DE3029266A1 - Catalysts for hydrogenating aromatic-contg. petroleum feeds - comprising combination of supported and unsupported nickel-tungsten oxide components - Google Patents
Catalysts for hydrogenating aromatic-contg. petroleum feeds - comprising combination of supported and unsupported nickel-tungsten oxide componentsInfo
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- DE3029266A1 DE3029266A1 DE19803029266 DE3029266A DE3029266A1 DE 3029266 A1 DE3029266 A1 DE 3029266A1 DE 19803029266 DE19803029266 DE 19803029266 DE 3029266 A DE3029266 A DE 3029266A DE 3029266 A1 DE3029266 A1 DE 3029266A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- USPVIMZDBBWXGM-UHFFFAOYSA-N nickel;oxotungsten Chemical compound [Ni].[W]=O USPVIMZDBBWXGM-UHFFFAOYSA-N 0.000 title 1
- 239000003208 petroleum Substances 0.000 title 1
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002283 diesel fuel Substances 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000008188 pellet Substances 0.000 abstract 1
- 231100000572 poisoning Toxicity 0.000 abstract 1
- 230000000607 poisoning effect Effects 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen containing Hydrocarbon Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
Abstract
Description
Titel der ErfindungTitle of the invention
Katalysatorkombination für die einstufige Hydrierung von Kohlenwasserstoffgemischen Anwendungsgebiet der Erfindung Die Erfindung betrifft eine Katalysatorkombination für die einstufige Hydrierung von Kohlenwasserstoffgemischen, insbesondere für die Ferhydrierung unraffinierter Dieselkraftstoff- und Vakuumdestiliatfraktionen.Catalyst combination for the one-stage hydrogenation of hydrocarbon mixtures Field of application of the invention The invention relates to a catalyst combination for the one-stage hydrogenation of hydrocarbon mixtures, especially for the Ferhydrogenation of unrefined diesel fuel and vacuum distillate fractions.
Charakteristik der bekannten technischen Lösungen 2'ür die Hydrierung von Kohlenwasserstofffraktionen mit dem Ziel der weitgehenden Entfernung von ungesättigten Anteilen und/oder aromatischen Strukturen verwendet man Edelmetall oder Nickelmetall enthaltende Katalysatoren. Sobald die Eoh-Lenwasserstofffraktionen jedoch Schwefel- sowie Stickstoffverbindungen enthalten, desaktivieren diese Katalysatoren sehr schnell.Characteristics of the known technical solutions for hydrogenation of hydrocarbon fractions with the aim of largely removing unsaturated ones Precious metal or nickel metal is used for proportions and / or aromatic structures containing catalysts. However, as soon as the Eoh hydrogen fractions are as well as containing nitrogen compounds, these catalysts deactivate very quickly.
Deshalb verwendet man für die Hydrierung von schwefel- und stickstoffhaltigen Kohlenwasserstolffraktionen vorzugsweise Mo- und W-haltige Katalysatoren, die meist mit hi promotiort sind und zur Steigerung der Aktivität und Stabilitit mit H2S oder organischen Schwefelverbindungen sulfidiert werden.That is why one uses for the hydrogenation of sulfur and nitrogen containing Hydrocarbon fractions preferably Mo- and W-containing catalysts, which are mostly promoted with hi and to increase activity and stability sulfided with H2S or organic sulfur compounds.
Diese Katalysatortypen, insbesondere solche, die mit einem Träger, wie Al2O3 oder Alglosilikat, kombiniert sind, besitzen jedoch nicht die Hydrierstärke bzw. Aktivität der Edelmetallkatalysatoren. In den Kohlenwasserstofffraktionen wird dadurch ein Teil der Aromaten nicht zu Naphthenen hydriert.These types of catalysts, especially those with a carrier, such as Al2O3 or alglosilicate, are combined, but do not have the hydrogenation starch or activity of the noble metal catalysts. In the hydrocarbon fractions as a result, some of the aromatics are not hydrogenated to naphthenes.
