CA2106259A1 - Hydrocarbon conversion catalysts - Google Patents
Hydrocarbon conversion catalystsInfo
- Publication number
- CA2106259A1 CA2106259A1 CA002106259A CA2106259A CA2106259A1 CA 2106259 A1 CA2106259 A1 CA 2106259A1 CA 002106259 A CA002106259 A CA 002106259A CA 2106259 A CA2106259 A CA 2106259A CA 2106259 A1 CA2106259 A1 CA 2106259A1
- Authority
- CA
- Canada
- Prior art keywords
- zeolite
- modified
- weight
- composition according
- catalyst
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 title abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 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 45
- 239000010457 zeolite Substances 0.000 claims abstract description 40
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 238000002835 absorbance Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000007858 starting material Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A B S T R A C T
HYDROCARBON CONVERSION CATALYSTS
Composition of matter suitable as catalyst base in hydroprocessing comprising a crystalline aluminosilicate and a binder wherein the crystalline aluminosilicate comprises a modified Y zeolite having a unit cell size below 24.37 .ANG., a water adsorption capacity (at 25 °C and a p/pO value of 0.2) of at least 8% by weight of modified Y zeolite, a pore volume of at least 0.25 ml/g wherein between 10% and 60% of the total pore volume is made up of pores having a diameter of at least 8 nm, which modified Y zeolite has an absorbance ratio of at most 0.040, expressed as the absorbance in the infra-red frequency region of 3670 + 10 cm-1 divided by the absorbance in the infra-red frequency region of 3630 + 10 cm-1 The invention further relates to hydroconversion catalysts and processes based on such hydroconversion catalysts.
HYDROCARBON CONVERSION CATALYSTS
Composition of matter suitable as catalyst base in hydroprocessing comprising a crystalline aluminosilicate and a binder wherein the crystalline aluminosilicate comprises a modified Y zeolite having a unit cell size below 24.37 .ANG., a water adsorption capacity (at 25 °C and a p/pO value of 0.2) of at least 8% by weight of modified Y zeolite, a pore volume of at least 0.25 ml/g wherein between 10% and 60% of the total pore volume is made up of pores having a diameter of at least 8 nm, which modified Y zeolite has an absorbance ratio of at most 0.040, expressed as the absorbance in the infra-red frequency region of 3670 + 10 cm-1 divided by the absorbance in the infra-red frequency region of 3630 + 10 cm-1 The invention further relates to hydroconversion catalysts and processes based on such hydroconversion catalysts.
Description
~
HYDROCARBON CONVERSION CATALYSTS
The present invention relates to compositions of matter suitable as catalyst base. in hydroprocessing. The present lnvention also relates to catalyst compositions which can suitably be used in hydrocarbon conversion processes, in particular hydrocracking 5 processes, and hydrocarbon conversion processes wherein use is made of such catalyst compositions.
Of the many hydroconversion processes known in the art, hydrocracking is becoming increasingly important since it offers product flexibility together with product quality. As it is also 10 possible to subjact rather heavy feedstocks to hydrocracking it will be clear that much attention has been devoted to the development of hydrocracking catalysts.
Whereas in the past catalytic hydrocracking was aimed primarily at the production of lower boiling points products such 15 as gasoline, nowadays hydrocracking is often aimed at meeting the increasing demand for high quality middle distillate products.
Therefore, the object in nowadays hydrocracking is to provide a hydrocracking catalyst having a high selectivity towards middle distillates and in addition a high activity and stability.
To this end modern hydrocracking catalysts are generally based on zeolitic materials which may have been adapted by techniques like a~Monium-ion exchange and various forms of calcination in order to improve the performance of the hydrocracking catalysts based on such zeolitic materials.
One of the zeolites which is considered to be a good starting material for the manufacture of hydrocracking catalysts is the well-known synthetic zeolite Y as described in US-A-3,130,007. a number of modifications has been reported for this material which include, inter alia, ultrastable Y (US-A-3,536,605) and 30 ultrahydrophobic Y (GB-A-2,014,970). In general, it can be said 2~ ~62~9 that the modifications cause a reduction in the unit cell size depending on the treatment carried out.
In EP-B-247679 compositions of matter have been described which can very attractively be used as components for hydrocracking catalysts Surprisingly, it has now been found that even more attractive results can be obtained in terms of gas make and middle distillate yield when use is made of a composition comprising a binder and a modified Y zeolite having a specific infrared feature.
Accordingly, the present invention relates to a composition of matter suitable as catalyst base in hydroprocessing comprising a crystalline aluminosilicate and a binder wherein the crystalline aluminosilicate comprises a modified Y zeolite having a unit cell size below 24.37 A, a water adsorption capacity (at 25 C and a p/pO value of 0.2) of at least 8% by weight of modified Y zeolite, a pore volume of at least 0.25 ml/g wherein between 10% and 60~ of the total pore volume is made up of pores having a diameter of at least 8 nm, which modified Y zeolite has an absorbance ratio of at most 0.040, expressed as the absorbance in the infra-red frequency region of 3670 + 10 cm divided by the absorbance in the infra-red frequency region of 3630 ~ 10 cm 1 Preferably, the absorbance ratio is at most 0.03, more preferably at most 0.02.
