US3190830A - Two stage hydrogenation process - Google Patents

Two stage hydrogenation process Download PDF

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Publication number
US3190830A
US3190830A US261224A US26122463A US3190830A US 3190830 A US3190830 A US 3190830A US 261224 A US261224 A US 261224A US 26122463 A US26122463 A US 26122463A US 3190830 A US3190830 A US 3190830A
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US
United States
Prior art keywords
catalyst
stage
hydrogen
nickel
hydrogenation
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
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US261224A
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English (en)
Inventor
Rowland John
Knight Warren Nevin Norton
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BP PLC
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BP PLC
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Publication of US3190830A publication Critical patent/US3190830A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0409Extraction of unsaturated hydrocarbons
    • C10G67/0427The hydrotreatment being a selective hydrogenation of diolefins or acetylenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00Purification; Separation; Use of additives
    • C07C7/148Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06Treatment 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

Definitions

  • the steam cracked gasoline may be given a mild hydrogenation treatment to remove part of the gumforming constituents before a distillation stage and thereafter a narrow cut, obtained by distillation, fed to a second hydrogenation over a nickel catalyst for the removal of substantially all of the remaining gum-forming constituents.
  • a major constituent of the gum-forming material will usually be in the form of dienes; these, under the hydrogenating conditions for the removal of gum-forming materials, will be mainly converted to mono-olefins.
  • hydrogenation may be carried out using a gas consisting of hydrogen together with inert constituents.
  • the gas contains at least mol percent of hydrogen, the proportion suitably lying within the range 2590 mol percent of hydrogen.
  • a preferred gas is a platforrner tail gas.
  • a gas is employed containing 70 mol percent of hydrogen.
  • a typical gas will consist of 70 mol percent of hydrogen and mol percent of methane.
  • Other suitable gases are steam cracker tail gas, catalytic cracker tail gas and tail gas derived from the dehydrogenation of hydrocarbons.
  • the olefin-removing stage is carried out in the presence of a catalyst comprising cobalt oxide and molybdenum oxides on a support.
  • a catalyst comprising cobalt oxide and molybdenum oxides on a support.
  • the support is alumina.
  • the catalyst contains 1 to 10% Wt. of cobalt oxide, expressed as C00 and 5 to wt. of molybdenum oxide, expressed as M00
  • the catalyst comprising cobalt oxide and molybdenum oxide is preferably used within the following ranges:
  • Pressure 100 to 1000 p.s.i.g. Temperature 150 to 480 C. Space velocity 0.5 to 8.0 v./v./hr. Gas recycle rate 500 to 8000 s.c.f./b.
  • the conditions of operation of the olefin-removing stage are selective to favour the desulphurisation of the feedstock which is fed to this stage.
  • the product being mainly a mixture of parafiins and aromatics, is very suitable for further treatment by solvent extraction, for example, by means of dior tri-ethylene glycols, for the recovery of an extract of high aromatic content.
  • the stabilised gasoline product had the following characteristics: Spccific gravity 60/60 F 0.817.
  • Type Nickel and cobalt hydroxides supported on aluminium silicate.
  • Reaction pressure 445 lbs./s in. gauge.
  • Table 2 o q Mean catalyst bed temperature--- 223 F. 1 Space velocity t 1.75 v./v./hr.
  • Recycle gas hydrogen content (H 3 free) 92-95 percent mol.
  • Hydrogen consumption was initially 160 s.c.f./b.; this value declined rapidly to zero at 336 hours on stream. During this run the pressure differential across the catalyst bed increased rapidly until the termination of the run at 336 hours. On examination of the reactor it was found that substantial blockage had occurred in the pre-heating zone prior to the catalyst bed. The catalyst was coated with polymer which probably accounted for the nil hydrogen consumption immediately prior to shut-down.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US261224A 1962-03-10 1963-02-26 Two stage hydrogenation process Expired - Lifetime US3190830A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8773/62A GB979257A (en) 1962-03-10 1962-03-10 Multi-stage hydrogenation process

Publications (1)

Publication Number Publication Date
US3190830A true US3190830A (en) 1965-06-22

Family

ID=9859000

Family Applications (1)

Application Number Title Priority Date Filing Date
US261224A Expired - Lifetime US3190830A (en) 1962-03-10 1963-02-26 Two stage hydrogenation process

Country Status (10)

