CA2103876A1 - Group viii metal containing tungsten oxide silica modified zirconia as acid catalyst - Google Patents
Group viii metal containing tungsten oxide silica modified zirconia as acid catalystInfo
- Publication number
- CA2103876A1 CA2103876A1 CA002103876A CA2103876A CA2103876A1 CA 2103876 A1 CA2103876 A1 CA 2103876A1 CA 002103876 A CA002103876 A CA 002103876A CA 2103876 A CA2103876 A CA 2103876A CA 2103876 A1 CA2103876 A1 CA 2103876A1
- Authority
- CA
- Canada
- Prior art keywords
- group viii
- tungsten oxide
- viii metal
- silica
- zirconia
- 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
Classifications
-
- 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
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
Abstract
ABSTRACT OF THE DISCLOSURE:
The invention is directed to a catalyst composition com-prising a Group VIII metal, preferably a Group VIII noble metal, and a zirconia support impregnated with silica and tungsten oxide and its use in an isomerization process.
The invention is directed to a catalyst composition com-prising a Group VIII metal, preferably a Group VIII noble metal, and a zirconia support impregnated with silica and tungsten oxide and its use in an isomerization process.
Description
-~ 1 03876 , FIELD OF THE INVENTION
Isomerization catalysts disclosed in the prior art continue to suffer major disadvantages when applied, for example, to long chain hydrocarbons e.g., C7+. For instance, large amounts of byproducts, consisting predominantly of cracked hydrocarbon matèrials, form in prior art isomerization methods along with the desired isomerate product. Cracking decreases the amount of long chain paraffins available for isomerization, thereby reducing the ultimate yield.
Applicants have discovered that a catalyst composition comprising a Group VIII metal, preferably a Group VIII noble metal, and a zirconia support having both silica and tungsten oxide simulta-neously present produces a solid acid catalyst that behaves different-ly from one having a Group VIII metal with either silica or tungsten oxide alone on the zirconia support. At 450C, Group VIII noble metal-containing zirconia impregnated with silica alone is not active for nC7 isomerization compared with either Group VIII noble metal containing tungsten oxide impregnated zirconia or Group VIII noble metal containing zirconia impregnated with both tungsten oxide and silica simultaneously. The tungsten oxide and silica impregnated Group VIII noble metal containing zirconia has comparable activity at 350-C to a tungsten oxide impregnated zirconia at 250C; however, the selectivity to cracked product is substantially higher on zirconia impregnated with only tungsten oxide than on zirconia impregnated with both silica and tungsten oxide. Therefore, applicants have discovered a new catalyst which can act as a solid acid catalyst useful in isomerization reactions and leading to much lower selectivity to undesirable cracked products.
SUMMARY OF THE INVENTION
The invention is directed to a catalyst composition compris-e ing a Group VIII metal, preferably a Group VIII noble metal, and a zirconia support impregnated with a mixture of silica and tungsten oxide.
.
~10387~
The invention is further directed to the use of the catalyst composition ;n an isomerization reaction.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the conversion (line A) and cracking (line B) selectivity in an isomerization reaction, of a zirconia support having impregnated therein tungsten oxide alone and containing 0.5% platinum and run at 250-C and the conversion (line C) and cracking selectivity (line D) of a zirconia support having both silica and tungsten oxide simultaneously impregnated therein and containing 0.5% platinum and run at 350-C. The figure shows that the impregnation of both tungsten oxide and silica affords a catalyst with lower cracking selectivity and comparable conversion.
DETAILED DESCRIPTION
The catalysts of this invention may be prepared by tech niques well-known in the art, such as incipient wetness, impregnation, etc., the choice being left to the practitioner. When using the impregnation technique, the impregnation solution is contacted with the support material for a time sufficient to deposit the precursor material onto the support either by selective adsorption or alterna-tively, the excess solvent may be evaporated during drying leaving behind the precursor salt. Advantageously, incipient wetness tech-niques may also be used. The choice of catalyst preparation method is left to the practitioner.