The infrared bands have been determined by means of in-situ cell measurements of dry samples at elevated temperature (450C).
Preferably, the modified Y zeolite has a unit cell size ranging from 24.27 to 24.35 A, more preferably from 24.29 to 24.33 A.
Preferably, between 10~ and 40~ of the total pore volume of the modified Y zeolite is made up of pores having a diamster of at least 8 nm.
Suitably, the modified Y zeolite has a water adsorption capacity of 8-12~ by weight of modified zeolite.
21~259 The pore diameter distribution and the water adsorption capacity can suitably be determined by the methods as described in EP-B-247679, which is herein incorporated by reference.
Preferably, the modified Y zeo:Lite has a SiO2/A1203 molar ratio of from 4 to 25, more preferably of from 8 to 15.
The compositions of matter according to the present invention suitably comprise 5-90% by weight of modified Y zeolite and 10-95%
by weight of binder. In a particular embodiment the compositions of matter comprise rather high amounts of modified Y zeolite: 50-85%
by weight of modified Y zeolite and 15-50% by weight of binder being preferred.
Suitably, the compositions of matter according to the present invention comprise in addition an amorphous cracking component.
Suitably, such a composition of matter comprises 50-90% by weight of modified Y zeolite and amorphous cracking component and 10-50 by weight of binder, preferably 60-85~ by weight of modified Y
zeolite and amorphous cracking component and 15-40~ by weight of binder. Suitably, the amount of modified Y zeolite ranges between 5 and 95%, preferably between 10 and 75%, of the combined amo~mt of modified Y zeolite and amorphous cracking component. Suitably, silica-based amorphous cracking components can be used. Preference is given to silica-alumina as amorphous cracking component. In another embodiment use can be made of a dispersion of silica-alumina in an alumina matrix as amorphous cracking component. When use is made of such an amorphous cracking component the composition of matter according to the present invention suitably comprises less than 25% by weight of the modified Y
zeolite, more than 25~ by weight of binder and in addition at least 30% by weight of the dispersion of silica-alumina in an alumina matrix.
Suitably, the composition of matter comprises at least 30% by weight of binder.
Preference is given to compositions of matter comprising less than 15% by weight of the modified ~ zeolite.
Preferably, the composition of matter has a binder/modified Y
21062~
HYDROCARBON CONVERSION CATALYSTS
The present invention relates to compositions of matter suitable as catalyst base. in hydroprocessing. The present lnvention also relates to catalyst compositions which can suitably be used in hydrocarbon conversion processes, in particular hydrocracking 5 processes, and hydrocarbon conversion processes wherein use is made of such catalyst compositions.
Of the many hydroconversion processes known in the art, hydrocracking is becoming increasingly important since it offers product flexibility together with product quality. As it is also 10 possible to subjact rather heavy feedstocks to hydrocracking it will be clear that much attention has been devoted to the development of hydrocracking catalysts.
Whereas in the past catalytic hydrocracking was aimed primarily at the production of lower boiling points products such 15 as gasoline, nowadays hydrocracking is often aimed at meeting the increasing demand for high quality middle distillate products.
Therefore, the object in nowadays hydrocracking is to provide a hydrocracking catalyst having a high selectivity towards middle distillates and in addition a high activity and stability.
To this end modern hydrocracking catalysts are generally based on zeolitic materials which may have been adapted by techniques like a~Monium-ion exchange and various forms of calcination in order to improve the performance of the hydrocracking catalysts based on such zeolitic materials.
One of the zeolites which is considered to be a good starting material for the manufacture of hydrocracking catalysts is the well-known synthetic zeolite Y as described in US-A-3,130,007. a number of modifications has been reported for this material which include, inter alia, ultrastable Y (US-A-3,536,605) and 30 ultrahydrophobic Y (GB-A-2,014,970). In general, it can be said 2~ ~62~9 that the modifications cause a reduction in the unit cell size depending on the treatment carried out.
In EP-B-247679 compositions of matter have been described which can very attractively be used as components for hydrocracking catalysts Surprisingly, it has now been found that even more attractive results can be obtained in terms of gas make and middle distillate yield when use is made of a composition comprising a binder and a modified Y zeolite having a specific infrared feature.
