NO152939B - PROCEDURES FOR EXTRACTION OF VANADIUM FROM A DEACTIVATED CATALYST - Google Patents
PROCEDURES FOR EXTRACTION OF VANADIUM FROM A DEACTIVATED CATALYST Download PDFInfo
- Publication number
- NO152939B NO152939B NO781027A NO781027A NO152939B NO 152939 B NO152939 B NO 152939B NO 781027 A NO781027 A NO 781027A NO 781027 A NO781027 A NO 781027A NO 152939 B NO152939 B NO 152939B
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- Prior art keywords
- catalyst
- vanadium
- deactivated
- water vapor
- mixture
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 121
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims description 49
- 229910052720 vanadium Inorganic materials 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 37
- 238000000605 extraction Methods 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 230000009849 deactivation Effects 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 229910052759 nickel Inorganic materials 0.000 description 23
- 239000007789 gas Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
Classifications
-
- 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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- 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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium 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
Description
Norsk patent nr. 143521 angår en fremgangsmåte Norwegian patent no. 143521 relates to a method
ved ekstraksjon av vanadium fra en katalysator som er blitt deaktivert ved bruk for behandling av en hydrocarbonolje som inneholder vanadium, med hydrogen ved forhøyet temperatur og trykk, idet katalysatorens vanadiuminnhold under denne behandling har øket med minst 10 vektdeler. Ifølge den nevnte norske patentsøknad utføres ekstraksjonen av vanadiumet, hvorved katalysatorens vanadiuminnhold minskes med minst 40 % av den mengde som den økte med under deaktiveringen, ved ekstraksjon av den deaktiverte katalysator med en vandig oppløsning av mineralsyre, hvoretter vanadium skilles fra den således erholdte vanadium-holdige oppløsning. Dersom fremgangsmåten anvendes for en katalysator som er blitt deaktivert ved hydrogenbehandling av en hydrocarbonolje som foruten vanadium inneholder nikkel og hvor også katalysatorens nikkelinnhold er øket under behandlingen, fjernes også nikkel fra katalysatoren ved prosessen. Foruten for ekstraksjon av vanadium og eventuelt nikkel fra deaktiverte katalysatorer er prosessen også anvendbar for regenerering av deaktiverte katalysatorer slik at disse igjen kan anvendes for katalytiske formål. by extracting vanadium from a catalyst that has been deactivated when used for treating a hydrocarbon oil containing vanadium, with hydrogen at elevated temperature and pressure, the catalyst's vanadium content during this treatment having increased by at least 10 parts by weight. According to the aforementioned Norwegian patent application, the extraction of the vanadium is carried out, whereby the vanadium content of the catalyst is reduced by at least 40% of the amount by which it increased during deactivation, by extraction of the deactivated catalyst with an aqueous solution of mineral acid, after which the vanadium is separated from the thus obtained vanadium- containing solution. If the method is used for a catalyst which has been deactivated by hydrogen treatment of a hydrocarbon oil which, in addition to vanadium, contains nickel and where the catalyst's nickel content has also been increased during the treatment, nickel is also removed from the catalyst during the process. In addition to the extraction of vanadium and possibly nickel from deactivated catalysts, the process can also be used for the regeneration of deactivated catalysts so that these can again be used for catalytic purposes.
Ifølge det nevnte norske patent utføres ekstrak- According to the aforementioned Norwegian patent, extraction is carried out
sjonen med syre fortrinnsvis i nærvær av et reduksjonsmiddel. Ifølge det nevnte norske patent foretrekkes det dessuten the reaction with acid preferably in the presence of a reducing agent. According to the aforementioned Norwegian patent, it is also preferred
å behandle den deaktiverte katalysator først med vanndamp for å fjerne svovel og deretter med en oxygenholdig gass for å fjerne carbon før katalysatoren ekstraheres med syre. Det bør bemer-kes at når målet ikke bare er å ekstrahere vanadium og eventuelt nikkel fra katalysatoren, men også å regenerere katalysatoren, treating the deactivated catalyst first with steam to remove sulfur and then with an oxygen-containing gas to remove carbon before the catalyst is extracted with acid. It should be noted that when the goal is not only to extract vanadium and possibly nickel from the catalyst, but also to regenerate the catalyst,
er behandlingen av den deaktiverte katalysator med en oxygenholdig gass som antydet i eksemplene i det nevnte norske is the treatment of the deactivated catalyst with an oxygen-containing gas as indicated in the examples in the aforementioned Norwegian
patent, hvorved en mindre andel av den deaktiverte kata- patent, whereby a smaller proportion of the deactivated cata-
lystor behandles med luft i 3 timer ved 550° C; ikke egnet for større mengder av deaktivert katalysator på grunn av den store varmemengde som da ville frigjøres. lystor is treated with air for 3 hours at 550° C; not suitable for larger amounts of deactivated catalyst due to the large amount of heat that would then be released.