The catalyst of the present invention may be prepared from precipitated zirconium hydroxide. For example, ZrOC12.8H20 can be dissolved in water and Zr(OH)4 precipitated with ammonium hydroxide.
Other compounds reacting to produce Zr(OH)4 may also be used. The solid Zr(OH)4 is then separated, for example, by filtration, washed and dried. A Group VIII metal may then be incorporated, for example, via the incipient wetness technique using a solution of chloroplatinic acid. The amount of Group VIII metal incorporated can range from .
.... ..
' ' ' ' ~
-, ' . ~ :' ' ''' .
.
~1~387 ~
about O.Ol to lO wt%, preferably 0.01-2 wt%, and most preferably from 0.3 to l.0 wt%.
The Group VIII ~etal may be selected from any of the Group VIII metals, and mixtures thereof. Preferably the Group VIII metal will be a noble metal selected from platinum, palladium, ruthenium, iridium, osmium, and mixtures thereof.
Tungsten oxide and silica may then be impregnated into the support. Tungsten oxide and silica may be incorporated directly or any compounds of tungsten and silicon capable of forming tungsten oxide and silica upon calcination may be used to provide these oxides.
Preferably the tungsten oxide and silica will be incorporated simulta-neously. For example, a solution containing ammonium metatungstate as the source or precursor of tungsten oxide, and aqueous colloidal silica can be prepared and the Zr(OH)4 or Zr(OH)4 containing Group VIII metal immersed therein.
Generally about 5 to about 25 wt%, preferably about lO to about 15 wt% tungsten oxide will be added to the support. The amount of silica impregnated will range form about l to about 10 wt%, prefer-ably about 3 to about 5 wt% based on the catalyst composition.
Following impregnation of the oxides, or oxide precursors, and the Group VIII metal, the catalyst is dried and ca1cined to convert the Zr(OH)4 to zirconia and the oxide precursors to oxides.
Drying is conducted at temperatures of about lOO-C to about 150-C and calcination at temperature of about 300-C to about 900-C. Preferably calcination temperatures will be about 400-C to about 600-C.
Calcination time will be at least 1 hour, preferably about 4 hours.
The impregnation of Group VIII metal, tungsten oxide and silica can be performed simultaneously or in any sequence. Though it is preferable to incorporate the Group VIII metal first, the order of addition is merely a matter of choice.
.
~ ~103~7~
The catalysts of the present invention are particularly useful for an isomerization reaction. The catalysts may be contacted with a Cs+ feedstream. Preferably a feedstream compris;ng Cs to C1o paraffins will be used. Isomerization can be conducted at tempera-tures below about 400-C, 100 to 3000 psi H2, 4/1 to 10/1 H2/n-paraffin, and 0.1 to 10.0 LHSV, preferably the reaction is carried out at temperatures between about 300-C and 400-C, 5/1 H2/n-paraffin, and 1 to 2 W/W/hr.
The invention is illustrated by the following example which is not limiting in any way.
EXAMPLE 1:
Preparation of Platinum Solution:
6.25 9 of chloroplatinic acid containing 407O platinum, were dissolved in and diluted to one liter with water. The resul-tant solution contains 0.05 9 Pt/20 cc of solution.
Preparation of Zr(OH)4:
360 9 of ZrOCl2.8H20 were dissolved in 2800 cc of water.
Concentrated ammonium hydroxide solution (~14M) was added with stirring at which point a precipitate forms. The addition of ammonium hydroxide solution is continued until the pH of solution reaches -10. The resulting slurry is then left to settle for two hours. The precipitate is filtered, washed with distilled water twice, then with water containing a sufficient quantity of ammonium hydroxide to keep the pH at ~10. In order to remove any residual chloride, the solid is then reslurried into a lM solution of ammonium hydroxide, the slurry is heated to 60-C, stirred and after one hour filtered and washed with water. The solid is then dried at llO-C overnight.
,- . . ............. . . , :. :
.
