EP1485446A2 - Method for the denitrization of hydrocarbon charges in the presence of a polymeric mass. - Google Patents
Method for the denitrization of hydrocarbon charges in the presence of a polymeric mass.Info
- Publication number
- EP1485446A2 EP1485446A2 EP03725297A EP03725297A EP1485446A2 EP 1485446 A2 EP1485446 A2 EP 1485446A2 EP 03725297 A EP03725297 A EP 03725297A EP 03725297 A EP03725297 A EP 03725297A EP 1485446 A2 EP1485446 A2 EP 1485446A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- monomer
- poly
- chosen
- polymeric mass
- 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- Withdrawn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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
Definitions
- the present invention relates to a process for denitrogenating hydrocarbon feedstocks in the presence of a polymeric mass capable of establishing specific bonds with neutral and basic nitrogenous compounds present in hydrocarbons. It also relates to the polymeric masses suitable for this process and the use of this process upstream of certain treatments of these hydrocarbon feedstocks.
- the presence of nitrogen compounds in petroleum fractions from the distillation of crude oils is well known and has been widely described, in particular in the article by D. Tourres, C. Langelier, D. Leborgne, entitled “Analysis of nitrogen compounds in petroleum cuts by GC on capillary column and specific detection by chemiluminescence ”, Analysis Magazine, vol.23, N ° 4, 1995.
- nitrogenous compounds are present in a distillation cut in variable quantities according to the nature of the crude oil and according to the initial and final distillation temperatures thereof.
- nitrogenous organic molecules are either basic, such as amines, anilines, pyridines, acridines, quinolines and their derivatives, or neutral such as, for example, pyrroles, indoles, carbazoles and their derivatives.
- these nitrogenous compounds poison the metal reforming catalysts or acidic catalysts for isomerization and catalytic cracking.
- These nitrogen compounds can also have an inhibiting action on the chemical reactions involved in hydrodesulfurization reactions. It is therefore necessary to eliminate them before these treatments, because they therefore have an indirect polluting effect on atmospheric pollution, by increasing the quantity of sulfur oxides released into the atmosphere.
- neutral nitrogen compounds such as pyrrole, indole, carbazole nitrogen compounds and their derivatives present in fuels
- Diesel fuels or domestic fuels constitute one of the direct sources of atmospheric pollution in the form of nitrogen oxides. These two combined pollution, one direct and the other indirect, favor the increase of the temperature of the globe and the deterioration of the ozone layer.
- hydrodenitrogenation consists in bringing the petroleum fraction with high temperatures and pressures into contact with hydrogen and a catalyst based on refractory oxides, in crystalline or amorphous form, supporting metals of groups NI and NUI of the periodic table.
- the most widely used catalysts are catalysts based on molybdenum oxide and nickel on an alumina support. This process allows the cracking of nitrogenous compounds into ammonia and light hydrocarbons.
- the hydrodenitrogenation processes employed do not make it possible to eliminate all of the nitrogenous compounds in a sufficiently complete manner, in particular the so-called neutral aromatic and polyaromatic derivatives of the pyrrole, indole and carbazole type.
- denitrogenation processes propose the extraction of basic and / or neutral nitrogen compounds by "adsorption on a solid generally consisting of an acid contact mass or an activated carbon, or by liquid / liquid extraction, as described in EP 278,694, FR 2,589,159, US 4,410,421, US 4,521,299 and US 4,529,504.
- Another method for extracting nitrogen compounds consists in passing over ion-exchange contact masses such as described by G. Marcelin in “Shale oil denitrogenation with ion exchange -Evaluation of ion-exchange absorbents and resin treatment procedures”, Ind. Eng. Chem. Process des. Dev., Nol.25, pp747-756, 1986, or by WO99 / 67345 and WO 00/64556.