Når større mengder deaktivert katalysator måtte behandles for å ekstrahere vanadium og eventuelt nikkel fra katalysatoren og for å regenerere denne, er inntil nylig den følgen-de tre-trinns prosess blitt betraktet som den mest fordelaktige utførelsesform av fremgangsmåten ifølge norsk patent, nr. When larger quantities of deactivated catalyst had to be treated in order to extract vanadium and possibly nickel from the catalyst and to regenerate it, until recently the following three-step process was considered the most advantageous embodiment of the method according to Norwegian patent, no.
143251. Den deaktiverte katalysator behandles først i 1 - 5 timer ved 250 - 4 50° C og atmosfæretrykk med en blanding av damp (vanndamp) og nitrogen og deretter i 1 - 5 dager ved 350 - 600° C og atmosfæretrykk med en blanding av luft og nitrogen, 143251. The deactivated catalyst is first treated for 1 - 5 hours at 250 - 450° C and atmospheric pressure with a mixture of steam (water vapor) and nitrogen and then for 1 - 5 days at 350 - 600° C and atmospheric pressure with a mixture of air and nitrogen,
og tilslutt ekstraheres katalysatoren med syre i nærvær av et reduksjonsmiddel i 0,5 - 3 timer ved 50 - 150° C. De behand-lingstider som er nødvendige i de forskjellige trinn, er blant annet avhengige av de på den deaktiverte katalysator tilstede-værende mengder svovel, carbon og metaller og av de valgte betingelser, dvs. behandlingstemperaturene, gasstrømmengdene og sammensetningene for behandlingsgasser og ekstraksjonsvæske. Hittil er den lange behandlingstid som var nødvendig i det and finally the catalyst is extracted with acid in the presence of a reducing agent for 0.5 - 3 hours at 50 - 150° C. The treatment times that are necessary in the various steps depend, among other things, on those present on the deactivated catalyst amounts of sulphur, carbon and metals and of the chosen conditions, i.e. the treatment temperatures, gas flows and compositions for treatment gases and extraction liquid. Until now, the long processing time was necessary in it
annet trinn av tre-trinns prosessen, blitt betraktet som en alvorlig ulempe ved anvendelse av fremgangsmåten ifølge det nevnte norske patent i teknisk målestokk. second step of the three-step process, has been considered a serious disadvantage when using the method according to the aforementioned Norwegian patent on a technical scale.
En fortsatt undersøkelse av fremgangsmåten beskrevet A continued investigation of the method described
i norsk patent nr. 143251 har ifølge oppfinnelsen vist at et resultat som er sammenligningsbart med det resultat som erholdes ved å utføre fremgangsmåten som den ovenfor beskrevne tre-trinns prosess, kan fås hva gjelder fjernelse av vanadium og nikkel fra og aktivitet for den regenererte katalysator, men i løpet av en langt kortere tid, dersom det før ekstraksjonen med syre i nærvær av et reduksjonsmiddel utføres en behandling av den deaktiverte katalysator ved en temperatur over 250° C in Norwegian patent no. 143251, according to the invention, it has been shown that a result which is comparable to the result obtained by carrying out the method as the three-step process described above, can be obtained in terms of the removal of vanadium and nickel from and activity for the regenerated catalyst , but within a much shorter time, if before the extraction with acid in the presence of a reducing agent, a treatment of the deactivated catalyst is carried out at a temperature above 250° C
med en blanding av vanndamp og luft i et forhold av over 1:1 ved et partialtrykk for vanndampen av over 1 bar. Foruten den kjennsgjer-ning at for fremgangsmåten ifølge oppfinnelsen er det til-strekkelig med en langt kortere behandlingstid for å oppnå et with a mixture of water vapor and air in a ratio of more than 1:1 at a partial pressure for the water vapor of more than 1 bar. Apart from the fact that for the method according to the invention, a much shorter processing time is sufficient to achieve a
sammenlignbart resultat hva gjelder fjernelse av vanadium og nikkel fra og aktivitet for den regenererte katalysator, byr den foreliggende fremgangsmåte på to ytterligere fordeler sam-menlignet med den ovennevnte tre-trinns prosess ved at antallet av behandlingstrinn og at antallet av gasser som er nødvendige for å behandle den deaktiverte katalysator før ekstraksjonen med syren, er blitt redusert med ett trinn hhv. med én gass. comparable result in terms of removal of vanadium and nickel from and activity for the regenerated catalyst, the present method offers two further advantages compared to the above three-step process in that the number of treatment steps and the number of gases necessary to treat the deactivated catalyst before the extraction with the acid, has been reduced by one step or with one gas.
