US3595780A - Process for stabilization of diolefin-containing hydrocarbons - Google Patents

Process for stabilization of diolefin-containing hydrocarbons Download PDF

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Publication number
US3595780A
US3595780A US820759A US3595780DA US3595780A US 3595780 A US3595780 A US 3595780A US 820759 A US820759 A US 820759A US 3595780D A US3595780D A US 3595780DA US 3595780 A US3595780 A US 3595780A
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United States
Prior art keywords
diolefin
hydrogen
hydrogenation
diolefins
feed
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Expired - Lifetime
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US820759A
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English (en)
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Charles T Adams
Richard E Fruit
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Shell USA Inc
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Shell Oil 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds

Definitions

  • This invention relates to a process for stabilizing diolefin-containing cracked hydrocarbon oils.
  • Such selective hydrogenation is appropriate and suitable for stabilization of pyrolysis by-products when the pyrolysis feed stock is relatively low boiling naphtha which contains only a small amount of heteroatomic impurities such as organic sulfur and nitrogen compounds.
  • mild selective hydrogenation does not generally reduce organic sulfur and nitrogen compounds to any appreciable extent and this treatment alone is insufficient to stabilize heavier fractions. This becomes an increasingly difficult problem as the pyrolysis feed stock boiling range is increased.
  • the heavy pyrolysis product usually must be further hydrofined a reaction requiring more severe conditions, particularly higher temperatures.
  • an initial treatment for the purpose of stabilizing the diolefin-containing oil to prevent polymerization with concomitant coking in the subsequent hydrofining preheaters and catalyst bed is required.
  • diolefin stabilization can be effectively accomplished by catalytic reaction of diolefin-containing feed with a sulfur compound in the presence of hydrogen. This treatment may be accompanied by hydrogenation but coincident hydrogenation is not essential to the effectiveness of the present process.
  • the invention is a process for catalytic conversion of diolefin-containing hydrocarbon oils by reaction with a sulfur compound whereby diolefins are at least partially converted to organic sulfur compounds in the presence of hydrogen.
  • the invention is a multistage process for the catalytic conversion of diolefin-containing hydrocarbon oils wherein diolefins are at least partially converted to sulfur compounds in a first reaction stage and thereafter the oil is contacted with a hydrogenation catalyst in the presence of hydrogen at elevated temperature and pressure to reduce the concentration of organic sulfur and nitrogen compounds.
  • Hydrocarbon oils suitable for treating according to the process of the invention include any diolefin-containing normally liquid oils, as for example, those obtained from the pyrolysis of heavy naphtha or gas oil petroleum fractions.
  • the feed stock can include fractions ranging from butane to pitch boiling above 800 F. In general, however, it is preferred that the feed consist principally of gasoline and gas oil boiling range materials (about to 800 F. boiling range).
  • hydrocarbon stocks as produced by pyrolysis have diolefin contents, as measured by the maleic anhydride condensation values (MAV), of 50 or above. It is generaly sufficient to achieve adequate stabilization by reducing diolefin content to a MAV value of about 25 or below.
  • MAV maleic anhydride condensation values
  • the process is carried out by reacting diolefin-containing oil with a sulfur compound in the presence of hydrogen and a catalyst.
  • Hydrogen sulfide is readily available, relatively inexpensive, and accomplishes the objectives of the invention.
  • the concentration should be at least about 0.5% by volume basis hydrogen, and preferably above about 1.0% by volume. Concentrations above about 5.0% may be used but generally are not required. It is especially preferred that the concentration be about l.5%-3.0% by volume.
  • Reaction temperature should not be above about 350 F. and preferably not above about 300 F. Temperatures of about 275 F. are particularly effective although temperatures as low as about 200 F. may be employed, as shown in Example II below. The unstable nature of the diolefins requires that temperature be minimized to prevent rapid polymerization which leads to coking. Hydrogen pressure should be in the range of between 400 to 2000 psi. and preferably in the range of about 600 to 1200 psi.
  • Catalysts which are suitable for the reaction of diolefins include transition metal sulfides comprising a hydrogenative metal component selected from the group consisting of the sulfides of cobalt, nickel, molybdenum, tungsten and mixtures thereof, preferably supported on a relatively non-acidic solid support, i.e., a support having little cracking activity. Supports with high surface area are preferred.
  • Particularly suitable catalysts are sulfided nickel or sulfided nickel and molybdenum supported on alumina. Such catalysts, which are well known in the art as hydrogenation catalysts, have been found to be especially effective in the process of the invention.
  • the catalyst may be produced by various means known to the art, such as, for example, impregnating the metal onan alumina support or incorporating the metal into an alumina hydrogel followed by drying and calcining. In most conventional preparation techniques the metal component will be initially present, after calcination, as the metal oxide. For the purpose of the present invention the catalyst is converted to the sulfide form. This, as it is well known, is easily accomplished by contacting the catalyst with a suitable sulfur compound, as for example, hydrogen sulfide.
  • a suitable sulfur compound as for example, hydrogen sulfide.
  • the diolefin reduction and stabilization does not depend upon hydrogenation and suitable stabilization is obtained with or without concurrent hydrogenation.
  • One important embodiment of the invention is a multistage process wherein diolefin-containing liquid hydrocarbon feed is first reacted with sulfur for stabilization by partial conversion of diolefins to organic sulfur compounds followed by hydrogenation at more severe conditions to remove or reduce organic sulfur and nitrogen compounds including those produced in the first reaction.
