AU2004261971A1 - Process to manufacture low sulfur fuels - Google Patents
Process to manufacture low sulfur fuels Download PDFInfo
- Publication number
- AU2004261971A1 AU2004261971A1 AU2004261971A AU2004261971A AU2004261971A1 AU 2004261971 A1 AU2004261971 A1 AU 2004261971A1 AU 2004261971 A AU2004261971 A AU 2004261971A AU 2004261971 A AU2004261971 A AU 2004261971A AU 2004261971 A1 AU2004261971 A1 AU 2004261971A1
- Authority
- AU
- Australia
- Prior art keywords
- naphtha
- process according
- boiling range
- catalyst
- sulfur
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 32
- 239000011593 sulfur Substances 0.000 title claims description 32
- 229910052717 sulfur Inorganic materials 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000446 fuel Substances 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 54
- 150000001336 alkenes Chemical class 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000009835 boiling Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000010457 zeolite Substances 0.000 claims description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000006317 isomerization reaction Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 229920001429 chelating resin Polymers 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 241000282326 Felis catus Species 0.000 claims description 2
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 150000002830 nitrogen compounds Chemical class 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 27
- 239000012188 paraffin wax Substances 0.000 description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 11
- 229910052794 bromium Inorganic materials 0.000 description 11
- -1 iso olefins Chemical class 0.000 description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 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
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001507939 Cormus domestica Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000899793 Hypsophrys nicaraguensis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052721 tungsten 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
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)
Description
WO 2005/012459 PCT/US2004/024128 -1 PROCESS TO MANUFACTURE LOW SULFUR FUELS FIELD OF THE INVENTION 10001] The instant invention relates to a process for upgrading of hydrocarbon mixtures boiling within the naphtha range. More particularly, the instant invention relates to a process to produce high octane, low sulfur naphtha products through the simultaneous skeletal isomerization of feed olefins and selective hydrotreating. BACKGROUND OF THE INVENTION 10002] Liquid hydrocarbon streams that boil within the naphtha range, i.e. below 232'C, and produced from the Fluidized Catalytic Cracking Unit ("FCC") are typically used as blending components for motor gasolines. Environmentally driven regulatory pressure concerning motor gasoline sulfur levels is expected to result in the widespread production of less than 50 wppm sulfur mogas by the year 2004. Levels below 10 wppm are being considered for later years in some regions of the world, and this will require deep desulfurization of naphthas in order to conform to emission restrictions that are becoming more stringent. The majority, i.e., 90% or more, of sulfur contaminants present in motor gasolines are typically present in naphtha boiling range hydrocarbon streams. However, the naphtha boiling range streams are also rich in olefins, which boost octane, a desirable quality in motor gasolines. [0003] Thus, many processes have been developed to produce low sulfur products from naphtha boiling range streams while attempting to minimize olefin loss, such as, for example, hydrodesulfurization processes. However, these processes also typically hydrogenate feed olefins to some degree, thus reducing the WO 2005/012459 PCT/US2004/024128 -2 octane number of the product. Therefore, processes have been developed that recover octane lost during desulfurization. Non-limiting examples of these processes can be found in United States Patent Numbers 5,298,150; 5,320,742; 5,326,462; 5,318,690; 5,360,532; 5,500,108; 5,510,016; and 5,554,274, which are all incorporated herein by reference. In these processes, in order to obtain desirable hydrodesulfurization with a reduced octane loss, it is necessary to operate in two steps. The first step is a hydrodesulfurization step, and a second step recovers octane lost during hydrodesulfurization. [00041 Other processes have also been developed that seek to minimize octane lost during hydrodesulfurization. For example, selective hydrodesulfurization is used to remove organically bound sulfur while minimizing hydrogenation of olefins and octane reduction by various techniques, such as the use of selective catalysts and/or process conditions. For example, one selective hydrodesulfurization process, referred to as SCANfining, has been developed by ExxonMobil Research & Engineering Company in which olefinic naphthas are selectively desulfurized with little loss in octane. U.S. Patent Nos. 5,985,136; 6,013,598; and 6,126,814, all of which are incorporated by reference herein, disclose various aspects of SCANfining. Although selective hydrodesulfurization processes have been developed to avoid significant olefin saturation and loss of octane, such processes have a tendency to liberate H 2 S a portion of which may react with retained olefins to form mercaptan sulfur by reversion. [0005] Thus, there still exists a need in the art for a process to reduce the sulfur content in naphtha boiling range hydrocarbon streams while minimizing octane loss and mercaptan reversion.