Die trägerfreien Typen (z.B. NiO - W0») sind zwar bei der Hydrierung aromatischer Strukturen wirksamer als die mit Al2O3 oder Alumosilikat kombinierten, jedoch erweist sich die geringe Festigkeit, die im Betrieb nach der Aufnahme des Schwefels unter Bildung der Metalleulfide des Ni und W beobachtet wird, als ein entscheidender Mangel. Durch die eintretende Quellung wird der Katalysatorformling weich, z.T. zerstört und damit technisch unbrauchbar (vgl. z.B. A.G. Martynenko in Chim. techn. topliv masel 19?5, 4, 19-22).The carrier-free types (e.g. NiO - W0 ») are in the hydrogenation aromatic structures more effective than those combined with Al2O3 or aluminosilicate, However, it turns out the low strength, which in operation after the inclusion of the Sulfur with formation of the metal sulfides of Ni and W is observed as a decisive deficiency. The formed catalyst is formed by the swelling that occurs soft, partly destroyed and therefore technically unusable (see e.g. A.G. Martynenko in Chim. techn. topliv masel 19? 5, 4, 19-22).
Schon früher hat man diesen Mangel umgangen, indem Ni-W-Sulfid-Katalysatoren eingesetzt wurden. Davon ist man jedoch wieder abgegangen, da Schwierigkeiten beim Einbau des Katalysators in den Reaktor durch H2S-Abgabe und Verhinderung der Wirksamkeit durch 02-Beeinflussung aus der Luft auftreten.Earlier this deficiency was circumvented by using Ni-W sulfide catalysts were used. However, this has been abandoned because of difficulties with Installation of the catalyst in the reactor by releasing H2S and preventing its effectiveness due to O2 influence from the air.
Die Aktivitätsstabilität solcher Typen ist wenig befriedigend, (vgl. z.B. Günther, G., Chem. Techn. J1 (1961) 427 und Münzing, E., Acta Chim. acad. sci. hung. 36 (1963), 279-287).The activity stability of such types is not very satisfactory (cf. e.g. Günther, G., Chem. Techn. J1 (1961) 427 and Münzing, E., Acta Chim. acad. sci. hung. 36: 279-287 (1963)).
Der reine WS2-Katalysator ist zwar sehr hydrieraktiv und arbeitet stabil, er fördert aber auch die Spaltung von C-C-Bindungen und liefert daher unerwünschte Nebenprodukte.The pure WS2 catalyst is very active in hydrogenation and works stable, but it also promotes the cleavage of C-C bonds and therefore provides undesirable Byproducts.
Ziel der Erfindung Ziel der Erfindung ist es, ein verbessertes Katalysatorsystem für einstufige Hydrierzwecke vorzuschlagen.OBJECT OF THE INVENTION The object of the invention is to provide an improved catalyst system to propose for single-stage hydrogenation purposes.
Darlegung des Wesens der Erfindung Die technische Aufgabe besteht darin, ein Katalysatorsystem aufzufinden, das folgende Eigenschaften aufweist: a) unempfindlich gegen Schwefel-, Sauerstoff- und Stickstoffverbindungen b) hohe Hydrierleistung (ähnlich den Edelmetallkatalysatoren) und geringe Spaltwirkung c) mechanisch stabil d) stabiles Langzeitverhalten.Statement of the essence of the invention The technical problem exists therein, a catalyst system find the following properties has: a) insensitive to sulfur, oxygen and nitrogen compounds b) high hydrogenation performance (similar to noble metal catalysts) and low cleavage effect c) mechanically stable d) stable long-term behavior.
Die technische Aufgabe wird durch eine erfindungsgemäße Katalysatorkombination gelöst, die aus einer pulverförmigen Mischung von a) einer trägerfreien NiO-WC3-Komponente und b) einer NiO-W03-Al203-SiO2-Komponente besteht, wobei die Komponente NiO-WO aus 30 bis 70 Masse-% NiO und 70 bis 30 Masse-% WO3 und die Komponente NiO-W03-Al203-S i02 aus 2 bis 5 Masse-% NiO und 15 bis 30 Masse-% WO3 besteht und das röntgenamorphe Alumosilikat, entsprechend der Komponente b), 5 bis 50 Masse-% SiO2 und 50 bis 95 Masse- Al203 enthält.The technical problem is achieved by a catalyst combination according to the invention dissolved, which consists of a powdery mixture of a) a carrier-free NiO-WC3 component and b) a NiO-WO3-Al203-SiO2 component, the component NiO-WO from 30 to 70 mass% NiO and 70 to 30 mass% WO3 and the component NiO-W03-Al203-S i02 consists of 2 to 5% by mass of NiO and 15 to 30% by mass of WO3 and is X-ray amorphous Aluminum silicate, corresponding to component b), 5 to 50% by mass SiO2 and 50 to 95 Contains mass Al203.
