EP0553920A1 - Procédé d'hydrotraitement - Google Patents
Procédé d'hydrotraitement Download PDFInfo
- Publication number
- EP0553920A1 EP0553920A1 EP93200165A EP93200165A EP0553920A1 EP 0553920 A1 EP0553920 A1 EP 0553920A1 EP 93200165 A EP93200165 A EP 93200165A EP 93200165 A EP93200165 A EP 93200165A EP 0553920 A1 EP0553920 A1 EP 0553920A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbon oil
- process according
- catalyst bed
- liquid
- containing gas
- 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.)
- Granted
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/002—Apparatus for fixed bed hydrotreatment processes
Definitions
- the present invention relates to a process for hydrotreating in a single reactor vessel comprising at least an upper and a lower catalyst bed a hydrocarbon oil which is substantially liquid at process conditions and to a reactor vessel suitable for carrying out such process.
- the present invention relates to a process for hydrotreating in a single reactor vessel comprising at least an upper and a lower catalyst bed, a hydrocarbon oil which is substantially liquid at process conditions, which process comprises:
- the final hydrotreating step is carried out in the presence of hydrogen which may contain a relatively small amount of hydrogen sulphide, which leads to good hydrotreating results.
- the present hydrotreating process differs from conventional hydrotreating processes, such as described in US patent specification 4,243,519, in the sequence of the process steps.
- the final hydrotreating step is carried out in the upper catalyst bed.
- the final hydrotreating step is carried out in a lower catalyst bed, which is situated further downstream the hydrogen gas flow.
- the present invention relates furthermore to a reactor vessel suitable for hydrotreating a hydrocarbon oil according to the invention, in which vessel:
- the process according to the present invention suitably comprises a hydrodesulphurization process in step (iii) followed by a further hydrodesulphurization process in step (i).
- a hydrodesulphurization process in step (iii) followed by a further hydrodesulphurization process in step (i).
- Other contaminants, such as nitrogen containing compounds can also to a certain extent be removed in a hydrodesulphurization process.
- the process suitably involves a hydrodesulphurization process in step (iii) followed by a hydrogenation process in step (i). In that way both the sulphur and the aromatics content of the fresh hydrocarbon oil can be diminished in a commercially attractive way.
- the hydrocarbon oil subjected to the present process is substantially liquid at process conditions.
- the liquid phase of the hydrocarbon oil makes that the separation of the hydrotreated hydrocarbon oil from the hydrogen containing gas in step (ii) can be attained in a simple way.
- this separation is carried out with the help of one or more separating trays consisting of a conventional liquid draw-off tray as used in distillation units.
- step (iv) can be carried out outside or inside the reactor vessel.
- the hydrocarbon oil will usually be cooled down and needs heating up before it can be used in step (i). Therefore, separation inside the reactor, preferably with the help of a separating tray as described above, is preferred.
- the pressure drop over the reactor vessel will generally be between 0.2 and 10 bar, more specifically between 0.5 and 5 bar. It is possible to add hydrogen to the lower catalyst bed. However, in general the hydrogen partial pressure will be higher in the upper catalyst bed than in the lower catalyst bed. The pressure drop will generally make that the hydrogen partial pressure in the upper catalyst bed is between 0.1 and 9 bar, more specifically between 0.4 and 4.5 bar higher than in the lower catalyst bed.
- clean hydrogen containing gas is meant a gas containing less than 3% by volume of hydrogen sulphide, preferably less than 1% by volume, more preferably less than 0.5 % by volume, most preferably less than 0.1 % by volume.
- contaminated hydrogen containing gas obtained in step (iv) is cleaned, e.g. by treating it with an amine, and subsequently used in step (i) as clean hydrogen containing gas.
- a hydrocarbon oil which is substantially liquid at process conditions is understood to comprise a hydrocarbon oil of which a major amount, for example more than 70 % by weight suitably more than 80 % by weight, and preferably more than 95 % by weight, is in the liquid phase.
- Hydrocarbon oils which can be suitably treated in the process according to the present invention comprise any hydrocarbon which is substantially liquid at process conditions, for example kerosene fractions.
- a hydrocarbon oil which could be suitably treated in the process would be a gas oil, as the environmental constraints on this oil fraction have become quite strict.
- a suitable gas oil would be a gas oil substantially, e.g. more than 75% by weight, boiling in the range between 150 and 400 °C.
