US3268437A - Hydrocracking of nitrogen containing hydrocarbon oils for the preparation of middle oils - Google Patents
Hydrocracking of nitrogen containing hydrocarbon oils for the preparation of middle oils Download PDFInfo
- Publication number
- US3268437A US3268437A US305543A US30554363A US3268437A US 3268437 A US3268437 A US 3268437A US 305543 A US305543 A US 305543A US 30554363 A US30554363 A US 30554363A US 3268437 A US3268437 A US 3268437A
- Authority
- US
- United States
- Prior art keywords
- catalyst
- percent
- hydrogen
- hydrocracking
- oils
- 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.)
- Expired - Lifetime
Links
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 28
- 239000003921 oil Substances 0.000 title description 70
- 229930195733 hydrocarbon Natural products 0.000 title description 4
- 239000004215 Carbon black (E152) Substances 0.000 title description 3
- 238000002360 preparation method Methods 0.000 title description 3
- -1 nitrogen containing hydrocarbon Chemical class 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 72
- 238000009835 boiling Methods 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 description 54
- 229910052739 hydrogen Inorganic materials 0.000 description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 42
- 239000003502 gasoline Substances 0.000 description 30
- 238000005336 cracking Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229910052736 halogen Inorganic materials 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 239000000295 fuel oil Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 150000002367 halogens Chemical class 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 5
- 239000010763 heavy fuel oil Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- XOROUWAJDBBCRC-UHFFFAOYSA-N nickel;sulfanylidenetungsten Chemical compound [Ni].[W]=S XOROUWAJDBBCRC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
Images
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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
Definitions
- This invention has for its object to provide improved procedure for hydrocracking of high boiling feed stocks into middle oils in relatively high ratios as compared with gasoline. Another object is to provide a relatively economical process for hydrocracking higher boiling stocks into middle oils. A still further object is to provide improved procedure in which a heavy stock is hydrocracked into a middle oil which has unusual properties which qualify it for use in viscosity reduction of heavy fuel oils. Another object is to improve the state of the art. Other objects will appear hereinafter.
- a feed stock which has a higher boiling point than the desired middle oil to hydrocracking in the presence of a two-component catalyst, one component of which comprises nickel-tungsten sulfide and the other component of which comprises a siliceous cracking base having a cracking activity of at least 45 Al.
- This treatment is carried out at between about 400 and 1200 psi. hydrogen partial pressure, at a temperature between about 800 and 900 F., at a space velocity between about 2 and 8 and maintaining conversion at between about 20 and 50 percent.
- the feed stock must contain at least about 100 ppm. of nitrogen as nitrogenous compounds. Amounts above about 600 ppm. are advantageous and may be as high as 0.3 percent nitrogen as nitrogenous compounds.
- the predominant part of the feed stock should boil above about 675 F. It may contain minor amounts of Patented August 23, 1966 "ice materials having a lower boiling point, but predominant amounts are not desirable since these lower boiling materials are the products which are to be produced.
- the feed stock may be a straight run atmospheric or vacuum distillate of petroleum. It may be a wide boiling range fraction boiling above about 675 P. such as would be ordinarily produced by atmospheric or vacuum distillation of petroleum. On the other hand it may be a narrow boiling fraction of petroleum which boils above about 675 F. Cracked gas oils or gas oils from coking or visbreaking can also be used for this process. Use of these stocks would have the advantage that they are lower value materials and would be more economical and appropriate for producing cutter oils for low-value residual fuels.
- the feed must contain at least p.p.m. of nitrogenous materials. If this nitrogen is not present, the highly active catalyst which is employed will result in extensive hydrocracking to form undesirably large amounts of gasoline. Also deposition of coke on the catalyst will take place at an excessive rate, necessitating uneconomically frequent regenerations. Furthermore absence of this amount of nitrogenous materials would increase hydrogen consumption, and it is an advantage of our invention that hydrogen consumption is reduced. These nitrogenous materials are usually present in these petroleum fractions in the required amounts. However, if the feed stock in question is low in nitrogen, it may be mixed with a petroleum fraction high in nitrogenous impurities or nitrogen compounds such as amines may be added. The feed should be substantially free of asphaltic materials.