Accordingly, the present invention relates to a composition of matter suitable as catalyst base in hydroprocessing comprising a crystalline aluminosilicate and a binder wherein the crystalline aluminosilicate comprises a modified Y zeolite having a unit cell size below 24.37 A, a water adsorption capacity (at 25 C and a p/pO value of 0.2) of at least 8% by weight of modified Y zeolite, a pore volume of at least 0.25 ml/g wherein between 10% and 60~ of the total pore volume is made up of pores having a diameter of at least 8 nm, which modified Y zeolite has an absorbance ratio of at most 0.040, expressed as the absorbance in the infra-red frequency region of 3670 + 10 cm divided by the absorbance in the infra-red frequency region of 3630 ~ 10 cm 1 Preferably, the absorbance ratio is at most 0.03, more preferably at most 0.02.
The infrared bands have been determined by means of in-situ cell measurements of dry samples at elevated temperature (450C).
Preferably, the modified Y zeolite has a unit cell size ranging from 24.27 to 24.35 A, more preferably from 24.29 to 24.33 A.
Preferably, between 10~ and 40~ of the total pore volume of the modified Y zeolite is made up of pores having a diamster of at least 8 nm.
Suitably, the modified Y zeolite has a water adsorption capacity of 8-12~ by weight of modified zeolite.
21~259 The pore diameter distribution and the water adsorption capacity can suitably be determined by the methods as described in EP-B-247679, which is herein incorporated by reference.
Preferably, the modified Y zeo:Lite has a SiO2/A1203 molar ratio of from 4 to 25, more preferably of from 8 to 15.
The compositions of matter according to the present invention suitably comprise 5-90% by weight of modified Y zeolite and 10-95%
by weight of binder. In a particular embodiment the compositions of matter comprise rather high amounts of modified Y zeolite: 50-85%
by weight of modified Y zeolite and 15-50% by weight of binder being preferred.
Suitably, the compositions of matter according to the present invention comprise in addition an amorphous cracking component.
Suitably, such a composition of matter comprises 50-90% by weight of modified Y zeolite and amorphous cracking component and 10-50 by weight of binder, preferably 60-85~ by weight of modified Y
zeolite and amorphous cracking component and 15-40~ by weight of binder. Suitably, the amount of modified Y zeolite ranges between 5 and 95%, preferably between 10 and 75%, of the combined amo~mt of modified Y zeolite and amorphous cracking component. Suitably, silica-based amorphous cracking components can be used. Preference is given to silica-alumina as amorphous cracking component. In another embodiment use can be made of a dispersion of silica-alumina in an alumina matrix as amorphous cracking component. When use is made of such an amorphous cracking component the composition of matter according to the present invention suitably comprises less than 25% by weight of the modified Y
zeolite, more than 25~ by weight of binder and in addition at least 30% by weight of the dispersion of silica-alumina in an alumina matrix.
Suitably, the composition of matter comprises at least 30% by weight of binder.
Preference is given to compositions of matter comprising less than 15% by weight of the modified ~ zeolite.
Preferably, the composition of matter has a binder/modified Y
21062~
zeolite weight ratio in the range of 2-40.
Suitably, the composition of matter comprises 40-70~ by weight of the dispersion.
Suitably, the alumina matrix comprises a transitional alumina matrix, preferably a gamma-alumina matrix.
The binder(s) present in the compositions of matter according to the present invention suitably comprise an inorganic oxide or a mixture of inorganic oxides. Both amorphous and crystalline binders can be applied. Examples of suitable binders comprise alumina, 0 magnesia, titania and clays. If desired, small amounts of other inorganic oxides such as zirconia, titania, magnesia and silica may be present. Alumina is a preferred binder. Suitably, the modified Y
zeolite has a degree of crystallinity which is at least retained at increasing SiO2/Al203 molar ratios (relative to a certain standard, e.g. Na-Y). Generally, the crystallinity will slightly improve when comparing modified Y zeolites with increasing SiO2/Al203 molar ratios.
The present invention further relates to a catalyst composition comprising in addition to the composition of matter as defined hereinbefore at least one hydrogenation component of a Group VI metal and/or at least one hydrogenation component of a Group VIII metal. Suitably, the catalyst composition according to the present invention comprises one or more components of nickel and/or cobalt and one or more components of molybdenum and/or tungstsn or one or more components of platinum and/or palladium.
The amount(s) of hydrogenation component(s) in the catalyst composition suitably ranges between Q.05 and 10% by weight of Group VIII metal component(s) and between 2 and 40~ by weight of Group VI metal component(s), calculated as metal(s) per 100 parts by weight of total catalyst. The hydrogenation components in the catalyst composition may be in the oxidic and/or sulphidic form, in particular in the sulphidic form. If a combination of at least a Group VI and a Group VIII metal component is present as (mixed) oxides, it will normally be subjected to a sulphiding treatment prior to proper use in hydrocracking.
2~062~9 The compositions of matter in accordance with the present invention are particularly useful in certain hydroconversion processes, in particular hydrocracking processes.
The present invention, therefore, also relates to a process for converting hydrocarbon oils into products of lower average molecular weight and lower average boiling point comprising contacting a hydrocarbon oil at elevated temperature and pressure in the presence of hydrogen with a catalyst composition as described hereinbefore.