Den foreliggende oppfinnelse angår der en forbedret fremgangsmåte ved ekstraksjon av vanadium fra en The present invention relates there to an improved method for the extraction of vanadium from a
deaktivert katalysator som er blitt deaktivert på grunn av at den er blitt anvendt ved behandling av en vanadiumholdig hydrocarbonolje med hydrogen ved forhøyet temperatur og trykk slik at katalysatorens vanadiuminnhold er blitt øket med minst 10 vektdeler og hvor den nevnte vanadiumekstraksjon, hvorved katalysatorens vanadiuminnhold minskes med minst 40% av den mengde som vanadiuminnholdet har øket med under deaktiveringen (katalysatorens vanadiuminnhold uttrykt som vektdeler vanadium/ 100 vektdeler katalysator), utføres ved å ekstrahere den deaktiverte katalysator med en vandig oppløsning av en mineralsyre, hvoretter vanadiumet skilles fra den således erholdte vanadiumhoIdige oppløsning. deactivated catalyst which has been deactivated because it has been used in the treatment of a vanadium-containing hydrocarbon oil with hydrogen at elevated temperature and pressure so that the catalyst's vanadium content has been increased by at least 10 parts by weight and where the mentioned vanadium extraction, whereby the catalyst's vanadium content is reduced by at least 40% of the amount by which the vanadium content has increased during the deactivation (the vanadium content of the catalyst expressed as parts by weight vanadium/100 parts by weight catalyst), is carried out by extracting the deactivated catalyst with an aqueous solution of a mineral acid, after which the vanadium is separated from the vanadium-containing solution thus obtained.
Det særpregede ved den foreliggende fremgangsmåte er The distinctive feature of the present method is
at før syreekstraksjonen som utføres i nærvær av et reduksjonsmiddel, behandles den deaktiverte katalysator ved en temperatur fra over 250°C opp til 600°C med en blanding av vanndamp og luft i et forhold vanndamp:luft fra over 1:1 opp til 10:1 ved et that before the acid extraction which is carried out in the presence of a reducing agent, the deactivated catalyst is treated at a temperature from above 250°C up to 600°C with a mixture of water vapor and air in a water vapor:air ratio from above 1:1 up to 10: 1 at a
partialtrykk for vanndampen fra over 1 bar opp til 5 bar. partial pressure for the water vapor from over 1 bar up to 5 bar.
Ved den foreliggende fremgangsmåte utføres behandlingen med blandingen av vanndamp og luft fortrinnsvis ved en temperatur mellom 325 og 425°C. Ved behandlingen av den deaktiverte katalysator med blandingen av vanndamp og luft skal vanndampens partialtrykk fortrinnsvis være mellom 2 og 4 bar. Forholdet mellom vanndamp og luft i blandingért skal fortrinnsvis være mellom 4:1 og 8:1. I den nedenstående beskrivelse er kortbe-tegnelsen "damp" anvendt for "vanndamp" ("steam"). In the present method, the treatment with the mixture of steam and air is preferably carried out at a temperature between 325 and 425°C. When treating the deactivated catalyst with the mixture of water vapor and air, the partial pressure of the water vapor should preferably be between 2 and 4 bar. The ratio between water vapor and air in the mixture should preferably be between 4:1 and 8:1. In the description below, the abbreviation "steam" is used for "steam".
Syreekstraksjonen i nærvær av et reduksjonsmiddel og som den deaktiverte katalysator skal utsettes for ved den foreliggende fremgangsmåte, utføres fortrinnsvis ved forhøyet temperatur, spesielt ved en temperatur over 50° C. Syre-ekstraks jonen utføres fortrinnsvis med en vandig oppløsning av svovelsyre som er blitt mettet med svoveldioxyd. The acid extraction in the presence of a reducing agent and to which the deactivated catalyst is to be subjected in the present process is preferably carried out at an elevated temperature, in particular at a temperature above 50° C. The acid extraction is preferably carried out with an aqueous solution of sulfuric acid which has been saturated with sulfur dioxide.
