution temperature is controlled at 40 ℃~45 ℃, adding mol ratio is 1: 1 (press the metering of vanadic acid sodium and hydrated barta reactive chemistry), reacts 20 minutes, and filtration can be with 95% vanadium separation in the solution; Solution is heated to 80~85 ℃, and continue adding mol ratio is 1.2: 1 (press the metering of Sodium orthomolybdate and hydrated barta reactive chemistry), reacts 50 minutes, and filtration can be with 92%~93% molybdenum separation in the solution.The principal reaction equation is as follows:
2Na
3VO
4+3Ba(OH)
2=6NaOH+Ba
3(VO
4)
2↓
Na
2MoO
4+Ba(OH)
2=2NaOH+BaMoO
4↓
7, will separate sodium aluminate solution Al behind vanadium, the molybdenum
2O
3Concentration be adjusted to 120g/l, and be heated to 80 ℃, in the carbonating groove, stir, to wherein feeding carbonic acid gas, 8 hours resolving times, it is neutral that aluminum hydroxide crystals is washed to washing lotion with tap water, in 130 ℃ of oven dry.Decomposition nut liquid contains Al
2O
34.6g/l, with the carbon mother liquid evaporation concentration, in concentrated mother liquor, adding lime and carry out causticizing reaction, the sodium hydroxide of causticizing reaction returns burden process and does the use of sodium roasting raw material.The rate of decomposition of carbon branch process sodium aluminate is 96.2%.The principal reaction equation is:
2NaAlO
2+CO
2+3H
2O=Na
2CO
3+2Al(OH)
3↓
Na
2CO
3+Ca(OH)
2=2NaOH+CaCO
3↓
8, aluminium hydroxide is carried out high-temperature calcination under 1200 ℃, preparation alumina product, Al
2O
3Content be 99.8%, reach the requirement of GB first class product.
Embodiment 2 is extracted the method for vanadium, molybdenum, nickel, cobalt, aluminium from aluminium scrap is catalyst based, carry out according to the following steps:
1, the oily waste water aluminium-based catalyst of natural particle size is sent into rotary kiln high temperature removal surface oil content, the material downbeam feeds in air-flow and the kiln, and controlled temperature is 850 ℃, and the time is 3 hours;
2, remove oil content after spent catalyst with addition of a certain amount of sodium hydroxide, sodium hydroxide and spent catalyst (are pressed Al
2O
3Meter) mol ratio is 3: 1, with spent catalyst and the abundant mixing of sodium hydroxide;
3, the material for preparing is carried out high-temperature roasting in Reaktionsofen, temperature is 800 ℃, and the time is 40 minutes, and the transformation efficiency of vanadium molybdenum is respectively 96.6% and 97.5%, and the transformation efficiency of aluminum oxide is 97.2%.The principal reaction equation is with the 3rd step of mode 1.
4, the grog after the roasting is leached in 80 ℃ hot water, solvent and solute weight ratio is 3: 1, and the time is 1.0 hours, and sodium aluminate, vanadic acid sodium, Sodium orthomolybdate all change liquid phase over to, and the nickel cobalt concentration ratio in the water logging slag is 6.0;
5, be that 20% the sulfuric acid nickel cobalt slag after to water logging leaches with volume ratio, the nickel cobalt is reclaimed in acidleach, and temperature of reaction is 85~90 ℃, liquid-solid ratio L/S=6: 1, and extraction time 6 hours, the leaching yield of nickel, cobalt is respectively 98.5%, 97.6%.The principal reaction equation is with the 5th step of mode 1.
6, add hydrated barta in infusion, solution temperature is controlled at 40 ℃~45 ℃, adding mol ratio is 1: 1 (press the metering of vanadic acid sodium and hydrated barta reactive chemistry), reacts 30 minutes, and filtration can be with 95.8% vanadium separation in the solution; Solution is heated to 80~85 ℃, and continuing to add mol ratio is 1.2: 1 (pressing the metering of Sodium orthomolybdate and hydrated barta reactive chemistry), reacts 1 hour, filters, and the deposition rate of molybdenum is 92.5% in the sodium aluminate solution.
7, will separate sodium aluminate solution Al behind vanadium, the molybdenum
2O
3Concentration be adjusted to 120g/l, and be heated to 80 ℃, in the carbonating groove, stir, to wherein feeding carbonic acid gas, 10 hours resolving times, it is neutral that aluminum hydroxide crystals is washed to washing lotion with tap water, in 150 ℃ of oven dry.Decomposition nut liquid contains Al
2O
35.1g/l, with the carbon mother liquid evaporation concentration, in concentrated mother liquor, adding lime and carry out causticizing reaction, the sodium hydroxide of causticizing reaction returns burden process and does the use of sodium roasting raw material.The rate of decomposition of carbon branch process sodium aluminate is 96.5%.
8, aluminium hydroxide is carried out high-temperature calcination under 1250 ℃, preparation alumina product, Al
2O
3Content be 99.7%.
Embodiment 3: condition is with example 1, in step 6, adopt adding barium aluminate substep from sodium aluminate solution to isolate vanadium, molybdenum, solution temperature is controlled at 40 ℃~45 ℃, adding mol ratio is 1: 1 (pressing the metering of vanadic acid sodium and barium aluminate reactive chemistry), reacted 20 minutes, and filtered, 95.6% vanadium in the solution can be separated; Solution is heated to 80~85 ℃, and continuing to add mol ratio is 1.2: 1 (pressing the metering of Sodium orthomolybdate and barium aluminate reactive chemistry), reacts 50 minutes, filters, and the deposition rate of molybdenum is 92.7% in the sodium aluminate solution.The principal reaction equation is as follows:
2Na
3VO
4+3BaAl
2O
4=6NaAlO
2+Ba
3(VO
4)
2?↓
Na
2MoO
4+BaAl
2O
4=2NaAlO
2+BaMoO
4↓
Reclaim the result of vanadium, molybdenum, nickel, cobalt, aluminium from aluminium scrap is catalyst based: the rate of recovery of vanadium is 92.3%, the rate of recovery of molybdenum is 90.8, the rate of recovery of nickel, cobalt is respectively 98.2% and 97.4% (the nickel cobalt calculates in the leach liquor by entering), and the rate of recovery of aluminium is 91% (to press Al
2O
3Calculate).
Embodiment 4 conditions are with example 2.In step 6, adopt adding barium aluminate substep from sodium aluminate solution to isolate vanadium, molybdenum, the sodium aluminate solution liquid temp is controlled at 40 ℃~45 ℃, adding mol ratio is 1.1: 1 (pressing the metering of vanadic acid sodium and barium aluminate reactive chemistry), reacted 20 minutes, and filtered, 96.4% vanadium in the solution can be separated; Solution is heated to 80~85 ℃, and continuing to add mol ratio is 1.3: 1 (pressing the metering of Sodium orthomolybdate and barium aluminate reactive chemistry), reacts 1.0 hours, filters, and the deposition rate of molybdenum is 93.0% in the sodium aluminate solution.The principal reaction equation is as follows:
2Na
3VO
4+3BaAl
2O
4=6NaAlO
2+Ba
3(VO
4)
2↓
Na
2MoO
4+BaAl
2O
4=2NaAlO
2+BaMoO
4↓
Reclaim the result of vanadium, molybdenum, nickel, cobalt, aluminium from aluminium scrap is catalyst based: the rate of recovery of vanadium is 92.5%, the rate of recovery of molybdenum is 91%, the rate of recovery of nickel, cobalt is respectively 98.3% and 97.6% (the nickel cobalt calculates in the leach liquor by entering), and the rate of recovery of aluminium is 91.2%.