Suitable process conditions for the hydroconversion process comprise temperatures between 250 and 500 C, partial hydrogen pressures of up to 300 bar and space velocities between 0.1 and 10 kg feed per litre catalyst per hour (kg/l/hr). Gas/feed ratios between 100 and 5000 Nl/kg can suitably be applied. Preferably, the hydroconversion process is carried out at a temperature between 300 and 450 C, a partial hydrogen pressure between 25 and 200 bar and a space velocity between 0.2 and 5 kg feed per litre catalyst per hour. Preferably, gas/feed ratios are applied between 250 and 2000 Nl/kg.
Feedstocks which can suitably be subjected to a hydroconversion process using a catalyst according to the present invention comprise gas oils, deasphalted oils, coker gas oils and other thermally cracked gas oils and syncrudes, optionally originating from tar sands, shale oils, residue upgrading processes or biomass. Combinations of various feedstocks can be applied.
It may be desirable to subject part or all of the feedstock to one or more (hydro)treatment steps prior to its use in the hydroconversion process. It is often convenient to sub~ect the feedstock to a (partial) hydrotreatment. The catalyst to be applied in such a hydrotreatment is suitably an amorphous hydrocracking catalyst which contains at least one metal of Group VI and/or at least one metal of Group VIII on an amorphous carrier. In an attractive embodiment of such a hydrotreatment use is made of two reaction zones arranged in series whereby the complete effluent from the first reaction zone can be passed to the second reaction 21~259 zone. The first reaction zone comprises a first amorphous hydrocracking catalyst as described hereinbefore and the second reaction zone comprises a second, zeolitic hydrocracking catalyst which contains at least one metal of Group VI and/or at least one metal of Group VIII. Preferablyl the zeolitic catalyst comprises a catalyst composition in accordance with the invention. In this way a very attractive hydrotreatment of a feedstock is established.
Therefore, the present invention also relates to a process for the hydrotreatment of a hydrocarbonaceous feedstock comprising contacting said feedstock in the presence of hydrogen with a first amorphous hydrocracking catalyst which contains at least one metal of Group VI and/or at least one metal of Group VIII on an amorphous carrier in a first reaction zone passing at least part of the effluent fro~ the first reaction zone, preferably the complete effluent, to a second reaction zone and contacting in the second reaction zone said effluent from the first reaction zone in the presence of hydrogen at elevated temperature and pressure with a second, zeolitic catalyst which comprises any composition of matter in accordance with the present invention as defined hereinabove and at least one hydrogenation component of a Group VI metal and/or at least one hydrogenation component of a Group VIII metal.
It is evident that the first reaction zone may comprise one or more beds of the alumina-containing catalyst and also the second reaction zone may contain one or more beds of the zeolitic catalyst. It is also evident that the first and second reactor zone or zones may be located in one or more reactors. Preferably, the reaction zones are arranged in a stacked-bed configuration. The hydrotreatment and the process according to the present invention can also suitably be carried out in reactors in series or in a stacked-bed configuration.
The reactor effluent so obtained can suitably be subjected to a further hydrocracking process, preferably to a process in accordance with the present i~vention.
The present invention will now be illustrated by means of the 3S following Example.
~062~
Example a) Preparation of a catalyst according to the present invention 77.7 g of a modified Y zeolite (ex-PQZ) having a unit cell size of 2.431 nm, a SiO2/A1203 molar ratio of 9.8, a water adsorption capacity (at 25 C and a p/pO value of 0.2) of 11.2% by weight, a nitrogen pore volume of 0.42 ml/g wherein 30% of the total pore volume is made up of pores having a diameter of at least 8 nm, a loss of ignition of 11% by weight and a 3670 cm 1/3630 cm 1 infrared absorbance ratio of less than 0.01 was mixed with 24 g of hydrated aluminium oxide (ex-Criterion). Subsequently, 36.12 g of a NiW solution (ex-Starck: 6% by weight Ni, 23~ by weight ~), 3.41 g of a nickel nitrate solution (14% by weight Ni) and 43.02 g of water were added to the powdery mixture. After mulling the mixture obtained it was extruded in a small Bonnot extruder provided with a die plate producing 1.5 mm extrudates. The extrudates obtained were dried for 2 hours at 120 C and finally calcined for 2 hours at 500 C. The extrudates obtained had a mercury pore volume of 0.61 ml/g.
They contained 2.6% by weight of nickel and 8.2% by weight of tungsten. The ready catalyst contained 80% by weight of modified Y
zeolite and 20% by weight of binder (based on total amount of zeolite and binder on a dry basis).
b) Hydrocracking experiment.