Når den foreliggende fremgangsmåte anvendes for behandling av deaktiverte katalysatorer som foruten vanadium When the present method is used for the treatment of deactivated catalysts such as vanadium
inneholder nikkel, kan det være gunstig å ekstrahere den deaktiverte katalysator med vann etter behandlingen med blandingen av damp og luft. Ved denne ekstraksjon med vann som fortrinnsvis utføres ved forhøyet temperatur, spesielt ved en temperatur over 50° C, fås en vandig nikkelholdig oppløsning hvorfra nikkelinnholdet kan ekstraheres. contains nickel, it may be beneficial to extract the deactivated catalyst with water after treatment with the mixture of steam and air. In this extraction with water, which is preferably carried out at an elevated temperature, especially at a temperature above 50° C, an aqueous nickel-containing solution is obtained from which the nickel content can be extracted.
Den foreliggende fremgangsmåte er av spesiell betydning hvor målet ikke bare er å ekstrahere vanadium og eventuelt nikkel fra den deaktiverte katalysator, men også å regenerere katalysatoren (som i fersk tilstand kan inneholde ett eller filere metaller med hydrogeneringsaktivitet) , slik at katalysatoren igjen kan anvendes for katalytiske formål. Oppfinnelsen angår derfor ikke bare en fremgangsmåte ved ekstraksjon av vanadium og eventuelt nikkel fra en deaktivert katalysator, men også en fremgangsmåte hvor denne ekstraksjon utføres på en slik måte at en regenerert katalysator fås som igjen kan anvendes for katalytiske formål, som sådan eller etter at en supplerende mengde metaller med hydrogeneringsaktivitet er blitt tilført til denne. Den foreliggende fremgangsmåte er av spesiell betydning for ekstraksjon av vanadium og eventuelt nikkel fra en katalysator som i det vesentlige består av siliciumdioxyd, sammen med regenerering av katalysatoren, idet katalysatoren er blitt anvendt i en fremgangsmåte for hydroavmetallisering av en hydrocarbonolje. The present method is of particular importance where the goal is not only to extract vanadium and possibly nickel from the deactivated catalyst, but also to regenerate the catalyst (which in its fresh state may contain one or more metals with hydrogenation activity), so that the catalyst can again be used for catalytic purposes. The invention therefore not only concerns a method for the extraction of vanadium and possibly nickel from a deactivated catalyst, but also a method where this extraction is carried out in such a way that a regenerated catalyst is obtained which can again be used for catalytic purposes, as such or after a supplementary quantity of metals with hydrogenation activity has been added to this. The present method is of particular importance for the extraction of vanadium and possibly nickel from a catalyst which essentially consists of silicon dioxide, together with regeneration of the catalyst, as the catalyst has been used in a method for hydrodemetallisation of a hydrocarbon oil.
Den foreliggende fremgangsmåte er nærmere forklart i de nedenstående eksempler. The present method is explained in more detail in the examples below.
Eksempel 1 Example 1
En katalysator som omfattet 0,5 vektdel nikkel og 2,0 vektdeler vanadium pr. 100 vektdeler av et bærermateriale bestående av siliciumdioxyd, ble fremstilt ved å impregnere et bærermateriale av siliciumdioxyd med en vandig oppløsning av nikkelnitrat og vanadyloxalat, hvoretter materialet ble tørket og kalsinert. Katalysatoren (katalysator A) ble anvendt i sulfidisert tilstand for hydroavmetallisering av en, hydrocarbonolje (olje A) med et samlet vanadium- og nikkelinnhold av 62 vektdeler pr. million (ppm), et C5~asfalteninnhold av 6,4 vekt% og et svovelinnhold av 3,9 vekt%, idet oljen var blitt erholdt som en rest etter destillasjon ved atmosfæretrykk av en råolje av midt-østen. Hydroavmetalliseringen ble utført ved å lede oljen sammen med hydrogen eller damp gjennom et sylindrisk, vértikalt anordnet, fast katalysatorlag ved en temperatur av 420° C, et samlet trykk av 150 bar, en volumhastighet av 5 kg/l pr. time og en gasstrømmengde (målt ved reaktorutløpet) av 250 NI H2/kg. Katalysatorens aktivitet, uttrykt som vekt% fjernet vanadium" (= gjennomsnitlig fjernelse av vanadium i løpet av katalysatorens levealder fra 1 tonn olje/kg katalysator til 4 tonn olje/kg katalysator), var 51. Etter at katalysatoren var blitt deaktivert ved denne prosess, ble den ekstrahert med toluen for å fjerne gjenværende restolje, og etter at toluenet var blitt fordampet fra katalysatoren, ble denne ana-lysert. Den deaktiverte katalysator (katalysator B) inneholdt 9,7 vektdeler carbon, 20,6 vektdeler svovel, 4,1 vektdeler nikkel og 24,3 