WO 2005/012459 PCT/US2004/024128 -3 SUMMARY OF THE INVENTION [00061 The instant invention is directed at a process for producing low sulfur naphtha products through simultaneous skeletal olefin isomerization and selective desulfurization. The process comprises: a) contacting a naphtha boiling range feedstream containing organically bound sulfur and olefins in a reaction zone, operated under effective hydrotreating conditions and in the presence of hydrogen-containing treat gas, with a supported catalyst comprising at least one medium pore zeolite selected from ZSM-23, ZSM-12, ZSM-22, ZSM-57, and ZSM-48, 0.1 to 27 wt.% of at least one Group VIII metal oxide, and I to 45 wt.% of at least one Group VI metal oxide to produce a desulfurized product. BRIEF DESCRIPTION OF THE FIGURES [0007] Figure 1 compares results obtained from the Examples herein at constant bromine number reduction. (00081 Figure 2 compares product iso-olefin to n-olefin ratios of products resulting from the Examples herein. (00091 Figure 3 compares product iso-paraffin to n-paraffin ratios of products resulting from the Examples herein.
WO 2005/012459 PCT/US2004/024128 -4 DETAILED DESCRIPTION OF THE INSTANT INVENTION [00101 It should be noted that the terms "hydrotreating" and "hydrodesulfurization" are sometimes used interchangeably herein, and the prefixes "i-" and "n" are meant to refer to "iso-" and "normal", respectively. [00111 In the hydrotreating of naphtha boiling range feedstreams, olefins are typically saturated in the hydrotreating zone resulting in a decrease in octane number of the desulfurized product. However, the present invention reduces the decrease in octane of the desulfurized product through the use of a novel process involving contacting a naphtha boiling range feedstream in a reaction zone operated under effective hydrotreating conditions. This reaction zone contains a supported catalyst comprising at least one medium pore zeolite, 0.1 to 27 wt.% of at least one Group VIII metal oxide, and 1 to 45 wt.% of at least one Group VI metal oxide supported on a suitable substrate. [00121 The desulfurized product thus obtained has a higher iso-paraffin to n paraffin ratio, and thus a higher octane than a desulfurized naphtha treated by a selective or non-selective hydrotreating process only, i.e., without an octane recovery step. The higher octane of the desulfurized product results from the unexpected finding by the inventors hereof that by operating the reaction zone under conditions effective for encouraging the skeletal isomerization of n-olefins to iso-olefins results in a desulfurized naphtha product having a higher octane number than a desulfurized product resulting from a selective hydrodesulfurization process only. The inventors hereof have found that the degree of skeletal isomerization of n-olefins to iso-olefins benefits the final product because the saturation of iso olefins to iso-paraffins that occurs in the reaction zone herein provides for less octane loss in the final product when compared to the saturation of n-olefins to n- WO 2005/012459 PCT/US2004/024128 -5 paraffins. It should be noted that iso-paraffins typically have a much higher octane than their corresponding n-paraffin. Further, the rate of saturation of iso-olefins is typically slower than that of n-olefins. Therefore, by increasing the ratio of iso olefins to n-olefins present in the reaction zone effluent, the resulting desulfurized naphtha product exiting the reaction zone also typically has a higher iso-olefin to n olefin ratio as well as a higher olefin content, and thus a higher octane than a desulfurized naphtha treated by a selective or non-selective hydrotreating process only. [00131 In the hydroprocessing of naphtha boiling range hydrocarbon feedstreams, it is typically highly desirable to remove sulfur-containing compounds from the naphtha boiling range feedstreams with as little olefin saturation as possible. It is also highly desirable to convert as much of the organic sulfur species of the naphtha to hydrogen sulfide with as little mercaptan reversion as possible. By mercaptan reversion we mean the reaction of hydrogen sulfide with olefins during the hydrotreating to form undesirable alkylmercaptans. The inventors hereof have unexpectedly found that through the use of the presently claimed invention, high levels of sulfur can be removed from an olefinic naphtha stream without excessive olefin saturation or mercaptan reversion taking place. [0014] Feedstreams suitable for use in the present invention include naphtha boiling range refinery streams that typically boil in the range of 50*F (10*C) to 450*F (232'C) containing both olefins and sulfur containing compounds. Thus, the term "naphtha boiling range feedstream" as used herein includes those streams having an olefin content of at least 5 wt.%. Non-limiting examples of naphtha boiling range feedstreams that can be treated by the present invention include fluid catalytic cracking unit naphtha (FCC catalytic naphtha or cat naphtha), steam WO 2005/012459 PCT/US2004/024128 -6 cracked naphtha, and coker naphtha. Also included are blends of olefinic naphthas with non-olefinic naphthas as long as the blend has an olefin content of at least 5 wt.%, based on the total weight of the naphtha feedstream. [0015] Cracked naphtha refinery streams generally contain not only paraffins, naphthenes, and aromatics, but also unsaturates, such as open-chain and cyclic olefins, dienes, and cyclic hydrocarbons with olefinic side chains. The olefin containing naphtha feedstream can contain an overall olefins concentration ranging as high as 70 wt.