CN102925693A - Method for extracting metal in waste catalyst RDS/HDS by acid leaching method - Google Patents
Method for extracting metal in waste catalyst RDS/HDS by acid leaching method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000002253 acid Substances 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- 238000002386 leaching Methods 0.000 title claims abstract description 31
- 239000002699 waste material Substances 0.000 title abstract 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 49
- 239000011733 molybdenum Substances 0.000 claims abstract description 49
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
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- 239000007788 liquid Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 17
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- 239000011259 mixed solution Substances 0.000 claims description 12
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- 238000007254 oxidation reaction Methods 0.000 claims description 12
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- 239000012530 fluid Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
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- 238000000746 purification Methods 0.000 claims description 7
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- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940077239 chlorous acid Drugs 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 37
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- 230000000694 effects Effects 0.000 description 7
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- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 3
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- 239000006200 vaporizer Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
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Images
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for extracting metal in waste catalyst RDS/HDS by using an acid leaching method. The waste catalyst is waste catalyst RDS or waste catalyst HDS generated after hydrodesulfurization, and the two waste catalysts are rich in vanadium, molybdenum, nickel, aluminum and heavy oil, and the method comprises the following operation steps of 1) acid leaching; 2) deoiling; 3) and (5) refining. The vanadium, molybdenum, nickel, aluminum and heavy oil in the waste catalyst RDS or the waste catalyst HDS are effectively recycled through the operation steps. The invention has the advantages that: the known sodium salt roasting or sodium salt roasting process after oil removal has the defects of high energy consumption, time consumption, sulfur pollution in air, high cost, low recovery rate, tailing waste and the like. The method has the advantages of simple operation process, low cost, no environmental pollution, higher recovery rate than the known technology, effective recovery of vanadium, molybdenum, nickel and aluminum metals in the RDS or HDS, the purity of the recovered metals meets the international standard, and the nitric acid used in the operation process and the heavy oil carried by the RDS or HDS can be directly recovered and reused.
Description
Technical field
The present invention relates to from useless catalyst, reclaim the method for metal, specifically with metallic method in the useless catalyst of Ore Leaching.
Technical background
Flourish along with petrochemical industry is so that be used for is used this kind catalyst normal operation Al in a large number to the catalyst of oil hydrogenating desulfurization in the refining of petroleum
2O
3Be carrier, and adhere to the metals such as molybdenum with activeconstituents, nickel, but because in the adsorption process, the elements such as a large amount of iron, vanadium, phosphorus can cause catalyst to lose efficacy and form RDS or the useless catalyst of HDS, if the useless catalyst of this kind will cause serious environment to poison without effective processing.
All contain just like useful metals such as vanadium, molybdenum, nickel, aluminium among useless catalyst RDS or the useless catalyst HDS, useless catalyst RDS is residual available heavy oil also.Therefore, very valuable to the recovery technical study of metal in the useless catalyst.
Roughly can classify as the recovery technique of metal in the useless catalyst at present:
1. sodium roasting method: this process application is the widest also at most, no matter which kind of material is for vanadium extraction, molybdenum is put forward technique and is mostly used these methods, although yet year more than the vanadium molybdenum recovery row of this process application in useless catalyst, its vanadium molybdenum recovery does not roughly wait 85 ~ 90%, but because of the needed temperature of sodium carbonate roasting up to more than 850 ℃, roasting time is long, very expend the energy, and contain a large amount of sulphur in the useless catalyst, in high-temperature calcination process, can originate in a large number in the air, cause air pollution problems inherent, the nickeliferous solid waste processing of inclining in addition after is difficult for, so this technique can only reclaim the vanadium molybdenum, can not reclaim nickel.
2. the lixiviate of wet method alkali is followed the example of: this method is that the metal that utilizes the high pressure base mode of soaking will give up in the catalyst is dissolved in the solution, and recycling ion exchange resin or extraction process go to extract.But there is useless catalyst aluminium too high levels in this method, filters to be difficult for, and is also infeasible on the production technique.