vektdeler vanadium pr. 100 vektdeler siliciumdioxyd . A catalyst that comprised 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of a carrier material consisting of silicon dioxide was prepared by impregnating a carrier material of silicon dioxide with an aqueous solution of nickel nitrate and vanadyl oxalate, after which the material was dried and calcined. The catalyst (catalyst A) was used in a sulphided state for the hydrodemetallation of a hydrocarbon oil (oil A) with a total vanadium and nickel content of 62 parts by weight. million (ppm), a C5-asphaltene content of 6.4% by weight and a sulfur content of 3.9% by weight, the oil having been obtained as a residue after distillation at atmospheric pressure of a Middle Eastern crude oil. The hydrodemetallation was carried out by passing the oil together with hydrogen or steam through a cylindrical, vertically arranged, fixed catalyst bed at a temperature of 420° C, a total pressure of 150 bar, a volume rate of 5 kg/l per hour and a gas flow rate (measured at the reactor outlet) of 250 NI H2/kg. The activity of the catalyst, expressed as "% by weight vanadium removed" (= average removal of vanadium during the lifetime of the catalyst from 1 ton oil/kg catalyst to 4 ton oil/kg catalyst), was 51. After the catalyst had been deactivated by this process, it was extracted with toluene to remove residual residual oil, and after the toluene was evaporated from the catalyst, it was analyzed The deactivated catalyst (catalyst B) contained 9.7 parts by weight of carbon, 20.6 parts by weight of sulphur, 4.1 parts by weight of nickel and 24.3 parts by weight of vanadium per 100 parts by weight of silicon dioxide.
Eksempel 2 Example 2
5 kg av katalysatoren B ble behandlet med en blanding av damp og nitrogen i et forhold av 4:1 i 3 timer ved 350° C, atmosfæretrykk og en gasstrømmengde av 2 NI gassblanding/g katalysator pr. time. Katalysatoren ble deretter behandlet med en blanding av luft og nitrogen i et forhold av 1:19 i 50 timer ved 4 00° C, atmosfæretrykk og en gasstrømmengde av 1 NI gass-blanding/g katalysator pr. time. Katalysatoren ble til slutt ekstrahert i 2 timer ved 90° C under omrøring med 40 1 2N svovelsyre som var blitt mettet med svoveldioxyd. Etter at den ekstraherte katalysator var blitt vasket med vann, ble den tør-ket ved 12 0° C og kalsinert i 3 timer ved 55 0° C. En analyse av den således erholdte katalysator (katalysator C) viste at 96 % av vanadiumet og 95 % av nikkelinnholdet var blitt fjernet fra katalysatoren ved denne behandling. 5 kg of the catalyst B was treated with a mixture of steam and nitrogen in a ratio of 4:1 for 3 hours at 350° C, atmospheric pressure and a gas flow amount of 2 NI gas mixture/g of catalyst per hour. The catalyst was then treated with a mixture of air and nitrogen in a ratio of 1:19 for 50 hours at 400° C, atmospheric pressure and a gas flow amount of 1 NI gas mixture/g of catalyst per hour. The catalyst was finally extracted for 2 hours at 90° C. under stirring with 40 L of 2N sulfuric acid which had been saturated with sulfur dioxide. After the extracted catalyst had been washed with water, it was dried at 120° C. and calcined for 3 hours at 550° C. An analysis of the thus obtained catalyst (catalyst C) showed that 96% of the vanadium and 95% of the nickel content had been removed from the catalyst by this treatment.
Eksempel 3 Example 3
5 kg av katalysatoren B ble behandlet med en blanding av damp og luft i et forhold av 7:1 i 25 timer ved 400° C, et partialtrykk for dampen av 3,5 bar og en gasstrømmengde av 5 kg of the catalyst B was treated with a mixture of steam and air in a ratio of 7:1 for 25 hours at 400° C, a partial pressure of the steam of 3.5 bar and a gas flow rate of
0,6 NI gassblanding/g katalysator pr. time. Katalysatoren ble deretter ekstrahert i 2 timer ved 9 0° C under omrøring med 40 1 2N svovelsyre som var blitt mettet med.svoveldioxyd. Etter at den ekstraherte katalysator var blitt vasket med vann, ble den tørket ved 120° C og kalsinert i 3 timer ved 550° C. En analyse av den således erholdte katalysator (katalysator D) viste at 96 % av vanadiumet og 95 % av nikkelinnholdet var blitt fjernet fra katalysatoren ved denne behandling. 0.6 NI gas mixture/g catalyst per hour. The catalyst was then extracted for 2 hours at 90°C while stirring with 40 L of 2N sulfuric acid which had been saturated with sulfur dioxide. After the extracted catalyst had been washed with water, it was dried at 120° C. and calcined for 3 hours at 550° C. An analysis of the catalyst thus obtained (catalyst D) showed that 96% of the vanadium and 95% of the nickel content had been removed from the catalyst by this treatment.