Außerdem weisen die Komponenten NiO-WO3 und NiO-WO3-Al2O3-SiO2 eine Korngröße von 0,1 mm und ein Verhältnis zueinander von 4:1 bis 1:4 auf.In addition, the components NiO-WO3 and NiO-WO3-Al2O3-SiO2 have a Grain size of 0.1 mm and a ratio of 4: 1 to 1: 4 to each other.
Die vorgeschlagene Katalysatorkombination zeigt bei der einstufigen hydrierenden Behandlung unraffinierter Kohlenwasserstoffgemische (wie Dieselkraftstoff- und Vakuumdestillatfraktionen) eine höhere Hydrierwirkung als die der Einzelkomponenten, was nicht zu erwarten war.The proposed catalyst combination shows in the single-stage hydrogenating treatment of unrefined hydrocarbon mixtures (such as diesel fuel and vacuum distillate fractions) have a higher hydrogenation effect than that of the individual components, which was not to be expected.
Die Hydrierleistung dieser Kombination ist mit der der Edelmetallkatalysatoren zu vergleichen.The hydrogenation performance of this combination is similar to that of the noble metal catalysts to compare.
Die Gegenwart von Schwefel-, Sauerstoff- und Stickstoffverbindungen, die auf Metallkatalysatoren einen starken schädigenden Einfluß haben, hat auf die erfindungsgemäße Eatalysatorkombination keine nachteiligen Folgen. Von Vorteil ist ebenso die hohe Festigkeit und das gute Aktivitätszeitverhalten.The presence of sulfur, oxygen and nitrogen compounds, which have a strong damaging influence on metal catalysts has on the Eatalyst combination according to the invention no disadvantageous consequences. Is beneficial likewise the high strength and the good activity time behavior.
Die Katalysatorkombination gemäß vorliegender Erfindung eignet sich insbesondere zur weitgehenden oder vollständigen Hydrierung (Perhydrierung) von Kohlenwasrn-erstoffen, die ungesättigte Verbindungen und Aromaten enthalten. Gleichzeitig ist die Katalysatorkombination in der Lage, organische Heteroatomverbindungen des Schwefels, Sauerstoffs, Stickstoffs und gewisser Schwermetallverbindungen (Nickel, Eisen, Vanadium, Kupfer in Spuren) abzubauen.The catalyst combination according to the present invention is suitable in particular for extensive or complete hydrogenation (perhydrogenation) of Hydrocarbons containing unsaturated compounds and aromatics. Simultaneously the catalyst combination is able to produce organic heteroatom compounds of the Sulfur, oxygen, nitrogen and certain heavy metal compounds (nickel, Iron, vanadium, copper in traces).
Die allgemeinenArbeitsparamter der Katalysatorkornbinationen umfassen vorzugsweise folgende Grenzwerte: H2-Druck 5 - 30 MPa Temperatur 473 - 723 K Belastung 0,2 - 2 v/vh Gas:Produkt-Verhältnis 200 - 2000:1 Nl/1.The general working parameters of the catalyst combinations include preferably the following limit values: H2 pressure 5 - 30 MPa temperature 473 - 723 K load 0.2-2 v / vh gas: product ratio 200-2000: 1 Nl / 1.
Während der Behandlung unraffinierter Rohstoffe nimmt die Katalysatorkombination bis zu 30 Masse-% Schwefel auf. Die Schwefelaufnahme in dieser Menge hat normalerweise bei NiO-WO3-Katalysatoren zur folge, daß die Formlinge ihre mechanische Stabilität verlieren. Überraschenderweise wurde gefunden, daß die Katalysatorkombination der vorliegenden Erfindung trotz der Aufnahme großer Schwefelmengen während der Arbeitsperiode eine ausreichende mechanische Festigkeit besitzt.During the treatment of unrefined raw materials, the catalyst combination decreases up to 30% by mass of sulfur. The sulfur intake in this amount usually has In the case of NiO-WO3 catalysts, the result is that the moldings retain their mechanical stability lose. Surprisingly, it has been found that the catalyst combination of present invention despite the ingestion of large amounts of sulfur during the working period has sufficient mechanical strength.
