DE3029266C2 - Catalyst for the one-stage hydrogenation of heteroatom compounds and aromatic hydrocarbon mixtures - Google Patents
Catalyst for the one-stage hydrogenation of heteroatom compounds and aromatic hydrocarbon mixturesInfo
- Publication number
- DE3029266C2 DE3029266C2 DE3029266A DE3029266A DE3029266C2 DE 3029266 C2 DE3029266 C2 DE 3029266C2 DE 3029266 A DE3029266 A DE 3029266A DE 3029266 A DE3029266 A DE 3029266A DE 3029266 C2 DE3029266 C2 DE 3029266C2
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- mass
- content
- hydrogenation
- hydrocarbon mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title claims description 40
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 title claims description 7
- 125000005842 heteroatom Chemical group 0.000 title claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000003658 tungsten compounds Chemical class 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 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
- 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
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007017 scission Effects 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002199 base oil Substances 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
- 238000001354 calcination Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Die Erfindung betrifft einen Katalysator für die einstufige Hydrierung von Kohlenwasserstoffgemischen, insbesondere für die Perhydrierung unraffinierter Dieselkraftstoff- und Vakuumdestillatfraktionen.The invention relates to a catalyst for the one-stage hydrogenation of hydrocarbon mixtures, especially for the perhydration of unrefined diesel fuel and vacuum distillate fractions.
Für 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 Kohlenwasserstofffraktionen jedoch Schwefel- sowie Stickstoffverbindungen enthalten, desaktivieren diese Katalysatoren sehr schnell.For the hydrogenation of hydrocarbon fractions with the aim of largely removing Noble metal or nickel metal is used for unsaturated components and / or aromatic structures containing catalysts. As soon as the hydrocarbon fractions, however, sulfur and nitrogen compounds contain, deactivate these catalysts very quickly.
Deshalb verwendet man für die Hydrierung von schwefel- und stickstoffhaltigen Kohlenwasserstofffraktionen vorzugsweise Mo- und W-haltige Katalysatoren, die meist mit Ni promotiert sind und zur Steigerung der Aktivität und Stabilität mit H2S oder organischen Schwefelverbindungen sulfidiert werden. Diese Katalysatortypen, insbesondere solche, die mit einem Träger, wie Al2O3 oder Alumosilikat, kombiniert sind, besitzen jedoch nicht die Hydrierstärke bzw. Aktivität der Edelmetallkatalysatoren. In den Kohlenwasserstofffraktionen wird dadurch ein Teil der Aromaten nicht zu Naphthenen hydriert. Die trägerfreien Typen (z. B. NiO — WO3) 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 Metallsulfide 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 1975,4,19—22).Therefore, for the hydrogenation of sulfur- and nitrogen-containing hydrocarbon fractions, preference is given to using Mo- and W-containing catalysts, which are usually promoted with Ni and sulfided with H 2 S or organic sulfur compounds to increase the activity and stability. However, these types of catalyst, in particular those which are combined with a support such as Al 2 O 3 or aluminosilicate, do not have the hydrogenation strength or activity of the noble metal catalysts. As a result, some of the aromatics in the hydrocarbon fractions are not hydrogenated to naphthenes. The carrier-free types (e.g. NiO - WO 3 ) are more effective in the hydrogenation of aromatic structures than those combined with Al 2 O 3 or aluminosilicate, but the low strength, which in operation after the absorption of the sulfur with the formation of the Metal sulfides of Ni and W are observed to be a critical deficiency. As a result of the swelling that occurs, the shaped catalyst piece becomes soft, partly destroyed and thus technically unusable (cf., for example, BAG Martynenko in Chim. Techn. Topliv masel 1975, 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 O2-Beeinflussung aus der Luft auftreten. Die Aktivitätsstabilität solcher Typen istThis deficiency has been circumvented earlier by using Ni-W sulfide catalysts. This has been abandoned, however, since difficulties arise when installing the catalyst in the reactor due to the release of H 2 S and the prevention of effectiveness due to the influence of O2 from the air. The activity stability of such types is
wenig befriedigend (vgL z. B. Günther, G, Chem. Techn. 13 [196Ij, 427 und Münzing, E, Acta Chim. acad. scL hung. 36 [1963], 279—287). Der reine WSrKatalysator ist zwar sehr hydrieraktiv und arbeitet stabil, er fördert aber auch die Spaltung von C-C-Bindungen und liefert daher unerwünschte Nebenprodukte.not very satisfactory (see e.g. Günther, G, Chem. Techn. 13 [196Ij, 427 and Münzing, E, Acta Chim. acad. scL hung. 36 [1963], 279-287). The pure WSr catalyst Although it is very active in hydrogenation and works in a stable manner, it also promotes the cleavage of C-C bonds and delivers hence undesirable by-products.
