US3847799A - Conversion of black oil to low-sulfur fuel oil - Google Patents
Conversion of black oil to low-sulfur fuel oil Download PDFInfo
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- US3847799A US3847799A US00296385A US29638572A US3847799A US 3847799 A US3847799 A US 3847799A US 00296385 A US00296385 A US 00296385A US 29638572 A US29638572 A US 29638572A US 3847799 A US3847799 A US 3847799A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 239000000295 fuel oil Substances 0.000 title claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 27
- 239000011593 sulfur Substances 0.000 title claims abstract description 27
- 239000003921 oil Substances 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 24
- 230000023556 desulfurization Effects 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012876 carrier material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100172879 Caenorhabditis elegans sec-5 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
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- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Definitions
- ABSTRACT [22] Filed. Oct 10 1972 An asphaltic. hydrocarbonaccous black oil. containing more than about 2.0 percent by weight of sulfur. is [21] Appl. No.: 296,385 converted to a low-sulfur fuel oil in a plurality of catalytic conversion zones. The process is designed to afford series-flow of hydrogen through the system, and Cl 3/ 208/100, 208/l03, permits the relatively easier desulfurization of lower- 203/212 boiling sulfurous compounds to be effected in a rela- [51] Int.
- the fuel oil product has a sulfur [56] References Cited concentration less than about 1.0 percent by weight, UNITED STATES PATENTS and concentrations of 0.5 percent by weight and less 3.717.571 2/1973 Schulman 208/210 a made. POSS-1pm exlst?
- Catalytic desulfurization is a well known process which is thoroughly described in petroleum technolinto hydrogen sulfide and hydrocarbons, and is often included in the'broad term hydrorefining. Hydrorefining is effected at operating conditions and severity levels which serve to promote denitrification and desulfurization primarily, and asphaltene conversion, nondistillable hydrocarbon conversion, hydrogenation and hydrocracking to a somewhat lesser extent.
- hydrorefining and desulfurization are generally employed synonymously to allude to a process wherein a hydrocarbon feedstock is cleaned-up in order to prepare a charge stock for subsequent utilization in a hydrocarbon conversion system, or for the purpose of recovering a product having an immediate utility.
- the combination process of my invention is beneficially utilized to produce a fuel oil containing less than about 1.0 percent by weight of sulfur, and often less than about 0.5 percent by weight, while simultaneously effecting at least partial conversion into lowerboiling hydrocarbon products.
- fuel oils meeting the limitations with respect to sulfur content, are derived by way of the desulfurization of atmospheric tower bottoms products, vacuum tower bottoms, heavy cycle stocks, crude oil residuum, topped crude oils, coal oils, oils extracted from tar sands, etcf
- Crude oils, and the heavier hydrocarbon fractions and/or distillates obtained therefrom contain nitrogenous and sulfurous compounds in exceedingly large quantities, the latter generally being in the range of about 2.5 percent to about 5.0 percent by weight, calculated as elemental sulfur.
- heavy hydrocarbon fractions sometimes referred to in the petroleum refining art as black oils," contain organometallic contaminants principally comprising nickel and vanadium, as well as high molecular weight asphaltic material.
- Illustrative of those charge stocks, to which the present invention is applicable, are a vacuum tower bottoms product, having a gravity of 7.l APl and containing 4.05 percent by weight of sulfur; a topped Middle-East crude oil, having a gravity of 11.0 APl, and containing 5.20 percent by weight of sulfur; and, a vacuum residuum having a gravity of about 8.8 APl, and containing 3.0 percent by weight of sulfur.
- the utilization of the process of the present invention affords the maximum recovery of low-sulfur fuel oil from these heavier hydrocarbonaceous charge stocks in a manner which affords significant economic advantages.
- OBJECTS AND EMBODIMENTS fied desulfurization process which permits the maximum recovery of a fuel oil product from black oil charge stocks, and at alower operating severity level.