The catalyst obtained was subjected to a hydrocracking performance test invol.ving a hydrotreated heavy vacuum gas oil having the following properties:
C (%wt) : 86.2 H (%wt) : 13.8 d (70/4) : 0.826 viscosity (100 C) : 4.87 cS (ASTM-D-445) viscosity (60 C) : 12.43 cS (ASTM-D-445) RCT (%wt) : 0.05 (ASTM-D-542) I.B.P. (C) : 205 C
10/20 : 332/370 30/40 : 392/410 50/60 : 428/44~
2~2~9 70/80 : 467/492 : 525 F.B.P. : 598 The catalyst was firstly subjected to a presulphiding treatment by slowly heating in a 10 ~v H2S/~I2-atmosphere to a temperature of 370 C. The catalyst was tested in a 1:1 dilution with 0.2 mm SiC particles under the following operating conditions:
WHSV of 1.1 kg/l/h, H2S partial pressure of 1.4 bar, total pressure of 130 bar and a gas/feed ratio of 1,000 Nl/kg. The experiment was carried out in once-through operation.
When operating the hydrocracking in a kerosene mode of operation, the catalyst performance is expressed at 70% by weight conversion of 300 C boiling point material in the feed after allowing the catalyst to stabilize.
The following results were obtained with the catalyst:
Temperature required (70% conv. of 300 C ): 328 C
Distribution of 300 C product (in % by weight):
Cl -C4 : 6 C5 - 130 C : 43 130 C - 300 C : 51 The chemical hydrogen consumption amounted to 1.2% by weight.
Comparative Exam~le A modified Y zeolite known from EP-B-247679 and having a unit cell size of 24.33 A, a SiO2/A1203 molar ratio of 9.85, a water adsorption capacity (at 25 C and a p/pO value of 0.2) of 11.3% by weight, a nitrogen pore volume of 0.40 ml/g wherein 18% of the total pore volume is made up of pores having a diameter of at least 8 nm, a loss of ignition of 14.1% by weight and a 3670 cm /3630 cm 1 infrared absorbance ratio of 0.043 was treated with hydrated aluminium oxide (ex-Criterion) and a solution of nickel nitrate and am~onium metatungstate so as to obtain a catalyst containing 2.6%
by weight of nlckel and 8.2% by weight of tungsten. The ready catalyst contained 77.5~ by weight of modified ~ zeolite and 22.5%
by weight of binder (based on total amount oi zeolite and binder on a dry basis).
~0~2~9 The comparative catalyst was subjected to a presulphiding treatment as described in the Example and subjected to the same feed. ~hen operating the hydrocracking in a kerosene mode (i.e.
expressing catalyst performance at 70% by weight conversion of 300 C boiling point material in the feed) after allowing the catalyst to stabilize, the following results were obtained:
Temperature required (70~ conv. of 300 C ): 318 C
Distribution of 300 C product (in ~ by weîght):
Cl - C4 7 C5 - 130 C : 46 130 C - 300 C : 47 The chemical hydrogen consumption amounted to 1.2% by weight.
It will be clear from the above that the catalyst in accordance with the present invention is more attractive in terms of gas make and middle distillate yield than the catalyst known from EP-B-247679.
Suitably, the composition of matter comprises 40-70~ by weight of the dispersion.
Suitably, the alumina matrix comprises a transitional alumina matrix, preferably a gamma-alumina matrix.
The binder(s) present in the compositions of matter according to the present invention suitably comprise an inorganic oxide or a mixture of inorganic oxides. Both amorphous and crystalline binders can be applied. Examples of suitable binders comprise alumina, 0 magnesia, titania and clays. If desired, small amounts of other inorganic oxides such as zirconia, titania, magnesia and silica may be present. Alumina is a preferred binder. Suitably, the modified Y
zeolite has a degree of crystallinity which is at least retained at increasing SiO2/Al203 molar ratios (relative to a certain standard, e.g. Na-Y). Generally, the crystallinity will slightly improve when comparing modified Y zeolites with increasing SiO2/Al203 molar ratios.
The present invention further relates to a catalyst composition comprising in addition to the composition of matter as defined hereinbefore at least one hydrogenation component of a Group VI metal and/or at least one hydrogenation component of a Group VIII metal. Suitably, the catalyst composition according to the present invention comprises one or more components of nickel and/or cobalt and one or more components of molybdenum and/or tungstsn or one or more components of platinum and/or palladium.
The amount(s) of hydrogenation component(s) in the catalyst composition suitably ranges between Q.05 and 10% by weight of Group VIII metal component(s) and between 2 and 40~ by weight of Group VI metal component(s), calculated as metal(s) per 100 parts by weight of total catalyst. The hydrogenation components in the catalyst composition may be in the oxidic and/or sulphidic form, in particular in the sulphidic form. If a combination of at least a Group VI and a Group VIII metal component is present as (mixed) oxides, it will normally be subjected to a sulphiding treatment prior to proper use in hydrocracking.
2~062~9 The compositions of matter in accordance with the present invention are particularly useful in certain hydroconversion processes, in particular hydrocracking processes.