- steps (i) and (iii) are suitably carried out at a temperature of between 150 and 450 °C, suitably between 300 and 400 °C, preferably between 325 and 390 °C, more preferably between 340 and 385 °C, and step (i) is suitably carried out at a pressure of between 20 and 85 bar, preferably between 30 and 65 bar, and step (iii) is suitably carried out at a pressure of between 15 and 80 bar, preferably between 25 and 60 bar.
- a lubricating oil can be hydrotreated, such as a lubricating oil substantially, e.g. more than 95% by weight, boiling in the range between 320 and 600 °C.
- steps (i) and (iii) are suitably carried out at a temperature of between 300 and 400 °C, preferably between 325 and 390 °C, more preferably between 340 and 385 °C, and a pressure of less than 250 bar, preferably less than 200 bar, more preferably less than 175 bar.
- the hydrotreating catalyst employed in the process according to the present invention suitably comprises one or more metals from Group 1b, 2a, 4b, 5b, 6b, 7b and 8 of the Periodic Table of the Elements in the Handbook of Chemistry and Physics, 63rd edition, on a solid carrier.
- the carrier can optionally comprise a zeolite.
- the hydrotreating process according to the present invention preferably involves in step (i) a hydrogenation process and in step (iii) a hydrodesulphurization process, or in both steps a hydrodesulphurization process.
- step (i) a hydrogenation catalyst is applied at hydrogenation conditions which include a temperature of between 150 and 350 °C, and in step (iii) a hydrodesulphurization catalyst is applied at hydrodesulphurization conditions.
- the hydrodesulphurization of step (iii) must in general be carried out such that a sulphur content is attained which is such that the specification on the sulphur tolerance of the hydrogenation catalyst of step (i) is met, as otherwise this hydrogenation catalyst could be poisoned.
- the hydrocarbon oil obtained in step (iv) contains not more than 15% by volume of sulphur containing compounds, based on volume of sulphur containing compounds present in the fresh hydrocarbon oil, preferably not more than 10%.
- step (i) in both step (i) and (iii) a hydrodesulphurization catalyst is applied at hydrodesulphurization conditions.
- the partly hydrotreated hydrocarbon oil obtained in step (iv) suitably contains between 1 and 30% by volume of sulphur containing compounds, based on volume of sulphur containing compounds present in the fresh hydrocarbon oil.
- the present invention can suitably be carried out in a reactor vessel as shown in Figure 1.
- the upper catalyst bed can contain either a hydrodesulphurization or a hydrogenation catalyst; the lower catalyst bed contains a hydrodesulphurization catalyst.
- Clean hydrogen containing gas is fed to the reactor via line 2, while partly hydrotreated hydrocarbon oil is introduced in the upper part of the reactor via line 1.
- the inlet for gas and the inlet for liquid can be combined. However, it is preferred to have separate inlets.
- the hydrotreated effluent from the upper catalyst bed is separated from gas with the help of a draw-off tray.
- the separated hydrotreated hydrocarbon effluent is removed from the reactor via line 3, while used hydrogen containing gas passes the separating tray and reaches the lower catalyst bed. Via line 4 fresh hydrocarbon oil is introduced between the separating tray and the lower catalyst bed.
- the partly hydrotreated effluent obtained after passing the fresh hydrocarbon oil over the lower catalyst bed, is removed from the reactor via line 5 and separated into partly hydrotreated hydrocarbon oil which is sent to line 1, and contaminated hydrogen containing gas.
- the contaminated hydrogen containing gas is suitably cleaned by treating it with an amine, so-called scrubbing.
- the cleaned gas obtained can then, optionally together with make-up hydrogen, be recycled to line 2 and be used again.
- the process was carried out in a set-up as described in Figure 1.
- the catalyst present both in the upper and the lower catalyst bed was a hydrodesulphurization catalyst, comprising 3.1% by weight of cobalt and 12.4% by weight of molybdenum, based on total amount of catalyst, on alumina.
- the catalyst particles were in the shape of 1.2 mm trilobes.
- a gas oil feedstock of which according to the ASTM distillation curve more than 78% by volume is in the gaseous phase at 383 °C, more than 50% by volume is in the gaseous phase at 345 °C and more than 20% is in the gaseous phase at 300 °C was led to the reactor via line 4.
- the overall process conditions comprise a temperature of 360 °C and a weight hourly space velocity of 2.0 kg/l.h and a hydrogen to oil ratio of 200 Nl/kg.
