CN104495924B - The method being produced ammonium metavanadate by oil plant catalytic cracking spent catalyst - Google Patents
The method being produced ammonium metavanadate by oil plant catalytic cracking spent catalyst Download PDFInfo
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- CN104495924B CN104495924B CN201410784293.7A CN201410784293A CN104495924B CN 104495924 B CN104495924 B CN 104495924B CN 201410784293 A CN201410784293 A CN 201410784293A CN 104495924 B CN104495924 B CN 104495924B
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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Abstract
The present invention relates to a kind of by oil plant catalytic cracking spent catalyst produce ammonium metavanadate method, dead catalyst add with sulphuric acid, calcium fluoride, water blender mixes after be discharged into ripening storehouse, ripening in ripening storehouse; Compound adds water pulp; Pulp liquid pump enters leaching tanks, leaching of heating; Pumping into plate pressure filter and carry out solid-liquor separation, leachate flows into crystallization tank and adds ammonium sulfate crystallization; Solid-liquor separation, obtains Burnt ammonium alum product and crystalline mother solution. Crystalline mother solution adds ammonium carbonate and adjusts pH, adds Ammonium persulfate., adds ammonium carbonate and adjusts pH temperature reaction, pumps into pressure filter, and solid-liquor separation obtains ammonium metavanadate. Separating medium also can enter heavy lanthanum cerium groove, adds ammonium oxalate and reacts to obtain lanthanum oxalate, Sedemesis.; Enter heavy nickel groove to add ammonium sulfide and react to obtain nickel sulfide. Oil plant catalytic cracking spent catalyst is recycled by the present invention, produces ammonium metavanadate; Efficiently solve dead catalyst contaminated environment, the problem of land occupation, to produce ammonium metavanadate purity and reach more than 99%, organic efficiency is high.
Description
Technical field
The present invention relates to a kind of technology that oil plant catalytic cracking spent catalyst is comprehensively utilized, be specifically related to a kind of method being produced ammonium metavanadate by oil plant catalytic cracking spent catalyst.
Background technology
During oil plant catalytic cracking process refining crude oil, the dead catalyst of output is mostly the little granule super-stable Y molecular sieves catalyst having supported a small amount of rare earth metal, catalysis activity decrease after using a period of time, comprehensive economic index is deteriorated, then must draw off from system, both contaminated environment, again land occupation after gushing. There is presently no better technique and method this dead catalyst is effectively treated so that it is eliminate pollution to environment, and can effective regeneration self-value of utility in it.
To dead catalyst, mostly current each oil plant is that limit adds raw catelyst limit and draws off the continuous process of mixed catalyst, and the mixture drawn off still has become refuse. Some methods utilizing dead catalyst are worked out for this, have for producing construction material, what have regenerates it, as with backflow leaching method regeneration catalyzing agent, adopt the catalyst nickel content after this PROCESS FOR TREATMENT can be down to 0.2% by 0.8%, activation recovering 95.7%, reaches commercial Application standard, is used further to catalysis.
Have not yet to see the document extracting useful rare earth metal from dead catalyst.
Summary of the invention
It is an object of the invention to for above-mentioned present situation, it is desirable to provide a kind of method that can be produced ammonium metavanadate by oil plant catalytic cracking spent catalyst.
The implementation of the object of the invention is, oil plant catalytic cracking spent catalyst the method producing ammonium metavanadate, specifically comprises the following steps that
1) ratio of dead catalyst and sulphuric acid, calcium fluoride, water 1:0.8-1.2:0.04-0.06:0.08-0.11 in mass ratio add blender mixes 4-6min after be discharged into ripening storehouse, ripening in ripening storehouse, curing temperature 150-220 DEG C, time 9-12h;
2) by step 1) compound after ripening adds water pulp 0.9-1.2h in the ratio of quality 1:2.5-3.5;
3) by step 2) pulp liquid pump enter leaching tanks, heat 90-95 DEG C, leaching 3h;
4) by step 3) leachate pump into plate pressure filter and carry out solid-liquor separation, the solid slag of separation is banked up after water washing, and leachate flows into crystallization tank;
5) when the temperature in crystallization tank being down to 35-45 DEG C, by leachate volume 76-84kg/m3Add ammonium sulfate, crystallization 2.3-2.6h at 38-42 DEG C of temperature;
6) step 5) solid-liquor separation after crystallization, obtain Burnt ammonium alum product and crystalline mother solution;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 1.5-2.0, then raising temperature to 60-70 DEG C, add Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again adding ammonium carbonate and adjust pH to 2.0, then raise temperature to 85-95 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation, obtains ammonium metavanadate.