., , . . : ' :' ~
, 21~387~
s Preparation of Pt/Zr(OH)4:
40 9 of Zr(OH)4 were immersed into 80 cc of the chloroplatinic acid solution, stirred and mixed for 5 minutes, filtered and dried overnight at llO-C.
Preparation of Pt/ZrO2/W03:
A solution was prepared containing 4 g of ammonium metatungstate (Sylvania 92.2% W03) dissolved in 40 cc of water.
20 9 of Pt/Zr(OH)4 was immersed into this solution, stirred and mixed for five minutes, filtered and dried at llO-C overnight.
This was then calcined at 600-C for three hours in air.
Preparation of Pt/ZrO2/(W03-SiO2), platinum on zirconia contain-ing tungsten oxide and silica.
A solution was prepared by dissolving 2 9 of ammonium metatungstate (92.2% W03) and 3.5 9 of Ludox HS-40 colloidal silica (Dupont) into 20 cc of water. 10 g of Pt/Zr(OH)4 was immersed into this solution, stirred and mixed for 5 minutes, filtered and dried at llO-C overnight. This was then calcined at 600-C for three hours in air.
The Pt/ZrO2/W03 and Pt/ZrO2/(W03-SiO2) catalysts were then compared in an isomerization reaction using a n-heptane feed.
The results, which are depicted in Figure 1 show that the silica tungsten oxide mixture (line C) has comparable activity at 350-C relative to the tungsten oxide only zirconia catalyst (line A) run at 250-C. However, the selectivity to cracked product is substantially higher on the tungsten oxide only zirconia (line B) than on the tungsten oxide-silica zirconia (line D).
, :~ .
.
210387~
As used herein, conversion means the fraction expressed as % of feed converted, selectivity means the wt% of product formed/wt%
of feed converted measured in %, activity is a measure of the amount in grams of feed converted per gram of catalyst per unit time.
, . . ..
.
Isomerization catalysts disclosed in the prior art continue to suffer major disadvantages when applied, for example, to long chain hydrocarbons e.g., C7+. For instance, large amounts of byproducts, consisting predominantly of cracked hydrocarbon matèrials, form in prior art isomerization methods along with the desired isomerate product. Cracking decreases the amount of long chain paraffins available for isomerization, thereby reducing the ultimate yield.
Applicants have discovered that a catalyst composition comprising a Group VIII metal, preferably a Group VIII noble metal, and a zirconia support having both silica and tungsten oxide simulta-neously present produces a solid acid catalyst that behaves different-ly from one having a Group VIII metal with either silica or tungsten oxide alone on the zirconia support. At 450C, Group VIII noble metal-containing zirconia impregnated with silica alone is not active for nC7 isomerization compared with either Group VIII noble metal containing tungsten oxide impregnated zirconia or Group VIII noble metal containing zirconia impregnated with both tungsten oxide and silica simultaneously. The tungsten oxide and silica impregnated Group VIII noble metal containing zirconia has comparable activity at 350-C to a tungsten oxide impregnated zirconia at 250C; however, the selectivity to cracked product is substantially higher on zirconia impregnated with only tungsten oxide than on zirconia impregnated with both silica and tungsten oxide. Therefore, applicants have discovered a new catalyst which can act as a solid acid catalyst useful in isomerization reactions and leading to much lower selectivity to undesirable cracked products.
SUMMARY OF THE INVENTION
The invention is directed to a catalyst composition compris-e ing a Group VIII metal, preferably a Group VIII noble metal, and a zirconia support impregnated with a mixture of silica and tungsten oxide.
.
~10387~
The invention is further directed to the use of the catalyst composition ;n an isomerization reaction.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the conversion (line A) and cracking (line B) selectivity in an isomerization reaction, of a zirconia support having impregnated therein tungsten oxide alone and containing 0.5% platinum and run at 250-C and the conversion (line C) and cracking selectivity (line D) of a zirconia support having both silica and tungsten oxide simultaneously impregnated therein and containing 0.5% platinum and run at 350-C. The figure shows that the impregnation of both tungsten oxide and silica affords a catalyst with lower cracking selectivity and comparable conversion.