The present invention, therefore, also relates to a process for converting hydrocarbon oils into products of lower average molecular weight and lower average boiling point comprising contacting a hydrocarbon oil at elevated temperature and pressure in the presence of hydrogen with a catalyst composition as described hereinbefore.
Suitable process conditions for the hydroconversion process comprise temperatures between 250 and 500 C, partial hydrogen pressures of up to 300 bar and space velocities between 0.1 and 10 kg feed per litre catalyst per hour (kg/l/hr). Gas/feed ratios between 100 and 5000 Nl/kg can suitably be applied. Preferably, the hydroconversion process is carried out at a temperature between 300 and 450 C, a partial hydrogen pressure between 25 and 200 bar and a space velocity between 0.2 and 5 kg feed per litre catalyst per hour. Preferably, gas/feed ratios are applied between 250 and 2000 Nl/kg.
Feedstocks which can suitably be subjected to a hydroconversion process using a catalyst according to the present invention comprise gas oils, deasphalted oils, coker gas oils and other thermally cracked gas oils and syncrudes, optionally originating from tar sands, shale oils, residue upgrading processes or biomass. Combinations of various feedstocks can be applied.
It may be desirable to subject part or all of the feedstock to one or more (hydro)treatment steps prior to its use in the hydroconversion process. It is often convenient to sub~ect the feedstock to a (partial) hydrotreatment. The catalyst to be applied in such a hydrotreatment is suitably an amorphous hydrocracking catalyst which contains at least one metal of Group VI and/or at least one metal of Group VIII on an amorphous carrier. In an attractive embodiment of such a hydrotreatment use is made of two reaction zones arranged in series whereby the complete effluent from the first reaction zone can be passed to the second reaction 21~259 zone. The first reaction zone comprises a first amorphous hydrocracking catalyst as described hereinbefore and the second reaction zone comprises a second, zeolitic hydrocracking catalyst which contains at least one metal of Group VI and/or at least one metal of Group VIII. Preferablyl the zeolitic catalyst comprises a catalyst composition in accordance with the invention. In this way a very attractive hydrotreatment of a feedstock is established.
Therefore, the present invention also relates to a process for the hydrotreatment of a hydrocarbonaceous feedstock comprising contacting said feedstock in the presence of hydrogen with a first amorphous hydrocracking catalyst which contains at least one metal of Group VI and/or at least one metal of Group VIII on an amorphous carrier in a first reaction zone passing at least part of the effluent fro~ the first reaction zone, preferably the complete effluent, to a second reaction zone and contacting in the second reaction zone said effluent from the first reaction zone in the presence of hydrogen at elevated temperature and pressure with a second, zeolitic catalyst which comprises any composition of matter in accordance with the present invention as defined hereinabove and at least one hydrogenation component of a Group VI metal and/or at least one hydrogenation component of a Group VIII metal.
It is evident that the first reaction zone may comprise one or more beds of the alumina-containing catalyst and also the second reaction zone may contain one or more beds of the zeolitic catalyst. It is also evident that the first and second reactor zone or zones may be located in one or more reactors. Preferably, the reaction zones are arranged in a stacked-bed configuration. The hydrotreatment and the process according to the present invention can also suitably be carried out in reactors in series or in a stacked-bed configuration.
The reactor effluent so obtained can suitably be subjected to a further hydrocracking process, preferably to a process in accordance with the present i~vention.
The present invention will now be illustrated by means of the 3S following Example.
~062~
Example a) Preparation of a catalyst according to the present invention 77.7 g of a modified Y zeolite (ex-PQZ) having a unit cell size of 2.431 nm, a SiO2/A1203 molar ratio of 9.8, a water adsorption capacity (at 25 C and a p/pO value of 0.2) of 11.2% by weight, a nitrogen pore volume of 0.42 ml/g wherein 30% of the total pore volume is made up of pores having a diameter of at least 8 nm, a loss of ignition of 11% by weight and a 3670 cm 1/3630 cm 1 infrared absorbance ratio of less than 0.01 was mixed with 24 g of hydrated aluminium oxide (ex-Criterion). Subsequently, 36.12 g of a NiW solution (ex-Starck: 6% by weight Ni, 23~ by weight ~), 3.41 g of a nickel nitrate solution (14% by weight Ni) and 43.02 g of water were added to the powdery mixture. After mulling the mixture obtained it was extruded in a small Bonnot extruder provided with a die plate producing 1.5 mm extrudates. The extrudates obtained were dried for 2 hours at 120 C and finally calcined for 2 hours at 500 C. The extrudates obtained had a mercury pore volume of 0.61 ml/g.
They contained 2.6% by weight of nickel and 8.2% by weight of tungsten. The ready catalyst contained 80% by weight of modified Y
zeolite and 20% by weight of binder (based on total amount of zeolite and binder on a dry basis).
b) Hydrocracking experiment.