Oil plant catalytic cracking spent catalyst is recycled by the present invention, produces ammonium metavanadate, lanthanum oxalate and Sedemesis. product; Ammonium metavanadate purity reaches more than 99%. The present invention efficiently solves dead catalyst contaminated environment, the problem of land occupation, and organic efficiency is high.
Generating the separating medium after ammonium metavanadate and enter heavy aluminum groove tune pH, pump into the heavy ferrum aluminum of pressure filter, solid-liquor separation, separating medium pumps into heavy lanthanum, cerium groove, adds ammonium oxalate reaction, and solid-liquid separation obtains lanthanum oxalate, Sedemesis.. Generating the separating medium after lanthanum oxalate, Sedemesis. to enter heavy nickel groove and add ammonium sulfide and react to obtain nickel sulfide, filtrate returns pulp workshop section.
Detailed description of the invention
The present invention dead catalyst is added with sulphuric acid, calcium fluoride, water blender mixes after be discharged into ripening storehouse, ripening in ripening storehouse; Compound adds water pulp; Pulp liquid pump enters leaching tanks, leaching of heating; Pumping into plate pressure filter and carry out solid-liquor separation, leachate flows into crystallization tank and adds ammonium sulfate crystallization; Solid-liquor separation, obtains Burnt ammonium alum product and crystalline mother solution.
Generating the separating medium after ammonium metavanadate and enter heavy aluminum groove tune pH, pump into the heavy ferrum aluminum of pressure filter, solid-liquor separation, separating medium pumps into heavy lanthanum, cerium groove, adds ammonium oxalate reaction, and solid-liquid separation obtains lanthanum oxalate, Sedemesis.. Generating the separating medium after lanthanum oxalate, Sedemesis. to enter heavy nickel groove and add ammonium sulfide and react to obtain nickel sulfide, filtrate returns pulp workshop section.
Dead catalyst is containing V0.5%, La2.77%, Ce0.62%, Ni0.38%, Al25.46%.
With specific embodiment in detail the present invention is described in detail below.
Example 1,
1) 45 tons of dead catalyst and 36 tons of sulphuric acid, 1.8 tons of calcium fluoride, 3.6 tons of water add in blenders and are discharged into ripening storehouse after mixing 4min, ripening in ripening storehouse, curing temperature 150 DEG C, time 9h;
2) by step 1) compound after ripening adds water pulp 0.9h in the ratio of quality 1:2.5;
3) by step 2) pulp liquid pump enter leaching tanks, heat 90 DEG C, leaching 3h; .
4) by step 3) leachate pump into plate pressure filter and carry out solid-liquor separation, the solid slag of separation is banked up after water washing, and leachate flows into crystallization tank;
5) when the temperature in crystallization tank being down to 35 DEG C, by leachate volume 76kg/m3Add ammonium sulfate, crystallization 2.3h at 38 DEG C of temperature;
6) step 5) solid-liquor separation after crystallization, obtain Burnt ammonium alum product and crystalline mother solution;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 1.5, then raise temperature to 60 DEG C, adding Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again add ammonium carbonate and adjust pH to 2.0, then raising temperature to 85 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation;Obtain ammonium metavanadate.
Example 2, with embodiment 1, the difference is that,
1) 45 tons of dead catalyst and 45 tons of sulphuric acid, 2.25 tons of calcium fluoride, 4.5 tons of water add in blenders and are discharged into ripening storehouse after mixing 5min, ripening in ripening storehouse, curing temperature 180 DEG C, time 10h;
2) by step 1) compound after ripening adds water pulp 1.0h in the ratio of quality 1:3;
3) by step 2) pulp liquid pump enter leaching tanks, heat 92 DEG C, leaching 3h;
5) when the temperature in crystallization tank being down to 40 DEG C, by leachate volume 80kg/m3Add ammonium sulfate, crystallization 2.5h at 40 DEG C of temperature;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 1.8, then raise temperature to 65 DEG C, adding Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again add ammonium carbonate and adjust pH to 2.0, then raising temperature to 90 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation; Obtain ammonium metavanadate.
Example 3, with embodiment 1, the difference is that,
1) 45 tons of dead catalyst and 49.5 tons of sulphuric acid, 1.8 tons of calcium fluoride, 4.05 tons of water add in blenders and are discharged into ripening storehouse after mixing 5min, ripening in ripening storehouse, curing temperature 190 DEG C, time 11h;
2) by step 1) compound after ripening adds water pulp 1.1h in the ratio of quality 1:2.8;
3) by step 2) pulp liquid pump enter leaching tanks, heat 93 DEG C, leaching 3h;
5) when the temperature in crystallization tank being down to 38 DEG C, by leachate volume 79kg/m3Add ammonium sulfate, crystallization 2.7h at 39 DEG C of temperature;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 1.9, then raise temperature to 63 DEG C, adding Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again add ammonium carbonate and adjust pH to 2.0, then raising temperature to 88 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation; Obtain ammonium metavanadate.