Country Link
US (1) US3190830A (da)
AT (1) AT242839B (da)
BE (1) BE629307A (da)
CS (1) CS151428B2 (da)
DE (1) DE1470495B2 (da)
DK (1) DK113661B (da)
FR (1) FR1352360A (da)
GB (1) GB979257A (da)
LU (1) LU43302A1 (da)
NL (1) NL289907A (da)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287259A (en) * 1963-12-17 1966-11-22 Exxon Research Engineering Co Electrical insulating oil
US3428697A (en) * 1966-07-21 1969-02-18 Air Prod & Chem Hydrogenation process
US3484496A (en) * 1965-10-04 1969-12-16 British Petroleum Co Desulphurisation and hydrogenation of aromatic hydrocarbons
US3494859A (en) * 1967-06-07 1970-02-10 Universal Oil Prod Co Two-stage hydrogenation of an aromatic hydrocarbon feedstock containing diolefins,monoolefins and sulfur compounds
US3511771A (en) * 1967-07-24 1970-05-12 Exxon Research Engineering Co Integrated hydrofining,hydrodesulfurization and steam cracking process
US3899412A (en) * 1972-03-13 1975-08-12 Ici Ltd Aromatics extraction process
US4113603A (en) * 1977-10-19 1978-09-12 The Lummus Company Two-stage hydrotreating of pyrolysis gasoline to remove mercaptan sulfur and dienes
US4392945A (en) * 1982-02-05 1983-07-12 Exxon Research And Engineering Co. Two-stage hydrorefining process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2872492A (en) * 1956-03-29 1959-02-03 Universal Oil Prod Co Production of aromatics in the presence of nitrogen compounds
US2953612A (en) * 1958-03-03 1960-09-20 American Oil Co Catalytic hydrogenation of dripolene
US3004914A (en) * 1958-07-25 1961-10-17 British Petroleum Co Catalysts and hydrogenation processes using the catalyst
US3098829A (en) * 1960-05-04 1963-07-23 British Petroleum Co Supported nickel catalysts
US3113097A (en) * 1959-10-13 1963-12-03 British Petroleum Co Reactivation of catalysts
US3113096A (en) * 1958-07-25 1963-12-03 British Petroleum Co Refining of petroleum hydrocarbons
US3116233A (en) * 1960-01-14 1963-12-31 Shell Oil Co Low-temperature selective hydrogenation of dienes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2872492A (en) * 1956-03-29 1959-02-03 Universal Oil Prod Co Production of aromatics in the presence of nitrogen compounds
US2953612A (en) * 1958-03-03 1960-09-20 American Oil Co Catalytic hydrogenation of dripolene
US3004914A (en) * 1958-07-25 1961-10-17 British Petroleum Co Catalysts and hydrogenation processes using the catalyst
US3113096A (en) * 1958-07-25 1963-12-03 British Petroleum Co Refining of petroleum hydrocarbons
US3113097A (en) * 1959-10-13 1963-12-03 British Petroleum Co Reactivation of catalysts
US3116233A (en) * 1960-01-14 1963-12-31 Shell Oil Co Low-temperature selective hydrogenation of dienes
US3098829A (en) * 1960-05-04 1963-07-23 British Petroleum Co Supported nickel catalysts

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287259A (en) * 1963-12-17 1966-11-22 Exxon Research Engineering Co Electrical insulating oil
US3484496A (en) * 1965-10-04 1969-12-16 British Petroleum Co Desulphurisation and hydrogenation of aromatic hydrocarbons
US3428697A (en) * 1966-07-21 1969-02-18 Air Prod & Chem Hydrogenation process
US3494859A (en) * 1967-06-07 1970-02-10 Universal Oil Prod Co Two-stage hydrogenation of an aromatic hydrocarbon feedstock containing diolefins,monoolefins and sulfur compounds
US3511771A (en) * 1967-07-24 1970-05-12 Exxon Research Engineering Co Integrated hydrofining,hydrodesulfurization and steam cracking process
US3899412A (en) * 1972-03-13 1975-08-12 Ici Ltd Aromatics extraction process
US4113603A (en) * 1977-10-19 1978-09-12 The Lummus Company Two-stage hydrotreating of pyrolysis gasoline to remove mercaptan sulfur and dienes
US4392945A (en) * 1982-02-05 1983-07-12 Exxon Research And Engineering Co. Two-stage hydrorefining process

Also Published As

Publication number Publication date
FR1352360A (fr) 1964-02-14
AT242839B (de) 1965-10-11
DE1470495A1 (de) 1968-12-19
CS151428B2 (da) 1973-10-19
LU43302A1 (da) 1963-05-06
DE1470495B2 (de) 1976-01-29
NL289907A (da) 1965-06-10
DK113661B (da) 1969-04-14
GB979257A (en) 1965-01-01
BE629307A (da) 1963-10-21

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