Neben der guten mechanischen festigkeit besitzt die Katalysatorkombination auch ein ausgezeichnetes Aktivitäts-Zeit-Verhalten, so daß sie ebenfalls mit Vorteil unter großtechnischen Bedingungen verwendet werden kann.In addition to good mechanical strength, the catalyst combination has also an excellent activity-time behavior, so that they are also an advantage can be used on an industrial scale.
Die Hydrierprodukte eignen sich insbesondere als Basisöl für Schmierstoffe oder als Einsatzmaterial zum technischen Cracken.The hydrogenation products are particularly suitable as base oils for lubricants or as a feedstock for technical cracking.
Die Herstellung der Katalysatorkomponenten geschieht folgendermaßen: Komponente a) kann beispielsweise erzeugt werden, indem basisches Nickelkarbonat und Wolfram (Vl)-oxid, beides in Pulverform, miteinander vermischt, auf einer Tablettiermaschine vorgeformt und bei 673 - 873 E geglüht werden (Ni0-Gehalt:30 - 70 Masse-%, WO3-Gehalt: 30 - 70 Masse -%).The production of the catalyst components takes place as follows: Component a) can be produced, for example, by adding basic nickel carbonate and tungsten (VI) oxide, both in powder form, mixed together on a tablet machine preformed and annealed at 673 - 873 E (Ni0 content: 30 - 70 Mass%, WO3 content: 30 - 70 mass%).
Komponente b) wird vorteilhafterweise erzeugt, indem ein röntgenamorphes Alumosilikat mit einem SiO2-Gehalt von 10 -50 Masse-% mit Ni(NO3)2 und (NH4)2 WO4 getränkt und anschliebend bei 673 - 873 K geglüht wird. Ni0-Gehalt:2 - 5 Masse-%, WO-Gehalt: 15 - 30 Masse-%).Component b) is advantageously produced by an X-ray amorphous Aluminum silicate with an SiO2 content of 10 -50% by mass with Ni (NO3) 2 and (NH4) 2 WO4 soaked and then annealed at 673 - 873 K. Ni0 content: 2 - 5 mass%, WO content: 15 - 30% by mass).
Die Komponenten a) und b.) werden auf aine Mahlfeinheit <0,1 mm gebracht, miteinander intensiv im Verhältnis 4:1 bis 1:4 gemischt und vorteilhafterweise zu Zylinderpreßlingen verformt.Components a) and b.) Are ground to a fineness of less than 0.1 mm brought, mixed together intensively in a ratio of 4: 1 to 1: 4 and advantageously deformed into cylinder moldings.
Die so hergestellte Katalysatorkombination wird vorzugsweise als Festbett in einem Reaktor in oxidischer Form eingebaut.The catalyst combination produced in this way is preferably used as a fixed bed installed in a reactor in oxidic form.
Die Inbetriebnahme erfolgt durch Aufheizen des Katalysators eis ca. 673 K in einem H2S-freien oder-armen H2-Gasstrom. Diese Kombination widerspricht den bisherigen Erfahrungen, nach denen die beste Wirksamkeit der S-unempfindlichen Ni-W-Katalysatoren dann erzielt wurde, wenn der Katalysator zuvor geschwefelt wird. Entgegen der Erwartung besitzt das erSindungsgemä-Be Katalysatorsystem die bessere Wirksamkeit, wenn es unter schwefelt eingesetzt wird.Commissioning takes place by heating up the catalytic converter for approx. 673 K in an H2S-free or poor H2 gas stream. This combination contradicts previous experience, according to which the best effectiveness of the S-insensitive Ni-W catalysts was achieved when the catalyst is previously sulphurized. Contrary to expectations, the catalyst system according to the invention has the better one Effectiveness when used under sulphurous conditions.
Ausführungebeispiele Beispiel 1 Herstellung der Komponente a): Vermischen von 56,2 kg pulverförmigen NiCO3 una 65 kg pulverförmigen WO3.Working examples Example 1 Production of component a): Mixing from 56.2 kg powdery NiCO3 to 65 kg powdery WO3.
Anschließend Verpillung zu 10 mm Preßlingen unQ Glähung bei 450°C. Erneutes Mahlen.Subsequently, pelletization to 10 mm compacts and annealing at 450 ° C. Grind again.
