EP1274811A2 - Procede de denitrogenation de fractions brutes - Google Patents
Procede de denitrogenation de fractions brutesInfo
- Publication number
- EP1274811A2 EP1274811A2 EP01920849A EP01920849A EP1274811A2 EP 1274811 A2 EP1274811 A2 EP 1274811A2 EP 01920849 A EP01920849 A EP 01920849A EP 01920849 A EP01920849 A EP 01920849A EP 1274811 A2 EP1274811 A2 EP 1274811A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- transfer agent
- phase transfer
- nitrogen
- phase
- distillate stream
- 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- Withdrawn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
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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
- C10G19/04—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions containing solubilisers, e.g. solutisers
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/06—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of alkaline solutions
Definitions
- the present invention relates to a method for denitrogenating certain refinery streams.
- Refinery streams that contain nitrogen compounds are typically problematic in refineries because the nitrogen components contained therein can have a negative impact on certain refinery operations.
- the catalysts used to accomplish these goals are adversely affected by the presence of nitrogen compounds in the feed.
- the present invention provides for a method for decreasing the nitrogen content of refinery streams by contacting a petroleum distillate stream in the presence of an effective amount of water, a base selected from Group IA and IIA hydroxides and ammonium hydroxide and a phase transfer agent at an effective temperature (i.e., at which the water is liquid to 180°C) for a time sufficient to produce a treated petroleum feed having a decreased nitrogen content.
- a base selected from Group IA and IIA hydroxides and ammonium hydroxide and a phase transfer agent at an effective temperature (i.e., at which the water is liquid to 180°C) for a time sufficient to produce a treated petroleum feed having a decreased nitrogen content.
- the process can be carried out in the presence of an oxygen containing gas, although this is not required.
- the present invention may suitably comprise, consist or consist essentially of the described elements and may be practiced in the absence of an element not disclosed.
- the present invention provides for a method for decreasing the nitrogen content of organic-nitrogen-containing hydrocarbonaceous feedstreams by contacting the stream (also referred to herein as a fraction, feedstream or feed) containing the nitrogen to be removed with an effective amount of aqueous base selected from Group IA and IIA hydroxides and ammonium hydroxide, and at least one phase transfer agent at an effective temperature at which the aqueous phase remains liquid, typically up to 180°C to produce a treated petroleum stream having a decreased nitrogen content.
- the contacting is carried out at a pressure that corresponds to the reaction temperature and is typically from zero to less than 10,000 kPa. Lower pressures are preferred because this can minimize the need for high-pressure treatment process units.
- the nitrogen containing species that are most desirably removed by the process of the present invention are organo-nitrogen, non-basic heterocyclic, nitrogen containing species, e.g., carbazoles, indoles and pyrroles.
- Bases preferred are strong bases, e.g., NaOH, KOH, ammonium hydroxide, sodium and potassium carbonates. These may be used as an aqueous solution of sufficient strength, typically at least 20 wt% of the aqueous phase or as a solid in the presence of an effective amount of water to produce an aqueous solution of the foregoing strength.
- strong bases e.g., NaOH, KOH, ammonium hydroxide, sodium and potassium carbonates.
- the phase transfer agent is present in a sufficient concentration to result in a treated feed having decreased nitrogen content.
- the phase transfer agent may be miscible or immiscible with the stream to be treated. Typically, this is influenced by the length of the hydrocarbyl chain in the molecule; and these may be selected by one skilled in the art. While this may vary with the agent selected typically concentrations of 0.05 to 10 wt%, preferably 0.1 to 5 wt% are used. Examples include quaternary ammonium salts, quaternary phosphonium salts, crown ethers, and open-chain polyethers such as polyethylene glycols, and others known to those skilled in the art either supported or unsupported.
- Process temperatures at which the aqueous phase remains liquid are used typically up to 180°C are suitable; however, temperatures of less than 150°C, less than 120°C can be used depending on the nature of the feed and phase transfer agent used.
- streams that may be treated according to the process of the present invention are nitrogen containing carbonaceous and hydrocarbona- ceous processed/distilled streams such as diesel, gasoline, vacuum gas oils (VGO) and light catalytic (cat) cycle oils (LCCO). These are typically 232- 566°C (450°F to 1050°F) fractions.
- the feed to be treated can have a range of nitrogen content. The average will vary by the feed but is typically about 50 ppm to 5000 ppm.
- the feed to be treated preferably should be in a liquid or fluid state at process conditions. This may be accomplished by heating the material or by use of a suitable non-interfering solvent as needed. These may be selected by those skilled in the art.
- oil droplets should be of sufficient mean droplet size to enable the nitrogen containing components to achieve intimate contact with the aqueous phase.
- Oil droplet particles having a mean droplet size of about 1 to 100 microns (diameter) should be typical, and 1 to 20 are preferably; larger droplet sizes of greater than 100 microns are not preferable.
- Contact can be achieved, e.g., by vigorous mixing for the components of the mixture.
- the process should be carried out for a time and at conditions within the ranges disclosed sufficient to achieve a decrease, preferably a maximum decrease, in nitrogen content of the nitrogen containing petroleum stream.
- Reaction temperatures will vary with the particular stream to be treated due to its viscosity. An increase in temperature may be used to facilitate removal of species. Within the process conditions disclosed a liquid or fluid phase or medium should be maintained.
- Treatment typically removes the nitrogen containing species from the petroleum fraction into an aqueous base phase or a third phase containing the phase transfer agent. Following treatment, the treated stream has a decreased content of nitrogen.