%, more typically as high as 60 wt.%, and most typically from 5 wt.% to 40 wt.%. The olefin-containing naphtha feedstream can also have a diene concentration up to 15 wt.%, but more typically less than 5 wt.% based on the total weight of the feedstock. The sulfur content of the naphtha feedstream will generally range from 50 wppm to 7000 wppm, more typically from 100 wppm to 5000 wppm, and most typically from 100 to 3000 wppm. The sulfur will usually be present as organically bound sulfur. That is, as sulfur compounds such as simple aliphatic, naphthenic, and aromatic mercaptans, sulfides, di- and polysulfides and the like. Other organically bound sulfur compounds include the class of heterocyclic sulfur compounds such as thiophene, tetrahydrothiophene, benzothiophene and their higher homologs and analogs. Feedstreams suitable for use herein can also contain nitrogen contaminants that are typically present in a range from 5 wppm to 500 wppm. [0016] The feedstreams used herein are typically preheated prior to entering the reaction zone herein and final heating is typically targeted to the effective hydrotreating temperatures. If the naphtha boiling range feedstream is preheated, it can be reacted with the hydrogen-containing treat gas stream prior to, during, and/or after preheating. At least a portion of the hydrogen-containing treat gas can WO 2005/012459 PCT/US2004/024128 -7 also be added at an intermediate location in the reaction zone. Hydrogen containing treat gasses suitable for use in the presently disclosed process can be comprised of substantially pure hydrogen or can be mixtures of other components typically found in refinery hydrogen streams. It is preferred that the hydrogen containing treat gas stream contains little, more preferably no, hydrogen sulfide. The hydrogen-containing treat gas purity should be at least 50% by volume hydrogen, preferably at least 75% by volume hydrogen, and more preferably at least 90% by volume hydrogen for best results. It is most preferred that the hydrogen-containing stream be substantially pure hydrogen. [00171 In the reaction zone, the above-described naphtha boiling range feedstream is contacted with a catalyst comprising at least one medium pore zeolite. Zeolites are porous crystalline materials, and medium pore zeolites as used herein can be any zeolite described as a medium pore zeolite in Atlas of Zeolite Structure Types, W.M. Maier and D.H. Olson, Butterworths. Typically, medium pore zeolites are defined as those having a pore size of 5 to 7 Angstroms, such that the zeolite freely sorbs molecules such as n-hexane, 3-methylpentane, benzene and p-xylene. Another common classification used for medium pore zeolites involves the Constraint Index test which is described in United States Patent Number 4,016,218, which is hereby incorporated by reference. Medium pore zeolites typically have a Constraint Index of 1 to 12, based on the zeolite alone without modifiers and prior to treatment to adjust the diffusivity of the catalyst. Preferred medium pore zeolites for use herein are selected from ZSM-23, ZSM-12, ZSM-22, ZSM-57, and ZSM-48, with ZSM-48 being the most preferred. [00181 Another means of describing zeolites is alpha value or number. Alpha value, or alpha number, is a measure of zeolite acidic functionality and is more WO 2005/012459 PCT/US2004/024128 -8 fully described together with details of its measurement in United States Patent Number 4,016,218, J. Catalysis, 6, pages 278-287 (1966) and J. Catalysis, 61, pages 390-396 (1980), which are all incorporated herein by reference. Generally the alpha value reflects the relative activity with respect to a high activity silica alumina cracking catalyst. To determine the alpha value as used herein, n-hexane conversion is determined at 800*F. Conversion is varied by variation in space velocity such that a conversion level of 10 to 60 percent of n-hexane is obtained and converted to a rate constant per unit volume of zeolite and compared with that of the silica-alumina catalyst, which is normalized to a reference activity of 1000"F. Catalytic activity is expressed as a multiple of this standard, i.e. the silica-alumina standard. The silica-alumina reference catalyst contains 10 wt.% A1 2 0 3 and the remainder is SiO 2 . Therefore, as the alpha value of a zeolite catalyst decreases, the tendency towards non-selective cracking also decreases. Zeolites suitable for use herein have an alpha value of up to 20, preferably between 0.1 and 20, more preferably I to 19, and most preferably between 10 and 20. [00191 The medium pore zeolites used herein are typically combined with a suitable porous binder or matrix material. Non-limiting examples of such materials include active and inactive materials such as clays, silica, and/or metal oxides such as alumina. Non-limiting examples of naturally occurring clays that can be composited include clays from the montmorillonite and kaolin families including the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays. Others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite may also be used. The clays can be used in the raw state as originally mixed or subjected to calcination, acid treatment, or chemical modification prior to being combined with the medium pore zeolite.