- the present invention therefore relates to a process for denitrogenating hydrocarbon compounds containing nitrogen compounds, characterized in that the hydrocarbon compounds are brought into contact with at least one polymeric mass comprising at least one polymer P obtained from at least a monomer A, non-styrenic, having at least one polar function generating hydrogen bonds with the polyaromatic nitrogen compounds.
- hydrogen bond is understood here to mean the bond established between at least one hydrogen bonded to an electronegative heteroatom present on the polymer and a negative heteroatom present in a nitrogenous hydrocarbon of acridine, quinoline and pyridine type. Likewise, this bond can be established between a hydrogen bonded to an electronegative heteroatom present in a nitrogenous hydrocarbon of the carbazole, pyrrole and indole type, and an electronegative heteroatom present on the polymer.
- the polymer P can be a homopolymer of the monomer A or a copolymer of the monomer A with at least one monomer B, this monomer B can be any monomer different from the monomer A, including a styrenic monomer.
- the polymeric mass can be formed by the polymer P alone or supported by a solid from the group consisting of another polymer, the supports refractory oxide type minerals (silica, alumina or others) and active carbon, or any other solid, this solid, in divided or aggregated form, being coated with the polymer P.
- a solid from the group consisting of another polymer, the supports refractory oxide type minerals (silica, alumina or others) and active carbon, or any other solid, this solid, in divided or aggregated form, being coated with the polymer P.
- the monomer A is chosen from the group consisting of acrylates, methacrylates, phenols, acrylamides, substituted ethylene oxides, isocyanates, acrylonitriles. These compounds, which may already have polar functions, may or may not be substituted by at least one polar function identical to, or different from, the first function.
- polar functions are preferably chosen from the alcohol, ester and ether functions of RO type, with R an alkyl group comprising from 1 to 18 carbon atoms, amine, amide, imide, nitrile, thiol, thioester, urea, carbamate, thiocarbamate and epoxy.
- Polymers P are chosen from the group consisting of poly (acrylates), poly (methac ⁇ ylates), poly (acrylamides), poly (methacrylamides), poly (ethylene glycols), poly (methanes), formo resins -phenolics and the copolymers of these products.
- the polymer P must comprise from 20 to
- the monomer A 100% by weight of the monomer A, preferably from 25 to 95% by weight, and even more preferably from 30 to 90% by weight of the monomer A.
- the monomer A is chosen from acrylates and methacrylates carrying ether and / or epoxide functions and phenols.
- the polymer P is chosen from polyglycidylmethacrylate and polyphenols.
- the operation is carried out with a weight ratio of the hydrocarbon compound to that of the polymer P of at least 1 and preferably greater than 3.
- the process according to the invention advantageously comprises at least a first step of adsorption of the nitrogenous compounds on the polymeric mass, and at least a second stage of regeneration of the polymeric mass P by washing the latter with a polar or aromatic solvent in which the nitrogen compounds are soluble.
- the regeneration solvent is preferably chosen from toluene, xylene, methanol, ethanol, rapeseed esters or aromatic petroleum fractions, preferably fractions highly concentrated in aromatics from Cg to C12.
- the process according to the invention can advantageously be carried out at a temperature between 0 and 300 ° C, preferably between 0 and 100 ° C, and under a pressure between 10 5 and 50.10 5 Pa, preferably at atmospheric pressure.
- a second object of the present invention is the polymeric mass used in the denitrogenation process.
- This polymeric mass is characterized in that it does not absorb more than 5% by weight of aromatic hydrocarbons, preferably not more than 1% by weight.
- the polymer P comprises a polymer P, obtained from at least one monomer A alone or in combination with at least one monomer B, the polymer P being alone or supported by a solid from the group consisting by another polymer, the mineral supports of the refractory oxide type and the activated carbon, or any other solid, this solid, in divided or aggregated form, being coated with the polymer P.
- the polymer P absorbs at most 5% of its weight of aromatic hydrocarbons, preferably at most 1% by weight.
