CA2170219A1 - Process for the demetallation of residual oils - Google Patents
Process for the demetallation of residual oilsInfo
- Publication number
- CA2170219A1 CA2170219A1 CA002170219A CA2170219A CA2170219A1 CA 2170219 A1 CA2170219 A1 CA 2170219A1 CA 002170219 A CA002170219 A CA 002170219A CA 2170219 A CA2170219 A CA 2170219A CA 2170219 A1 CA2170219 A1 CA 2170219A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- demetallation
- carrier
- oil
- group
- 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
- 238000007324 demetalation reaction Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003921 oil Substances 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 239000010779 crude oil Substances 0.000 claims abstract description 6
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000011149 active material Substances 0.000 claims abstract description 3
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 description 9
- 238000011068 loading method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Process for the demetallation of petroleum crude oil by contacting the oil together with hydrogen with a catalyst having at least one metal or compound thereof of Group VIII and/or Group VI of the Periodic Table as its active material supported on a carrier comprising a zeolite with a SiO2/Al2O3 ratio of at least 5 and a unit cell size of between 24.30 and 24.60.
Description
~7~2~
The present invention relates to demetallation of petroleum crude oil, and, more particular, to the removal of metals in the oil by contact with a catalyst having Ni, Mo and/or CoMo supported on a zeolitic carrier.
Petroleum crudes are known to contain metals such as Ni, V, Fe, Co, etc. in ppm levels. To a large extent, these components are associated with the heaviest parts of the resid, i.e. the part of the resid with the highest boiling points. This means that these components are con-centrated in the bottom fractions often designated atm. or vacuum residuum.
The presence of metallic compounds is generally undesirable as they are poisonous to many subsequent up-grading steps usually used to convert or treat the atm. or vacuum residuum in refineries, e.g. fuel oil desulphurisation, resid hydrocracking or resid FCC.
Heavy oil fractions containing metal compounds are predominantly those with an atmospheric boiling point above 350C. The heavy oil fractions will typically contain 50-500 ppm cf mainly Ni and V. Those trace metals are normally removed in a fixed bed catalytic process, where the residual oil comes into contact with a demetallation catalyst at high temperature, typically at 300-450C at a high H2 pressure, e.g. 20-200 bars and at a space veloc-ity in the range of 0.25-4 h-1. When the oil comes into contact with the demetallation catalyst, the metals pres-ented in the feedstock will react and accumulate on the catalyst surface.
In order to be able efficiently to treat residual oils, it is important that metallic compounds be removed from the oil. Conventional demetallation catalysts consist of Ni and Mo or CoMo supported on alumina. It has now been found that metals are removed from petroleum crude oil with a high efficiency in a demetallation process, when employ-ing a demetallat on catalyst supported on a carrier com-prising zeolitic material.
~17~9 -Accordingly, this invention provides a process for the demetallation of petroleum crude oil by contacting the oil together with hydrogen with a catalyst having at least one metal or compound thereof of Group VIII and/or Group VI
of the Periodic Table as active material supported on a carrier, wherein the carrier comprises a zeolite with a SiO2/Al2O3 ratio of at least 5 and a unit cell size of between 24.30 and 24.60. Preferred metals for use in the process are Ni, Mo, CoMo or mixtures thereof.
It is furthermore preferred to composite the car-rier material of the catalyst of 30-70% by weight with the above zeolitic material and 30-70% by weight with alumina.
The catalyst may be prepared by any method being conventional in the art and including impregnation of the calcined carrier with an aqueous solution of salts of the active metal or metals, drying the impregnated carrier and finally calcinating the carrier to obtain the active cata-lyst.
In operating the inventive process, the catalyst is arranged as fixed bed in a demetallation reactor and crude oil feedstock passed together with hydrogen in a ratio of typically 200-2000 Nl/l through the catalyst bed. During demetallation, the bed temperature is maintained at elev-ated temperature and pressure of usually 350-450C and 120-170 atm.
By passage through the catalyst bed, the metal content in the feedstock is reduced to few ppm.