WO 2005/012459 PCT/US2004/024128 -9 [0020] It is preferred that the porous matrix or binder material comprises silica, alumina, or a kaolin clay. It is more preferred that the binder material comprise alumina. In this embodiment the alumina is present in a ratio of less than 15 parts zeolite to one part binder, preferably less than 10, more preferably less than 5, and most preferably 2. [0021] The catalysts used herein also comprises 0.1 to 27 wt.% of at least one Group VIII metal oxide and 1 to 45 wt.% of at least one Group VI metal oxide, The at least one Group VIII metal oxide concentration of the catalysts used herein is preferably 0.1 to 10 wt.%, more preferably I to 8 wt.%, and most preferably I to 5 wt.%, and the at least one Group VIII metal oxide concentration of the catalysts used herein is preferably 1 to 30 wt.%, more preferably 1 to 20 wt.%, and most preferably 2 to 10 wt.%. Preferred Group VIII metal oxides are those selected from Fe, Co and Ni, more preferably Co and/or Ni, and most preferably Co. Preferred Group VI metal oxides are those selected from Mo and W, more preferably Mo. The at least one Group VIII metal oxide and the at least one Group VI metal oxide can be incorporated onto the above-described supported medium pore zeolite by any means known to be effective at doing so. Non-limiting examples of suitable incorporation means include incipient wetness, ion exchange, mechanical mixing of metal oxide precursor(s) with zeolite and binder, or a combination thereof. 100221 The reaction zone used herein can be comprised of one or more fixed bed reactors or reaction zones each of which can comprise one or more catalyst beds of the same or different catalyst. Thus, it is within the scope of the instant invention that catalysts comprising different zeolites, different Group VIII and Group VI metal oxides, and mixtures thereof be used in the same reaction vessel. Although other types of catalyst beds can be used, non-limiting examples of suitable bed WO 2005/012459 PCT/US2004/024128 -10 types include fluidized beds, ebullating beds, slurry beds, and moving beds. Preferred are fixed catalyst beds. Interstage cooling or heating between reactors or reaction zones, or between catalyst beds in the same reactor, can be employed since some olefin saturation can take place, and olefin saturation and the desulfurization reaction are generally exothermic. A portion of the heat generated during hydrodesulfurization can be recovered. Where this heat recovery option is not available, conventional cooling may be performed through cooling utilities such as cooling water or air, or through use of a hydrogen quench stream. In this manner, optimum reaction temperatures can be more easily maintained. [00231 As stated above, the above-defined naphtha boiling range feedstream containing organically bound sulfur and olefins is contacted with the supported catalyst described herein in a reaction zone operated under effective hydrotreating conditions. By effective hydrotreating conditions, it is meant those conditions that provide for the skeletal isomerization of at least 20 wt.% of the n-olefins present in the feedstream to iso-olefins, preferably at least 40 wt.%, more preferably at least 50 wt.%. By skeletal isomerization, it is meant the reorientation of the molecular structure of the normal olefins (n-olefins) with a preference for branched chain iso olefins over straight. Thus, skeletal isomerization, as used herein, refers to the conversion of a normal olefin to a branched olefin or to the rearranging or moving of branch carbon groups, which are attached to the straight chain olefin molecule, to a different carbon atom, and non-skeletal isomerization can be described as the rearranging of the position of the double bond within the straight chain or branched olefin molecule. [00241 By effective hydrotreating conditions, it is also meant those conditions chosen that will achieve a resulting desulfurized naphtha product having less than WO 2005/012459 PCT/US2004/024128 -11 100 wppm sulfur, preferably less than 50 wppm sulfur, more preferably less than 30 wppm sulfur. Typical effective hydrotreating conditions will be those that include temperatures ranging from 150'C to 425"C, preferably 200'C to 370'C, more preferably 230C to 350'C. Typical weight hourly space velocities ("WHSV") range from 0.1 to 20hr~1, preferably from 0.5 to 5hr~1. Any effective pressure can be utilized, and pressures typically range from 4 to 70 atmospheres, preferably 10 to 40 atmospheres. In a most preferred embodiment, the effective hydrotreating conditions are selective hydrotreating conditions configured to achieve a sulfur level and degree of skeletal isomerization within the above-defined ranges, most preferably the conditions are selected such that the desulfurized naphtha