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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
  • C07C5/05—Partial hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/75—Cobalt
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/755—Nickel
• • 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

• the present invention relates generally to a process for selectively hydrogenating a mixture of hydrocarbons, and particularly to hydrogenating liquid mixtures of hydrocarbons in the presence of a catalyst containing metallic nickel and/or metallic cobalt.
• vol. 3 of Catalysis the subject of selective hydrogenation is treated on pages 8l89 and 103 with particular references to the selective hydrogenation of olefins in cracked naphtha to produce motor fuel with high octane number on page 83, and the deliberate poisoning of catalysts for selective hydrogenation on page 103.
• the preparation and activity of nickel, cobalt and nickel-alumina catalysts is particularly set forth on pages 98, 101 and 104, of vol. 3 of Catalysis.
• Still other objects of the invention are improved nickel and/or cobalt selective catalysts.
• Another object of the present invention is an improved selective catalyst resulting from deliberate poisoning.
• a particular object of the present invention is the improved mixed hydrocarbon hydrogenation process having a. selective catalyst obtained by carbon monoxide poisonmg.
• a normally liquid mixture of hydrocarbons particularly including gum-producing hy- 3,471,400 Patented Oct. 7, 1969 ice drocarbons and having less than 50 parts per million by weight of sulfur is selectively hydrogenated by contact with hydrogen at a temperature between about 50 and 250 C. in the presence of a catalyst containing metallic nickel and/or metallic cobalt and carbon monoxide, wherein the carbon monoxide is added in the ratio of 10 to 1000 parts per million parts by volume of the hydrogen.
• gum-producing hydrocarbons diolefinic and/or alkenyl-aromatic hydrocarbons. These hydrocarbons have a boiling point range between about 20 and 220 C. under 76 cm. of mercury and are present in particular refinery fractions, such as the products of pyrolysis, cracking, steam cracking and dehydrogenation, and generally are present in a concentration of 1 to 40 volume percent.
• diolefinic hydrocarbons have 5 to 14 carbon atoms, such as isoprene, piperylene, 2,4-heptadiene, 1,3-decadiene, phenyl-2-butadiene-1,3, cyclohexadiene and cyclopentadiene.
• alkenyl-aromatic hydrocarbons have 8 to 12 carbon atoms, such as styrene, a-methylstyrene and 2butenylbenzene.
• the diolefinic and/or alkenyl-aromatie hydrocarbons are converted into monoolefinic and/ or alkylaromatic hydrocarbons without appreciable hydrogenation of the monoolefinic, aromatic or alkyl-aromatic unsaturated hydrocarbons already present.
• Stable fractions as indicated by a good period of induction, are produced without lowering the commercial value as measured by the octane number.
• a good period of induction is defined in the present invention as being at least 360 minutes.
• metallic nickel or metallic cobalt cannot be used alone because of their low selectivity. It is known in the prior art, however, to improve the selectivity of catalysts by the addition of sulfur compounds. These sulfur compounds can be added to the charge or to the hydrogenating gas, or else can be present naturally in the gas or in the charge, as for example, in certain fractions produced during the cracking process.
• the charge does not contain any sulfur compounds or only small proportions, for example, in amounts less than 50 p.p.m., and especially less than 30 ppm. by weight, it is generally not desirable to add sulfur compounds because such an addition, besides being troublesome, can be detrimental to the quality of the final products.
• some or all of the fraction after having been subjected to a first hydrogenation stage for the elimination of the diolefines and/or the alkenyl-arornatics, is delivered to a second hydro-desulfurization and hydrogenation stage which decomposes the sulfide and hydrogenates the olefins in such a manner as to produce a suitable charge for the extraction of aromatic hydrocarbons.
• the present invention makes use of carbon monoxide which can be easily removed from the fraction and has the ability to selectively inhibit the activity of the catalysts. This selectivity is often superior to that produced by sulfur compounds.
• carbon monoxide is, of course, inexpensive, and easily produced.
• the catalyst can be dispersed in the charge or disposed in a layer which may be stationary, mobile, or fluid.