The catalyst obtained was subjected to a hydrocracking performance test invol.ving a hydrotreated heavy vacuum gas oil having the following properties:
C (%wt) : 86.2 H (%wt) : 13.8 d (70/4) : 0.826 viscosity (100 C) : 4.87 cS (ASTM-D-445) viscosity (60 C) : 12.43 cS (ASTM-D-445) RCT (%wt) : 0.05 (ASTM-D-542) I.B.P. (C) : 205 C
10/20 : 332/370 30/40 : 392/410 50/60 : 428/44~
2~2~9 70/80 : 467/492 : 525 F.B.P. : 598 The catalyst was firstly subjected to a presulphiding treatment by slowly heating in a 10 ~v H2S/~I2-atmosphere to a temperature of 370 C. The catalyst was tested in a 1:1 dilution with 0.2 mm SiC particles under the following operating conditions:
WHSV of 1.1 kg/l/h, H2S partial pressure of 1.4 bar, total pressure of 130 bar and a gas/feed ratio of 1,000 Nl/kg. The experiment was carried out in once-through operation.
When operating the hydrocracking in a kerosene mode of operation, the catalyst performance is expressed at 70% by weight conversion of 300 C boiling point material in the feed after allowing the catalyst to stabilize.
The following results were obtained with the catalyst:
Temperature required (70% conv. of 300 C ): 328 C
Distribution of 300 C product (in % by weight):
Cl -C4 : 6 C5 - 130 C : 43 130 C - 300 C : 51 The chemical hydrogen consumption amounted to 1.2% by weight.
Comparative Exam~le A modified Y zeolite known from EP-B-247679 and having a unit cell size of 24.33 A, a SiO2/A1203 molar ratio of 9.85, a water adsorption capacity (at 25 C and a p/pO value of 0.2) of 11.3% by weight, a nitrogen pore volume of 0.40 ml/g wherein 18% of the total pore volume is made up of pores having a diameter of at least 8 nm, a loss of ignition of 14.1% by weight and a 3670 cm /3630 cm 1 infrared absorbance ratio of 0.043 was treated with hydrated aluminium oxide (ex-Criterion) and a solution of nickel nitrate and am~onium metatungstate so as to obtain a catalyst containing 2.6%
by weight of nlckel and 8.2% by weight of tungsten. The ready catalyst contained 77.5~ by weight of modified ~ zeolite and 22.5%
by weight of binder (based on total amount oi zeolite and binder on a dry basis).
~0~2~9 The comparative catalyst was subjected to a presulphiding treatment as described in the Example and subjected to the same feed. ~hen operating the hydrocracking in a kerosene mode (i.e.
expressing catalyst performance at 70% by weight conversion of 300 C boiling point material in the feed) after allowing the catalyst to stabilize, the following results were obtained:
Temperature required (70~ conv. of 300 C ): 318 C
Distribution of 300 C product (in ~ by weîght):
Cl - C4 7 C5 - 130 C : 46 130 C - 300 C : 47 The chemical hydrogen consumption amounted to 1.2% by weight.
It will be clear from the above that the catalyst in accordance with the present invention is more attractive in terms of gas make and middle distillate yield than the catalyst known from EP-B-247679.
Claims (17)
1. Composition of matter suitable as catalyst base in hydroprocessing comprising a crystalline aluminosilicate and a binder wherein the crystalline aluminosilicate comprises a modified Y zeolite having a unit cell size below 24.37 A, a water adsorption capacity (at 25 °C and a p/pO value of 0.2) of at least 8% by weight of modified Y zeolite, a pore volume of at least 0.25 ml/g wherein between 10% and 60% of the total pore volume is made up of pores having a diameter of at least 8 nm, which modified Y zeolite has an absorbance ratio of at most 0.040, expressed as the absorbance in the infra-red frequency region of 3670 * 10 cm 1 divided by the absorbance in the infra-red frequency region of 3630 + 10 cm-1.
2. Composition according to claim 1, wherein the absorbance ratio is at most 0.03.
3. Composition according to claim 1 or 2, wherein the unit cell size ranges from 24.27 to 24.35 .ANG..
4. Composition according to claim 3, wherein the unit cell size ranges from 24.29 to 24.33 .ANG..
5. Composition according to any one of claims 1-4, wherein between 10% and 40% of the total pore volume of the modified Y
zeolite is made up of pores having a diameter of at least 8 nm.
zeolite is made up of pores having a diameter of at least 8 nm.
6. Composition according to any one of claims 1-5, wherein the modified Y zeolite has a water adsorption capacity of 8-12% by weight of modified Y zeolite.
7. Composition according to any one of claims 1-6, wherein the modified Y zeolite has a SiO2/Al2O3 molar ratio of from 4 to 25.