3. wet method acid immersion extraction method after the roasting: this method is used at incline tailings after of sodium carbonate roasting mostly for useless catalyst, or after the metal-salt behind the sodium carbonate roasting carried out acidleach and process with sulfuric acid, reclaims vanadium, molybdenum, nickel with extraction again.But this method can only be processed the program after sodium carbonate roasting leaches, and is still unresolved for highly energy-consuming and the sulphur air pollution problems inherent of roasting, and tailings must just can leach metal in the high pressure acidleach after the roasting, and required equipment is very expensive.
Summary of the invention
The present invention provides a kind of with metallic method in the useless catalyst of Ore Leaching in order to overcome the shortcoming of prior art.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
1. with metallic method in the useless catalyst of Ore Leaching, described useless catalyst refers to the useless catalyst RDS or the useless catalyst HDS that produce after hydrogenating desulfurization, all be rich in vanadium, molybdenum, nickel, aluminium and heavy oil in these two kinds of useless catalyst, hereinafter to be referred as useless catalyst compound, the method step is as follows:
1) Ore Leaching step:
In the hyperoxia voltinism acid solution that useless catalyst compound is soaked in, make sulphur in this useless catalyst compound and the acid liquid reaction of this hyperoxia voltinism, obtain mixed solution, acidity is higher selects to have added auxiliary acid in order to make in the process; Mixed solution includes heavy oil, leach liquor and residue, and wherein leach liquor and residue contain the oxidation state metal; The acid solution of described hyperoxia voltinism is nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid or the vitriol oil, and the weight ratio of the acid solution of hyperoxia voltinism and catalyst compound is 1: 1～4, and the concentration expressed in percentage by weight of the acid solution of hyperoxia voltinism is 5～40%; Described auxiliary acid is that concentration expressed in percentage by weight is 0.5%～25% strongly acidic solution example hydrochloric acid; Soaking temperature is 70～90 ℃;
2) deoiling step:
Above-mentioned mixed solution is separated, remove residue, leave standstill, treat leach liquor and heavy oil layering, separate removal heavy oil, vanadium, molybdenum, nickel, the aluminium that obtains the containing oxidation state fluid of inclining;
3) purification step:
Above-mentioned residue is soaked in the alkali lye, obtain residue leach liquor and a large amount of aluminium slag, obtain the first extraction liquid with extraction agent extraction residue leach liquor, with a basic solution or an acidic solution the first extraction liquid is stripped again, obtain the first anti-stripping agent, with known technique the first extraction liquid is extracted molybdenum; With step 2) De extracts with extraction agent Dao De Pour fluid, obtain the second extraction liquid, with a basic solution or an acidic solution the second extraction liquid is stripped again, obtain the second anti-stripping agent, with known technique the second anti-stripping agent is extracted respectively a large amount of vanadium, nickel and a small amount of aluminium, molybdenum; Described basic solution is yellow soda ash, sodium hydroxide, ammonium hydroxide or sodium chloride solution; Described acidic solution is that the described extraction agent of sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid comprises N-235, Alamine336, Aliquit306, P204, P507, N236, TOA, wherein one or more.
Advantage of the present invention:
1. provided by the inventionly can reclaim institute's containing metal in the catalyst that gives up with metallic method in the useless catalyst of Ore Leaching, the heavy oil that simultaneously it is rich in is directly recycled, and has reduced energy consumption, has reduced environmental pollution comprehensively.
2. provided by the inventionly leach in the useless catalyst compound metallic method with hyperoxia voltinism acid solution and can directly extract oxidation state metal in the catalyst that gives up, reduced the difficulty of subsequent disposal, improved extraction yield.
3. provided by the invention with behind institute's containing metal in the useless catalyst compound of hyperoxia voltinism acid solution leaching, the NO of hyperoxia voltinism acid solution
xBut efficient recovery, the Cost reduction expenditure.
Description of drawings
Fig. 1 is operating process one of the present invention.