product has a sulfur level sufficiently low to meet current regulatory standards in place at that time. By selective hydrotreating conditions, it is meant conditions such as those contained in U.S. Patent Nos. 5,985,136; 6,013,598; and 6,126,814, all of which have already been incorporated by reference herein, which disclose various aspects of SCANfining, a process developed by the ExxonMobil Research and Engineering Company in which olefinic naphthas are selectively desulfurized with little loss in octane. [0025] As previously stated, the desulfurized product thus obtained will typically have a higher iso-paraffin to n-paraffin ratio, and thus a higher octane than a desulfurized naphtha treated by a selective or non-selective hydrotreating process. Typical iso-paraffin to n-paraffin ratios in the desulfurized product resulting from the present process are greater than 1, preferably 2, more preferably 3. Thus, compared to selective hydrodesulfurization catalyst systems, the processing of the naphtha boiling range feedstream over the present catalyst system results in a desulfurized naphtha product with a higher octane at constant olefin saturation even WO 2005/012459 PCT/US2004/024128 -12 when both catalyst systems maintain similar desulfurization/olefin saturation selectivity. [0026] In one embodiment of the instant invention, the nitrogen content of the naphtha boiling range feedstreams is reduced in a feed pre-treatment step because catalytic treatments are impeded by nitrogen-containing compounds present in the feedstream. Thus, one embodiment of the instant invention involves treating the naphtha boiling range feedstream with an acidic material to reduce the nitrogen content of the feedstreams. Non-limiting examples of suitable acidic materials include sulfuric acid, Amberlyst, alumina, spent sulfuric acid obtained from an alkylation unit, and any other material known to be effective at reducing the nitrogen concentration of a naphtha boiling range feedstream. Preferred acidic materials are Amberlyst and alumina. In the feed pretreatment step, the naphtha boiling range feedstream can be contacted with the acidic material under conditions effective for removing at least a portion of the nitrogen-containing compounds present in the naphtha boiling range feedstream. By at least a portion, it is meant at least 10 wt.% of the nitrogen-containing compounds present in the feedstream. Preferably, at least that amount of nitrogen-containing compounds that will result in a first reaction zone effluent containing less than 50 wppm total nitrogen, based on the first reaction zone effluent. More preferably the first reaction zone effluent contains less than 25 wppm total nitrogen, most preferably less than 10 wppm nitrogen, and in an ideally suitable case, less than 5 wppm total nitrogen. Thus, by "conditions effective for removal of at least a portion of the nitrogen-containing compounds", it is meant those conditions under which the first reaction zone effluent will have the above described total nitrogen concentrations, i.e., 10 wt.% removal, etc. It should be noted that if sulfuric acid or spent sulfuric acid obtained from an alkylation unit is used, the acid concentration should be adjusted by adding WO 2005/012459 PCT/US2004/024128 -13 a diluent before either is contacted with the naphtha boiling range feedstream to avoid polymerizing olefins. [00271 The above description is directed to several embodiments of the present invention. Those skilled in the art will recognize that other embodiments that are equally effective could be devised for carrying out the spirit of this invention. [00281 The following examples will illustrate the effectiveness of the present invention, but is not meant to limit the present invention in any fashion. EXAMPLES EXAMPLE 1 - CATALYST PREPARATION [0029] A base ZSM-48 catalyst comprising 65% ZSM-48 / 35% Alumina was used to prepare a catalyst as contemplated herein. The properties of the base catalyst are given in Table 1 below. [0030] 100 grams of the base catalyst was charged to a rotary cone for impregnation with Mo. The Mo solution used for impregnation was prepared by dissolving 22.6 grams of ammonium heptamolybdate in a quantity of water sufficient to completely wet it. The Mo solution was sprayed onto the base catalyst and the resulting catalyst was dried at 250'F for 12 hours. The Mo containing base catalyst was calcined in a tube furnace for 3 hours at 1 000"F using an air circulation rate of 5 vol. air/vol. catalyst. [0031] The Mo impregnated catalyst was again charged to the rotary cone for impregnation with Co. The Co solution used for impregnation was prepared by WO 2005/012459 PCT/US2004/024128 -14 dissolving 18.3 grams of cobalt nitrate in a quantity of water sufficient to wet the entire cobalt nitrate solid. The Co solution was sprayed onto the base catalyst and the resulting catalyst was dried at 250'F for 12 hours. The Co/Mo containing base catalyst was calcined in a tube furnace for 3 hours at 1 000F using an air circulation rate of 5 vol. air/vol. catalyst. [00321 The finished catalyst contained 2.59 wt.