- the catalyst which is employed in our progress must be a highly active catalyst.
- a nickel-tungsten sulfide catalyst is the only catalyst which We have found which has satisfactory activity and life under the conditions we employ.
- the catalyst may contain between about 5 and 40 percent and preferably 10 to 25 percent of nickel plus tungsten (determined as metals).
- the atomic ratio may be between 1 atom of tungsten to 0.1 of nickel to 1 atom of tungsten to 5 atoms of nickel.
- the catalyst may be pro-sulfided or it may be sulfided in situ, i.e., by the presence of sulfur in the hydrogen and/ or feed streams. We prefer to employ a pre-sulfided catalyst.
- the catalyst must be maintained in sulfided condition duringuse.
- Sulfur in an amount above about 0.1 percent of the feed is desirable. Amounts of about 0.1 to 2 percent are advantageous.
- This sulfur content includes the sulfur in the recycle hydrogen, the recycle feed and the fresh feed.
- any organic or inorganic sulfur compound having a hydrogen-to-sulfur or a carbon-to-sulfur linkage as Well as elemental sulfur can be used such as butyl mercaptan, thiophene, hydrogen sulfide, etc. While we have referred to the catalyst as being sulfided, this does not necessarily mean that the metals are necessarily sulfides. It does mean that the catalyst contains sulfur.
- These supports may also contain additional components
- the metals may be present in form of other sulfur compounds than sulfides,
- the nickel and tungsten components may be composited with the siliceous cracking support in any desired manner.
- the nickel and tungsten may be co-precipitated thereon or the two components may be deposited in sequence.
- a catalyst which contains between about 0.1 and 5 percent halogen such as fluorine or chlorine. This increases the initial activity of the catalyst as well as extending its life at the moderate pressures and high temperatures employed in our process.
- the halogen is advantageously incorporated in the siliceous cracking base during its preparation. However, it may be incorporated in the catalyst during use by adding the halogen to the feed stock and/ or hydrogen.
- Our invention is carried out at a hydrogen partial pressure between about 400 and L200 p.s.i. While higher partial pressures can be used, we do not include them within the scope of our invention for several reasons. Thus it is an objective of our invention to provide a moderate pressure procedure for this particular type of hy-drocracking operation. Also higher pressures are not only relatively costly but result in a lower ratio of middle oil to gasoline which is contrary to the objectives of our invention. Also these higher pressures increase hydrogen consumption, which is contrary to one of the objectives of our invention. It is necessary to employ a temperature between about 800 and 900 F. during the onstream reaction and to keep conversion at a relatively low rate of 20 to 50 percent in order to obtain economically attractive throughputs.
- Conversion is maintained in this range by selecting a temperature and space velocity which will result in the desired conversion. Usually a space velocity of between about 2 and 8 volumes of feed stock per volume of catalyst per hour will be found satisfactory at the 800 to 900 F. temperature. By conversion we mean net make of gasoline plus furnace oil having a boiling point from 100 to 675 F.
- the process of our invention is carried out at a temperature between about 800 and 900 F.
- these fresh catalysts have exceedingly high activity and While high activity is essential in our invention, this excessive activity would cause rapid initial coking if the catalyst were initially employed at the relatively high temperatures of our invention. Therefore the catalyst is contacted with the feed stock at this lower temperature until this high activity edge has been taken off the catalyst. This will ordinarily be accomplished after about 8 to 24 hours.
- the temperature is then increased to a temperature within the range of 800 to 900 R, which temperature gives the desired conversion of 20 to 50 percent at the selected space velocity between 2 and 8.
- the regenerated catalyst is then re-used in the process preferably after sulfiding and incorporation of halogen lost during the reaction and/ or regeneration. It is advantageous to gradually increase the temperature as the catalyst becomes deactivated in order to maintain conversion approximately constant. When a point is reached where an excessive rate of temperature increase is necessary to maintain desired conversion or when the maximum temperature of 900 F. is reached, the reaction is terminated. The catalyst is regenerated in the usual manner and then re-used.