  • This combined process facilitates the conversion of unstable diolefin-containing pyrolysis liquid products to stable products suitable for storage of further refining.
  • Diolefin-containing feed such as a gasoline and gas oil boiling range pyrolysis liquid product
  • the mixture enters the first reaction zone 3 via common line 13.
  • the first reaction zone serves primarily to convert diolefins to organic sulfur compounds and by other unknown means to render the feed sufficiently stable to allow further heating and/or storage without appreciable polymerization or gum formation.
  • This reaction zone contains a supported metal sulfide catalyst and is operated below about 350 F. and preferably below about 300 F., at a pressure between about 600 to about 2000 p.s.i.g.
  • the stabilized eflluent from the first reaction zone passes via line 15 to heater 5, and then to hydrogenation zone 7 where olefins are substantially saturated and organic nitrogen and sulfur compounds are, at least in part, converted to ammonia and hydrogen sulfide, respectively.
  • any conventional hydrogenation catalyst or mixture thereof is suitable.
  • oxides or sulfides of metals of Groups VI and VIII of the Periodic Table of Elements can be used. These catalytic metals or compounds are conventionally supported on a suitable refractory oxide support. Examples of suitable support include oxides of aluminum, magnesium, zirconium, etc. It is preferred that the sup port have no substantial cracking activity. Alumina is preferred.
  • Particularly suitable hydrogenation catalysts are sulfided nickel/ tungsten, nickel/molybdenum or cobalt molybdenum supported on alumina. Operating conditions will depend upon the nature of the feed, the amount and desired degree of removal of olefins, organic sulfur and nitrogen and other factors known in the art.
  • Suitable conditions will generally be in the range of 400600 F. and 600-2000 p.s.i.g. pressure.
  • space velocity will be in the range of about 0.1 to 5 LHSV (volume of feed/volume of catalyst/ hour). In most cases hydrogen uptake in this reaction zone will be about 2004500 s.c.f. Hz/bbl. feed.
  • the effluent from reaction 7 is removed via line 17 and may be treated in various ways as will be apparent to those skilled in the art.
  • the effluent may be distilled into fractions prior to gas separation.
  • the efliuent passes to a gas separation zone 9 (for example, a flash zone) where the gas is removed.
  • Liquid efiiuent having been substantially degassed passes via line 18 for further treatment, use or storage.
  • the gas containing principally hydrogen with smaller amounts of hydrocarbon gases, hydrogen sulfide and am monia, is removed via line 19. A portion of this gas is recycled via line 23 to the first reaction zone to supply the required hydrogen and hydrogen sulfide.
  • the composition of the gas entering the first reaction zone 3 is controlled by regulation of the amount of recycle gas from line 23, hydrogen make-up from via line 11 and hydrogen sulfide-containing gas via line 12.
  • EXAMPLE I A gasoline/gas oil boiling pyrolysis liquid feed was treated in a small flow reactor.
  • the feed had a density of 0.954 gm./cc. at 60 R, an organic sulfur content of about 0.3% w. and a MAV value of about 50.
  • Comparison runs were made at 275 F., 1000 p.s.i.g., 3.5 H /oil (mole) and 1.0 LHSV with and without hydrogen sulfide addition to the feed hydrogen. The results of these runs are summarized in Table 1.
  • the MAV value are average values obtained from daily analytical results.
  • the catalyst used was a sulfided nickel/molybdenum/ alumina hydrotreating catalyst. As can be seen, hydrogenation activity was lost rapidly as evidenced by the H consumption which dropped to zero after about 300 hours of operation.
  • EXAMPLE II This example illustrates the effect of H 8 addition during the combined stabilization-hydrogenation of a pyrolysis gas-oil/gasoline blend.
  • the feed had an API gravity of 18.1 at 60 F. and a MAV value of 92.
  • This feed was processed in a pilot plant consisting of five reactors in series.
  • the fresh feed rate was 1500 cc./hr. together with 199 cc./hr. recycle of total liquid product.
  • the catalyst used was a sulfided nickel/molybdenum on alumina hydrotreating catalyst as in Example I.
  • the reactor catalyst loading ratio was 1:1:1: 1.5 1.5 in the five reactors, respectively.
  • Pressure was p.s.i.g. with 36 s.c.f./hr. of hydrogen gas provided to the first reactor (fresh plus recycle gas).
  • the product MAV from the third reactor was 18 and essentially zero after the fifth reactor, which indicated efficient removal of diolefins.
  • a process for stabilization of a diolefin-containing hydrocarbon fraction whereby diolefins are at least partially converted to organic sulfur compounds which comprises reacting said fraction in the presence of hydrogen with a sulfur compound and a catalyst comprising a hydrogenative metal component selected from the group consisting of the sulfides of cobalt, nickel, molybdenum, tungsten and mixtures thereof supported on a relatively nonacidic inorganic refractory oxide at a temperature from about 200 F. to 350 F.
  • hydrocarbon fraction is a cracked petroleum fraction boiling at least partially in the gas-oil boiling range.
  • a process for stabilization of a diolefin-containing cracked petroleum fraction boiling at least partially in the gas-oil boiling range and containing organic sulfur compounds whereby diolefins are at least partially converted to organic sulfur compounds which comprises reacting said fraction in the presence of hydrogen with a sulfur compound and a catalyst comprising a hydrogenative metal component selected from the group consisting of the sulfides of cobalt, nickel, molybdenum, tungsten and mixtures thereof supported on a relatively non-acidic inorganic refractory oxide at a temperature from about 200 -F. to 350 F. and a pressure between about 600 psi. and 2000 p.s.i.
  • the contacted petroleum fraction is increased in organic sulfur compound content, followed by contacting the fraction in the presence of hydrogen with a hydrofining catalyst at a temperature above about 400 F. and a pressure above about 600 p.s.i.g. to reduce the organic sulfur compound content to below the level of that in the original petroleum fraction.

