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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline

Definitions

• This invention relates to a process for the hydrogenation of steam cracked naphtha. More particularly, the invention relates to a process for the hydrogenation of steam cracked naphtha having a very high bromine number at critical conditions which make such a process feasible.
• the raw pyrolysis gasoline from steam cracking is treated to remove unstable mate-rials, to improve odor and to improve octane sensitivity, usually by heat soaking or hydrogenation in one or more stakes.
• the feed to the steam cracking process is one of the heavier feeds, such as gas oil or crude oil
• the pyrolysis gasoline I is extremely unstable.
• the catalyst bed rapidly plugs with polymer. Heat soaking is not suitable because the treated gasoline is still too unstable for use as a blending component in finished gasoline. Multistep hydrogenation processes are too expensive and complicated.
• the object of this invention is to provide a feasible process for hydrogenating extremely unstable pyrolysis gasoline. I have found that the desired hydrogenation can be carried out over long periods employing a sulfided nickel-tungsten catalyst and critical hydrogenation conditions.
• the feed is a highly unstable byproduct naphtha recovered from the steam cracking of a petroleum hydrocarbon material.
• the feed is characterized by a boiling range of F. to 475 PI, preferably 100 F. to 430 F., a high content of olefins and diolefins, -i.e., from 30 to 50 wt. percent, and correspondingly a high bromine number of 50 to 135 cg./g.
• Steam States Patent 0 "ice cracking feeds having a major proportion (90-100%) of hydrocarbons boiling in the range of 3001200 usually 4001000 R, are the sources of these unstable pyrolysis naphthas.
• a material of particular interest is gas oil boiling in the range of from about 400 F.
• the raw feed to the process is so unstable that some of it polyme-rizes on standing and it may be necessary to remove polymer by any appropriate means. If desired, fresh stock may be mixed with some polymerized (aged) stock and/or with recycled product.
• Any suitable reactor can be used for the process.
• the reaction is usually started by flowing the hydrogen containing gas through the reactor to obtain the desired temperature in the catalyst bed, then adding the steam cracked naphtha.
• Any suitable hydrogen-containing gas having a hydrogen content of to 100% H can be used.
• the catalyst is nickel-tungsten on an inert support such as alumina, keiselguhr, silica-free clay, bauxite, .mullite, etc.
• Alumina is the preferred support.
• the catalyst contains from 4 to 6 wt. percent nickel, 14 to 20 wt. percent tungsten, and the balance alumina.
• the tungsten to nickel ratio is preferably 4 to one to 5 to one.
• the catalyst is sulfided with H S or CS prior to use.
• the most popular catalyst for hydrogenation reactions is cobaltmolybdate on alumina. However, the examples will show that this catalyst is not acceptable for use in the process of the invention.
• the feed use-d in the following examples was a steam cracked naphtha obtained from the steam cracking of a gas oil.
• This naphtha had the following inspection data:
• Table I shows that superior results are obtained with the nickel-tungsten-alumina catalyst.
• reactor inlet temperature be maintained at less than about 300 F. Rapid plugging of the reactor bed occurred at 350 F. Operating periods of i 90 days or more can be achieved by hydrogenating steam cracked naphtha according to the process of the invention.
• a process for hydrogenating steam cracked naphtha comprising contacting said naphtha in a reactor with a sulfided nickel-tungsten catalyst supported on an inert carrier with a hydrogen-containing gas under critical hydrogenating conditions including (1) a reactor inlet temperature ranging from about 200 F. to about 300 F., (2) a AT across the catalyst bed of from about 50 to about 200 F., (3) a pressure of 300 to 1200 p.s.i.g., (4) a space velocity of 0.25 to 2.0 v./hr./v., (5) a hy' drogen to naphtha ratio of 500 to 2500 s.c.f./b., and recovering a stable motor gasoline component.
• critical hydrogenating conditions including (1) a reactor inlet temperature ranging from about 200 F. to about 300 F., (2) a AT across the catalyst bed of from about 50 to about 200 F., (3) a pressure of 300 to 1200 p.s.i.g., (4) a space velocity of 0.25 to
• Process for hydrogenating highly unstable byproduct naphtha having a bromine number of 85-135 recovered from the steam cracking of a petroleum hydrocarbon feed boiling in the range of 400l000 F. to produce a maximum quantity of ethylene comprising the steps of contacting said naphtha in a reactor with a sulfided nickel-tungsten-alurnina catalyst with a gas containing 50100% hydrogen under critical hydrogenating conditions including (1) a reactor inlet temperature of 200 to 300 F., (2) a pressure of 300 to 1200 p.s.i.g., (3) a space velocity of 0.25 to 2.0 v./hr./v., (4) a hydrogen to naphtha ratio of 500 to 2500 s.c.f./b., and recovering a stable [motor gasoline component having a bromine number of less than 85, a copper beaker gum content of less than 20 mg./ ml., and a good odor.

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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)

Priority Applications (9)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24292069

Family Applications (1)

Country Status (8)

Cited By (2)

Families Citing this family (1)

Citations (5)

• 1966
  • 1966-08-19 US US573458A patent/US3388056A/en not_active Expired - Lifetime
• 1967
  • 1967-08-01 GB GB35329/67A patent/GB1147415A/en not_active Expired
  • 1967-08-07 BE BE702361D patent/BE702361A/xx not_active IP Right Cessation
  • 1967-08-12 NO NO169355A patent/NO119435B/no unknown
  • 1967-08-12 DE DE1645732A patent/DE1645732C3/de not_active Expired
  • 1967-08-16 GR GR670136395A patent/GR36395B/el unknown
  • 1967-08-16 NL NL6711282.A patent/NL159707B/xx not_active IP Right Cessation
  • 1967-08-17 SE SE11574/67A patent/SE334698B/xx unknown

Patent Citations (5)

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