- a nitrogen recovery or extraction step may be added, as needed to recover the nitrogen containing species removed from the treated distillate stream from the aqueous phase.
- the nature of any such step(s) depends on the nature of the bed/reactor, solubility or insolubility of the removed nitrogen containing species in the aqueous phase.
- the phase into which extraction occurs can be the second phase, i.e., the phase containing transfer agent and aqueous base or a third phase containing primarily aqueous base, with the second (intermediate) phase containing primarily phase transfer agent.
- the first phase is the treated (denitrogenated) distillate stream.
- the nature and amount of the phase transfer agent and may be chosen by one skilled in the art.
- the nitrogen decreased (i.e., upgraded) product may be used in refining operations using catalysts that are adversely affected by higher levels of nitrogen.
- a benefit to the present invention is that the process may be operated under mild temperatures and pressures resulting in a minimization of undesirable side reactions and an enhancement of yield also may be achieved as needed.
- One hundred grams of a Baton Rouge Refinery virgin LCCO was combined with 400 ml of 50 wt% sodium hydroxide and 25 grams of 40 wt% tetrabutylammonium hydroxide. This mixture was subjected to homogenization/ dispersion (10,000 rpm) in a one liter glass flask using a Beckman Model 300 homogenizer, fitted with a standard generator with saw teeth. The solution warmed from 25°C to 65°C due to frictional heating of the rotor/stator. Homogenization was stopped after fifteen minutes. The LCCO and the aqueous caustic phase were separated by use of a separatory funnel.
- a low sulfur (hydrotreated) diesel oil was treated with three different aqueous solutions in separate experiments.
- the aqueous solutions differed in their sodium hydroxide concentrations, of 25, 33 and 50 wt%. These were prepared by adding the appropriate quantity of sodium hydroxide solid to 100 grams of distilled water and stirring until completely dissolved. To each of these caustic solutions was added 25 grams of polyethylene glycol (“PEG”) 400. Separately, 50 mis of diesel were added to each of these aqueous solutions and homogenized at 6000 rpm for 15 minutes to ensure good contacting. Then the mixtures were transferred to glass separatory funnels and allowed to phase separate. The top layer was isolated and washed with equal volumes of distilled water, 2% HC1 in water and with distilled water again.
- PEG polyethylene glycol
- Example 3 The same procedure as detailed in Example 3 was repeated, except that, after preparing the 50 wt% caustic solution, the PEG 400 was added and then the aqueous solution was stirred and bubbled with nitrogen for thirty minutes to drive air from the solution. Previously nitrogen-sparged low-sulfur diesel was then added and nitrogen-sparged for an additional thirty minutes. After all of the air had been sparged from the system, the two phases were mixed thoroughly by homogenization at 6000 rpm for 15 minutes. The product (treated) diesel was worked-up as described in Example 3. The nitrogen content of the product diesel was found to be 10 ppm. This experiment demonstrates that the nitrogen removal does not require oxygen.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
La présente invention concerne un procédé de dénitrogénation d'un courant de distillat, consistant à mettre un distillat de pétrole contenant de l'azote organique en présence d'une base aqueuse sélectionnée parmi les hydroxydes des groupes IA et IIA et de l'hydroxyde d'ammonium et des mélanges de ces produits, et un agent de transfère de phase à une température et à une pression permettant de produire un pétrole traité appauvri en azote organique.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US551657 | 1995-11-01 | ||
US55165700A | 2000-04-18 | 2000-04-18 | |
PCT/US2001/010006 WO2001079385A2 (fr) | 2000-04-18 | 2001-03-28 | Procede de denitrogenation de fractions brutes |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1274811A2 true EP1274811A2 (fr) | 2003-01-15 |
Family
ID=24202154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01920849A Withdrawn EP1274811A2 (fr) | 2000-04-18 | 2001-03-28 | Procede de denitrogenation de fractions brutes |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1274811A2 (fr) |
JP (1) | JP2004501218A (fr) |
AU (1) | AU2001247859A1 (fr) |
CA (1) | CA2401871A1 (fr) |
WO (1) | WO2001079385A2 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8608943B2 (en) * | 2009-12-30 | 2013-12-17 | Uop Llc | Process for removing nitrogen from vacuum gas oil |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5635056A (en) * | 1995-05-02 | 1997-06-03 | Exxon Research And Engineering Company | Continuous in-situ process for upgrading heavy oil using aqueous base |
US6007705A (en) * | 1998-12-18 | 1999-12-28 | Exxon Research And Engineering Co | Method for demetallating petroleum streams (LAW772) |
-
2001
- 2001-03-28 CA CA002401871A patent/CA2401871A1/fr not_active Abandoned
- 2001-03-28 EP EP01920849A patent/EP1274811A2/fr not_active Withdrawn
- 2001-03-28 AU AU2001247859A patent/AU2001247859A1/en not_active Abandoned
- 2001-03-28 WO PCT/US2001/010006 patent/WO2001079385A2/fr not_active Application Discontinuation
- 2001-03-28 JP JP2001577369A patent/JP2004501218A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO0179385A3 * |
Also Published As
Publication number | Publication date |
---|---|
JP2004501218A (ja) | 2004-01-15 |
AU2001247859A1 (en) | 2001-10-30 |
CA2401871A1 (fr) | 2001-10-25 |
WO2001079385A3 (fr) | 2002-07-04 |
WO2001079385A2 (fr) | 2001-10-25 |
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