Ziel der Erfindung ist es, einen verbesserten Katalysator für einstufige Hydrierzwecke vorzuschlagen. The aim of the invention is to propose an improved catalyst for single-stage hydrogenation purposes.
Die technische Aufgabe besteht darin, einen Katalysator aufzufinden, der folgende Eigenschaften aufweist:The technical task is to create a catalyst find which has the following properties:
a) unempfindlich gegen Schwefel-, Sauerstoff- und Stickstoffverbindungen,a) insensitive to sulfur, oxygen and nitrogen compounds,
b) hohe Hydrierleistung (ähnlich den Edelmetallkatalysatoren) und geringe Spaltwirkung,b) high hydrogenation performance (similar to noble metal catalysts) and low cleavage effect,
c) mechanisch stabil,c) mechanically stable,
d) stabiles Langzeitverhalten.d) stable long-term behavior.
Die technische Aufgabe wird durch einen Katalysator für die einstufige Hydrierung von Heteroatomverbindungen
und Aromaten enthaltenden Kohlenwasserstoffgemischen bei Wasserstoffdrücken von 5 bis
30MPa, erhalten durch Imprägnieren eines röntgenamorphen
Alumosilikats mit einem SiO2-Gehalt von 5
bis 50 Masse-% und einem Al2O3-Gehalt von 50 bis 95
Masse-% mit einer Nickel- und einer Wolframverbindung sowie anschließendes Glühen bei 673 bis 873° K,
wobei der NiO-Gehalt 2 bis 5 Masse-% und der W03-GehaIt 15 bis 30 Masse-% beträgt, gelöst, indem
erfindungsgemäß das so erhaltene röntgenamorphe Alumosilikat in Pulverform mit einer zweiten pulverförmigen
Komponente im Verhältnis 4 :1 bis 1 :4 intensiv gemischt wird, die 30 bis 70 Masse-% NiO und 70 bis 30
Masse-% WO3 enthält und durch Vermischen von basischem Nickelcarbonat und Wolfram(VI)-oxid, Formen
und anschließendes Glühen bei 673 bis 873° K hergestellt wurde, und daß das Gemisch der beiden
Komponenten anschließend verformt wird.
Das Katalysatorschüttgewicht beträgt vorteilhafterweise 1,3 kg/1. Der vorgeschlagene Katalysator zeigt bei
der einstufigen hydrierenden Behandlung unraffinierter Kohlenwasserstoffgemische (wie Dieselkraftstoff- und
Vakuumdestillatfraktionen) eine höhere Hydrierwirkung als die der Einzelkomponenten, was nicht zu
erwarten war. Die Hydrierleistung ist mit der der Edelmetallkatalysatoren zu vergleichen. Die Gegenwart
von Schwefel-, Sauerstoff- und Stickstoffverbindungen, die auf Metallkatalysatoren einen starken schädigenden
Einfluß haben, hat auf den erfindungsgemäßen Katalysator keine nachteiligen Folgen. Von Vorteii ist ebenso
die hohe Festigkeit und das gute Aktivitätszeitverhalten.The technical problem is achieved by a catalyst for the one-stage hydrogenation of heteroatom compounds and aromatic hydrocarbon mixtures at hydrogen pressures of 5 to 30MPa, obtained by impregnating an X-ray amorphous aluminosilicate with an SiO 2 content of 5 to 50 mass% and an Al 2 O 3 - Content of 50 to 95% by mass with a nickel and a tungsten compound and subsequent annealing at 673 to 873 ° K, the NiO content being 2 to 5% by mass and the W0 3 content being 15 to 30% by mass, solved by, according to the invention, the X-ray amorphous aluminosilicate thus obtained in powder form is intensively mixed with a second powdery component in a ratio of 4: 1 to 1: 4, which contains 30 to 70% by mass of NiO and 70 to 30% by mass of WO 3 , and by mixing of basic nickel carbonate and tungsten (VI) oxide, molding and subsequent annealing at 673 to 873 ° K, and that the mixture of the two components is then shaped.
The bulk catalyst density is advantageously 1.3 kg / l. In the single-stage hydrogenation treatment of unrefined hydrocarbon mixtures (such as diesel fuel and vacuum distillate fractions), the proposed catalyst shows a higher hydrogenation effect than that of the individual components, which was not to be expected. The hydrogenation performance can be compared with that of the noble metal catalysts. The presence of sulfur, oxygen and nitrogen compounds, which have a highly damaging influence on metal catalysts, has no disadvantageous consequences for the catalyst according to the invention. The high strength and the good activity time behavior are also advantageous.