Example 4, with embodiment 1, the difference is that,
1) 45 tons of dead catalyst and 40.5 tons of sulphuric acid, 1.8 tons of calcium fluoride, 4.5 tons of water add in blenders and are discharged into ripening storehouse after mixing 5min, ripening in ripening storehouse, curing temperature 210 DEG C, time 11h;
2) by step 1) compound after ripening adds water pulp 1.0h in the ratio of quality 1:3.2;
3) by step 2) pulp liquid pump enter leaching tanks, heat 94 DEG C, leaching 3h;
5) when the temperature in crystallization tank being down to 42 DEG C, by leachate volume 82kg/m3Add ammonium sulfate, crystallization 2.4h at 41 DEG C of temperature;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 1.9, then raise temperature to 68 DEG C, adding Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again add ammonium carbonate and adjust pH to 2.0, then raising temperature to 92 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation; Obtain ammonium metavanadate.
Example 5, with embodiment 1, the difference is that,
1) 45 tons of dead catalyst and 54 tons of sulphuric acid, 2.7 tons of calcium fluoride, 4.95 tons of water add in blenders and are discharged into ripening storehouse after mixing 6min, ripening in ripening storehouse, curing temperature 220 DEG C, time 12h;
2) by step 1) compound after ripening adds water pulp 1.2h in the ratio of quality 1:3.5;
3) by step 2) pulp liquid pump enter leaching tanks, heat 95 DEG C, leaching 3h;
5) when the temperature in crystallization tank being down to 45 DEG C, by leachate volume 84kg/m3Add ammonium sulfate, crystallization 2.6h at 42 DEG C of temperature;
6) step 5) solid-liquor separation after crystallization, obtain Burnt ammonium alum product and crystalline mother solution;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 2.0, then raise temperature to 70 DEG C, adding Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again add ammonium carbonate and adjust pH to 2.0, then raising temperature to 95 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation;Obtain ammonium metavanadate.
Claims (2)
1. the method being produced ammonium metavanadate by oil plant catalytic cracking spent catalyst, it is characterised in that specifically comprise the following steps that
1) ratio of dead catalyst and sulphuric acid, calcium fluoride, water 1:0.8-1.2:0.04-0.06:0.08-0.11 in mass ratio add blender mixes 4-6min after be discharged into ripening storehouse, ripening in ripening storehouse, curing temperature 150-220 DEG C, time 9-12h;
2) by step 1) compound after ripening adds water pulp 0.9-1.2h in the ratio of quality 1:2.5-3.5;
3) by step 2) pulp liquid pump enter leaching tanks, heat 90-95 DEG C, leaching 3h;
4) by step 3) leachate pump into plate pressure filter and carry out solid-liquor separation, the solid slag of separation is banked up after water washing, and leachate flows into crystallization tank;
5) when the temperature in crystallization tank being down to 35-45 DEG C, by leachate volume 76-84kg/m3Add ammonium sulfate, crystallization 2.3-2.6h at 38-42 DEG C of temperature;
6) step 5) solid-liquor separation after crystallization, obtain Burnt ammonium alum product and crystalline mother solution;
7) at normal temperatures, to step 6) crystalline mother solution add ammonium carbonate adjust pH to 1.5-2.0, then raising temperature to 60-70 DEG C, add Ammonium persulfate., solution is glassy yellow, after blackish green vestige, again adding ammonium carbonate and adjust pH to 2.0, then raise temperature to 85-95 DEG C, insulation 2h pumps into the heavy ammonium metavanadate of pressure filter, solid-liquor separation, obtains ammonium metavanadate.
2. the method being produced ammonium metavanadate by oil plant catalytic cracking spent catalyst according to claim 1, it is characterised in that dead catalyst is containing V0.5%, La2.77%, Ce0.62%, Ni0.38%, Al25.46%.
Priority Applications (1)
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| CN201410784293.7A CN104495924B (en) | 2014-12-17 | 2014-12-17 | The method being produced ammonium metavanadate by oil plant catalytic cracking spent catalyst |
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| CN1631797A (en) * | 2003-12-23 | 2005-06-29 | 朴俊民 | Method for extracting vanadium pentoxide from vanadium-containing spent catalyst and petroleum ash |
| US7485267B2 (en) * | 2005-07-29 | 2009-02-03 | Chevron U.S.A. Inc. | Process for metals recovery from spent catalyst |
| CN102367520A (en) * | 2011-10-08 | 2012-03-07 | 昆明理工大学 | Comprehensive recovery method for recovering vanadium from waste aluminium base catalyst |
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