Fig. 2 is operating process two of the present invention.
Embodiment
The invention will be further described below in conjunction with accompanying drawing and preferred embodiment.
The useless catalyst of indication of the present invention is the useless catalyst of the RDS after hydrogenating desulfurization or the useless catalyst of HDS, the useless catalyst compound of general designation in the present invention, and the two all includes the useful metals such as vanadium, molybdenum, nickel, aluminium, and also residual in the useless catalyst of RDS have a large amount of heavy oil compositions.
Most preferred embodiment flow process of the present invention comprises Ore Leaching step 1, deoiling step 2 and purification step 3 with metallic method in the useless catalyst of Ore Leaching as shown in Figure 1.
Ore Leaching step 1 is that useless catalyst compound is soaked in the hyperoxia voltinism acid solution, makes sulphur in this useless catalyst compound and the acid liquid reaction of this hyperoxia voltinism, obtains mixed solution, and acidity is higher selects to have added auxiliary acid in order to make in the process; Mixed solution includes heavy oil, leach liquor and residue, wherein has been rich in the oxidation state metal in leach liquor and the residue; The acid solution of described hyperoxia voltinism is nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid or the vitriol oil, and the weight ratio of the acid solution of hyperoxia voltinism and catalyst compound is 1: 1～4, and the concentration expressed in percentage by weight of the acid solution of hyperoxia voltinism is 5～40%; Described auxiliary acid is that concentration expressed in percentage by weight is 0.5%～25% strongly acidic solution example hydrochloric acid.Soaking temperature is 70～90 ℃.
Specifically, sulphur in the acid solution of tool hyperoxia voltinism and the useless catalyst compound produces vulcanization reaction, the useless catalyst compound that is immersed in this acid solution can be mixed with vulcanization reaction, through a large amount of vanadium of sour stripping, nickel and a small amount of aluminium, molybdenum, and the hyperoxia voltinism by this acid solution make vanadium, molybdenum, nickel, aluminium and unreacted completely element sulphur be converted into the oxidation state of easy extraction through oxidizing reaction.Therefore, process the mixed solution that generates through this acid solution, except residual heavy oil, produce simultaneously leach liquor and the residue that is rich in the oxidation state metal.Contain a large amount of vanadium, nickel and a small amount of aluminium, molybdenum in this leach liquor, contain a large amount of aluminium slag and molybdenum in the residue.
In Ore Leaching step 1, also can generate sulfocompound and vaporizer because of vulcanization reaction.Wherein vaporizer is the acid solution that can again react for this hyperoxia voltinism, recycles in Ore Leaching step 1.Be the oxidation state acid group that generates after this acid solution oxidation because of this vaporizer, it can be reacted into this acid solution again with the water effect, re-uses in Ore Leaching step 1; This sulfocompound can reduce the pH value of this acid solution, reaches to improve the metal leaching effect of this useless catalyst compound in acid solution.
The mixed solution that this Ore Leaching step 1 produces includes heavy oil, leach liquor and residue, for fear of the follow-up METAL EXTRACTION effect of heavy oil impact, can with the direct recycling of heavy oil, therefore be chosen in Ore Leaching step 1 and carry out afterwards, first deoiling step 2.
This deoiling step 2 is that this mixed solution is separated, and removes residue, leaves standstill, treats leach liquor and heavy oil layering, separates and removes heavy oil, obtains the fluid of inclining.Say in detail, from this mixed solution, separate residue with filter screen after because leach liquor is different from heavy oil proportion, utilize the two proportion different, with the run by gravity mode heavy oil is separated, heavy oil can recycling, has saved conventional high-temperature burn spent time and the energy; In addition, the residue that separates first and do not contain the fluid of inclining of heavy oil then can be again in follow-up purification step 3, select appropriate ways extraction institute's containing metal in the fluid that inclines according to the two different attribute, could all sidedly metal in the catalyst that gives up be recycled again.