- the hydrogen partial pressure at the outlet of the upper catalyst bed was 24.4 bar, while the hydrogen partial pressure at the outlet of the lower catalyst bed was 23.1 bar. At these process conditions about 7 % by weight of the gas oil feedstock was in the gaseous phase.
- the sulphur content of the feed, the partly hydrotreated feed and the hydrotreated feed are shown in Table 1, in amount of elemental sulphur on total amount of feed.
- fresh feedstock as described hereinabove was processed in a set-up similar to the one of Figure 1, at process conditions substantially as described hereinabove. No intermittent hydrogen separation took place between the catalyst beds; no hydrocarbon oil was added or removed between the catalyst beds. The hydrogen partial pressure at the reactor outlet was 23.1 bar. The hydrotreated hydrocarbon oil obtained had a sulphur content of 0.11%wt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92200212 | 1992-01-24 | ||
EP92200212 | 1992-01-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0553920A1 true EP0553920A1 (fr) | 1993-08-04 |
EP0553920B1 EP0553920B1 (fr) | 1996-09-18 |
Family
ID=8210385
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93200165A Revoked EP0553920B1 (fr) | 1992-01-24 | 1993-01-21 | Procédé d'hydrotraitement |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0553920B1 (fr) |
JP (1) | JP3157323B2 (fr) |
CA (1) | CA2087904C (fr) |
DE (1) | DE69304725T2 (fr) |
DK (1) | DK0553920T3 (fr) |
ES (1) | ES2092742T3 (fr) |
NO (1) | NO306262B1 (fr) |
SG (1) | SG73396A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5705052A (en) * | 1996-12-31 | 1998-01-06 | Exxon Research And Engineering Company | Multi-stage hydroprocessing in a single reaction vessel |
US5720872A (en) * | 1996-12-31 | 1998-02-24 | Exxon Research And Engineering Company | Multi-stage hydroprocessing with multi-stage stripping in a single stripper vessel |
US5968347A (en) * | 1994-11-25 | 1999-10-19 | Kvaerner Process Technology Limited | Multi-step hydrodesulfurization process |
EP1151060A1 (fr) * | 1998-12-08 | 2001-11-07 | ExxonMobil Research and Engineering Company | Production de distillats a faible teneur en soufre et en aromatiques |
US6444865B1 (en) | 1997-12-01 | 2002-09-03 | Shell Oil Company | Process wherein a hydrocarbon feedstock is contacted with a catalyst |
US6623622B2 (en) | 2000-10-10 | 2003-09-23 | Exxonmobil Research And Engineering Company | Two stage diesel fuel hydrotreating and stripping in a single reaction vessel |
EP1352946A1 (fr) * | 2000-11-17 | 2003-10-15 | Jgc Corporation | Proc d de d sulfuration de fraction gazole, gazole d sulfur , et d sulfurant pour fraction gazole |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008157193A2 (fr) | 2007-06-12 | 2008-12-24 | Rhodia Inc. | Esters de mono-, di- et polyol phosphate utilisés dans des formulations d'hygiène personnelle |
AU2008261634B2 (en) | 2007-06-12 | 2014-04-24 | Rhodia Inc. | Detergent composition with hydrophilizing soil-release agent and methods for using same |
CN101677933B (zh) | 2007-06-12 | 2013-07-17 | 罗迪亚公司 | 口腔护理制剂中的烷氧基化的磷酸一元醇酯、二元醇酯和多元醇酯及其使用方法 |
CN101679915B (zh) | 2007-06-12 | 2013-01-23 | 罗迪亚公司 | 具有亲水剂的硬质表面清洁组合物以及清洁硬质表面的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2971900A (en) * | 1958-10-17 | 1961-02-14 | Socony Mobil Oil Co Inc | Hydrocracking of hydrocarbons |
BE755266A (fr) * | 1969-08-25 | 1971-02-01 | Evans & Son Ltd J | Appareil pour le travail de manches ou corps de |
US4243519A (en) * | 1979-02-14 | 1981-01-06 | Exxon Research & Engineering Co. | Hydrorefining process |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE755268A (fr) * | 1970-08-01 | 1971-02-25 | Texaco Development Corp | Production de carburants pour moteurs et moteurs a reaction, |