~ya~rle A catalyst support was prepared by mixing 70 g of dried C~3 500 ~TM Zeolite (available from P.Q. Zeolites), having a unit cell size of 24.53 and a SiO2/Al2O3 = 5.4 with a gel obtained by adding 29 g of cATAPALTM (Vista Cor-poration) to 1.8 g of 65% HN03 and 78 g of water. The ~17~
components were thoroughly mixed in a Z-KNEADERT~I with 11 g CATAPALTM un~il a pasta was formed. The pasta was then extruded ;~t 0 1/32" extrudates. After extrusion, the wet extrudate~ were dried at room temperature for 16 hours. The dried extrudates were then calcined at 550C for 2 hours in a laboratory furnace.
The calcined carrier was impregnated by pore volume filling with an impregnation solution conta~ n ing 18.3 g of Co(NO3)2 6H2O, 15 g of ammonium dimolybdate and distilled water up to 82 ml. After impregnation, the catalyst was dried at room temperature for 16 hrs. The dried and impreg-nated catalyst was finally calcined at 500C for 2 hours.
The catalyst thus prepared is designated A.
Example 2 Using a similar procedure to that of Example 1, a catalyst carrier was prepared by mixing 30 g of dried CVB 500 HY
Zeolite with 62 g ofvERsALTM 300 alumina and 126 g of alumina gel. The catalyst carrier was dried, calcined, impregnated and decomposed at the same conditions as described under Example 1. The catalyst thus prepared is designated B.
Example 3 Using the procedure of Example 2, a catalyst was prepared where thec~ 500 ~TM zeolitic component was exchanged for a c~ 600 ~ (available from P.Q. Zeolites) with a unit cell size of 24.34 A and a SiO2/Al2O3 = 5.4. The catalyst thus prepared is designated C.
le 4 As comparison catalyst in the evaluation of the catalysts prepared in Examples 1-3, commercial Al2O3 based catalysts were used. These catalysts are commercially available from Haldor Tops0e A/S under the trade name TK-711T~/TR-751,I,M and TK-771TM-~7~2~
The ability of removing metals from a residual oil was tested in a fixed bed pilot plant. For the test, a residual oil of Middle East origin was used. The properties of the feedstock used in the test are listed in Table 1.
Table 1 Feed~tock PropertieR
SG 0.9513 Sulphur, wt~ 2.964 Nitrogen, ppm 1850 Ni + V, ppm 38 CCR, wt~ 8.15 Asph., wt~ 2.0 C, wt~ 11.60 H, wt~ 84.8 GC Dist.
IBP-190C,wt~ 2.1 IBP-343C,wt~ 7.3 IBP-440C,wt~ 27.6 IBP-565C,wt~ 60.6 The conditions used in the test are listed in Table 2. As apparent from Table 2, the tests were conducted at different temperatures ranging from 385C to 405C. Each temperature level was maintained for one week in order to reach a stable activity level for the catalyst.
- ~7~
Table 2 Process Conditions LHSV 0.26h-H~/oil 500 Pressure 150 atm.
Temp. 385/400/405/385C
The catalysts of Examples 1-3 were tested in a fixed bed with a small protective layer of commercial demetallation catalysts, in order to control the amounts of metals that will deposit on the catalyst of the invention.
The catalyst bed lay-out used in the test is summarized in Table 3.
Table 3 Catalyst Bed Lay-Out Vol.- Loading 1 Loading 2 Loading 3 Loading 4 %
10TK-711 1/32"C
25TK-751 1/32"C
60Catalyst A Catalyst B Catalyst C Comparative Cat. TK-771 ) Vol% of total loading.
~7Q~l9 In the accompanying drawings:
F~g. 1-3 show the catalyst activity of catalyst loadings 1-3 in comparison with the conventional Al2O3 based system.