- conversions in the range of .20 to 50 percent is an important factor in accomplishing the objectives of our invention. Thus if a conversion above about 50 percent is employed it will be found that the throughput will be markedly reduced, i.e., the activity of the catalyst will be rapidly reduced due to deposition of coke at these excessive conversions. While conversions below about 20 are satisfactory insofar as throughput is concerned, they are not economically attractive. A conversion of between about 30 and 40 percent is especially advantageous.
- the effluent from the hydrocracking reactor is separated in known manner.
- the hydrogen may be separated in .a high pressure separator and the separated hydrogen may be recycled for re-use in the process. Since hydrocarbon gases, ammonia, hydrogen sulfide, etc. are formed during hydrocracking, at least some of the hydrogen should be bled from the system and make-up hydrogen of a higher concentration added.
- the liquid products from hydrocracking are subjected to distillation to separate gasoline, middle oil, etc. and the unconverted material, i.e., that boiling above about 675 F. may be recycled to the hydrocracking step if desired. It is substantially upgraded and may be used in other applicaiions where a low nitrogen and low sulfur feed is required.
- the middle oil i.e., that having a boiling range in the range between about 300 and 675 F., constitutes a good quality furnace oil which may be used as such or which may be blended with a straight run furnace oil to obtain a high quality product.
- middle oil fraction is advantageously employed for reducing the viscosity of residual petroleum fractions such as atmospheric and vacuum reduced crude. These low-grade residual stocks have such a high viscosity that it is necessary to dilute them with higher quality and more valuable lighter hydrocarbons to improve their free-flowing properties.
- the middle oil produced in our invention is particularly advantageous for this purpose. Thus, the middle oil produced in accordance with.
- our invention has a higher heat of combustion than a middle oil produced by conventional hydrocracking.
- the preferred middle distillate is produced at a much lower cost, resulting from the use of a lower operating pressure, a higher space velocity, and a lower hydrogen consumption.
- the relatively low cost of this oil makes it especially advantageous for use as cutter oil for residual fuels.
- This low cost oil can be used to replace high value straight run kerosene, which is often currently used as cutter oil to decrease viscosity and pour points of residual fuels.
- a feed stock boiling above 675 F. and containing at least ppm. of nitrogenous compounds is fed by means of line 10 into bydrocracking reactor 12.
- Hydrogen is charged to reactor :12 by means of line 14 at a rate of at least 5,000 standard cubic feet of hydrogen per barrel of feed introduced through line '10.
- the hydrogen of line 14 is contacted with the feed of line in hydrocracking reactor 12 at a hydrogen partial pressure in the range from 400 to 1200 p.s.i. and at a temperature between 800 and 900 F. in the presence of a sulfided nickel-tungsten-halogen catalyst composited with a siliceous cracking base, which base has a cracking activity index above about 45. This is the catalyst required by our invention and described previously.
- the particular conditions employed in reactor 12 are selected so as to maintain a conversion, i.e., a net make of products boiling in the range of 100 to 675 F., between about and 50 percent.
- the effluent is removed from reactor 12 by means of line 16 and passed to distillation column 18.
- distillation column 18 the hydrocracked product boiling below 675 F. is removed overhead by means of line 20, while that portion of the effluent boiling above 675 F. is removed from the bottom of distillation column 18 by means of line 22 and passed to catalytic cracker 24.
- the operating conditions and catalyst employed in cracker 24 can be selected from those catalysts and conditions wellknown to the art.
- the catalytically cracked efiiuent is removed from cracker 24 by means of line 26.
- the third major advantage of our invention is the lower cost of operation. This results from :the use of a lower operating pressure and a high liquid hourly space velocity, as well as a low hydrogen consumption. This is especially advantageous where the objective of the process is to produce a middle distillate suitable for use as cutter oil in low-value residual fuels.
- the hydrocracking process for preparing a middle oil without substantially deactivating the catalyst which comprises subjecting a feed stock having less than 5 percent by volume of components boiling below about 675 F., containing at least about 100 p.p.m. of nitrogenous compounds to treatment with hydrogen in an amount of at least 5000 s.c.f. of hydrogen per barrel of feed stock at a hydrogen partial pressure between about 400 and 1200 p.s.i., at a temperature between about 800 and 900 F.