- the present invention encompassesa process for producing a fuel oil, containing less than about 1.0 percent by weight of sulfur, from a sulfurous black oil charge stock, which process comprises the steps: (a) reacting said charge stock with hydrogen in a first catalytic reaction zone, at desulfurization conditions selected to convert sulfurous compounds into hydrogen sulfide and hydrocarbons; (b) separating at least a portion of the resulting first reaction zone effluent, in a first separation zone, at substantially the same temperature and pressure, to provide a first principally vaporous phase and a first principally liquid phase; (ciseparating at least a portion of said first vaporous phase, in a second separation zone, at substantially the same pressure and a temperature in the range of about 60F.
- the present invention utilizes at least two fixed-bed catalytic reaction systems in combination with a particular series of separation facilities which afford more efficient utilization of series-flow hydrogen throughout the entire process. It is understood that each reaction system may consist of one or more reaction vessels having suitable heat-exchange facilities therebetween.
- the combination process is effected by initially reacting the charge stock with a relatively impure (from the standpoint of hydrogen sulfide concentration) hydrogen stream in a first reaction zone. In effect, this first reaction zone accomplishes the relatively easy desulfurization of the lower-boiling sulfurous compounds within the black oil charge stock.
- the product effluent is separated, at substantially the same temperature and pressure, to provide a higher-boiling normally liquid phase which is reacted in the second reaction system with a relatively pure hydrogen phase.
- the second reaction system will function under an imposed pressure less than that imposed upon the first reaction system. This enables the process to be effected without the necessity for providing the hot pump normally required to introduce the first principally liquid phase into the second reaction system.
- the operating conditions within both reaction systems will include a pressure from about 200 to about 3,000 psig., a hydrogen concentration in the range of about 500 to about 30,000 scf./Bbl., a liquid hourly space velocity of about 0.25 to about 2.50 and a maximum catalyst bed temperature in the range of about 600F. to about 900F.
- Preferred operating techniques dictate that the increasing temperature gradient, resulting from the exothermic reactions being effected, be limited to a maximum of about 100F.
- quench streams either normally liquid, or normally gaseous, introduced at one or more intermediate loci of the catalyst bed.
- the advantages of the described process are numerous; however, principal among these is a significant reduction in the maximum catalyst bed temperature to achieve the desired degree of desulfurization.
- the maximum catalyst bed temperature may be within the range of about 600F. to about 900F., it is not uncommon to conduct the present combination process at maximum catalyst bed temperatures below about 800F.
- the present combination process permits the utilization of a relatively impure hydrogen stream to effect the desulfurization of lowerboiling sulfurous compounds in the first catalytic reaction system.
- Still another advantage concerns an extension of the effective acceptable life of the catalytic composites employed in both reaction zones.
- the catalytic composites will possess different physical and chemical characteristics in many situations, they may be identical. Regardless, the catalytic composites employed in the present combination process comprise metallic components selected from the metals of Groups VI-B and VIII of the Periodic Table, as well as compounds thereof.
- suitable metallic components are those selected from the group consisting of chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.
- the charge stock to the present combination process is generally of a highboiling nature, it is preferred that the catalytically active components possess the propensity to effect hydrocracking while simultaneously promoting the conversion of sulfurous compounds into hydrogen sulfide and hydrocarbons.
- concentrations of the catalytically active metallic component, or components is principally dependent upon the particular metal as well as the physical and/or chemical characteristics of the charge stock.
- the metallic components of Groups VI-B are generally present in an amount within the range of about 4.0 to about 30.0 percent by weight, the iron'group metals in an amount within the range of about 0.2 to about 10.0 percent by weight, whereas the noble metals of Group VIII are preferably present in an amount within the range of about 0.1 to about 5.0 percent by weight.
- a zinc and/or bismuth component is employed, the same will generally be present in an amount within the range of about 0.01 to about 2.0 percent by weight. All concentrations of the metallic components are calculated as if they existed in the composite in the elemental state.