Der Katalysator gemäß vorliegender ErfindungThe catalyst of the present invention
eignet sich insbesondere zur. weitgehenden oder vollständigen Hydrierung (Perhydrierung) von Kohlen-Wasserstoffen, die ungesättigte Verbindungen und Aromaten enthalten. Gleichzeitig ist der Katalysator in der Lage, organische Heteroatomverbindungen des Schwefels, Sauerstoffs, Stickstoffs und gewisser Schwermetallverbindungen (Nickel, Eisen, Vanadium, Kupfer in Spuren) abzubauen.is particularly suitable for. extensive or complete hydrogenation (perhydration) of hydrocarbons, which contain unsaturated compounds and aromatics. At the same time, the catalyst is in capable of organic heteroatom compounds of sulfur, oxygen, nitrogen and certain heavy metal compounds (Nickel, iron, vanadium, copper in traces).
Die allgemeinen Arbeitsparameter des Katalysators umfassen vorzugsweise folgende Grenzwerte:The general working parameters of the catalytic converter preferably include the following limit values:
H2-DruckH 2 pressure
Temperaturtemperature
Belastungload
Gas : Produkt-VerhältnisGas: product ratio
5-30 MPa
473-723° K
0,2-2 v/vh
200-2000 :1 Nl/1 5-30 MPa
473-723 ° K
0.2-2 v / vh
200-2000: 1 Nl / 1
Während der Behandlung unraffinierter RohstoffeDuring the treatment of unrefined raw materials
nimmt der Katalysator 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 der Katalysator s der vorliegenden Erfindung trotz der Aufnahme großer Schwefelmengen während der Arbeitsperiode eine ausreichende mechanische Festigkeit besitztthe catalyst absorbs up to 30% by mass of sulfur. In the case of NiO-WO 3 catalysts, the uptake of sulfur in this amount normally has the consequence that the moldings lose their mechanical stability. Surprisingly, it has been found that the catalyst of the present invention has sufficient mechanical strength despite the uptake of large amounts of sulfur during the working period
Neben der guten mechanischen Festigkeit besitzt der Katalysator auch ein ausgezeichnetes Aktivitäts-Zeit-Verhalten, so daß er ebenfalls mit Vorteil unter großtechnischen Bedingungen verwendet werden kann.In addition to good mechanical strength, the catalyst also has excellent activity-time behavior, so that it can also be used with advantage large-scale conditions can be used.
Die Hydrierprodukte eignen sich insbesondere als Basisöle für Schmierstoffe oder als Einsatzmaterial zum technischen Kracken.The hydrogenation products are particularly suitable as base oils for lubricants or as feedstock for technical cracks.
Die Herstellung des Katalysators geschieht folgendermaßen: .The catalyst is produced as follows:.
Die eine Komponente kann beispielsweise erzeugt werden, indem basisches Nickelkarbonat und WoIfram(VI)-oxid, beides in Pulverform, miteinander ver- mischt, auf einer Tablettiermaschine vorgeformt und bei 673-873° K geglüht werden (NiO-Gehalt: 30-70 Masse-%, WO3-Gehalt: 30-70 Masse-%).One component can be produced, for example, by mixing basic nickel carbonate and WoIfram (VI) oxide, both in powder form, preforming them on a tablet machine and calcining them at 673-873 ° K (NiO content: 30-70 mass -%, WO 3 content: 30-70% by mass).
Die andere Komponente wird vorteilhafterweise erzeugt, indem ein röntgenamorphes Alumosilikat mit einem SiO2-Gehalt von 10—50 Masse-% mit Ni(NO3J2 und (NH4J2WO4 getränkt und anschließend bei 673-8730K geglüht wird (NiO-Gehalt: 2-5 Masse-%, WOrGehalt: 15-30 Masse-%).The other component is advantageously generated, by an X-ray amorphous aluminosilicate having a SiO 2 content of 10-50% by mass of Ni (NO 3 impregnated J 2 and (NH 4 J 2 WO 4, and then annealed at 673-873 0 K (NiO content: 2-5% by mass, WOr content: 15-30% by mass).