DETAILED DESCRIPTION
The catalysts of this invention may be prepared by tech niques well-known in the art, such as incipient wetness, impregnation, etc., the choice being left to the practitioner. When using the impregnation technique, the impregnation solution is contacted with the support material for a time sufficient to deposit the precursor material onto the support either by selective adsorption or alterna-tively, the excess solvent may be evaporated during drying leaving behind the precursor salt. Advantageously, incipient wetness tech-niques may also be used. The choice of catalyst preparation method is left to the practitioner.
The catalyst of the present invention may be prepared from precipitated zirconium hydroxide. For example, ZrOC12.8H20 can be dissolved in water and Zr(OH)4 precipitated with ammonium hydroxide.
Other compounds reacting to produce Zr(OH)4 may also be used. The solid Zr(OH)4 is then separated, for example, by filtration, washed and dried. A Group VIII metal may then be incorporated, for example, via the incipient wetness technique using a solution of chloroplatinic acid. The amount of Group VIII metal incorporated can range from .
.... ..
' ' ' ' ~
-, ' . ~ :' ' ''' .
.
~1~387 ~
about O.Ol to lO wt%, preferably 0.01-2 wt%, and most preferably from 0.3 to l.0 wt%.
The Group VIII ~etal may be selected from any of the Group VIII metals, and mixtures thereof. Preferably the Group VIII metal will be a noble metal selected from platinum, palladium, ruthenium, iridium, osmium, and mixtures thereof.
Tungsten oxide and silica may then be impregnated into the support. Tungsten oxide and silica may be incorporated directly or any compounds of tungsten and silicon capable of forming tungsten oxide and silica upon calcination may be used to provide these oxides.
Preferably the tungsten oxide and silica will be incorporated simulta-neously. For example, a solution containing ammonium metatungstate as the source or precursor of tungsten oxide, and aqueous colloidal silica can be prepared and the Zr(OH)4 or Zr(OH)4 containing Group VIII metal immersed therein.
Generally about 5 to about 25 wt%, preferably about lO to about 15 wt% tungsten oxide will be added to the support. The amount of silica impregnated will range form about l to about 10 wt%, prefer-ably about 3 to about 5 wt% based on the catalyst composition.
Following impregnation of the oxides, or oxide precursors, and the Group VIII metal, the catalyst is dried and ca1cined to convert the Zr(OH)4 to zirconia and the oxide precursors to oxides.
Drying is conducted at temperatures of about lOO-C to about 150-C and calcination at temperature of about 300-C to about 900-C. Preferably calcination temperatures will be about 400-C to about 600-C.
Calcination time will be at least 1 hour, preferably about 4 hours.
The impregnation of Group VIII metal, tungsten oxide and silica can be performed simultaneously or in any sequence. Though it is preferable to incorporate the Group VIII metal first, the order of addition is merely a matter of choice.
.
~ ~103~7~
The catalysts of the present invention are particularly useful for an isomerization reaction. The catalysts may be contacted with a Cs+ feedstream. Preferably a feedstream compris;ng Cs to C1o paraffins will be used. Isomerization can be conducted at tempera-tures below about 400-C, 100 to 3000 psi H2, 4/1 to 10/1 H2/n-paraffin, and 0.1 to 10.0 LHSV, preferably the reaction is carried out at temperatures between about 300-C and 400-C, 5/1 H2/n-paraffin, and 1 to 2 W/W/hr.
The invention is illustrated by the following example which is not limiting in any way.
EXAMPLE 1:
Preparation of Platinum Solution:
6.25 9 of chloroplatinic acid containing 407O platinum, were dissolved in and diluted to one liter with water. The resul-tant solution contains 0.05 9 Pt/20 cc of solution.
Preparation of Zr(OH)4:
360 9 of ZrOCl2.8H20 were dissolved in 2800 cc of water.