% Co and 9.51 wt.% Mo. TABLE 1 BASE CATALYST PROPERTIES Alpha 20 Surface Area 224 m2Ig Density 0.66 g/cc Water sorption 8.8 wt.% Hexane sorption 8 wt.% Cyclohexane sorption 9 wt.% EXAMPLE 2 [00331 An FCC naphtha was treated at ambient conditions and liquid hourly space velocities ("LHSV") of 2-3 hr- with Amberlyst-15 to reduce the nitrogen content of the feed to 3wppm. The feed having the properties described in Table 2 below was then contacted with the catalyst described in Example 1 above. The contacting conditions included various temperatures within the range of 480-650'F, i.e. 480, 482, 400, 518, 525, 536, 552, 624, 649'F, hydrogen treat rates of 2000scf/bbl of 100% pure hydrogen, pressures of 250psig, and LHSV of 2hr-. The results of this experiment are described in the Figures below.
WO 2005/012459 PCT/US2004/024128 -15 EXAMPLE 3- COMPARATIVE (I) [0034] An FCC naphtha was treated at ambient conditions and liquid hourly space velocities ("LHSV") of 2-3 hf with Amberlyst-15 to reduce the nitrogen content of the feed to lwppm. The feed having the properties described in Table 2 below was then contacted with a commercial hydrotreating catalyst having 1.2 wt.% CoO and 4.2 wt.% MoO. The contacting conditions were selected from those known in the art to be "selective" and included various temperatures within the range of 450-600F, i.e. 480, 503, 421, 537, and 557 0 F hydrogen treat rates of 2000scf/bbl of 100% pure hydrogen, pressures of 250psig and LHSV of 4hr-1. The results of this experiment are described in the Figures below. The concentration of mercaptans produced in this Example was also compared to the concentration of mercaptans produced in Example 2 at 525'F. These results are contained in Table 3 below. EXAMPLE 4 - COMPARATIVE (II) [0035] An FCC naphtha feed having the properties described in Table 2 below was contacted with a commercial hydrotreating catalyst having 1.2 wt.% CoO and 4.2 wt.% MoO. The contacting conditions included a temperature of 525*F, hydrogen treat rates of 3000scf/bbl of 100% pure hydrogen, pressures of 170psig and LHSV of 2.3hr- . The results of this experiment are described in the Figures below. The concentration of mercaptans produced in this Example was also compared to the concentration of mercaptans produced in Example 2 at 525 0 F. These results are contained in Table 3 below.
WO 2005/012459 PCT/US2004/024128 -16 TABLE 2 FEED PROPERTIES Example 2 Example 3 Example 4 API Gravity 56.6 56.7 57.1 Total S, wppm 711 603 735 Nitrogen, wppm 3 1 48 Bromine Number 69.8 70.2 71 Hydrogen 13.27 13.29 13.23 Road Octane 92.2 92.5 93.5 Number("RON") Paraffins (wt.%) n-Paraffins 3 3.22 3.02 iso-Paraffins 21.91 23.22 22.08 Total Paraffins 24.91 26.43 25.11 Naphthenes 8.42 8.37 9.28 Aromatics 28.44 29.69 25.19 Olefins (wt.%) n-Olefins 12.6 11.95 12.83 iso-Olefins 17.68 17.35 17.01 Other olefins 7.91 6.2 10.61 Total olefins 37.97 35.5 40.43 Distillation ('F) (ASTM D2887) 5% 95 90 85 10% 109 107 105 50% 230 228 222 90% 350 346 341 95% 373 371 365 WO 2005/012459 PCT/US2004/024128 -17 TABLE 3 Feed S, Treat Total iso to Product S, Mercaptan/ wppm Gas Pressure, n-olefin wppm Bromine Number scf/bbl psig ratio Ratio Example 2 711 2000 250 2.9 30 0.24 Example 3 603 2000 250 1.5 100 0.41 Example 4 735 3000 170 N/A 30 0.63 [0036] As described above, mercaptans are generally formed by the reversion reaction of olefins with hydrogen sulfide. Thermodynamics for model compounds show that mercaptan reversion equilibrium for branched olefins, i.e. iso-olefins, is lower than that for normal olefins. Consequently, the isomerization of n-olefins to iso-olefins can give a lower mercaptan concentration at constant bromine number. This benefit is readily illustrated by comparing mercaptan/bromine number ratios at constant temperature. Thus, by comparing the mercaptan/bromine number ratios of the products produced at 525'F in Examples 2, 3, and 4, the results contained in Table 3 show that the catalyst used in Example 2 above produced less mercaptans that the catalysts used in Examples 3 and 4. It should be noted that the mercaptan/bromine number ratio is sensitive to the equilibrium constant for feeds with similar sulfur concentrations subjected to catalysis with similar treat gas rates, which is a function of the ratio of iso to n-paraffins. [00371 Figure 1 shows that at constant bromine number reduction, the octane loss was much lower for Example 1 than for the comparative Examples. The reduction in bromine number was measured according to ASTM 1159.