Above-mentioned purification step 3 is that the metal in this residue is leached, and obtains the residue leach liquor, respectively the fluid of inclining of residue leach liquor and Ore Leaching step 1 is extracted and extract metal.Say in detail, because after Ore Leaching step 1, contained a large amount of vanadium, nickel and a small amount of aluminium, molybdenum have inclined in this leach liquor in the useless catalyst, so leach liquor can be selected directly with these metal extractions out; But residue in a large amount of aluminium and molybdenum in the residue, with alkaline leaching molybdenum wherein, after extraction, obtain molybdenum again.
Purification step 3 flow processs of the present invention can also be as shown in Figure 2, and figure Central Plains purification step 3 comprises the first extraction step 31 and the second extraction step 32.
The first extraction step 31 is with extraction agent the vanadium in the fluid of inclining, molybdenum to be extracted, obtain coextraction liquid, with a basic solution or an acidic solution coextraction liquid is stripped again, after obtaining anti-stripping agent, with known technique anti-stripping agent is extracted respectively vanadium, molybdenum, the vanadium that is recycled, molybdenum; Then, with after extracting remaining liquid behind vanadium, the molybdenum and removing wherein sulphur with calcium carbonate, output calcium sulfate, and make the pH value be adjusted into 7-8, the water solution obtains nickel aluminium concentrate.Wherein extraction agent be among N-235, Alamine336, Aliquit306, P204, P507, N236, the TOA one or more; The basic solution of extraction usefulness can be yellow soda ash, sodium hydroxide, ammonium hydroxide or sodium chloride solution; The acidic solution of extraction usefulness can be sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid.
The second extraction step 32 is that residue is soaked in the alkali lye, obtains the residue leach liquor, is extracted liquid and a large amount of aluminium slag with extraction agent extraction residue leach liquor again, with known technique extraction liquid is extracted molybdenum.Say in detail, the second extraction step 32 is directly to use the dipping by lye residue, and the molybdenum in the residue is leached in the residue leach liquor; Recycle the same procedure extraction residue leach liquor of the first extraction step 31, obtain the molybdenum in the residue.Wherein alkali lye can be yellow soda ash, sodium hydroxide, ammonium hydroxide or sodium chloride solution.
Specify, in the first extraction step 31 and the second extraction step 32, utilize extraction, back extraction fetch the technology of extracting vanadium, molybdenum, nickel or aluminium be those skilled in the art of the present technique oneself know technology, be not technical characteristics of the present invention, therefore repeat no more.
In addition, the present invention adds a small amount of auxiliary acid in Ore Leaching step 1, is the potential of hydrogen that reduces this acid solution with auxiliary acid, improves useless catalyst compound and is immersed in metal in this this acid solution and inclines and rate.Wherein, auxiliary acid can be selected the strongly acidic solutions such as example hydrochloric acid, sulfuric acid, and its concentration expressed in percentage by weight is 0.5%～25%.
In sum, the present invention not only can leach contained vanadium, molybdenum, nickel and aluminium in the useless catalyst compound by hyperoxia voltinism acid solution, and make vanadium, molybdenum, nickel and aluminium through the oxidation state of high oxidation role transformation for easily extracting of acid solution, the difficulty that this has just reduced follow-up extraction and has extracted metal reaches and improves metal fall and with the effect of the comprehensive recycling of metal.In addition, when improving metal fall by the present invention, also can select directly to utilize the difference of specific gravity of material, leach the heavy oil that this useless catalyst compound is held under the arm with light oil liquid separate mode, during the useless catalyst of the RDS that particularly selects the present invention to process to contain a large amount of heavy oil, more a large amount of heavy oil can be recycled again, be produced new economic worth.This not only can save power consumption that traditional combustion heavy oil produces, consuming time, also can avoid flying away in air because of sulphur or its compound that burning causes being dissolved in the heavy oil thereupon, reaches the purpose that reduces environmental pollution.
