EP1485446A2 - Verfahren für die entstickstoffung von kohlenwasserstoffbeschickungen in anwesenheit einer polymermasse. - Google Patents
Verfahren für die entstickstoffung von kohlenwasserstoffbeschickungen in anwesenheit einer polymermasse.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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 title claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- -1 nitrogenous hydrocarbon compounds Chemical class 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 17
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 150000002924 oxiranes Chemical class 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 150000003926 acrylamides Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 5
- 235000013824 polyphenols Nutrition 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000012948 isocyanate Chemical group 0.000 claims description 4
- 150000002513 isocyanates Chemical group 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000007970 thio esters Chemical class 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 239000002574 poison Substances 0.000 claims description 3
- 231100000614 poison Toxicity 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 239000002683 reaction inhibitor Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003673 urethanes Chemical group 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 244000188595 Brassica sinapistrum Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VJASJHNHBZQZAK-UHFFFAOYSA-N [N].C1=CC=C2C3=CC=CC=C3NC2=C1 Chemical class [N].C1=CC=C2C3=CC=CC=C3NC2=C1 VJASJHNHBZQZAK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 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
- 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)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0203314A FR2837212B1 (fr) | 2002-03-18 | 2002-03-18 | Procede de deazotation de charges hydrocarbonees en presence d'une masse polymerique |
| FR0203314 | 2002-03-18 | ||
| PCT/FR2003/000856 WO2003078545A2 (fr) | 2002-03-18 | 2003-03-18 | Procede de deazotation de charges hydrocarbonees en presence d'une masse polymerique. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1485446A2 true EP1485446A2 (de) | 2004-12-15 |
Family
ID=27772203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03725297A Withdrawn EP1485446A2 (de) | 2002-03-18 | 2003-03-18 | Verfahren für die entstickstoffung von kohlenwasserstoffbeschickungen in anwesenheit einer polymermasse. |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20060131213A1 (de) |
| EP (1) | EP1485446A2 (de) |
| JP (1) | JP2005527657A (de) |
| AU (1) | AU2003227842A1 (de) |
| FR (1) | FR2837212B1 (de) |
| WO (1) | WO2003078545A2 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2878252B1 (fr) | 2004-11-23 | 2008-08-22 | Inst Francais Du Petrole | Procede de desulfuration d'une coupe hydrocarbonee en lit mobile simule |
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 (fr) * | 1984-06-21 | 1991-10-18 | Elf Aquitaine | Additifs polymeriques utilisables pour l'inhibition du depot de paraffines dans les huiles brutes |
| 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 (de) * | 1994-08-03 | 1996-02-08 | Roehm Gmbh | Motorenöle mit hohem Dispergiervermögen und gutem Verschleißschutz |
| US5820749A (en) * | 1996-11-22 | 1998-10-13 | Exxon Chemical Patents, Inc. | Hydrogenation process for unsaturated hydrocarbons |
| JP4391014B2 (ja) * | 1997-08-22 | 2009-12-24 | エボニック ローマックス アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツング | 高−及び低分子量ポリマー添加剤混合物を用いる潤滑油の低温流動性の改良法 |
| 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/fr not_active Expired - Fee Related
-
2003
- 2003-03-18 JP JP2003576541A patent/JP2005527657A/ja active Pending
- 2003-03-18 WO PCT/FR2003/000856 patent/WO2003078545A2/fr active Application Filing
- 2003-03-18 EP EP03725297A patent/EP1485446A2/de 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
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03078545A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2837212B1 (fr) | 2004-10-01 |
| AU2003227842A1 (en) | 2003-09-29 |
| JP2005527657A (ja) | 2005-09-15 |
| US20060131213A1 (en) | 2006-06-22 |
| WO2003078545A3 (fr) | 2004-04-15 |
| FR2837212A1 (fr) | 2003-09-19 |
| WO2003078545A2 (fr) | 2003-09-25 |
| AU2003227842A8 (en) | 2003-09-29 |
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