- the hydrocra-cking process for preparing a middle oil without substantially deactivating the catalyst which comprises subjecting a feed stock having less than 5 percent by volume of components boiling below about 675 F., containing at least about 100 p.p.m. of nitrogenous compounds to treatment with hydrogen in an amount of at least 5000 s.c.f. of hydrogen per barrel of feed stock at a hydrogen partial pressure between about 400 and 1200 p.s.i., at a temperature between about 800 and 900 F.
- the hydrocracking process for preparing a middle oil without substantially deactivating the catalyst which comprises subjecting a heavy gas oil having less than 5 percent by volume of components boiling below about 675 F., containing at least about 100 ppm. of nitrogenous compounds .to treatment with hydrogen in an amount of at least 5000 s.c.-f. of hydrogen per barrel of feed stock at a hydrogen partial pressure between about 400 and 1200 p.s.i. at a temperature between about 800 and 900 F.
- the hydrocracking process for preparing middle oils without substantially deactivating the catalyst which comprises subjecting a straight run heavy gas oil having less than 5 percent by volume of components boiling below about 675 F., containing at least about 100 ppm. of nitrogenous compounds to treatment with hydrogen in an amount of at least 5000 s.c.f. of hydrogen per barrel of feed stock at a hydrogen partial pressure between about 400 and 1200 p.s.i. at a temperature between about 600 and 800 F.
- the hydrocracking process for preparing middle 'oils without substantially deactivating the catalyst which comprises subjecting a straight run heavy gas oil having less than 5 percent by volume of components boiling below about 67 5 F., containing at least about 100 ppm. of nitrogenous compounds to treatment with hydrogen in anamount of at least 5000 s.c.f. of hydrogen per barrel of feed stock at a hydrogen partial pressure between about 400 and 1200 p.s.i., at a temperature between about 800 and 900 F.
- a sulfided nickel-tungsten-halogen catalyst composited with a siliceous cracking base which base has a cracking activity index above about 4'5, maintaining conversion (net make of gasoline plus middle oil B.P. 100- 675 F.) between about 20 and 50 percentwith a ratio of middle oil (400675 F.) to gasoline (C -400 F.) in the converted product of at least 2:1, subjecting the liquid portion of the product to distillation to separate a middle oil fraction having a boiling range in the range of 300 to 750 3 F., adding this fraction to a residual petroleum fraction and continuing said hydrogen treatment for a throughput of at least 1200 volumes of feed per volume of catalyst.
- the hydrocracking process for preparing middle oils without substantially deactivating the catalyst which comprises subjecting a straight run heavy gas oil having less than 5 percent by volume of components boiling below about 675 F., containing at least about ppm. of nitrogenous compounds to treatment with hydrogen in an amount of at least 5000 s.c.f. of hydrogen per barrel of feed stock at a hydrogen partial pressure between about 400 and 1200 p.s.i., at a temperature between about 600 and 800 F.
- a process for producing a middle oil without substantially deactivating the catalyst boiling in the range from about 400 to about 675 F. which comprises subjecting a heavy gas oil having less than 5 percent by volume of components boiling below 675 F. and containing at least 100 ppm. of nitrogenous compounds to treatment with hydrogen in an amount of at least 5,000 standard cubic feet of hydrogen per barrel of feed stock in the presence of a sulfided nickel-tungstenhalogen catalyst composited with a silica-alumina cracking base, said nickel and tungsten being present in the approximate mol ratio of about 1:1, said nickel and tungsten combined comprising about 25 percent by weight of the total catalyst composite, said halogen being present in the amount of 2 percent by weight based on the total catalyst composite, said base being comprised of about 75 percent silica and about 25 percent by weight alumina and said base having a cracking activity index above about 45, at a hydrogen partial pressure between about 400 and 1200 p.s.i., at a temperature between about 800 and 900 F.