- the porous carrier material comprises a refractory inorganic oxide of the character thoroughly described in the literature.
- amorphous type, alumina, or alumina in combination with 10.0 to about 90.0 percent by weight silica is preferred. It may be appropriate to utilize a carrier material containing a crystalline aluminosilicate, or zeolitic molecular sieve. In many instances, such a carrier material will be utilized in processing the partially desulfurized feed stock to the second reaction zone.
- Suitable zeolitic material includes mordenite, faujasite, Type A or Type U molecular sieves, etc., and these may be employed in a substantially pure state; however, it is understood that the zeolitic material may be included within an amorphous matrix such as silica, alumina, or mixtures of alumina and silica. It is further contemplated that the catalytic composites may have incorporated therein a halogen component, such component being selected from the group consisting of fluorine, chlorine, iodine, bromine, and mixtures thereof. The halogen component will be composited with the carrier material in such a manner as results in a final catalytic composite containing from about 0.1 to about 2.0 percent by weight.
- the metallic components may be incorporated within the catalytic composite in any suitable manner including coprecipitation or cogellation with the carrier material, ion-exchange or impregnation of the carrier material, or during a co-extrusion procedure.
- the composite is dried and subjected to a high temperature calcination or oxidation technique at a temperature of about 750F. to about l, 300F.
- the upper limit for the calcination technique is preferably about l,000F.
- the operating conditions imposed upon the catalytic reaction zones are selected primarily to effect the conversion of sulfurous compounds to hydrogen sulfide and hydrocarbons.
- the operating conditions imposed upon the second reactionzone will often result in a greater operating severity, although such technique is not essential.
- the variance in operating severity levels between the two operating reaction zones is obtained by maintaining the first reaction zone at a lower maximum catalyst bed temperature, greater liquid hourly space velocity and at a higher pressure.
- the first reaction zones maximum catalyst bed temperature will be at least about F. less than that of the second catalytic reaction zone, while the pressure is preferably about 50 psig. greater.
- a pressure substantially the same as, or a temperature substantially the same as, is intended to connote the pressure or temperature on a downstream vessel, allowing only for the normal pressure drop due to fluid flow through the system, and the normal temperature loss due to transfer of material from one zone to another.
- the first separation zone will function at substantially the same pressure and temperature, about 2,125 psig. and 700F., respectively.
- the utilization of this phrase at least a portion of, when referring to either a principally vaporous phase, or a principally liquid phase, is intended to encompass both an aliquot portion as well as a select fraction.
- at least a portion of the second principally vaporous phase is introduced into the second reaction zone following the removal of hydrogen sulfide therefrom, while at least a portion (in this case an ali- 6 quot portion) of 'the first principally liquid phase may be recycled to the first catalytic reaction zone.
- the charge stock in an amount of about 40,000 Bbl./day, is introduced into the process by way of line 1, admixed with a hydrogen-rich recycled gaseous phase in line 2 (the source of which is hereinafter set forth), the mixture continuing through line 1 into catalytic reaction zone 3.
- Reaction zone 3 is maintained under an imposed pressure of about 2,000 psig., and the reactants contact the catalyst bed at a temperature of about 750F.
- the catalyst is a composite of about 2.0 percent nickel and 16.0 percent molybdenum combined with a carrier of 63.0 percent alumina and 37.0 percent silica.
- the reactants traverse the catalyst bed at a liquid hourly space velocity of about 0.80, and the maximum catalyst bed temperature is controlled at a level of about 800F.
- the product effluent is withdrawn by way of line 4 and introduced, at substantially the same temperature and pressure into hot separator 5 from which a principally vaporous phase is withdrawn by way of line 6.
- the first principally liquid phase withdrawn from hot separator 5 by way of line-13, constitutes the normally liquid charge to reactor 15.