Eksempel 4 Example 4
5 kg av katalysatoren B ble behandlet med en blanding av damp og luft i et forhold av 5:1 i 20 timer ved 350° C, et partialtrykk for dampen av 3,0 bar og en gasstrømmengde av 0,6 NI gassblanding/g katalysator pr. time. Katalysatoren ble deretter ekstrahert med syre på samme måte som beskrevet i eksempel 3. En analyse av den således erholdte katalysator (katalysator E) viste at 94 % av vanadiumet og 92 % av nikkelinnholdet var blitt fjernet fra katalysatoren ved denne behandling. 5 kg of the catalyst B was treated with a mixture of steam and air in a ratio of 5:1 for 20 hours at 350° C, a partial pressure of the steam of 3.0 bar and a gas flow rate of 0.6 NI gas mixture/g of catalyst per hour. The catalyst was then extracted with acid in the same way as described in example 3. An analysis of the catalyst thus obtained (catalyst E) showed that 94% of the vanadium and 92% of the nickel content had been removed from the catalyst by this treatment.
Eksempel 5 Example 5
5 kg av katalysatoren B ble behandlet med en blanding .av damp og luft i et forhold av 1:2 i 20 timer ved 400° C, et partialtrykk for dampen av 0,6 bar og en gasstrømmenqde av 0,4 NI gassblanding/g katalysator pr. time. Katalysatoren ble deretter ekstrahert med syre på samme måte som beskrevet i eksempel 3. En analyse av den således erholdte katalysator (katalysator F) viste at 95 % av vanadiumet og 95 % av nikkelinnholdet var blitt fjernet fra katalysatoren ved denne behandling . 5 kg of the catalyst B was treated with a mixture of steam and air in a ratio of 1:2 for 20 hours at 400° C, a partial pressure of the steam of 0.6 bar and a gas flow rate of 0.4 NI gas mixture/g catalyst per hour. The catalyst was then extracted with acid in the same way as described in example 3. An analysis of the thus obtained catalyst (catalyst F) showed that 95% of the vanadium and 95% of the nickel content had been removed from the catalyst by this treatment.
Eksempel 6 Example 6
5 kg av katalysatoren B ble behandlet med en blanding av damp og luft i et forhold av 2:1 i 25 timer ved 150° C, et partialtrykk for dampen av 1,5 bar og en gasstrømmengde av 2 NI gassblanding/g katalysator pr. time. Katalysatoren ble deretter ekstrahert med syre på samme måte som beskrevet i eksempel 3. En analyse av den således erholdte katalysator (katalysator G) viste at 40 % av vanadiumet og 45 % av nikkelinnholdet var blitt fjernet fra katalysatoren ved denne behandling. 5 kg of the catalyst B was treated with a mixture of steam and air in a ratio of 2:1 for 25 hours at 150° C., a partial pressure for the steam of 1.5 bar and a gas flow rate of 2 NI gas mixture/g of catalyst per hour. The catalyst was then extracted with acid in the same way as described in example 3. An analysis of the thus obtained catalyst (catalyst G) showed that 40% of the vanadium and 45% of the nickel content had been removed from the catalyst by this treatment.
Ek sempel 7 Oak sample 7
Katalysatorer som inneholdt 0,5 vektdeler nikkel og 2,0 vektdeler vanadium pr. 10 0 vektdeler siliciumdioxyd som bærermateriale ble fremstilt ved å impregnere katalysatorene C og F med en vandig oppløsning av nikkelnitrat og vanadyloxalat, hvoretter materialene ble tørket og kalsinert. De således erholdte katalysatorer C og F<1> ble anvendt i sulfidisert tilstand for hydroavmetallisering av oljen A under de samme betingelser som hydroavmetalliseringen av denne olje med katalysatoren A beskrevet i eksempel 1. Katalysatorenes C og F<1 >aktiviteter, uttrykt som "% vanadium fjernet", var hhv. 48 og 10. Catalysts which contained 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silicon dioxide as carrier material was prepared by impregnating the catalysts C and F with an aqueous solution of nickel nitrate and vanadyl oxalate, after which the materials were dried and calcined. The thus obtained catalysts C and F<1> were used in a sulphidized state for the hydrodemetallation of oil A under the same conditions as the hydrodemetallation of this oil with the catalyst A described in example 1. The activities of the catalysts C and F<1>, expressed as "% vanadium removed", was respectively 48 and 10.