Concentrated ammonium hydroxide solution (~14M) was added with stirring at which point a precipitate forms. The addition of ammonium hydroxide solution is continued until the pH of solution reaches -10. The resulting slurry is then left to settle for two hours. The precipitate is filtered, washed with distilled water twice, then with water containing a sufficient quantity of ammonium hydroxide to keep the pH at ~10. In order to remove any residual chloride, the solid is then reslurried into a lM solution of ammonium hydroxide, the slurry is heated to 60-C, stirred and after one hour filtered and washed with water. The solid is then dried at llO-C overnight.
,- . . ............. . . , :. :
.
., , . . : ' :' ~
, 21~387~
s Preparation of Pt/Zr(OH)4:
40 9 of Zr(OH)4 were immersed into 80 cc of the chloroplatinic acid solution, stirred and mixed for 5 minutes, filtered and dried overnight at llO-C.
Preparation of Pt/ZrO2/W03:
A solution was prepared containing 4 g of ammonium metatungstate (Sylvania 92.2% W03) dissolved in 40 cc of water.
20 9 of Pt/Zr(OH)4 was immersed into this solution, stirred and mixed for five minutes, filtered and dried at llO-C overnight.
This was then calcined at 600-C for three hours in air.
Preparation of Pt/ZrO2/(W03-SiO2), platinum on zirconia contain-ing tungsten oxide and silica.
A solution was prepared by dissolving 2 9 of ammonium metatungstate (92.2% W03) and 3.5 9 of Ludox HS-40 colloidal silica (Dupont) into 20 cc of water. 10 g of Pt/Zr(OH)4 was immersed into this solution, stirred and mixed for 5 minutes, filtered and dried at llO-C overnight. This was then calcined at 600-C for three hours in air.
The Pt/ZrO2/W03 and Pt/ZrO2/(W03-SiO2) catalysts were then compared in an isomerization reaction using a n-heptane feed.
The results, which are depicted in Figure 1 show that the silica tungsten oxide mixture (line C) has comparable activity at 350-C relative to the tungsten oxide only zirconia catalyst (line A) run at 250-C. However, the selectivity to cracked product is substantially higher on the tungsten oxide only zirconia (line B) than on the tungsten oxide-silica zirconia (line D).
, :~ .
.
210387~
As used herein, conversion means the fraction expressed as % of feed converted, selectivity means the wt% of product formed/wt%
of feed converted measured in %, activity is a measure of the amount in grams of feed converted per gram of catalyst per unit time.
, . . ..
.
Claims (8)
1. A catalyst composition comprising a Group VIII metal and a zirconia support impregnated with a mixture of silica and tungsten oxide.
2. A catalyst composition according to claim 1 wherein said silica is present in an amount from about 1 to about 10 wt%.
3. A catalyst composition according to claim 1 wherein said tungsten oxide is present in an amount from about 5 to about 25 wt%.
4. A catalyst composition according to claim 1 wherein said Group VIII metal is present in an amount from about 0.01 to about 10 wt%.
5. A catalyst composition according to claim 1 wherein said Group VIII metal is a Group VIII noble metal selected from the group consisting of platinum, palladium, ruthenium, osmium, iridium, and mixtures thereof.
6. A catalytic isomerization process comprising contacting a C5+ feed, under isomerization conditions, with a catalyst composi-tion comprising a Group VIII metal and a zirconia support impregnated with tungsten oxide and silica.