-
1993
- 1993-01-21 DK DK93200165T patent/DK0553920T3/da active
- 1993-01-21 ES ES93200165T patent/ES2092742T3/es not_active Expired - Lifetime
- 1993-01-21 DE DE1993604725 patent/DE69304725T2/de not_active Revoked
- 1993-01-21 EP EP93200165A patent/EP0553920B1/fr not_active Revoked
- 1993-01-21 SG SG1996005939A patent/SG73396A1/en unknown
- 1993-01-22 NO NO930233A patent/NO306262B1/no unknown
- 1993-01-22 JP JP02595293A patent/JP3157323B2/ja not_active Expired - Fee Related
- 1993-01-22 CA CA 2087904 patent/CA2087904C/fr not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2971900A (en) * | 1958-10-17 | 1961-02-14 | Socony Mobil Oil Co Inc | Hydrocracking of hydrocarbons |
BE755266A (fr) * | 1969-08-25 | 1971-02-01 | Evans & Son Ltd J | Appareil pour le travail de manches ou corps de |
US4243519A (en) * | 1979-02-14 | 1981-01-06 | Exxon Research & Engineering Co. | Hydrorefining process |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5968347A (en) * | 1994-11-25 | 1999-10-19 | Kvaerner Process Technology Limited | Multi-step hydrodesulfurization process |
US5720872A (en) * | 1996-12-31 | 1998-02-24 | Exxon Research And Engineering Company | Multi-stage hydroprocessing with multi-stage stripping in a single stripper vessel |
EP0958245A1 (fr) * | 1996-12-31 | 1999-11-24 | Exxon Research And Engineering Company | Hydrotraitement en etages multiples dans un reacteur unique |
US5705052A (en) * | 1996-12-31 | 1998-01-06 | Exxon Research And Engineering Company | Multi-stage hydroprocessing in a single reaction vessel |
EP0958245B2 (fr) † | 1996-12-31 | 2012-05-02 | ExxonMobil Research and Engineering Company | Hydrotraitement en etages multiples dans un reacteur unique |
EP0958245B1 (fr) * | 1996-12-31 | 2004-06-09 | ExxonMobil Research and Engineering Company | Hydrotraitement en etages multiples dans un reacteur unique |
US6444865B1 (en) | 1997-12-01 | 2002-09-03 | Shell Oil Company | Process wherein a hydrocarbon feedstock is contacted with a catalyst |
EP1151060A4 (fr) * | 1998-12-08 | 2010-08-18 | Exxonmobil Res & Eng Co | Production de distillats a faible teneur en soufre et en aromatiques |
EP1151060A1 (fr) * | 1998-12-08 | 2001-11-07 | ExxonMobil Research and Engineering Company | Production de distillats a faible teneur en soufre et en aromatiques |
US6623622B2 (en) | 2000-10-10 | 2003-09-23 | Exxonmobil Research And Engineering Company | Two stage diesel fuel hydrotreating and stripping in a single reaction vessel |
US7276150B2 (en) | 2000-11-17 | 2007-10-02 | Jgc Corporation | Method of desulfurizing gas oil fraction, desulfurized gas oil, and desulfurizer for gas oil fraction |
EP1352946A4 (fr) * | 2000-11-17 | 2004-12-01 | Jgc Corp | Proc d de d sulfuration de fraction gazole, gazole d sulfur , et d sulfurant pour fraction gazole |
EP2280056A3 (fr) * | 2000-11-17 | 2011-02-09 | JGC Corporation | Appareillage pour la désulfurisation des coupes gazole |
EP1352946A1 (fr) * | 2000-11-17 | 2003-10-15 | Jgc Corporation | Proc d de d sulfuration de fraction gazole, gazole d sulfur , et d sulfurant pour fraction gazole |
Also Published As
Publication number | Publication date |
---|---|
DE69304725D1 (de) | 1996-10-24 |
JPH05271668A (ja) | 1993-10-19 |
ES2092742T3 (es) | 1996-12-01 |
CA2087904C (fr) | 2004-04-27 |
CA2087904A1 (fr) | 1993-07-25 |
DK0553920T3 (da) | 1996-10-14 |
SG73396A1 (en) | 2000-06-20 |
JP3157323B2 (ja) | 2001-04-16 |
EP0553920B1 (fr) | 1996-09-18 |
NO930233D0 (no) | 1993-01-22 |
NO306262B1 (no) | 1999-10-11 |
NO930233L (no) | 1993-07-26 |
DE69304725T2 (de) | 1997-03-06 |
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