- Make-up hydrogen, to supplant that consumed in the first catalytic reaction zone, is introduced by way of line 14, and combined with the normally liquid phase in line 13 and the hydrogenenriched stream in line 11; the mixture continues through line 11 into reactor 15.
- Reactor 15 contains a catalytic composite comprising about 1.8 percent by weight of nickel and 16.0 percent by weight of molybdenum combined with a carrier material of 88.0 percent by weight of alumina and 12.0 percent by weight of silica, the liquid hourly space velocity therethrough being about 0.66.
- the maximum catalyst bed temperature is maintained at a level of about 775F., the imposed pressure being about 1,850
- the product effluent from reactor 15 is withdrawn by way of line 16 and introduced thereby into hot separator 17 at substantially the same temperature and pressure.
- a hydrogen-rich stream, containing hydrogen sulfide, is withdrawn by way of line 18 and introduced into cold separator 19 at a temperature of about 90F.
- a principally vaporous phase is withdrawn through line 2 and recycled to first catalytic reaction zone 3.
- the average molecular weight of the fourth vaporous phase, being recycled through line 2 via compressive means, is about 4.0 to 5.0.
- This third vaporous phase has an average molecular weight of about 7.0 to 12.0 which increases the pressure drop, and, consequently, the load on the compressor required to recycle the same.
- the second normally liquid phase withdrawn from cold separator 7, via line 12, constitutes a portion of the product of the present combination process, and is transmitted therethrough to suitable stabilization facilities.
- the third principally liquid stream from line 20 is admixed with the product in line 12, as is the fourth principally liquid phase from line 21.
- a portion of the principally liquid phase in line 13 may be diverted to combine with the charge stock in line 1, serving as a diluent therefor; similarly, a portion may be combined with the product effluent from reactor 3 for introduction into hot separator 5.
- a portion of the normally liquid phase in line 20 may be diverted to combine with the normally liquid phase is line 13, and- /or diverted to combine with the product effluent from reactor 15.
- Inclusive is a hydrogen consumption of about 1.26 percent by weight of the fresh feed charge stock (approximately 800 scf./Bbl.).
- the desired fuel oil product, 650F.-plus is recov ered in an amount of 88.96 percent by volume of the fresh feed charge stock (about 35,600 Bbl./day).
- the fuel oil has a gravity of about 23.0 APl, and contains only 0.32 percent by weight of sulfur.
- the 400650F. middle-distillate contains about 0.05 percent by weight of sulfur, while the heptane-400F. naphtha fraction contains less than about 0.01 percent by weight of sulfur.
- a process for producing a fuel oil, containing less than about 1.0 percent by weight of sulfur, from a sulfurous black oil charge stock which process comprises the steps of:
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00296385A US3847799A (en) | 1972-10-10 | 1972-10-10 | Conversion of black oil to low-sulfur fuel oil |
CA181,962A CA997699A (en) | 1972-10-10 | 1973-09-26 | Conversion of black oil to low-sulfur fuel oil |
JP11108273A JPS5321405B2 (enrdf_load_stackoverflow) | 1972-10-10 | 1973-10-04 | |
DE19732349840 DE2349840C3 (de) | 1972-10-10 | 1973-10-04 | Verfahren zur Herstellung von Brennoder Heizöl |