WO 2005/012459 PCT/US2004/024128 -18 [0038] Figure 2 shows that at constant bromine number, the catalyst of Example 1 provided a higher iso-olefin to n-olefin ratio than the catalysts of the comparative Examples. Higher branched olefin concentrations, i.e. iso-olefins, results in higher octane at constant bromine number since octane numbers for branched olefins are typically higher than those for normal olefins. [0039] Figure 3 shows that the catalysts of the catalyst of Example 1, one contemplated by the instant invention produced a product having a higher iso paraffin to n-paraffin ratio. A higher iso-paraffin to n-paraffin ratio in a product will result in a product having a higher octane than a product with a lower ratio.
Claims (16)
1. A process for producing low sulfur naphtha products from an olefin and sulfur containing naphtha boiling range feedstream comprising: a) contacting a naphtha boiling range feedstream containing organically bound sulfur and olefins in a reaction zone, operated under effective hydrotreating conditions and in the presence of hydrogen-containing treat gas, with a supported catalyst comprising at least one medium pore zeolite selected from ZSM-23, ZSM-12, ZSM-22, ZSM-57, and ZSM-48, 0.1 to 27 wt.% of at least one Group VIII metal oxide, and 1 to 45 wt.% of at least one Group VI metal oxide to produce a desulfurized product.
2. The process according to claim 1 wherein said naphtha boiling range feedstream boils in the range of 50*F (10*C) to 450*F (232*C), an olefin content of at least 5 wt.%, and a sulfur content of 50 to 7000 wppm sulfur.
3. The process according to any preceding claim wherein said naphtha boiling range feedstream is selected from fluid catalytic cracking unit naphtha (FCC catalytic naphtha or cat naphtha), steam cracked naphtha, coker naphtha, blends of olefinic naphthas with non-olefinic naphthas wherein the blend has an olefin content of at least 5 wt.%, based on the total weight of the naphtha boiling range feedstream.
4. The process according to any preceding claim wherein said naphtha boiling range feedstream has a nitrogen content of 5 wppm to 500 wppm nitrogen. WO 2005/012459 PCT/US2004/024128 -20
5. The process according to any preceding claim wherein said reaction zone comprises one or more catalyst beds selected from fluidized beds, ebullating beds, slurry beds, fixed beds, and moving beds wherein each of said one or more catalyst beds contains a catalyst suitable for the reaction zone in which the catalyst bed is located.
6. The process according to any preceding claim wherein said process further comprises interstage cooling between catalyst beds in said reaction zone.
7. The process according to any preceding claim wherein said medium pore size zeolite has an alpha value of up to 20.
8. The process according to any preceding claim wherein said medium pore size zeolite is selected from ZSM-23 and ZSM-48.
9. The process according to any preceding claim wherein said catalyst comprises 0.1 to 10 wt.% of a Group VIII metal oxide and I to 30 wt.% of a Group VI metal oxide. I to 45 wt.% of at least one Group VI metal oxide.
10. The process according to any preceding claim wherein said effective hydrotreating conditions are selected to cause skeletal isomerization of at least 20 wt.% of the n-olefins present in said naphtha boiling range feedstream.
11. The process according to any preceding claim wherein said support is a suitable binder or matrix material selected from clays, silica, and metal oxides. WO 2005/012459 PCT/US2004/024128 -21
12. The process according to any preceding claim wherein said effective hydrotreating conditions are selected in such a manner that said desulfurized naphtha product has less than 100 wppm sulfur.