Fig. 1-3 are Arrhenius plots giving the first order rate cons~ants for demetallation. The first order rate constant is calculated according to equation 1 as follows:
k1 = LHSV ln MMep ( 1 ) where:
k1: is the first order rate constant for demetallation, h~l Feed flow rate(ml/h) LHSV: lS the space veloclty Catalyst vol. (ml) MeF,MeP: feed and product metal content in ppm In Fig. 1-3, the activity obtained on a conven-tional catalyst system is given as solid lines. Each of the catalysts of this invention shows an improved activity for demetallation as apparent from the data in Fig. 1-3. The level of improvement in relation to known catalysts are in the order of 20-40~, which for the test conditions and feeds tested results in a substantially completely demetal-lized hydrocarbon product.
The present invention relates to demetallation of petroleum crude oil, and, more particular, to the removal of metals in the oil by contact with a catalyst having Ni, Mo and/or CoMo supported on a zeolitic carrier.
Petroleum crudes are known to contain metals such as Ni, V, Fe, Co, etc. in ppm levels. To a large extent, these components are associated with the heaviest parts of the resid, i.e. the part of the resid with the highest boiling points. This means that these components are con-centrated in the bottom fractions often designated atm. or vacuum residuum.
The presence of metallic compounds is generally undesirable as they are poisonous to many subsequent up-grading steps usually used to convert or treat the atm. or vacuum residuum in refineries, e.g. fuel oil desulphurisation, resid hydrocracking or resid FCC.
Heavy oil fractions containing metal compounds are predominantly those with an atmospheric boiling point above 350C. The heavy oil fractions will typically contain 50-500 ppm cf mainly Ni and V. Those trace metals are normally removed in a fixed bed catalytic process, where the residual oil comes into contact with a demetallation catalyst at high temperature, typically at 300-450C at a high H2 pressure, e.g. 20-200 bars and at a space veloc-ity in the range of 0.25-4 h-1. When the oil comes into contact with the demetallation catalyst, the metals pres-ented in the feedstock will react and accumulate on the catalyst surface.
In order to be able efficiently to treat residual oils, it is important that metallic compounds be removed from the oil. Conventional demetallation catalysts consist of Ni and Mo or CoMo supported on alumina. It has now been found that metals are removed from petroleum crude oil with a high efficiency in a demetallation process, when employ-ing a demetallat on catalyst supported on a carrier com-prising zeolitic material.
~17~9 -Accordingly, this invention provides a process for the demetallation of petroleum crude oil by contacting the oil together with hydrogen with a catalyst having at least one metal or compound thereof of Group VIII and/or Group VI
of the Periodic Table as active material supported on a carrier, wherein the carrier comprises a zeolite with a SiO2/Al2O3 ratio of at least 5 and a unit cell size of between 24.30 and 24.60. Preferred metals for use in the process are Ni, Mo, CoMo or mixtures thereof.
It is furthermore preferred to composite the car-rier material of the catalyst of 30-70% by weight with the above zeolitic material and 30-70% by weight with alumina.
The catalyst may be prepared by any method being conventional in the art and including impregnation of the calcined carrier with an aqueous solution of salts of the active metal or metals, drying the impregnated carrier and finally calcinating the carrier to obtain the active cata-lyst.
In operating the inventive process, the catalyst is arranged as fixed bed in a demetallation reactor and crude oil feedstock passed together with hydrogen in a ratio of typically 200-2000 Nl/l through the catalyst bed. During demetallation, the bed temperature is maintained at elev-ated temperature and pressure of usually 350-450C and 120-170 atm.
By passage through the catalyst bed, the metal content in the feedstock is reduced to few ppm.
~ya~rle A catalyst support was prepared by mixing 70 g of dried C~3 500 ~TM Zeolite (available from P.Q. Zeolites), having a unit cell size of 24.53 and a SiO2/Al2O3 = 5.4 with a gel obtained by adding 29 g of cATAPALTM (Vista Cor-poration) to 1.8 g of 65% HN03 and 78 g of water. The ~17~
components were thoroughly mixed in a Z-KNEADERT~I with 11 g CATAPALTM un~il a pasta was formed. The pasta was then extruded ;~t 0 1/32" extrudates. After extrusion, the wet extrudate~ were dried at room temperature for 16 hours. The dried extrudates were then calcined at 550C for 2 hours in a laboratory furnace.