- This polymer P can be chosen from the group consisting of poly (acrylates), poly (methac ⁇ ylates), poly (acrylamides), poly (methacrylamides), poly (ethylene glycols), poly (methanes), resins formo-phenolics and the copolymers of these products.
- This polymer can be a copolymer.
- This copolymer can be substituted or unsubstituted with at least one polar function chosen from alcohol, ether, ester, amine, amide, imide, nitrile, thiol, thioester, urea, carbamate, thiocarbamate and epoxide functions.
- the monomer A is chosen from the group consisting of acrylates, methacrylates, phenols, acrylamides, substituted ethylene oxides, isocyanates, acrylonitriles.
- the monomer A is chosen from acrylates and methacrylates carrying ether and / or epoxide functions and phenols.
- the preferred polymers P are chosen from polyglycidylmethacrylate and polyphenols.
- the polymeric mass constituting the second object of the invention can be regenerated by a polar or aromatic solvent commonly available on the market.
- a third object of the invention is the use of this denitrogenation process upstream of the hydrocarbon treatment processes, for which the nitrogenous compounds present are poisons or reaction inhibitors.
- polymers P are described which can be used in the process according to the invention. Their effectiveness with regard to denitrogenation is compared to that of other polymers which do not have polar functions or which consist mainly of polystyrenes.
- the polymers P are: - polyglycidylmethacrylate or PGMA, hereinafter PG, which is synthesized according to the procedure described by Svec, F.; Hradil, J.; Coupek, J.; Kalal, J.; Y. Angew.Makromol.Chem. 48, 135-143, (1975);
- Duolite XAD 761 The polyphenol marketed by Rohm and Haas under the name of Duolite XAD 761, hereinafter Duolite.
- the other polymers tested are:
- Retention of aromatics absorbed by the polymer corresponds to the ratio of grams of aromatic compounds absorbed per kilogram of polymer P.
- Aromatics corresponds to the mass of aromatics present in hydrocarbons, expressed in mg. According to this table, when one seeks to denitrate in several stages (tests 1 to 4) of the LCO, one observes a regular decrease in the nitrogen content (> 90%). When this charge is brought into contact with the H + resin (test 5), no significant reduction in the nitrogen level is observed. Similarly, after two stages of denitrogenation of LCO or GO
- the retention of aromatics in the polystyrene PA is approximately 17% o while it is less than or equal to 6% o by weight with the polymer of the invention.
- the polymers according to the invention are perfectly regenerable.
- the efficiency of the polymer PG, used to denitrogenate a diesel fuel charge or an LCO charge is measured after regeneration of the polymer P with toluene, after several cycles of use and regeneration.
- Example III The nitrogen and GO are nitrogenated under the conditions described in Example I. After each first denitrogenation step, the polymer PG is regenerated with toluene in a soxhlet, then it is reused in denitrogenation. The results are given in Table III below.