In order to prove really energy effective separation heavy oil of the present invention, the effect of avoiding the heavy oil impact to leach, reach the effect of further raising vanadium, molybdenum, nickel and aluminum metal leaching yield, following examples are take nitric acid as hyperoxia voltinism acid solution, make specific embodiment take the useless catalyst of RDS as useless catalyst, carry out following analysis.
It is in 20% nitric acid liquid that the useless catalyst compound of RDS that 1000 grams are contained 22.4% aluminium, 3.2% molybdenum, 2.5% nickel, 7.6% vanadium is immersed in weight concentration, and useless catalyst compound: the weight ratio of nitric acid liquid is 1:1～1:4, and the reaction times respectively is 4 hours; Utilize extraction equipment after the Chemical formula 1 vaporization, to collect by nitronic acid root NOx, and in upper reaction, generate the nitric acid recycling through Chemical formula 2.
HO-NO
2+2H
2SO
4→NO
2 ++2HSO
4 -+H
3O
+ (1)
NO
2 ++H
2O→HNO
3 (2)
After contained metal settles out individually in this inclines fluid and residue, analyze for last tailings, measure the content of aluminium, molybdenum, nickel and vanadium metal in this tailings, as shown in table 1.
The metal content that records during the different ratio of the useless catalyst compound of table 1: nitric acid: RDS
As seen from the above table, when liquid-solid ratio was higher than 2:1, the rate of recovery of vanadium, molybdenum and nickel all can be higher than more than 99%.
The useless catalyst of RDS that 1000 grams is contained 22.4% aluminium, 3.2% molybdenum, 2.5% nickel, 7.6% vanadium at the useless catalyst of RDS and salpeter solution than carrying out acidleach under the 1:3, the concentration expressed in percentage by weight of salpeter solution is respectively 5%, 10%, 20%, 30%, 40%, and the reaction times respectively is 4 hours; After contained metal settles out individually in leach liquor and residue, analyze for last tailings, record the content of aluminium in the tailings, molybdenum, nickel and vanadium metal, as shown in table 2.
Table 2: the metal content that records during different salpeter solution
By shown in the table 2, when the concentration expressed in percentage by weight of salpeter solution was higher than 10%, the rate of recovery of vanadium, molybdenum and nickel metal was all up to more than 99%.
Get system by the table 1 of embodiment 1 and table 2 explanation the present invention of embodiment 2 take salpeter solution as main acidleach, can improve the rate of recovery of vanadium, molybdenum and nickel metal in the useless catalyst, and can not be subject to the impact of heavy oil in the useless catalyst, can the situation when low power consuming, low consumption be issued to the effect of vanadium, molybdenum and nickel metal in the useless catalyst of comprehensive recovery RDS.
Show the aluminium that has in the last tailings up to 90%-95% by the table 1 of embodiment 1 and the table 2 of embodiment 2 in addition, the leaching process of this explanation vanadium, molybdenum and nickel metal can not be subject to the interference that aluminium leaches simultaneously, the quality of vanadium, molybdenum and nickel metal after guaranteeing to leach.
Embodiment 3
The useless catalyst of RDS that 1000 grams is contained 22.4% aluminium, 3.2% molybdenum, 2.5% nickel, 7.6% vanadium, at the useless catalyst of RDS and salpeter solution than carrying out the salpeter solution acidleach under the 1:3 condition, the concentration expressed in percentage by weight of salpeter solution is 20%, and the strong acid (example hydrochloric acid) of interpolation 1%-25%, reaction times was respectively 4 hours, after question response is finished, for the fluid analysis of inclining behind the Ore Leaching, record the rate of recovery of final vanadium, molybdenum, nickel and aluminum metal, as shown in table 3.
Table 3: record vanadium, molybdenum, nickel and aluminum metal content in the leach liquor behind the Ore Leaching during hydrochloric acid auxiliary acid of adding different concns.
By table 3 result as can be known, the acidleach leaching yield when not adding the hydrochloric acid auxiliary acid is all little when adding the hydrochloric acid auxiliary acid, and leaching yield increases with addition.Therefore, but prove the rate of recovery of adding auxiliary acid Effective Raise vanadium, molybdenum and nickel metal.