The calcined carrier was impregnated by pore volume filling with an impregnation solution conta~ n ing 18.3 g of Co(NO3)2 6H2O, 15 g of ammonium dimolybdate and distilled water up to 82 ml. After impregnation, the catalyst was dried at room temperature for 16 hrs. The dried and impreg-nated catalyst was finally calcined at 500C for 2 hours.
The catalyst thus prepared is designated A.
Example 2 Using a similar procedure to that of Example 1, a catalyst carrier was prepared by mixing 30 g of dried CVB 500 HY
Zeolite with 62 g ofvERsALTM 300 alumina and 126 g of alumina gel. The catalyst carrier was dried, calcined, impregnated and decomposed at the same conditions as described under Example 1. The catalyst thus prepared is designated B.
Example 3 Using the procedure of Example 2, a catalyst was prepared where thec~ 500 ~TM zeolitic component was exchanged for a c~ 600 ~ (available from P.Q. Zeolites) with a unit cell size of 24.34 A and a SiO2/Al2O3 = 5.4. The catalyst thus prepared is designated C.
le 4 As comparison catalyst in the evaluation of the catalysts prepared in Examples 1-3, commercial Al2O3 based catalysts were used. These catalysts are commercially available from Haldor Tops0e A/S under the trade name TK-711T~/TR-751,I,M and TK-771TM-~7~2~
The ability of removing metals from a residual oil was tested in a fixed bed pilot plant. For the test, a residual oil of Middle East origin was used. The properties of the feedstock used in the test are listed in Table 1.
Table 1 Feed~tock PropertieR
SG 0.9513 Sulphur, wt~ 2.964 Nitrogen, ppm 1850 Ni + V, ppm 38 CCR, wt~ 8.15 Asph., wt~ 2.0 C, wt~ 11.60 H, wt~ 84.8 GC Dist.
IBP-190C,wt~ 2.1 IBP-343C,wt~ 7.3 IBP-440C,wt~ 27.6 IBP-565C,wt~ 60.6 The conditions used in the test are listed in Table 2. As apparent from Table 2, the tests were conducted at different temperatures ranging from 385C to 405C. Each temperature level was maintained for one week in order to reach a stable activity level for the catalyst.
- ~7~
Table 2 Process Conditions LHSV 0.26h-H~/oil 500 Pressure 150 atm.
Temp. 385/400/405/385C
The catalysts of Examples 1-3 were tested in a fixed bed with a small protective layer of commercial demetallation catalysts, in order to control the amounts of metals that will deposit on the catalyst of the invention.
The catalyst bed lay-out used in the test is summarized in Table 3.
Table 3 Catalyst Bed Lay-Out Vol.- Loading 1 Loading 2 Loading 3 Loading 4 %
10TK-711 1/32"C
25TK-751 1/32"C
60Catalyst A Catalyst B Catalyst C Comparative Cat. TK-771 ) Vol% of total loading.
~7Q~l9 In the accompanying drawings:
F~g. 1-3 show the catalyst activity of catalyst loadings 1-3 in comparison with the conventional Al2O3 based system.
Fig. 1-3 are Arrhenius plots giving the first order rate cons~ants for demetallation. The first order rate constant is calculated according to equation 1 as follows:
k1 = LHSV ln MMep ( 1 ) where:
k1: is the first order rate constant for demetallation, h~l Feed flow rate(ml/h) LHSV: lS the space veloclty Catalyst vol. (ml) MeF,MeP: feed and product metal content in ppm In Fig. 1-3, the activity obtained on a conven-tional catalyst system is given as solid lines. Each of the catalysts of this invention shows an improved activity for demetallation as apparent from the data in Fig. 1-3. The level of improvement in relation to known catalysts are in the order of 20-40~, which for the test conditions and feeds tested results in a substantially completely demetal-lized hydrocarbon product.
Claims (3)
1. Process for the demetallation of petroleum crude oil by contacting the oil together with hydrogen with a catalyst having at least one metal or compound thereof of at least one of Group VIII and Group VI the Periodic Table as active material supported on a carrier, wherein the carrier com-prises a zeolite with a SiO2/Al2O3 ratio of at least 5 and a unit cell size of between 24.30 and 24.60.