13. The process according to any preceding claim wherein said effective hydrotreating conditions are selective hydrotreating conditions.
14. The process according to any preceding claim wherein said desulfurized naphtha product has a higher concentration of iso-paraffins than n-paraffins.
15. The process according to any preceding claim wherein said process further comprises a feed pretreatment step wherein said feed pretreatment step comprises: a) contacting the naphtha boiling range feedstream containing organically bound sulfur, nitrogen-containing compounds, and olefins in a reaction zone, operated under conditions effective at removing at least a portion of said nitrogen-containing compounds, with an acidic material to produce a first reaction zone effluent having a reduced amount of nitrogen-containing compounds.
16. The process according to any preceding claim wherein said acidic material is selected from Amberlyst, alumina, sulfuric acid, spent sulfuric acid obtained from an alkylation unit, and any other acidic material known to be effective at removing nitrogen compounds from a naphtha boiling range hydrocarbon stream.
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US7288181B2 (en) * | 2003-08-01 | 2007-10-30 | Exxonmobil Research And Engineering Company | Producing low sulfur naphtha products through improved olefin isomerization |
EP2253608B2 (en) * | 2009-05-19 | 2021-06-16 | Neste Oyj | Method for the manufacture of branched saturated hydrocarbons |
US8314281B2 (en) * | 2009-06-25 | 2012-11-20 | Uop Llc | Light paraffin isomerization with improved feed purification |
US9453167B2 (en) | 2013-08-30 | 2016-09-27 | Uop Llc | Methods and apparatuses for processing hydrocarbon streams containing organic nitrogen species |
RU2609264C1 (en) * | 2015-12-09 | 2017-01-31 | Акционерное Общество "Газпромнефть - Московский Нпз" (Ао "Газпромнефть - Мнпз") | Method for producing high-octane components from olefins of catalytic cracking |
WO2019236265A1 (en) * | 2018-06-07 | 2019-12-12 | Exxonmobil Research And Engineering Company | Naphtah hydrodesulfurization |
FI130130B (en) * | 2021-12-03 | 2023-03-09 | Neste Oyj | Waste plastic-based thermal cracking feed and method for upgrading the same |
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US5348641A (en) * | 1991-08-15 | 1994-09-20 | Mobil Oil Corporation | Gasoline upgrading process |
US5500108A (en) * | 1991-08-15 | 1996-03-19 | Mobil Oil Corporation | Gasoline upgrading process |
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US5320742A (en) * | 1991-08-15 | 1994-06-14 | Mobil Oil Corporation | Gasoline upgrading process |
US5318690A (en) * | 1991-08-15 | 1994-06-07 | Mobil Oil Corporation | Gasoline upgrading process |
US5326462A (en) * | 1991-08-15 | 1994-07-05 | Mobil Oil Corporation | Gasoline upgrading process |
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US5554274A (en) * | 1992-12-11 | 1996-09-10 | Mobil Oil Corporation | Manufacture of improved catalyst |
US5770047A (en) * | 1994-05-23 | 1998-06-23 | Intevep, S.A. | Process for producing reformulated gasoline by reducing sulfur, nitrogen and olefin |
US6126814A (en) * | 1996-02-02 | 2000-10-03 | Exxon Research And Engineering Co | Selective hydrodesulfurization process (HEN-9601) |
US6013598A (en) * | 1996-02-02 | 2000-01-11 | Exxon Research And Engineering Co. | Selective hydrodesulfurization catalyst |
US5863419A (en) * | 1997-01-14 | 1999-01-26 | Amoco Corporation | Sulfur removal by catalytic distillation |
US5985136A (en) * | 1998-06-18 | 1999-11-16 | Exxon Research And Engineering Co. | Two stage hydrodesulfurization process |
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US6042719A (en) * | 1998-11-16 | 2000-03-28 | Mobil Oil Corporation | Deep desulfurization of FCC gasoline at low temperatures to maximize octane-barrel value |
IT1311512B1 (en) * | 1999-03-12 | 2002-03-13 | Agip Petroli | CATALYTIC COMPOSITION FOR UPGRADING OF HYDROCARBONIC MIXTURES. |
US6599417B2 (en) * | 2000-01-21 | 2003-07-29 | Bp Corporation North America Inc. | Sulfur removal process |
US6602405B2 (en) * | 2000-01-21 | 2003-08-05 | Bp Corporation North America Inc. | Sulfur removal process |
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