Above embodiment is the embodiment under the optimum process condition of the present invention; be not to limit the present invention with this; anyly know this operator in not departing from the scope of the present invention, above-described embodiment is made amendment and is still belonged to the present invention and protect category relatively, and the present invention protects category to be as the criterion with claims.
Claims (1)
1. with metallic method in the useless catalyst of Ore Leaching, it is characterized in that, described useless catalyst is useless catalyst RDS or the useless catalyst HDS that produces after hydrogenating desulfurization, all is rich in vanadium, molybdenum, nickel, aluminium and heavy oil in these two kinds of useless catalyst, hereinafter to be referred as useless catalyst compound, the method step is as follows:
1) Ore Leaching step:
In the hyperoxia voltinism acid solution that useless catalyst compound is soaked in, make sulphur in this useless catalyst compound and the acid liquid reaction of this hyperoxia voltinism, obtain mixed solution, in the process for making the higher auxiliary acid of having added of acidity; Mixed solution includes heavy oil, leach liquor and residue, and wherein leach liquor and residue contain the oxidation state metal; The acid solution of described hyperoxia voltinism is nitric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid or the vitriol oil, and the weight ratio of the acid solution of hyperoxia voltinism and catalyst compound is 1: 1～4, and the concentration expressed in percentage by weight of the acid solution of hyperoxia voltinism is 5～40%; Described auxiliary acid is that concentration expressed in percentage by weight is 0.5%～25% strongly acidic solution example hydrochloric acid; Soaking temperature is 70～90 ℃;
2) deoiling step:
Above-mentioned mixed solution is separated, remove residue, leave standstill, treat leach liquor and heavy oil layering, separate removal heavy oil, vanadium, molybdenum, nickel, the aluminium that obtains the containing oxidation state fluid of inclining;
3) purification step:
Above-mentioned residue is soaked in the alkali lye, obtain residue leach liquor and a large amount of aluminium slag, obtain the first extraction liquid with extraction agent extraction residue leach liquor, with a basic solution or an acidic solution the first extraction liquid is stripped again, obtain the first anti-stripping agent, with known technique the first extraction liquid is extracted molybdenum; With step 2) De extracts with extraction agent Dao De Pour fluid, obtain the second extraction liquid, with a basic solution or an acidic solution the second extraction liquid is stripped again, obtain the second anti-stripping agent, with known technique the second anti-stripping agent is extracted respectively a large amount of vanadium, nickel and a small amount of aluminium, molybdenum; Described basic solution is yellow soda ash, sodium hydroxide, ammonium hydroxide or sodium chloride solution; Described acidic solution is that the described extraction agent of sulfuric acid, hydrochloric acid, phosphoric acid or perchloric acid solution comprises N-235, Alamine336, Aliquit306, P204, P507, N236, TOA, wherein one or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110029224A (en) * | 2019-05-31 | 2019-07-19 | 宜昌银钒科技有限公司 | A kind of environment friendly and pollution-free vanadic anhydride high efficiency extraction technique |
| CN111154990A (en) * | 2019-12-27 | 2020-05-15 | 眉山顺应动力电池材料有限公司 | Method for separating and recovering nickel in organic nickel catalyst |
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- 2012-10-12 CN CN2012103844370A patent/CN102925693A/en active Pending
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| Title |
|---|
| 胡建锋: "《从废钒触媒中提钒新工艺的研究》", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110029224A (en) * | 2019-05-31 | 2019-07-19 | 宜昌银钒科技有限公司 | A kind of environment friendly and pollution-free vanadic anhydride high efficiency extraction technique |
| CN111154990A (en) * | 2019-12-27 | 2020-05-15 | 眉山顺应动力电池材料有限公司 | Method for separating and recovering nickel in organic nickel catalyst |
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| TW201404890A (en) | 2014-02-01 |
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