2. The process of claim 1, wherein the carrier con-sists of 30-70% by weight of the zeolite and 30-70% by weight of alumina.
3. The process of claim 1, wherein the Group VIII
metal comprises Ni and the Group VI metal comprises at least one of Mo and Co.
metal comprises Ni and the Group VI metal comprises at least one of Mo and Co.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK0200/95 | 1995-02-24 | ||
| DK020095A DK20095A (en) | 1995-02-24 | 1995-02-24 | Process for demethylation of residual oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2170219A1 true CA2170219A1 (en) | 1996-08-25 |
Family
ID=8090881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002170219A Abandoned CA2170219A1 (en) | 1995-02-24 | 1996-02-23 | Process for the demetallation of residual oils |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0728832A1 (en) |
| JP (1) | JPH08245967A (en) |
| AU (1) | AU4567896A (en) |
| BR (1) | BR9600797A (en) |
| CA (1) | CA2170219A1 (en) |
| DK (1) | DK20095A (en) |
| NO (1) | NO960739L (en) |
| NZ (1) | NZ286000A (en) |
| TW (1) | TW394789B (en) |
| ZA (1) | ZA961475B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6520286B1 (en) | 1996-09-30 | 2003-02-18 | Silentor Holding A/S | Silencer and a method of operating a vehicle |
| CA2267628C (en) | 1996-09-30 | 2007-05-15 | Silentor Notox A/S | Gas flow silencer |
| CN103801378B (en) * | 2012-11-13 | 2016-01-20 | 中国石油化工股份有限公司 | Containing the hydrogenation catalyst of molecular sieve and aluminium oxide |
| CN103801380B (en) * | 2012-11-13 | 2015-12-16 | 中国石油化工股份有限公司 | Containing the preparation method of the hydrogenating catalyst composition of molecular sieve |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109064A3 (en) * | 1982-11-16 | 1985-06-19 | W.R. Grace & Co. | Hydrocarbon conversion catalysts |
| JPS59206048A (en) * | 1983-05-10 | 1984-11-21 | Shokubai Kasei Kogyo Kk | Hydrogenation catalyst for heavy oil |
| JPH0536099B1 (en) * | 1985-03-29 | 1993-05-28 | ||
| US5183561A (en) * | 1990-01-25 | 1993-02-02 | Mobil Oil Corp. | Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material |
| JP2547115B2 (en) * | 1990-03-30 | 1996-10-23 | 財団法人石油産業活性化センター | Hydrotreating catalyst composition for hydrocarbon oil and hydrotreating method using the same |
-
1995
- 1995-02-24 DK DK020095A patent/DK20095A/en not_active Application Discontinuation
-
1996
- 1996-02-12 EP EP96101974A patent/EP0728832A1/en not_active Withdrawn
- 1996-02-13 TW TW085101764A patent/TW394789B/en not_active IP Right Cessation
- 1996-02-16 NZ NZ286000A patent/NZ286000A/en unknown
- 1996-02-22 AU AU45678/96A patent/AU4567896A/en not_active Abandoned
- 1996-02-23 BR BR9600797A patent/BR9600797A/en active Search and Examination
- 1996-02-23 JP JP8036414A patent/JPH08245967A/en not_active Withdrawn
- 1996-02-23 ZA ZA961475A patent/ZA961475B/en unknown
- 1996-02-23 CA CA002170219A patent/CA2170219A1/en not_active Abandoned
- 1996-02-23 NO NO960739A patent/NO960739L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0728832A1 (en) | 1996-08-28 |
| BR9600797A (en) | 1997-12-23 |
| NZ286000A (en) | 1997-02-24 |
| ZA961475B (en) | 1996-11-27 |
| DK20095A (en) | 1996-10-04 |
| NO960739L (en) | 1996-08-26 |
| NO960739D0 (en) | 1996-02-23 |
| AU4567896A (en) | 1996-09-05 |
| JPH08245967A (en) | 1996-09-24 |
| TW394789B (en) | 2000-06-21 |
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