Eksempel 8 Example 8
På samme måte som beskrevet i eksempel 7 ble katalysatorer D' og E' fremstilt fra katalysatorene D og E og anvendt ved hydroavmetallisering av oljen A. Katalysatorenes D' og E' aktiviteter, uttrykt som "% fjernet vanadium", var hhv. 50 og 49. In the same way as described in example 7, catalysts D' and E' were prepared from catalysts D and E and used in the hydrodemetallation of oil A. The activities of catalysts D' and E', expressed as "% removed vanadium", were respectively 50 and 49.
Av eksemplene 1-8 angår eksemplene 3, 4 og 8 den foreliggende fremgangsmåte. De andre eksempler er blitt tatt med for sammenlignings skyld. Of examples 1-8, examples 3, 4 and 8 relate to the present method. The other examples have been included for comparison.
Eksempel 1 angår hydroavmetallisering hvor en fersk katalysator A deaktiveres under dannelse av den deaktiverte katalysator B. Example 1 concerns hydrodemetallation where a fresh catalyst A is deactivated to form the deactivated catalyst B.
Eksempel 2 angår den ovenfor beskrevne tre-trinns prosess hvor en regenerert katalysator C fremstilles fra den deaktiverte katalysator B og hvor det samlet tar 53 timer for å utføre de første to trinn. Example 2 relates to the three-stage process described above where a regenerated catalyst C is produced from the deactivated catalyst B and where it takes a total of 53 hours to carry out the first two stages.
Eksemplene 3 og 4 angår den foreliggende fremgangsmåte hvor regenererte katalysatorer D og E fremstilles fra den deaktiverte katalysator B. En sammenligning mellom eksemplene 2, 3 og 4 viser at den foreliggende fremgangsmåte fører til den samme utmerkede fjernelse av metall som 3-trinns prosessen. Imidlertid tar behandlingen med blandingen av damp og luft og som har erstattet det første og det annet trinn av tre-trinns-prosessen, bare 20 - 25 timer. Examples 3 and 4 relate to the present process where regenerated catalysts D and E are prepared from the deactivated catalyst B. A comparison between Examples 2, 3 and 4 shows that the present process leads to the same excellent metal removal as the 3-step process. However, the treatment with the mixture of steam and air, which has replaced the first and second stages of the three-stage process, takes only 20 - 25 hours.
Eksemplene 5 og 6 angår behandling av den deaktiverte katalysator med en blanding av damp og luft, fulgt av ekstraksjon med syren, hvor "regenererte" katalysatorer F og G fremstilles fra den deaktiverte katalysator B. Under behandlingen med blandingen av damp og luft var partialtrykket for damp og forholdet mellom damp og luft for lave i eksempel 5, og tem-peraturen var for lav i eksempel 6. Dette førte til en util-strekkelig fjernelse av metall for katalysatoren G (og dermed til en lav aktivitet!), og dessuten, som det fremgår av eksempel 7, til en lav aktivitet for katalysatoren F. Examples 5 and 6 relate to treatment of the deactivated catalyst with a mixture of steam and air, followed by extraction with the acid, where "regenerated" catalysts F and G are prepared from the deactivated catalyst B. During the treatment with the mixture of steam and air, the partial pressure of steam and the ratio of steam to air too low in example 5, and the temperature was too low in example 6. This led to an insufficient removal of metal for the catalyst G (and thus to a low activity!), and furthermore, as can be seen from example 7, to a low activity for the catalyst F.
Det fremgår av eksemplene 7 og 8 at katalysatorer som er blitt regenerert ved den foreliggende fremgangsmåte (katalysatorene D<1> og E<1>), viser den samme høye aktitivitet som en katalysator som er blitt regenerert ved tre-trinns prosessen (katalysatoren C). It appears from examples 7 and 8 that catalysts that have been regenerated by the present method (catalysts D<1> and E<1>) show the same high activity as a catalyst that has been regenerated by the three-step process (catalyst C ).