Herstellung der Komponente b): Fällung eines Alumosilikate mit 20 % SiO2 durch kontinuierliches Zusammenleiten einer Lösung von Aluminiumnitrat/Wasserglas und einer Salmiakgeistlösung. Die weiteren Arbeitsschritte sind Altern, Filtrieren, Waschen, Trocknen, Tränken mit einer Lösung von Nickelnitrat und Ammoniumwolframat, Abdampfen der überschüssigen Flüssigkeit, Trocknen und Mahlen.Production of component b): Precipitation of an aluminosilicate with 20 % SiO2 by continuously bringing together a solution of aluminum nitrate / water glass and an ammonia solution. The further steps are aging, filtering, Washing, drying, soaking with a solution of nickel nitrate and ammonium tungstate, Evaporation of the excess liquid, drying and grinding.
Die Komponenten a) und b) werden im Masseverhältnis von 4:1 (bzw. 1:4) vermischt und zu 5 mm-Preblingen verpillt.The components a) and b) are in a mass ratio of 4: 1 (resp. 1: 4) mixed and pelleted to form 5 mm prebles.
Das Schüttgewicht beträgt 1,3 kg/l.The bulk weight is 1.3 kg / l.
Beispiel 2 Die gemäß Beispiel 1 hergestellte Katalysatorkombination wird bei der Perhydrierung einer Dieselölfraktion verwendet.Example 2 The catalyst combination produced according to Example 1 is used in the perhydration of a diesel oil fraction.
Zum Vergleich wurden Katalysatoren in den gleichen Abmessungen verwendet, die gemäR Beispiel 1 aus der Komponente a) und der Komponente b), jeweils allein, bestanden.For comparison, catalysts were used in the same dimensions, those according to example 1 from component a) and component b), each alone, passed.
Parameter des Dieselkraftstoffes: Dichte bei 293 K 0,830 Siedebereich 493 - 623 K Basenzahl 33 mg NH3/l Schwefelgehalt 0,85 Masse-% Aromaten 25,0 Vol.-S Die Hydrierung wurde unter folgenden Bedingungen vorgenommen: Druck 19,0 MPa Temperatur +663 K Belastung 1,5 v/vh Gas:Produktverhältnis 1000:1 Nl/l Unter diesen Bedingungen wurden an den Katalysatoren a) und b) sowie an der erfindungsgemäßen Katalysatorkombination folgende Aromatenrestgehalte ermittelt: Komponente a 2,8 Vol.-S Aromaten Komponente b 10,5 Vol.-S Aromaten Katalysatorkombination 0,5 Vol.-% Aromaten Nach dem Ausbau der Katalysatoren (nach 600 Stunden) wies der Katalysator der Komponente a) nur noch geringe Festigkeit auf, was eine technische Verwendung praktisch ausschließt, während die erfindungsgemäße Katalysatorkombination keinen Abrieb zeigte und eine technisch brauchbare Festigkeit besaß.Diesel fuel parameters: Density at 293 K 0.830 boiling range 493 - 623 K base number 33 mg NH3 / l sulfur content 0.85 mass% aromatics 25.0 vol.-p The hydrogenation was carried out under the following conditions: pressure 19.0 MPa temperature +663 K load 1.5 v / vh gas: product ratio 1000: 1 Nl / l under these conditions were on the catalysts a) and b) and on the catalyst combination according to the invention the following residual aromatic contents are determined: Component a 2.8 Vol.-S aromatic component b 10.5 vol. S aromatics Catalyst combination 0.5 vol.% aromatics After removal of the catalysts (after 600 hours), the catalyst of component a) only showed still low strength, which practically excludes technical use, while the catalyst combination according to the invention showed no abrasion and one technically usable strength possessed.
Die Überlegenheit der erfindungsgemäßen Katalysatorkombination gegenüber den beiden Ausgangskomponentenkatalysatoren ist somit nachgewiesen.The superiority of the catalyst combination according to the invention the two starting component catalysts is thus proven.
Zusammenfassung Katalysatorkombination für die einstufige Hydrierung von Kohlenwasserstoffgemischen Die Erfindung betrifft eine Katalysatorkombinatlon für die einstufige Hydrierung unraffinierter Dieselkraftstoff- und Vakuumdestillatfraktionen bei H2-Drücken von 5 bis 20 MPa mit dem Ziel der weitgehenden Absenkung des Aromatengehalts.Summary of catalyst combination for one-step hydrogenation of hydrocarbon mixtures The invention relates to a catalyst combination for the one-stage hydrogenation of unrefined diesel fuel and vacuum distillate fractions at H2 pressures of 5 to 20 MPa with the aim of largely reducing the aromatic content.