- the operating conditions for regeneration are as follows:
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0203314 | 2002-03-18 | ||
FR0203314A FR2837212B1 (en) | 2002-03-18 | 2002-03-18 | PROCESS FOR DENITROGENIZATION OF HYDROCARBON FEEDS IN THE PRESENCE OF A POLYMERIC MASS |
PCT/FR2003/000856 WO2003078545A2 (en) | 2002-03-18 | 2003-03-18 | Method for the denitrization of hydrocarbon charges in the presence of a polymeric mass. |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1485446A2 true EP1485446A2 (en) | 2004-12-15 |
Family
ID=27772203
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03725297A Withdrawn EP1485446A2 (en) | 2002-03-18 | 2003-03-18 | Method for the denitrization of hydrocarbon charges in the presence of a polymeric mass. |
Country Status (6)
Country | Link |
---|---|
US (1) | US20060131213A1 (en) |
EP (1) | EP1485446A2 (en) |
JP (1) | JP2005527657A (en) |
AU (1) | AU2003227842A1 (en) |
FR (1) | FR2837212B1 (en) |
WO (1) | WO2003078545A2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2878252B1 (en) | 2004-11-23 | 2008-08-22 | Inst Francais Du Petrole | PROCESS FOR DESULFURIZING A HYDROCARBON CUT IN A SIMPLE MOBILE BED |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4591430A (en) * | 1984-05-18 | 1986-05-27 | Exxon Research And Engineering Co. | Process for the denitrogenation of nitrogen-containing hydrocarbon compounds |
FR2566288B1 (en) * | 1984-06-21 | 1991-10-18 | Elf Aquitaine | POLYMERIC ADDITIVES FOR USE INHIBITING THE DEPOSITION OF PARAFFINS IN RAW OILS |
US4952746A (en) * | 1986-11-14 | 1990-08-28 | Uop | Process for the removal of hydrogenatable hydrocarbonaceous compounds from a hydrocarbonaceous stream and hydrogenating these compounds |
US5047437A (en) * | 1988-11-23 | 1991-09-10 | American Cyanamid | Porous polyacrylonitrile beads and process for their production |
US5374600A (en) * | 1990-01-29 | 1994-12-20 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Oil-absorbent polymer and use therefor |
US5229021A (en) * | 1991-12-09 | 1993-07-20 | Exxon Research & Engineering Company | Wax isomerate having a reduced pour point |
US5244926A (en) * | 1992-06-16 | 1993-09-14 | The Dow Chemical Company | Preparation of ion exchange and adsorbent copolymers |
DE4427473A1 (en) * | 1994-08-03 | 1996-02-08 | Roehm Gmbh | Motor oils with high dispersibility and good wear protection |
US5820749A (en) * | 1996-11-22 | 1998-10-13 | Exxon Chemical Patents, Inc. | Hydrogenation process for unsaturated hydrocarbons |
BR9811959B1 (en) * | 1997-08-22 | 2010-03-09 | A method for improving the low temperature flowability of lubricating oils by using mixtures of high and low molecular weight polymer additives, lubricating oil and concentrate compositions for use in said compositions. | |
US6299760B1 (en) * | 1999-08-12 | 2001-10-09 | Exxon Research And Engineering Company | Nickel molybodtungstate hydrotreating catalysts (law444) |
US7276152B2 (en) * | 2004-11-23 | 2007-10-02 | Cpc Corporation, Taiwan | Oxidative desulfurization and denitrogenation of petroleum oils |
-
2002
- 2002-03-18 FR FR0203314A patent/FR2837212B1/en not_active Expired - Fee Related
-
2003
- 2003-03-18 JP JP2003576541A patent/JP2005527657A/en active Pending
- 2003-03-18 EP EP03725297A patent/EP1485446A2/en not_active Withdrawn
- 2003-03-18 AU AU2003227842A patent/AU2003227842A1/en not_active Abandoned
- 2003-03-18 US US10/508,085 patent/US20060131213A1/en not_active Abandoned
- 2003-03-18 WO PCT/FR2003/000856 patent/WO2003078545A2/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO03078545A3 * |
Also Published As
Publication number | Publication date |
---|---|
WO2003078545A2 (en) | 2003-09-25 |
JP2005527657A (en) | 2005-09-15 |
FR2837212B1 (en) | 2004-10-01 |
AU2003227842A8 (en) | 2003-09-29 |
WO2003078545A3 (en) | 2004-04-15 |
AU2003227842A1 (en) | 2003-09-29 |
FR2837212A1 (en) | 2003-09-19 |
US20060131213A1 (en) | 2006-06-22 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: LOUTATY, ROBEN Inventor name: SEVIGNON, MARC Inventor name: SCHULZ, EMMANUELLE Inventor name: FAVRE-REGUILLON, ALAIN Inventor name: MACAUD, MATHIEU Inventor name: LEMAIRE, MARC |
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STAA | Information on the status of an ep patent application or granted ep patent |
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Effective date: 20081001 |