FR7336012A FR2202148B2 (enrdf_load_stackoverflow) | 1972-10-10 | 1973-10-09 | |
GB4707673A GB1437527A (en) | 1972-10-10 | 1973-10-09 | Conversion of black oil to low-sulphur fuel oil |
IT53021/73A IT1050216B (it) | 1972-10-10 | 1973-10-09 | Procedimento per la produzione in piu stadi di olio pesante a basso contenuto di zolfo |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00296385A US3847799A (en) | 1972-10-10 | 1972-10-10 | Conversion of black oil to low-sulfur fuel oil |
Publications (1)
Publication Number | Publication Date |
---|---|
US3847799A true US3847799A (en) | 1974-11-12 |
Family
ID=23141789
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00296385A Expired - Lifetime US3847799A (en) | 1972-10-10 | 1972-10-10 | Conversion of black oil to low-sulfur fuel oil |
Country Status (6)
Country | Link |
---|---|
US (1) | US3847799A (enrdf_load_stackoverflow) |
JP (1) | JPS5321405B2 (enrdf_load_stackoverflow) |
CA (1) | CA997699A (enrdf_load_stackoverflow) |
FR (1) | FR2202148B2 (enrdf_load_stackoverflow) |
GB (1) | GB1437527A (enrdf_load_stackoverflow) |
IT (1) | IT1050216B (enrdf_load_stackoverflow) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3992284A (en) * | 1975-09-17 | 1976-11-16 | Uop Inc. | Black oil conversion process startup and shutdown methods |
US4243519A (en) * | 1979-02-14 | 1981-01-06 | Exxon Research & Engineering Co. | Hydrorefining process |
US4392945A (en) * | 1982-02-05 | 1983-07-12 | Exxon Research And Engineering Co. | Two-stage hydrorefining process |
US4551238A (en) * | 1984-11-06 | 1985-11-05 | Mobil Oil Corporation | Method and apparatus for pressure-cascade separation and stabilization of mixed phase hydrocarbonaceous products |
WO1990013617A1 (en) * | 1989-05-10 | 1990-11-15 | Davy Mckee (London) Limited | Multi-step hydrodesulphurisation process |
WO1992008772A1 (en) * | 1989-05-10 | 1992-05-29 | Davy Mckee (London) Limited | Hydrodesulphurisation process |
AU658131B2 (en) * | 1990-11-07 | 1995-04-06 | Davy Process Technology Limited | Hydrodesulphurisation process |
US6096190A (en) * | 1998-03-14 | 2000-08-01 | Chevron U.S.A. Inc. | Hydrocracking/hydrotreating process without intermediate product removal |
US6179995B1 (en) | 1998-03-14 | 2001-01-30 | Chevron U.S.A. Inc. | Residuum hydrotreating/hydrocracking with common hydrogen supply |
US6200462B1 (en) | 1998-04-28 | 2001-03-13 | Chevron U.S.A. Inc. | Process for reverse gas flow in hydroprocessing reactor systems |
US6224747B1 (en) | 1998-03-14 | 2001-05-01 | Chevron U.S.A. Inc. | Hydrocracking and hydrotreating |
US6843906B1 (en) | 2000-09-08 | 2005-01-18 | Uop Llc | Integrated hydrotreating process for the dual production of FCC treated feed and an ultra low sulfur diesel stream |
TWI697557B (zh) * | 2017-12-29 | 2020-07-01 | 美商魯瑪斯科技有限責任公司 | 轉化重質燃料油為化學品之技術 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3193495A (en) * | 1961-05-05 | 1965-07-06 | Esso Standard Eastern Inc | Desulfurization of wide boiling range crudes |
US3475327A (en) * | 1966-10-28 | 1969-10-28 | Exxon Research Engineering Co | Hydrodesulfurization of blended feedstock |
US3691152A (en) * | 1971-03-10 | 1972-09-12 | Texaco Inc | Hydrodesulfurization and blending of residue-containing petroleum oil |
US3717571A (en) * | 1970-11-03 | 1973-02-20 | Exxon Research Engineering Co | Hydrogen purification and recycle in hydrogenating heavy mineral oils |
-
1972
- 1972-10-10 US US00296385A patent/US3847799A/en not_active Expired - Lifetime