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7703181A NL7703181A (en) | 1977-03-24 | 1977-03-24 | IMPROVED METHOD FOR RECOVERING VANADIUM FROM DEACTIVATED CATALYSTS. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO781027L NO781027L (en) | 1978-09-26 |
| NO152939B true NO152939B (en) | 1985-09-09 |
| NO152939C NO152939C (en) | 1985-12-18 |
Family
ID=19828224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO781027A NO152939C (en) | 1977-03-24 | 1978-03-22 | PROCEDURE FOR THE EXTRACTION OF VANADIUM FROM A DEACTIVATED CATALYST. |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS53119209A (en) |
| AU (1) | AU516502B2 (en) |
| BE (1) | BE864852R (en) |
| CA (1) | CA1116582A (en) |
| DE (1) | DE2812597A1 (en) |
| FR (1) | FR2384854A2 (en) |
| GB (1) | GB1567140A (en) |
| IT (1) | IT1093669B (en) |
| MX (1) | MX147986A (en) |
| NL (1) | NL7703181A (en) |
| NO (1) | NO152939C (en) |
| SE (1) | SE444581B (en) |
| SU (1) | SU688108A3 (en) |
| ZA (1) | ZA781661B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1163810A (en) * | 1980-02-20 | 1984-03-20 | Petrus J.W.M. Van Den Bosch | Process for the removal of vanadium-containing acid from an acid-extracted deactivated demetallization catalyst |
| DE4216798A1 (en) * | 1992-05-21 | 1993-11-25 | Metallgesellschaft Ag | Process for processing residues containing vanadium |
| JP2985647B2 (en) * | 1993-02-26 | 1999-12-06 | 住友金属鉱山株式会社 | Dissolution method of spent catalyst |
| JP2751093B2 (en) * | 1994-03-11 | 1998-05-18 | 住友金属鉱山株式会社 | Method for recovering valuable metals from spent catalyst |
| AU4323796A (en) * | 1995-12-22 | 1997-07-17 | Commonwealth Scientific And Industrial Research Organisation | Oxidation catalyst system |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1272899B (en) * | 1964-05-22 | 1968-07-18 | Inst Njeftjechimitscheskogo Si | Process for the regeneration of coked oxidic hydrogenation catalysts |
| FR1602405A (en) * | 1968-06-11 | 1970-11-23 | ||
| FR1603515A (en) * | 1968-11-05 | 1971-05-03 | Regeneration of catalysts used in the hydro-treatment - of sulphurous hydrocarbon charges containing metallic | |
| JPS5144114A (en) * | 1974-06-01 | 1976-04-15 | Kawasaki Heavy Ind Ltd | TAISUISEISETSUKOBUROTSUKU MATAHA PANERUNOSEIZOHOHO |
| JPS51121A (en) * | 1974-06-20 | 1976-01-05 | Fujimori Sangyo | CHUKUSURA BUKOZOTAI |
| GB1526927A (en) * | 1974-10-15 | 1978-10-04 | Shell Int Research | Process for recovering vanadium from deactivated catalyst |
-
1977
- 1977-03-24 NL NL7703181A patent/NL7703181A/en not_active Application Discontinuation
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1978
- 1978-02-09 CA CA000296567A patent/CA1116582A/en not_active Expired
- 1978-03-14 BE BE1008766A patent/BE864852R/en not_active IP Right Cessation
- 1978-03-17 MX MX17281478A patent/MX147986A/en unknown
- 1978-03-22 FR FR7808313A patent/FR2384854A2/en active Granted
- 1978-03-22 IT IT2145378A patent/IT1093669B/en active
- 1978-03-22 ZA ZA00781661A patent/ZA781661B/en unknown
- 1978-03-22 AU AU34435/78A patent/AU516502B2/en not_active Expired
- 1978-03-22 GB GB11405/78A patent/GB1567140A/en not_active Expired
- 1978-03-22 DE DE19782812597 patent/DE2812597A1/en not_active Withdrawn
- 1978-03-22 JP JP3179278A patent/JPS53119209A/en active Granted
- 1978-03-22 SU SU782591397A patent/SU688108A3/en active
- 1978-03-22 SE SE7803322A patent/SE444581B/en not_active IP Right Cessation
- 1978-03-22 NO NO781027A patent/NO152939C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO781027L (en) | 1978-09-26 |
| SE444581B (en) | 1986-04-21 |
| DE2812597A1 (en) | 1978-09-28 |
| GB1567140A (en) | 1980-05-14 |
| ZA781661B (en) | 1979-03-28 |
| BE864852R (en) | 1978-09-14 |
| FR2384854B2 (en) | 1980-10-24 |
| FR2384854A2 (en) | 1978-10-20 |
| NO152939C (en) | 1985-12-18 |
| SU688108A3 (en) | 1979-09-25 |
| IT1093669B (en) | 1985-07-26 |
| JPS53119209A (en) | 1978-10-18 |
| MX147986A (en) | 1983-02-22 |
| AU3443578A (en) | 1979-09-27 |
| NL7703181A (en) | 1978-09-26 |
| CA1116582A (en) | 1982-01-19 |
| IT7821453A0 (en) | 1978-03-22 |
| JPS637819B2 (en) | 1988-02-18 |
| SE7803322L (en) | 1978-09-25 |
| AU516502B2 (en) | 1981-06-04 |
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