- the heavy gas oil contains at least 600 ppm. of nitrogenous compounds
- the heavy gas oil is treated with at least 10,000 standard cubic feet of hydrogen per barrel of feed
- the cracking base has an activity index above about 70
- the liquid hourly space velocity is from about 3.0 to about 7.0
- the conversion is between about 20 and 30' percent
- the production of gasoline is less than 10 percent.
- a process for producing a middle oil without substantially deactivating the catalyst boiling in the range from about 350 to about 675 F. which comprises subjecting a heavy gas oil having less than 5 percent by volume of components boiling below 675 F. and containing at least 100 ppm. of nitrogenous compounds to treatment with hydrogen in an amount of at least 5,000
- a sulfided nickel-tungsten-hal ogen catalyst composited with a silica-a1umina cracking base said nickel and tungsten being present in the approximate mol ratio of about 1:1, said nickel and tungsten combined comprising about 25 percent by weight of the total catalyst composite, said halogen being present in the amount of 2 percent by weight based on the total catalyst composite, said base being comprised of about 75 percent silica and about 25 percent by weight alumina and said base having a cracking activity index above about 45, at a hydrogen partial pressure between about 400 and 1200 psi, at a temperature between about 800 and 900 F.
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)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL129736D NL129736C (enrdf_load_html_response) | 1963-08-29 | ||
US305543A US3268437A (en) | 1963-08-29 | 1963-08-29 | Hydrocracking of nitrogen containing hydrocarbon oils for the preparation of middle oils |
DE19641470566 DE1470566A1 (de) | 1963-08-29 | 1964-07-28 | Verfahren zur Herstellung von OElen mittlerer Siedelage durch hydrierende Spaltung von hochsiedenden Erdoelfraktionen |
GB31210/64A GB1042710A (en) | 1963-08-29 | 1964-08-04 | Hydrocracking process for preparing middle oils |
LU46702D LU46702A1 (enrdf_load_html_response) | 1963-08-29 | 1964-08-05 | |
CH1069664A CH433220A (fr) | 1963-08-29 | 1964-08-17 | Procédé d'hydrocraquage |
BE652082D BE652082A (enrdf_load_html_response) | 1963-08-29 | 1964-08-20 | |
NL6410024A NL6410024A (enrdf_load_html_response) | 1963-08-29 | 1964-08-28 | |
FR986480A FR1407410A (fr) | 1963-08-29 | 1964-08-28 | Procédé d'hydrocraquage |
DK426264AA DK112262B (da) | 1963-08-29 | 1964-08-28 | Hydrogenkrakningsfremgangsmåde til fremstilling af en middelsvær olie. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US305543A US3268437A (en) | 1963-08-29 | 1963-08-29 | Hydrocracking of nitrogen containing hydrocarbon oils for the preparation of middle oils |
Publications (1)
Publication Number | Publication Date |
---|---|
US3268437A true US3268437A (en) | 1966-08-23 |
Family
ID=23181225
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US305543A Expired - Lifetime US3268437A (en) | 1963-08-29 | 1963-08-29 | Hydrocracking of nitrogen containing hydrocarbon oils for the preparation of middle oils |
Country Status (9)
Country | Link |
---|---|
US (1) | US3268437A (enrdf_load_html_response) |
BE (1) | BE652082A (enrdf_load_html_response) |
CH (1) | CH433220A (enrdf_load_html_response) |
DE (1) | DE1470566A1 (enrdf_load_html_response) |
DK (1) | DK112262B (enrdf_load_html_response) |
FR (1) | FR1407410A (enrdf_load_html_response) |
GB (1) | GB1042710A (enrdf_load_html_response) |
LU (1) | LU46702A1 (enrdf_load_html_response) |
NL (2) | NL6410024A (enrdf_load_html_response) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2062935A1 (enrdf_load_html_response) * | 1969-12-22 | 1971-06-24 | ||
US3944481A (en) * | 1973-11-05 | 1976-03-16 | The Dow Chemical Company | Conversion of crude oil fractions to olefins |