Es wird eine Katalysatorkombination vorgeschlaben, die eine hohe Hydrierleistung, vergleichbar mit Edelmetallkatalysatoren, hat, und die gleichzeitig gegen Heteroatomvberbindungen unempfindlich ist, wobei die Spaltaktivität unerheblich ist. Die vorgeschlagene Katalysatorkombination ist weiterhin während des Einsatzes mechanisch stabil und weist ein stabiles Langzeitverhalten auf.A catalyst combination is proposed which has a high hydrogenation performance, comparable to noble metal catalysts, and which at the same time act against heteroatom compounds is insensitive, the cleavage activity being insignificant. The proposed Catalyst combination is still mechanically stable and during use shows stable long-term behavior.
Die Katalysatorkombination besteht aus einer pulverförmigen Mischung aus a) einer trägerfreien NiO-WO3-Komponente und b) einer NiO-WO3Al2O3-SiO2-Komponente.The catalyst combination consists of a powdery mixture from a) a carrier-free NiO-WO3 component and b) a NiO-WO3Al2O3-SiO2 component.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD79214805A DD145231A1 (en) | 1979-08-06 | 1979-08-06 | CATALYST COMBINATION FOR THE 1-STAGE HYDROGENATION OF HYDROCARBON MIXTURES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3029266A1 true DE3029266A1 (en) | 1981-02-26 |
| DE3029266C2 DE3029266C2 (en) | 1982-08-05 |
Family
ID=5519559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE3029266A Expired DE3029266C2 (en) | 1979-08-06 | 1980-08-01 | Catalyst for the one-stage hydrogenation of heteroatom compounds and aromatic hydrocarbon mixtures |
Country Status (2)
| Country | Link |
|---|---|
| DD (1) | DD145231A1 (en) |
| DE (1) | DE3029266C2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000041810A1 (en) * | 1999-01-15 | 2000-07-20 | Akzo Nobel N.V. | A mixed metal catalyst composition, its preparation and use |
| US6534437B2 (en) | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| EP2103347A1 (en) | 2008-03-17 | 2009-09-23 | ExxonMobil Research and Engineering Company | Hydrocarbon hydroprocessing using bulk catalyst composition |
| US9708548B2 (en) | 2007-12-04 | 2017-07-18 | Exxonmobil Research And Engineering Company | Hydrocarbon hydroprocessing using bulk catalyst composition |
| WO2017134090A1 (en) | 2016-02-01 | 2017-08-10 | Albemarle Europe Sprl | Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their application |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
| US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2707013B2 (en) * | 1976-02-23 | 1979-06-28 | Uop Inc., Des Plaines, Ill. (V.St.A.) | Catalyst and its use |
-
1979
- 1979-08-06 DD DD79214805A patent/DD145231A1/en not_active IP Right Cessation
-
1980
- 1980-08-01 DE DE3029266A patent/DE3029266C2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2707013B2 (en) * | 1976-02-23 | 1979-06-28 | Uop Inc., Des Plaines, Ill. (V.St.A.) | Catalyst and its use |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000041810A1 (en) * | 1999-01-15 | 2000-07-20 | Akzo Nobel N.V. | A mixed metal catalyst composition, its preparation and use |
| US6534437B2 (en) | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| US6652738B2 (en) | 1999-01-15 | 2003-11-25 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| US9708548B2 (en) | 2007-12-04 | 2017-07-18 | Exxonmobil Research And Engineering Company | Hydrocarbon hydroprocessing using bulk catalyst composition |
| EP2103347A1 (en) | 2008-03-17 | 2009-09-23 | ExxonMobil Research and Engineering Company | Hydrocarbon hydroprocessing using bulk catalyst composition |
| WO2017134090A1 (en) | 2016-02-01 | 2017-08-10 | Albemarle Europe Sprl | Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their application |
| US10953389B2 (en) | 2016-02-01 | 2021-03-23 | Albemarle Europe Sprl | Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their applications |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3029266C2 (en) | 1982-08-05 |
| DD145231A1 (en) | 1980-12-03 |
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