EP0728832A1 - Demetallisierungsverfahren von Rückstandölen - Google Patents
Demetallisierungsverfahren von Rückstandölen Download PDFInfo
- Publication number
- EP0728832A1 EP0728832A1 EP96101974A EP96101974A EP0728832A1 EP 0728832 A1 EP0728832 A1 EP 0728832A1 EP 96101974 A EP96101974 A EP 96101974A EP 96101974 A EP96101974 A EP 96101974A EP 0728832 A1 EP0728832 A1 EP 0728832A1
- Authority
- EP
- European Patent Office
- 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.)
- Withdrawn
Links
- 238000007324 demetalation reaction Methods 0.000 title claims abstract description 16
- 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 43
- 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
- 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
- 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
- 229910052750 molybdenum Inorganic materials 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
Images
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
Definitions
- 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 concentrated in the bottom fractions often designated atm. or vacuum residuum.
- Heavy oil fractions containing metal compounds are predominantly those with an atmospheric boiling point above 350°C.
- the heavy oil fractions will typically contain 50-500 ppm of 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 300-450°C at a high H 2 pressure, such as 20-200 bars and at a space velocity in the range of 0.25-4 h -1 .
- the metals presented in the feedstock will react and accumulate on the catalyst surface.
- 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 employing a demetallation catalyst supported on a carrier comprising zeolitic material.
- 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 SiO 2 /Al 2 O 3 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.
- 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 catalyst.
- 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.
- the bed temperature is maintained at elevated temperature and pressure of usually 350-450 o C and 120-170 atm.
- the metal content in the feedstock is reduced to few ppm.
- the calcined carrier was impregnated by pore volume filling with an impregnation solution containing 18.3 g of Co(NO 3 ) 2 ⁇ 6H 2 O, 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 impregnated catalyst was finally calcined at 500°C for 2 hours.
- the catalyst thus prepared is designated A.
- a catalyst carrier was prepared by mixing 30 g of dried HY Zeolite CBV 500 with 62 g of Versal 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.
- 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.-% 1) Loading 1 Loading 2 Loading 3 Loading 4 10 TK-711 1/32"C 25 TK-751 1/32"C 60
- Fig. 1-3 show the catalyst activity of catalyst loadings 1-3 in comparison with the conventional Al 2 O 3 based system.
- Fig. 1-3 are Arrhenius plots giving the first order rate constants for demetallation.
- Fig. 1-3 the activity obtained on a conventional 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 demetallized hydrocarbon product.
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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK200/95 | 1995-02-24 | ||
DK020095A DK20095A (da) | 1995-02-24 | 1995-02-24 | Fremgangsmåde til afmetallisering af residualolie |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0728832A1 true EP0728832A1 (de) | 1996-08-28 |
Family
ID=8090881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96101974A Withdrawn EP0728832A1 (de) | 1995-02-24 | 1996-02-12 | Demetallisierungsverfahren von Rückstandölen |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0728832A1 (de) |
JP (1) | JPH08245967A (de) |
AU (1) | AU4567896A (de) |
BR (1) | BR9600797A (de) |
CA (1) | CA2170219A1 (de) |
DK (1) | DK20095A (de) |
NO (1) | NO960739L (de) |
NZ (1) | NZ286000A (de) |
TW (1) | TW394789B (de) |
ZA (1) | ZA961475B (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6332510B1 (en) | 1996-09-30 | 2001-12-25 | Silentor Holding A/S | Gas flow silencer |
US6520286B1 (en) | 1996-09-30 | 2003-02-18 | Silentor Holding A/S | Silencer and a method of operating a vehicle |
CN103801380A (zh) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | 含分子筛的加氢催化剂组合物的制备方法 |
CN103801378A (zh) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | 含分子筛和氧化铝的加氢催化剂 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0109064A2 (de) * | 1982-11-16 | 1984-05-23 | W.R. Grace & Co. | Kohlenwasserstoffumwandlungskatalysator |
US4554263A (en) * | 1983-05-10 | 1985-11-19 | Catalysts & Chemicals Industries Co., Ltd. | Catalysts for hydrotreating heavy oils |
EP0216938A1 (de) * | 1985-03-29 | 1987-04-08 | Catalysts & Chemicals Industries Co., Ltd. | Katalysator für wasserbehandlung |
EP0449144A2 (de) * | 1990-03-30 | 1991-10-02 | Cosmo Oil Company, Ltd | Katalytische Zusammensetzung für die Hydrobehandlung von Kohlenwasserstoffen und Hydrobehandlungsverfahren unter Anwendung dieser Zusammensetzung |
WO1993002158A1 (en) * | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material |
-
1995
- 1995-02-24 DK DK020095A patent/DK20095A/da not_active Application Discontinuation
-
1996
- 1996-02-12 EP EP96101974A patent/EP0728832A1/de not_active Withdrawn
- 1996-02-13 TW TW085101764A patent/TW394789B/zh 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/pt active Search and Examination
- 1996-02-23 JP JP8036414A patent/JPH08245967A/ja not_active Withdrawn
- 1996-02-23 ZA ZA961475A patent/ZA961475B/xx unknown
- 1996-02-23 CA CA002170219A patent/CA2170219A1/en not_active Abandoned
- 1996-02-23 NO NO960739A patent/NO960739L/no not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0109064A2 (de) * | 1982-11-16 | 1984-05-23 | W.R. Grace & Co. | Kohlenwasserstoffumwandlungskatalysator |
US4554263A (en) * | 1983-05-10 | 1985-11-19 | Catalysts & Chemicals Industries Co., Ltd. | Catalysts for hydrotreating heavy oils |
EP0216938A1 (de) * | 1985-03-29 | 1987-04-08 | Catalysts & Chemicals Industries Co., Ltd. | Katalysator für wasserbehandlung |
EP0449144A2 (de) * | 1990-03-30 | 1991-10-02 | Cosmo Oil Company, Ltd | Katalytische Zusammensetzung für die Hydrobehandlung von Kohlenwasserstoffen und Hydrobehandlungsverfahren unter Anwendung dieser Zusammensetzung |
WO1993002158A1 (en) * | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6332510B1 (en) | 1996-09-30 | 2001-12-25 | Silentor Holding A/S | Gas flow silencer |
US6520286B1 (en) | 1996-09-30 | 2003-02-18 | Silentor Holding A/S | Silencer and a method of operating a vehicle |
CN103801380A (zh) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | 含分子筛的加氢催化剂组合物的制备方法 |
CN103801378A (zh) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | 含分子筛和氧化铝的加氢催化剂 |
CN103801380B (zh) * | 2012-11-13 | 2015-12-16 | 中国石油化工股份有限公司 | 含分子筛的加氢催化剂组合物的制备方法 |
CN103801378B (zh) * | 2012-11-13 | 2016-01-20 | 中国石油化工股份有限公司 | 含分子筛和氧化铝的加氢催化剂 |
Also Published As
Publication number | Publication date |
---|---|
BR9600797A (pt) | 1997-12-23 |
NZ286000A (en) | 1997-02-24 |
ZA961475B (en) | 1996-11-27 |
DK20095A (da) | 1996-10-04 |
NO960739L (no) | 1996-08-26 |
NO960739D0 (no) | 1996-02-23 |
AU4567896A (en) | 1996-09-05 |
JPH08245967A (ja) | 1996-09-24 |
CA2170219A1 (en) | 1996-08-25 |
TW394789B (en) | 2000-06-21 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IE IT LI LU MC NL SE |
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17P | Request for examination filed |
Effective date: 19970228 |
|
17Q | First examination report despatched |
Effective date: 19990331 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19990811 |