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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)
  • Catalysts (AREA)
US820759A 1969-05-01 1969-05-01 Process for stabilization of diolefin-containing hydrocarbons Expired - Lifetime US3595780A (en)

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US82075969A 1969-05-01 1969-05-01

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US (1) US3595780A (nl)
JP (1) JPS5027045B1 (nl)
BE (1) BE749300A (nl)
CA (1) CA937885A (nl)
DE (1) DE2021087C2 (nl)
FR (1) FR2049083B1 (nl)
GB (1) GB1301351A (nl)
NL (1) NL165493C (nl)
ZA (1) ZA702885B (nl)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414102A (en) * 1981-05-15 1983-11-08 Mobil Oil Corporation Process for reducing nitrogen and/or oxygen heteroatom content of a mineral oil
US20230013013A1 (en) * 2021-06-23 2023-01-19 Saudi Arabian Oil Company Method of producing pyrolysis products from a mixed plastics stream and integration of the same in a refinery
EP4424796A1 (de) * 2023-03-02 2024-09-04 OMV Downstream GmbH Verfahren zur reinigung eines synthetischen rohölstroms

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3030563B1 (fr) * 2014-12-18 2018-06-29 IFP Energies Nouvelles Procede d'adoucissement en composes du type sulfure d'une essence olefinique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113983A (en) * 1959-04-07 1963-12-10 Air Prod & Chem Selective hydrogenation of diolefins
NL257123A (nl) * 1960-10-21
US3394199A (en) * 1961-02-20 1968-07-23 Exxon Research Engineering Co Hydrocarbon conversion process
NL135913C (nl) * 1961-12-18 1900-01-01
US3309307A (en) * 1964-02-13 1967-03-14 Mobil Oil Corp Selective hydrogenation of hydrocarbons

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414102A (en) * 1981-05-15 1983-11-08 Mobil Oil Corporation Process for reducing nitrogen and/or oxygen heteroatom content of a mineral oil
US20230013013A1 (en) * 2021-06-23 2023-01-19 Saudi Arabian Oil Company Method of producing pyrolysis products from a mixed plastics stream and integration of the same in a refinery
EP4424796A1 (de) * 2023-03-02 2024-09-04 OMV Downstream GmbH Verfahren zur reinigung eines synthetischen rohölstroms
WO2024180216A1 (de) 2023-03-02 2024-09-06 OMV Downstream GmbH Verfahren zur reinigung eines synthetischen rohölstroms

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NL165493C (nl) 1981-04-15
NL7006259A (nl) 1970-11-03
FR2049083A1 (nl) 1971-03-26
BE749300A (nl) 1970-10-22
ZA702885B (en) 1971-01-27
FR2049083B1 (nl) 1973-07-13
GB1301351A (nl) 1972-12-29
CA937885A (en) 1973-12-04
DE2021087C2 (de) 1982-07-01
JPS5027045B1 (nl) 1975-09-04
DE2021087A1 (de) 1970-11-12

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