-
1973
- 1973-09-26 CA CA181,962A patent/CA997699A/en not_active Expired
- 1973-10-04 JP JP11108273A patent/JPS5321405B2/ja not_active Expired
- 1973-10-09 GB GB4707673A patent/GB1437527A/en not_active Expired
- 1973-10-09 IT IT53021/73A patent/IT1050216B/it active
- 1973-10-09 FR FR7336012A patent/FR2202148B2/fr not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3193495A (en) * | 1961-05-05 | 1965-07-06 | Esso Standard Eastern Inc | Desulfurization of wide boiling range crudes |
US3475327A (en) * | 1966-10-28 | 1969-10-28 | Exxon Research Engineering Co | Hydrodesulfurization of blended feedstock |
US3717571A (en) * | 1970-11-03 | 1973-02-20 | Exxon Research Engineering Co | Hydrogen purification and recycle in hydrogenating heavy mineral oils |
US3691152A (en) * | 1971-03-10 | 1972-09-12 | Texaco Inc | Hydrodesulfurization and blending of residue-containing petroleum oil |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3992284A (en) * | 1975-09-17 | 1976-11-16 | Uop Inc. | Black oil conversion process startup and shutdown methods |
US4243519A (en) * | 1979-02-14 | 1981-01-06 | Exxon Research & Engineering Co. | Hydrorefining process |
US4392945A (en) * | 1982-02-05 | 1983-07-12 | Exxon Research And Engineering Co. | Two-stage hydrorefining process |
US4551238A (en) * | 1984-11-06 | 1985-11-05 | Mobil Oil Corporation | Method and apparatus for pressure-cascade separation and stabilization of mixed phase hydrocarbonaceous products |
US5292428A (en) * | 1989-05-10 | 1994-03-08 | Davy Mckee (London) Ltd. | Multi-step hydrodesulphurization process |
WO1992008772A1 (en) * | 1989-05-10 | 1992-05-29 | Davy Mckee (London) Limited | Hydrodesulphurisation process |
WO1990013617A1 (en) * | 1989-05-10 | 1990-11-15 | Davy Mckee (London) Limited | Multi-step hydrodesulphurisation process |
AU658131B2 (en) * | 1990-11-07 | 1995-04-06 | Davy Process Technology Limited | Hydrodesulphurisation process |
US6096190A (en) * | 1998-03-14 | 2000-08-01 | Chevron U.S.A. Inc. | Hydrocracking/hydrotreating process without intermediate product removal |
US6179995B1 (en) | 1998-03-14 | 2001-01-30 | Chevron U.S.A. Inc. | Residuum hydrotreating/hydrocracking with common hydrogen supply |
US6224747B1 (en) | 1998-03-14 | 2001-05-01 | Chevron U.S.A. Inc. | Hydrocracking and hydrotreating |
US6200462B1 (en) | 1998-04-28 | 2001-03-13 | Chevron U.S.A. Inc. | Process for reverse gas flow in hydroprocessing reactor systems |
US6843906B1 (en) | 2000-09-08 | 2005-01-18 | Uop Llc | Integrated hydrotreating process for the dual production of FCC treated feed and an ultra low sulfur diesel stream |
TWI697557B (zh) * | 2017-12-29 | 2020-07-01 | 美商魯瑪斯科技有限責任公司 | 轉化重質燃料油為化學品之技術 |
Also Published As
Publication number | Publication date |
---|---|
FR2202148B2 (enrdf_load_stackoverflow) | 1978-04-21 |
CA997699A (en) | 1976-09-28 |
FR2202148A2 (enrdf_load_stackoverflow) | 1974-05-03 |
JPS5321405B2 (enrdf_load_stackoverflow) | 1978-07-03 |
JPS5058102A (enrdf_load_stackoverflow) | 1975-05-20 |
DE2349840A1 (de) | 1974-04-25 |
GB1437527A (en) | 1976-05-26 |
DE2349840B2 (de) | 1977-05-18 |
IT1050216B (it) | 1981-03-10 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD;REEL/FRAME:005006/0782 Effective date: 19880916 |
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AS | Assignment |
Owner name: UOP, A GENERAL PARTNERSHIP OF NY, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UOP INC.;REEL/FRAME:005077/0005 Effective date: 19880822 |