JPS5428402B1 (enrdf_load_html_response) * | 1970-09-28 | 1979-09-17 | ||
US4169040A (en) * | 1978-04-26 | 1979-09-25 | Chevron Research Company | Staged process for the production of middle distillate from a heavy distillate |
US4859309A (en) * | 1987-11-17 | 1989-08-22 | Shell Oil Company | Process for the preparation of light hydrocarbon distillates by hydrocracking and catalytic cracking |
FR2854163A1 (fr) * | 2003-04-25 | 2004-10-29 | Inst Francais Du Petrole | Procede de valorisation de charges lourdes par desasphaltage et hydrocraquage en lit bouillonnant |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2839450A (en) * | 1954-03-26 | 1958-06-17 | Basf Ag | Production of gasolines having high knock rates from nitrogenous middle oils |
US2932611A (en) * | 1954-06-08 | 1960-04-12 | California Research Corp | Process of catalytic desulfurization and hydrocracking of hydrocarbons followed by catalytic cracking |
US3078221A (en) * | 1959-07-24 | 1963-02-19 | Gulf Research Development Co | Hydrogenation process for preparation of lubricating oils |
US3099617A (en) * | 1960-08-04 | 1963-07-30 | Union Oil Co | Pretreatment of catalyst employed in the hydrocracking of hydrocarbons |
US3145160A (en) * | 1961-06-30 | 1964-08-18 | California Research Corp | Hydrogenation of high boiling oils |
US3172838A (en) * | 1962-08-03 | 1965-03-09 | Hydrocarbon conversion process and catalyst |
-
0
- NL NL129736D patent/NL129736C/xx active
-
1963
- 1963-08-29 US US305543A patent/US3268437A/en not_active Expired - Lifetime
-
1964
- 1964-07-28 DE DE19641470566 patent/DE1470566A1/de active Pending
- 1964-08-04 GB GB31210/64A patent/GB1042710A/en not_active Expired
- 1964-08-05 LU LU46702D patent/LU46702A1/xx unknown
- 1964-08-17 CH CH1069664A patent/CH433220A/fr unknown
- 1964-08-20 BE BE652082D patent/BE652082A/xx unknown
- 1964-08-28 DK DK426264AA patent/DK112262B/da unknown
- 1964-08-28 FR FR986480A patent/FR1407410A/fr not_active Expired
- 1964-08-28 NL NL6410024A patent/NL6410024A/xx unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2839450A (en) * | 1954-03-26 | 1958-06-17 | Basf Ag | Production of gasolines having high knock rates from nitrogenous middle oils |
US2932611A (en) * | 1954-06-08 | 1960-04-12 | California Research Corp | Process of catalytic desulfurization and hydrocracking of hydrocarbons followed by catalytic cracking |
US3078221A (en) * | 1959-07-24 | 1963-02-19 | Gulf Research Development Co | Hydrogenation process for preparation of lubricating oils |
US3099617A (en) * | 1960-08-04 | 1963-07-30 | Union Oil Co | Pretreatment of catalyst employed in the hydrocracking of hydrocarbons |
US3145160A (en) * | 1961-06-30 | 1964-08-18 | California Research Corp | Hydrogenation of high boiling oils |
US3172838A (en) * | 1962-08-03 | 1965-03-09 | Hydrocarbon conversion process and catalyst |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2062935A1 (enrdf_load_html_response) * | 1969-12-22 | 1971-06-24 | ||
JPS5428402B1 (enrdf_load_html_response) * | 1970-09-28 | 1979-09-17 | ||
US3944481A (en) * | 1973-11-05 | 1976-03-16 | The Dow Chemical Company | Conversion of crude oil fractions to olefins |
US4169040A (en) * | 1978-04-26 | 1979-09-25 | Chevron Research Company | Staged process for the production of middle distillate from a heavy distillate |
DE2915982A1 (de) * | 1978-04-26 | 1979-11-08 | Chevron Res | Verfahren zur herstellung eines mitteldestillatoels aus einem schwerdestillatoel mit einem gehalt an stickstoffhaltigen kohlenwasserstoffen |
FR2424313A1 (fr) * | 1978-04-26 | 1979-11-23 | Chevron Res | Procede en plusieurs etapes pour la production d'un distillat moyen a partir d'un distillat lourd d'hydrocarbures |