Die beiden Komponenten werden auf eine Mahlfeinheit <0,l mm gebracht, miteinander intensiv im Verhältnis 4 :1 bis 1 :4 gemischt und vorteilhafterweise zu Zylinderpreßlingen verformt Der so hergestellte Katalysator wird vorzugsweise als Festbett in einem Reaktor in oxidischer Form eingebaut Die Inbetriebnähme erfolgt durch Aufheizen des Katalysators bis 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 der erfindungsgemäße Katalysator die bessere Wirksamkeit, wenn er ungeschwefelt eingesetzt wird.The two components are brought to a fineness of grinding <0.1 mm, mixed intensively with one another in a ratio of 4: 1 to 1: 4 and advantageously shaped into cylinder moldings The catalyst is heated up to approx. 673 ° K in an H 2 S-free or low-H 2 gas stream. This combination contradicts previous experience, according to which the best effectiveness of the S-insensitive Ni-W catalysts was achieved if the catalyst was previously sulphurized. Contrary to expectations, the catalyst according to the invention is more effective when it is used without sulfur.
4545
Beispiel Herstellung der Komponente a)example Production of component a)
Vermischen von 56,2 kg pulverförmigen NiCO3 und 65 kg pulverförmigen WO3.Mixing 56.2 kg powdery NiCO 3 and 65 kg powdery WO 3 .
Anschließend Verpülung zu 10-mm-Preßlingen und Glühung bei 4500C Erneutes Mahlen.Subsequently Verpülung to 10 mm compacts and annealing at 450 0 C remilling.
Fällung eines Alumosilikats 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. Die Komponenten a) und b) werden im Masseverhältnis von 4:1 (bzw. 1:4) vermischt und zu 5-mm- Preßlingen verpillt Das Schüttgewicht beträgt 13 kg/1.Precipitation of an aluminosilicate with 20% SiO 2 by continuously bringing together a solution of aluminum nitrate / water glass and an ammonia solution. The further work steps are aging, filtering, washing, drying, soaking with a solution of nickel nitrate and ammonium tungstate, evaporation of the excess liquid, drying and grinding. Components a) and b) are mixed in a mass ratio of 4: 1 (or 1: 4) and pelletized to give 5 mm pellets. The bulk density is 13 kg / 1.
Der hergestellte Katalysator wird bei der Perhydrierung einer Dieselölfraktion verwendet Zum Vergleich wurden Katalysatoren in den gleichen Abmessungen verwendet die aus der Komponente a) und der Komponente b), jeweils allein, bestanden.The catalyst produced is used in the perhydrogenation of a diesel oil fraction. For comparison Catalysts were used in the same dimensions as those from component a) and the Component b), each alone, passed.
Dichtedensity
BasenzahlBase number
AromatenAromatics
bei 293° K 0,830 493-623° K 33 mg NH3/1 0,85 Masse-% 25,0 Vol.-%at 293 ° K 0.830 493-623 ° C 33 mg NH 3/1 0.85% by mass of 25.0 vol .-%
Die Hydrierung wurde unter folgenden Bedingungen vorgenommen:The hydrogenation was carried out under the following conditions:
Druckpressure
Belastungload
19,0 MPa + 663° K l,5v/vh 1000:1 Nl/119.0 MPa + 663 ° K l, 5v / vh 1000: 1 Nl / 1
Unter diesen Bedingungen wurden mit den Katalysatoren a) und b) sowie mit dem erfindungsgemäßen Katalysator folgende Aromatenrestgehalte ermittelt:Under these conditions were with the catalysts a) and b) and with the invention Catalyst determined the following residual aromatic contents:
Komponente a Komponente b KatalysatorkombinationComponent a Component b Catalyst combination
2,8 Vol.-% Aromaten2.8 vol% aromatics
10,5 Vol.-% Aromaten10.5% by volume aromatics
0,5 Vol.-% Aromaten0.5 vol% aromatics
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 der erfindungsgemäße Katalysator keinen Abrieb zeigte und eine technisch brauchbare Festigkeit besaß.After removal of the catalysts (after 600 hours), the catalyst of component a) only showed still low strength, which practically rules out industrial use, while the catalyst according to the invention showed no abrasion and possessed a technically useful strength.
Claims (1)
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 DE3029266A1 (en) | 1981-02-26 |
| DE3029266C2 true 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6534437B2 (en) | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| TR200102023T2 (en) * | 1999-01-15 | 2002-02-21 | Akzo Nobel N.V. | Mixed metal catalyst composition, its preparation and use |
| EP2237881A4 (en) | 2007-12-04 | 2013-10-02 | Exxonmobil Res & Eng Co | 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 |
| CN108698039A (en) | 2016-02-01 | 2018-10-23 | 阿尔比马尔欧洲有限公司 | Nickeliferous mixed-metal oxides/carbon integration hydrotreating catalyst and its application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040979A (en) * | 1976-02-23 | 1977-08-09 | Uop Inc. | Hydrocarbon conversion catalytic composite |
-
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
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| DD145231A1 (en) | 1980-12-03 |
| DE3029266A1 (en) | 1981-02-26 |
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