8. Composition according to claim 8, wherein the modified Y
zeolite has a SiO2/Al2O3 molar ratio of from 8 to 15.
zeolite has a SiO2/Al2O3 molar ratio of from 8 to 15.
9. Composition according to any one of claims 1-8, wherein the composition comprises 5-90% by weight of modified Y zeolite and
10-95% by weight of binder.
10. Composition according to any one of claims 1-9, wherein the binder comprises an inorganic oxide or a mixture of inorganic oxides.
10. Composition according to any one of claims 1-9, wherein the binder comprises an inorganic oxide or a mixture of inorganic oxides.
11. Catalyst composition comprising a binder, a modified Y zeolite according to any one of claims 1-10 and at least one hydrogenation component of a Group VI metal and/or at least one hydrogenation component of a Group VIII metal.
12. Catalyst composition according to claim 11, wherein the hydrogenation component comprises one or more components of nickel and/or cobalt and one or more components of molybdenum and/or tungsten or one or more components of platinum and/or palladium.
13. Catalyst composition according to claim 12, wherein the hydrogenation component comprises between 0.05 and 10% by weight of nickel and between 2 and 40% by weight of tungsten, calculated as metals per 100 parts by weight of total catalyst.
14. Catalyst composition according to any one of claims 11-13, wherein the hydrogenation component(s) is (are) present in the sulphided form.
15. Process for converting hydrocarbon oils into products of lower average molecular weight and lower-average boiling point comprising contacting a hydrocarbon oil at elevated temperature and pressure in the presence of hydrogen with a catalyst composition according to any one of claims 11-14.
16. Process according to claim 15, which is carried out at a temperature in the range of from 250 °C to 500 °C, a partial hydrogen pressure up to 300 bar and a space velocity between 0.1 and 10 kg feed per litre of catalyst per hour.
17. Process according to claim 16, which is carried out at a temperature between 300 °C and 450 °C, a hydrogen partial pressureof 25 and 200 bar and a space velocity between 0.2 and 5 kg feed per litre of catalyst per hour.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92202855 | 1992-09-17 | ||
| EP92202855.0 | 1992-09-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2106259A1 true CA2106259A1 (en) | 1994-03-18 |
Family
ID=8210919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002106259A Abandoned CA2106259A1 (en) | 1992-09-17 | 1993-09-15 | Hydrocarbon conversion catalysts |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPH06210178A (en) |
| KR (1) | KR940006639A (en) |
| CN (1) | CN1112954A (en) |
| AU (1) | AU663970B2 (en) |
| BR (1) | BR9303790A (en) |
| CA (1) | CA2106259A1 (en) |
| FI (1) | FI934047A (en) |
| NZ (1) | NZ248669A (en) |
| SG (1) | SG94675A1 (en) |
| ZA (1) | ZA936790B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790803B2 (en) * | 2001-08-17 | 2004-09-14 | Intevep, S.A. | Catalytic system for hydroconversion of naphtha |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8601384A (en) * | 1986-05-29 | 1987-12-16 | Texas Instruments Holland | COMBUSTION ENGINE WITH FUEL INJECTION SYSTEM AND AN INJECTION VALVE INTENDED FOR SUCH AN ENGINE. |
| GB8613131D0 (en) * | 1986-05-30 | 1986-07-02 | Shell Int Research | Hydrocarbon conversion |
| GB8613132D0 (en) * | 1986-05-30 | 1986-07-02 | Shell Int Research | Hydrocarbon conversion catalysts |
-
1993
- 1993-09-14 JP JP5250906A patent/JPH06210178A/en active Pending
- 1993-09-14 KR KR1019930018454A patent/KR940006639A/en not_active Application Discontinuation
- 1993-09-15 CA CA002106259A patent/CA2106259A1/en not_active Abandoned
- 1993-09-15 CN CN93117528A patent/CN1112954A/en active Pending
- 1993-09-15 AU AU47384/93A patent/AU663970B2/en not_active Ceased
- 1993-09-15 BR BR9303790A patent/BR9303790A/en not_active Application Discontinuation
- 1993-09-15 ZA ZA936790A patent/ZA936790B/en unknown
- 1993-09-15 FI FI934047A patent/FI934047A/en unknown
- 1993-09-15 NZ NZ248669A patent/NZ248669A/en unknown
- 1993-09-16 SG SG9601693A patent/SG94675A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SG94675A1 (en) | 2003-03-18 |
| KR940006639A (en) | 1994-04-25 |
| FI934047A0 (en) | 1993-09-15 |
| AU4738493A (en) | 1994-03-24 |
| CN1112954A (en) | 1995-12-06 |
| NZ248669A (en) | 1994-09-27 |
| BR9303790A (en) | 1994-05-10 |
| ZA936790B (en) | 1994-04-14 |
| FI934047A (en) | 1994-03-18 |
| JPH06210178A (en) | 1994-08-02 |
| AU663970B2 (en) | 1995-10-26 |
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