• a layer which may be stationary, mobile, or fluid.
• it is composed of metallic nickel or cobalt, or it is mixed with other catalytic constituents, as, for example, compounds of Group VI metals, especially of molybdenum.
• Inert nonacidic supporting materials are also useful, for example, alumina, silica, or magnesia.
• the nickel and/or cobalt is advantageously present in amounts of about 2 to 50% by weight of the catalyst.
• the catalyst of the present invention can be prepared by known methods, as disclosed, for example, in the books Chemistry of Petroleum Hydrocarbons, vol. 3, and Catalysis, v01. 3.
• the total pressure is kept sufliciently high, at least equal in most cases to 10 atm., and preferably between 30 and 80 atm.
• the spatial rate (volume of the liquid charge/volume of the catalyst/ hour) is between 0.5 and 10, and preferably between 1 and 4.
• the rate of gaseous hydrogen relative to the rate of the liquid charge is, for example, between 50 and 500 liters/liter, but variation beyond these last two values is to be understood as within the operational variables of the process.
• the reaction temperature is between 50 and 250 C., preferably between about 120 and 180 C.
• the hydrogen is used in the pure state or is diluted by an inert gas, especially by saturated lower hydrocarbons.
• the presence of sulfur compounds in the hydrogen gas is to be avoided since there should be less than 50 p.p.m., and preferably less than 5 p.p.m. of sulfur by weight in this gas.
• the liquid charge and the hydrogen do not contain an inhibitor compound.
• the liquid charge contains 300 p.p.m. by weight of sulfur in the form of thiophene (the hydrogen is pure)
• the charge does not contain any sulfur but the hydrogen contains 300 p.p.m. by volume of carbon monoxide.
• the products indicate that nickel in the absence of inhibitor does not have good selectively because on the one hand it permits the complete hydrogenation of the intermediate olefins, and on the other hand a large portion of the benzene is also hydrogenated.
• inhibitor compounds makes it possible to obtain a selectivity resulting in a minimum formation of saturated hydrocarbons (isopentane). It is found that carbon monoxide confers a selectivity that is definitely superior to that of thiophene.
• the catalyst is the same as the previous example.
• the proportion of carbon monoxide in the hydrogen is 600 p.p.m. (by volume).
• the gums are measured directly on the crude fraction at the outlet of the reactor and not after distillation.
• the various measurements indicated are made according to the A.S.T.M. standards.
• the maleic anhydride index is measured according to U.O.P. standard method 326.58.
• a very stable product, as indicated by a very high period of induction, is obtained, with only a very small loss of clear octane index.
• the antioxidant is N,N-di-sec.- butyl-paraphenylene-diamine.
• Example 3 The process of Example 2 is repeated at a temperature of 140 C., with different ratios of carbon monoxide to hydrogen.
• EXAMPLE 4 The process of Example 3 is repeated at the temperature of about 105 C. It is found that in this case the tolerance in carbon monoxide is still less, the minimum tolerable limit for the induction period being reached at about 1000 p.p.m. of carbon monoxide in the hydrogen.
• Example 5 The process of Example 2 is repeated with a cobalt catalyst substituted for the nickel catalyst. The results are comparable with the results of Example 2.
• Example 6 The process of Example 2 is repeated, with a mixed cobalt/nickel catalyst substituted for the nickel catalyst. The results are comparable with the results obtained in Example 2.
• said hy- 10 NELSON Asslstan Exammer drogenation catalyst further comprises a compound of US. Cl. X.R.

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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)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)

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Citations (4)

• 1965
  • 1965-09-23 FR FR32687A patent/FR1498268A/fr not_active Expired
• 1966
  • 1966-09-16 DE DE1545315A patent/DE1545315C3/de not_active Expired
  • 1966-09-19 US US580193A patent/US3471400A/en not_active Expired - Lifetime
  • 1966-09-20 BE BE687155D patent/BE687155A/xx unknown
  • 1966-09-21 NL NL666613318A patent/NL146204B/xx unknown
  • 1966-09-22 ES ES0331510A patent/ES331510A1/es not_active Expired
  • 1966-09-22 IL IL26557A patent/IL26557A/en unknown
  • 1966-09-23 GB GB42651/66A patent/GB1141256A/en not_active Expired

Patent Citations (4)

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