7. A catalytic isomerization process according to claim 6 wherein said C5+ feed comprises C5 to C10 paraffins.
8. A catalytic isomerization process according to claim 6 wherein said Group VIII metal is a Group VIII noble metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93580092A | 1992-08-27 | 1992-08-27 | |
| US935,800 | 1992-08-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2103876A1 true CA2103876A1 (en) | 1994-02-28 |
Family
ID=25467675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002103876A Abandoned CA2103876A1 (en) | 1992-08-27 | 1993-08-11 | Group viii metal containing tungsten oxide silica modified zirconia as acid catalyst |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US5422327A (en) |
| EP (1) | EP0585065B1 (en) |
| JP (1) | JPH06170228A (en) |
| CA (1) | CA2103876A1 (en) |
| DE (1) | DE69309189T2 (en) |
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| DE102010050312A1 (en) | 2010-11-03 | 2012-05-03 | Süd-Chemie AG | Ammonia oxidation catalyst with low N2O by-product formation |
| SA113340632B1 (en) | 2012-06-11 | 2015-12-06 | رينوفيا، انك. | Process for production of adipic acid from 1,6-hexanediol |
| EP3002058A1 (en) * | 2014-10-02 | 2016-04-06 | Evonik Degussa GmbH | Catalyst system for the production of ketones from epoxides |
| GB2609806A (en) * | 2020-04-14 | 2023-02-15 | Kellogg Brown & Root Llc | Method for catalyst production for C5-C12 paraffin's isomerization |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4005048A (en) * | 1971-04-27 | 1977-01-25 | Imperial Chemical Industries Limited | Treating hydrocarbons |
| GB1391453A (en) * | 1971-04-27 | 1975-04-23 | Ici Ltd | Treating hydrocarbons |
| US3755146A (en) * | 1971-09-17 | 1973-08-28 | Phillips Petroleum Co | Isomerization and hydrocracking of paraffins |
| US4233139A (en) * | 1978-07-25 | 1980-11-11 | Exxon Research & Engineering Co. | Acid catalyzed hydrocarbon conversion processes utilizing a catalyst comprising a Group IVB, VB or VIB metal oxide on an inorganic refractory oxide support |
| US4440872A (en) * | 1978-07-25 | 1984-04-03 | Exxon Research And Engineering Co. | Transition metal oxide acid catalysts |
| US4240934A (en) * | 1978-09-28 | 1980-12-23 | Standard Oil Company (Indiana) | Reforming catalyst comprising iridium, zirconia, and alumina |
| US4284531A (en) * | 1979-09-05 | 1981-08-18 | Union Oil Co. Of California | Methanation catalysts and process for their preparation |
| JPS6115739A (en) * | 1984-04-25 | 1986-01-23 | Toa Nenryo Kogyo Kk | Hydrogenating-treatment catalyst |
| DE3586228D1 (en) * | 1984-09-10 | 1992-07-23 | Light Oil Utilization Res Ass | SOLID STRONG ACID CATALYST. |
| US4692428A (en) * | 1985-12-31 | 1987-09-08 | Exxon Research And Engineering Company | Preparation and use of catalysts comprising mixtures of tungsten oxide and silica on alumina |
| DE68916285D1 (en) * | 1988-03-12 | 1994-07-28 | Akira Igarashi | Process for the steam reforming of hydrocarbons. |
| US4956519A (en) * | 1988-09-21 | 1990-09-11 | Sun Refining And Marketing Company | Catalyst for hydrocarbon conversion and conversion process utilizing the same |
| US4918041A (en) * | 1988-09-21 | 1990-04-17 | Sun Refining And Marketing Company | Catalyst for hydrocarbon conversion and conversion process utilizing the same |
-
1993
- 1993-08-11 CA CA002103876A patent/CA2103876A1/en not_active Abandoned
- 1993-08-20 EP EP93306593A patent/EP0585065B1/en not_active Expired - Lifetime
- 1993-08-20 DE DE69309189T patent/DE69309189T2/en not_active Expired - Fee Related
- 1993-08-23 JP JP5207507A patent/JPH06170228A/en active Pending
- 1993-10-26 US US08/143,423 patent/US5422327A/en not_active Expired - Lifetime
-
1995
- 1995-04-21 US US08/426,378 patent/US5648589A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0585065B1 (en) | 1997-03-26 |
| DE69309189D1 (en) | 1997-04-30 |
| DE69309189T2 (en) | 1997-08-28 |
| JPH06170228A (en) | 1994-06-21 |
| US5422327A (en) | 1995-06-06 |
| EP0585065A1 (en) | 1994-03-02 |
| US5648589A (en) | 1997-07-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |