US3481864A - Plural-stage hydrorefining of a naphtha - containing full - boiling range feedstock - Google Patents

Plural-stage hydrorefining of a naphtha - containing full - boiling range feedstock Download PDF

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US3481864A
US3481864A US611593A US3481864DA US3481864A US 3481864 A US3481864 A US 3481864A US 611593 A US611593 A US 611593A US 3481864D A US3481864D A US 3481864DA US 3481864 A US3481864 A US 3481864A
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hydrogen
naphtha
feedstock
hydrocarbons
zone
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Newt M Hallman
Robin J Parker
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Universal Oil Products Co
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Universal Oil Products Co
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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
    • 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

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  • This invention relates to a conversion method. It particularly relates to a method for hydrogen-ating constituents present in petroleum feed stocks in order to saturate olefinic hydrocarbons, to remove sulfur compounds, and/ or to remove nitrogen-containing constituents. It specifically relates to an improved method for conducting hydrogenating reactions wherein naphtha-containing fullboiling range feedstocks are processed through a plurality of hydrogenating stages in the presence of hydrogen-contalning gas.
  • the present invention is based upon the discovery that contaminants such as sulfur and nitrogen compounds tend to migrate from relatively heavy hydrocarbon to relatively light hydrocarbon during the hydrogenation reaction. It is believed that this migration is caused at least in part by concomitant cracking of hydrocarbons to lower boiling hydrocarbons during the hydrogenation reaction.
  • a method for refining a naphtha-containing full-boiling range hydrocarbon feedstock for removal of sulfur compounds therefrom which comprise contacting said feedstock in a first catalytic reaction zone with hydrogen under relatively severe hydrogenating conditions; introducing the total effiuent from said first zone into separation means under conditions suflicient to produce a gaseous stream comprising hydrogen and relatively light hydrocarbons, and a liquid stream comprising relatively heavy refined hydrocarbons; passing said gaseous stream into a second catalytic reaction zone under relatively mild hydrogenating conditions in the absence of added hydrogen; withdrawing from said second zone an efiluent stream comprising hydrogen and relatively light refined hydrocarbons; separating hydrogen from refined hydrocarbons; and recovering refined hydrocarbons having reduced sulfur content.
  • Another embodiment of the invention includes the method wherein the efiluent from said second zone is admixed with said liquid stream to form a total product stream containing refined hydrocarbons having reduced sulfur content.
  • a particular embodiment of the invention includes the method wherein said gaseous stream on a liquid basis comprises from 2% to 50% by volume of said total efliuent.
  • the present invention provides a method for hydrogenating a naphtha-containing fullboiling range feedstock by using a plural-stage (preferably, a two-stage) reaction zone having a flash zone between the stages. Contrary to the usual teachings of the prior art, the present invention provides that the lighter material and residual hydrogen from the flash zone comprises the sole feed to the next or second reaction zone. It was found that by operating in the manner described that efficient desulfurization of full-boiling range materials could be easily achieved with a minimum of capital investment and operating expense.
  • the preferred embodiment encompasses admixing the various efiluent streams prior to hydrogen separation, followed by fractionation of the admixed effiuent into suitable typical fractions for further handling in accordance with means well-known to those skilled in the art.
  • the naphtha fraction of the feedstock can be separated from the combined effluent and, then, passed directly without intervening treatment to a catalytic reforming zone maintained under conditions suflicient to produce upgraded gasoline boiling range products therefrom.
  • the prior art schemes were faced with the prospect of prefractionating the feedstock into separate and distinct fractions so that each distinct fraction could be subjected to catalytic hydrogenation under different operating conditions to produce satisfactory desired sulfur reduction in the hydrocarbon component.
  • the present invention provides a method for hydrogenating a fullboiling range feedstock in a more facile and economical manner than heretofore practiced by the prior art.
  • feedstock full-boiling range materials, charge stock, naphtha-containing full-boiling range hydrocarbon feedstock
  • feedstock full-boiling range materials, charge stock, naphtha-containing full-boiling range hydrocarbon feedstock
  • refinery processes include crude oil fractionation, catalytic and/or thermal cracking of petroleum, the destructive distillation of wood or coal, shale oil retorting, delayed and fluid coking operations, and various other pyrolytic reactions.
  • the full-boiling range feedstock for the present invention must contain a significant quantity of what is commonly called naphtha.
  • the naphtha fraction will have a boiling range from about 160 F. to 400 F.; although, minor deviations from these limits may still provide a naphtha fraction within the intended scope of the present feedstock.
  • the full-boiling range feedstock for the present invention must also contain at least one other common fraction, heavier boiling, usually connoted as kerosene, diesel oil, gas oil, etc. and may also contain C and C hydrocarbons.
  • satisfactory feedstocks to the present invention include those hydrocarbon mixtures containing sulfur which boil within the range from 100 F. to 1100 F.
  • the recited satisfactory feedstocks are subjected to relatively severe hydrogenating conditions in a first catalytic reaction zone.
  • These relatively severe conditions include a temperature from 500 F. to 800 F., a pressure from 500 p.s.i.g. to 1500 p.s.i.g., liquid hourly space velocity (LHSV) of 0.3 to 6 volumes of oil per hour per volume of catalyst present therein, and a hydrogen-to-hydrocarbon ratio of from 500 to 5,000 standard cubic feet per barrel.
  • LHSV liquid hourly space velocity
  • operating a hydrogenation reaction at temperatures above 500 F. could cause polymerization of any diolefins present in the feedstock.
  • the lighter feedstocks such as those boiling within the range from 100 F. to 550 F. will contain significant diolefins such that undesirable polymerization may take place; then, .such diolefin-containing feedstocks shall be pretreated such as by mild hydrogenation prior to charging to the method of the present invention.
  • the total effluent from the first catalytic reaction zone of the invention is charged into separation means, such as a single stage flash zone, in order to remove hydrogen and relatively light hydrocarbons from the relatively heavy refined hydrocarbons.
  • separation means such as a single stage flash zone
  • the amount of gaseous materials removed from the flash zone should comprise at least v 4 2% by volume of the total eflluent charged to the flash zone but should not comprise more than 50% by volume of such efiluent. If the gaseous stream is less than 2% it has been found that the second reaction zone, more fully discussed hereinbelow, usually cannot be economically justified.
  • an amount greater than 50% by volume is flashed; then, significant heavy material may be charged to the second reaction stage thereby negating, to some extent at least, the benefits to be derived from the practice of the present invention.
  • this carryover heavy material is not satisfactorily desulfurized under the relatively mild conditions maintained in the second reaction zone.
  • the amount of material vaporized is on a liquid basis, i.e., the percentages by volume exclude normally gaseous materials such as hydrogen and hydrogen sulfide.
  • the amount of material flashed should be selected so that the 90% point (ASTM distillation) of the hydrocarbon fraction in the vapor phase is no more than 500 F., and preferably is about 400 F. In any event, since the flash zone operates under equilibrium flash conditions, suitable adjustments in temperature of the flash zone may be necessary to flash into the vapor phase substantially only the naphtha portion of the original feedstock.
  • reaction conditions for the second reaction zone are relatively mild. These relatively mild conditions include a temperature within the range V of 500 F. to 750 F., a pressure from 500 p.s.i.g. to
  • the amount of hydrogen present in the second reaction zone is wholly dependent upon the hydrogen separated in the previous intervening flash zone as discussed hereinabove.
  • the sole feed to the second reaction zone consists entirely of the gaseous material separated in the separation means between the two reaction stages.
  • the method of the present invention is a catalytic method and the catalyst employed may be of the same chemical and physical compositions in both of the reaction zones.
  • the present invention broadly includes a plurality of reaction zones even though the description thereof is more or less limited to only two reaction zones.
  • Suitable hydrorefining catalytic composites comprise at least one metallic component selected from the group consisting of metals of Groups VI-B and VIII of the Periodic Table and compounds thereof.
  • the catalyst will comprise at least one metallic component selected from the group consisting of chromium, molybdenum, tungsten, iron, cobalt, nickel, rhodium, ruthenium, palladium, osmium, iridium, platinum, and mixtures of two or more, etc.
  • the preferred catalytic composite for utilization in the practice of the present invention comprises molybdenum and at least one metallic component selected from the iron group of the Periodic Table.
  • the molybdenum component will generally be in the greater concentration from about 4% to about 30% by weight, while the iron group metallic component will be present in the amount in the range from about 1% to about 6% by weight calculated on the basis of the elemental metal.
  • catalytically active metallic component hereinabove set forth be composited with a nonacidic carrier material.
  • catalytically active metallic components are composited with any suitable refractory inorganic oxide material including alumina, silica, zirconia, thoria, boria, titania, hafnia, mixtures of two or more, etc.
  • other components are often combined with the metallic components and carrier material, such as members of the halogen family, such as fluorine and/or chlorine.
  • the preferred embodiment of the invention provides a method for hydrogenating a naphtha-containing fullboiling range hydrocarbon feedstock for removal of sulfur compounds therefrom which comprises: (a) contacting said feedstock with hydrogen in a first reaction zone containing a catalytic composite of a nonacidic refractory inorganic oxide, molybdenum, and at least one metallic component of the metals of the iron group of the Periodic Table, under relatively severe hydrogenating conditions including a temperature from 500 F. to 800 F.
  • step (d) admixing the effluent from said second zone with said liquid stream; (e) separating hydrogen from the admixture of step (d); and (f) recovering hydrocarbons having reduced sulfur content.
  • the distinctly preferred method includes the use of a feedstock having a boiling range from C to 900 F., wherein said first zone conditions include a temperature from 725 F. to 775 F., and a space velocity from 0.5 to 1.5; and wherein said second zone conditions include a temperature from 630 F. to 700 F., and a space velocity from 6 to 9.
  • the feedstock to the invention comprises a full-boiling range coker distillate boiling between C and 889 F. having a sulfur content of 0.52 wt. percent, a bromine number of about 28, and a nitrogen content of about 880 parts per million (p.p.m.).
  • this feedstock enters the method via line 10 where it is admixed with hydrogen from line 11 in an amount sufficient to provide 3000 standard cubic feet per barrel of hydrogen in line 12.
  • the admixture of feed hydrocarbons and hydrogen is passed through heater 13 wherein it is elevated in temperature to about 750 F. in line 14.
  • the heated mixture is passed from line 14 into reactor 15 which contains a catalyst consisting essentially of about 2.2% by weight of cobalt and about 5.7% by weight of molybdenum calculated as the elements thereof deposited on alumina particles of suitable size and shape.
  • Relatively severe operating conditions are maintained in reactor 15 and include a reactor outlet temperature of 750 F., a pressure of 1100 p.s.i.g., and a space velocity (LHSV) of 1.5.
  • the total efiiuent from reactor 15 s withdrawn via line 16 and passed into separator 17, which is a single stage flash zone, maintained under substantially the same pressure as is maintained in reactor 15.
  • separator 17 which is a single stage flash zone, maintained under substantially the same pressure as is maintained in reactor 15.
  • no independent cooling takes place in line 16 and suflicient equilibrium flashing is accomplished so that approximately 10% by volume of the material (excluding hydrogen and hydrogen sulfide) in line 16 is flashed and withdrawn via line 19.
  • the hydrocarbon material in line 19 has a point of about 330 F.
  • the material in line 19, containing relatively light hydrocarbons boiling in the range, typically, from C to 330 F. and containing sulfur compounds, is passed in admixture with the flashed hydrogen and hydrogen sulfide into reactor 20 which is maintained under relatively mild operating conditions.
  • the operating conditions in reactor 20 are maintained at a temperature of about 650 F. with the pressure being that obtained through the system allowing for normal pressure drop between reactor 15 and reactor 20.
  • the space velocity in reactor 20 is approximately 8.0 LHSV based on the flashed material.
  • sufiicient hydrogen is present in the flashed stream from separator 17 to accomplish hydrogenation of the relatively light hydrocarbons present in line 19 for sulfur removal.
  • heating means not shown in line 19 in order to maintain proper operating conditions in reactor 20 to convert sulfur compounds to hydrogen sulfide.
  • the eflluent from reactor 20 is withdrawn via line 21 and preferably is admixed with the relatively heavy refined hydrocarbons previously removed in separator 17 via line 18.
  • the admixed material in line 22 is cooled by means not shown and passed into separator 23 which is maintained under conditions sufficient to separate hydrogen from the refined hydrocarbons.
  • the separated hydrogen is removed via line 11 and, preferably, recycled for admixture with the feed as previously mentioned. Since a small amount of hydrogen (about 1% by weight) is consumed in the hydrogenation reaction, makeup hydrogen is added to the system via line 25.
  • the refined hydrocarbons are removed from separator 23 via line 24 and passed into product separation means, not shown, such as a fractionation system for recovery of the individual commonly known hydrocarbon fractions originally present in the feedstock.
  • a distinct advantage of the present invention is embodied in the fact that the feedstock which contains a significant amount of naphtha (from, for example, 10% to 50% by weight of the fresh feed) produces a refined naphtha fraction containing about 1 p.p.m. sulfur which may nOW be passed directly to a catalytic reforming unit without intervening treatment.
  • the prior art schemes as discussed hereinabove require an additional hydrogenation treatment of the naphtha fraction before it was of suitable quality to be charged to a catalytic reforming reaction zone. Therefore, it is clear that the present invention has provided an improved hydrogenation method wherein the naphtha portion of the full-boiling range feedstock is converted into satisfactory quality for reforming purposes.
  • catalytic reforming operations utilize a platinum containing catalyst to upgrade relatively low grade naphtha fractions into relatively high grade gasoline quality fractions.
  • the important chemical reactions taking place in catalytic reforming are isomerization of alkylcyclopentane to cyclohexanes; dehydrogenation of hexane to aromatic hydrocarbons; dehydrocyclozation of paraflins to aromatic hydrocarbons; hydrocracking of paraffins and naphthenes; etc. These various reactions take place more or less simultaneously to convert naphtha fractions into gasoline quality fractions.
  • the platinum catalyst may be poisoned by the presence of sulfur and other contaminants and there fore, care must be taken to clean up the feedstock prior to contact with the platinum-containing catalyst.
  • the present invention provides an improved hydrogenation process which produces refining grade naphtha in a more facile and economical manner while simultaneously desulfurizing relatively heavy hydrocarbons boiling up to an end point of about 1100 F.
  • operating conditions for the catalytic reforming operations include a temperature within the range of from 800 F. to 900 F., a pressure from about 200 p.s.i.g. to 700 p.s.i.g., and a space velocity from about 1 t0 6.
  • Suflicient hydrogen also must be maintained within the catalytic reforming reaction zone in order to improve catalyst life by minimizing coke deposition.
  • Those skilled in the art are familiar with the catalytic reforming operation and its proper conditions; therefore, a detailed presentation of this process need not be presented herein.
  • Method for refining a hydrocarbon feedstock comprising a naphtha fraction and at least one other higher boiling hydrocarbon fraction for removal of sulfur compounds therefrom which comprises contacting said feedstock in a first catalytic reaction zone with hydrogen and a catalyst comprising a hydrogenating metal selected from Groups VI-B and VIII of the Periodic Table under relatively severe hydrogenating conditions wherein the reaction temperature is from about 725 F. to about 775 F.
  • the space velocity is from about 0.5 to about 1.5; introducing the total efiiuent from said first zone into separation means under conditions sufficient to produce a gaseous stream comprising hydrogen and relatively light hydrocarbons, and a liquid stream comprising relatively heavy refined hydrocarbons; passing said gaseous stream into a second catalytic reaction zone under milder hydrogenating conditions than the conditions maintained in said first zone and in the absence of added hydrogen and in contact with a catalyst comprising a hydrogenating metal selected from Groups VI-B and VIII of the Periodic Table, wherein the reaction temperature of said last named milder conditions is from about 630 F. to about 700 F.
  • the space velocity is from about 6 to about 9; withdrawing from said second zone an eflluent stream comprising hydrogen and relatively light refined hydrocarbons; separating hydrogen from said refined hydrocarbons; and recovering said refined hydrocarbons having reduced sulfur content from each of said zones.
  • gaseous stream on a liquid basis comprises from 2% to 50% by volume of said total effiuent and has a 90% point (ASTM distillation) within the range from about 330 F. to about 500 F.
  • Method for hydrogenating a hydrocarbon feedstock comprising a naphtha fraction and at least one other higher boiling hydrocarbon fraction for removal of sulfur compounds therefrom which comprises:
  • step (e) separating hydrogen from the admixture of step (f) recovering hydrocarbons having reduced sulfur content from the separation step of step (e).
  • step (b) on a liquid basis comprises from 2% to by volume of said total eflluent and has a point (ASTM distillation) within the range from about 330 F. to about 500 F.

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  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US611593A 1967-01-25 1967-01-25 Plural-stage hydrorefining of a naphtha - containing full - boiling range feedstock Expired - Lifetime US3481864A (en)

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US (1) US3481864A (de)
JP (1) JPS4818081B1 (de)
DE (1) DE1645830C3 (de)
ES (1) ES349701A1 (de)
FR (1) FR1560525A (de)
GB (1) GB1204201A (de)
NL (1) NL158839B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3668112A (en) * 1968-12-06 1972-06-06 Texaco Inc Hydrodesulfurization process
US3969222A (en) * 1974-02-15 1976-07-13 Universal Oil Products Company Hydrogenation and hydrodesulfurization of hydrocarbon distillate with a catalytic composite

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50117390A (de) * 1974-02-18 1975-09-13

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA612265A (en) * 1961-01-10 Sun Oil Company Desulfurization of reformer charge
US3119765A (en) * 1959-10-19 1964-01-28 Exxon Research Engineering Co Catalytic treatment of crude oils
US3347779A (en) * 1964-04-28 1967-10-17 Shell Oil Co Manufacture of petroleum distillates by hydrodesulfurization and hydrogenation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA612265A (en) * 1961-01-10 Sun Oil Company Desulfurization of reformer charge
US3119765A (en) * 1959-10-19 1964-01-28 Exxon Research Engineering Co Catalytic treatment of crude oils
US3347779A (en) * 1964-04-28 1967-10-17 Shell Oil Co Manufacture of petroleum distillates by hydrodesulfurization and hydrogenation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3668112A (en) * 1968-12-06 1972-06-06 Texaco Inc Hydrodesulfurization process
US3969222A (en) * 1974-02-15 1976-07-13 Universal Oil Products Company Hydrogenation and hydrodesulfurization of hydrocarbon distillate with a catalytic composite

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DE1645830C3 (de) 1974-08-15
ES349701A1 (es) 1969-04-01
DE1645830A1 (de) 1970-07-16
NL6801126A (de) 1968-07-26
DE1645830B2 (de) 1974-01-17
NL158839B (nl) 1978-12-15
GB1204201A (en) 1970-09-03
FR1560525A (de) 1969-03-21
JPS4818081B1 (de) 1973-06-04

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