US4859309A (en) * | 1987-11-17 | 1989-08-22 | Shell Oil Company | Process for the preparation of light hydrocarbon distillates by hydrocracking and catalytic cracking |
FR2854163A1 (fr) * | 2003-04-25 | 2004-10-29 | Inst Francais Du Petrole | Procede de valorisation de charges lourdes par desasphaltage et hydrocraquage en lit bouillonnant |
US20050006279A1 (en) * | 2003-04-25 | 2005-01-13 | Christophe Gueret | Method for the valorization of heavy charges by bubbling-bed deasphalting and hydrocracking |
EP1505142A1 (fr) * | 2003-04-25 | 2005-02-09 | Institut Francais Du Petrole | Procédé de valorisation de charges lourdes par désasphaltage et hydrocraquage en lit bouillonnant |
RU2344160C2 (ru) * | 2003-04-25 | 2009-01-20 | Энститю Франсэ Дю Петроль | Способ обогащения тяжелых загрузок при помощи дезасфальтации и гидрокрекинга в кипящем слое |
US20110062055A1 (en) * | 2003-04-25 | 2011-03-17 | Christophe Gueret | Method for the valorization of heavy charges by bubbling-bed deasphalting and hydrocracking |
US8636896B2 (en) | 2003-04-25 | 2014-01-28 | IFP Energies Nouvelles | Method for the valorization of heavy charges by bubbling-bed deasphalting and hydrocracking |
Also Published As
Publication number | Publication date |
---|---|
CH433220A (fr) | 1967-04-15 |
FR1407410A (fr) | 1965-07-30 |
DE1470566A1 (de) | 1968-12-12 |
NL6410024A (enrdf_load_html_response) | 1965-03-01 |
NL129736C (enrdf_load_html_response) | 1965-03-01 |
DK112262B (da) | 1968-11-25 |
LU46702A1 (enrdf_load_html_response) | 1964-10-05 |
GB1042710A (en) | 1966-09-14 |
BE652082A (enrdf_load_html_response) | 1964-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3968024A (en) | Catalytic hydrodewaxing | |
US4035285A (en) | Hydrocarbon conversion process | |
US3779897A (en) | Hydrotreating-hydrocracking process for manufacturing gasoline range hydrocarbons | |
US3072560A (en) | Conversion of residual oil to gasoline | |
US4022682A (en) | Hydrodenitrogenation of shale oil using two catalysts in series reactors | |
US4798665A (en) | Combination process for the conversion of a distillate hydrocarbon to maximize middle distillate production | |
US3730875A (en) | Combination process for black oil conversion | |
US4324935A (en) | Special conditions for the hydrogenation of heavy hydrocarbons | |
US3779895A (en) | Treatment of heavy petroleum oils | |
US3238118A (en) | Conversion of hydrocarbons in the presence of a hydrogenated donor diluent | |
US3617483A (en) | Hydrocracking process | |
US4792390A (en) | Combination process for the conversion of a distillate hydrocarbon to produce middle distillate product | |
EP0082555B1 (en) | Process for the production of hydrocarbon oil distillates | |
US3308055A (en) | Hydrocracking process producing lubricating oil | |
US4427534A (en) | Production of jet and diesel fuels from highly aromatic oils | |
CA1132075A (en) | Staged process for the production of middle distillate from a heavy distillate | |
US3472759A (en) | Process for removal of sulfur and metals from petroleum materials | |
US3666658A (en) | Hydroprocessing product separation | |
IL28518A (en) | Process for the production of gasoline | |
US2944006A (en) | Hydrocracking of a hydrocarbon distillate employing a sulfide of nickel or cobalt, disposed on an active siliceous cracking catalyst support | |
US3268437A (en) | Hydrocracking of nitrogen containing hydrocarbon oils for the preparation of middle oils | |
US3444071A (en) | Process for the hydrogenative cracking of a hydrocarbon oil to produce lubricating oil | |
US3185639A (en) | Hydrocarbon conversion process | |
US2945806A (en) | Hydrocracking hydrocarbons with a platinum group metal deposited on an active cracking catalyst base | |
US4022683A (en) | Hydrodenitrogenation of shale oil using two catalysts in parallel reactors |