Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
  • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
• • 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
• • 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
• • 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
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
  • C07C2523/44—Palladium
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S585/00—Chemistry of hydrocarbon compounds
  • Y10S585/949—Miscellaneous considerations
  • Y10S585/951—Reaction start-up procedure
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S585/00—Chemistry of hydrocarbon compounds
  • Y10S585/949—Miscellaneous considerations
  • Y10S585/952—Reaction stopping or retarding

Definitions

• ABSTRACT A method of preventing double bond migration of a monoolefin hydrocarbon during the selective hydrogenation of a polyunsaturated hydrocarbon coexisting with a mono-olefinic hydrocarbon, each of the mono-olefinic hydrocarbons and polyunsaturated hydrocarbons having at least four carbon atoms, in the presence of hydrogen, using a palladiumor nickel-hydrogenation catalyst, which comprises adding carbon monoxide to the reaction System in an amount of from 1 to 50 mol. based on said hydrogen during the initial stage of the selective hydrogenation reaction and following the initial stage, lowering the content of carbon monoxide to a range of from 005-! mol. based on the hydrogen.
• the present invention relates to a method of preventing the double bond migration of mono-olefinic hydrocarbons during the selective hydrogenation of polyunsaturated hydrocarbons of polyolefinic and/or acetylenic types coexisting with said mono-olefinic hydrocarbons, each of the mono-olefinic hydrocarbons and the polyunsaturated hydrocarbons having at least four carbon atoms.
• a polyunsaturated hydrocarbon of the polyolefinic and/or acetylenic type having at least four carbon atoms, coexisting with a mono-olefmic hydrocarbon having at least four carbon atoms may be hydrogenated in the presence of a hydrogenation catalyst, such as palladium, platinum or nickel, by hydrogen to selectively convert said polyunsaturated hydrocarbons into the corresponding monoolefinic hydrocarbons.
• a hydrogenation catalyst such as palladium, platinum or nickel
• selective hydrogenation Such a process is hereinafter referred to as selective hydrogenation.”
• a butene fraction containing C -diolefins and/or C,-acetylenes may be selectively hydrogenated in the presence of a palladium, platinum or nickel catalyst by hydrogen to convert said C -diolefins and/or C -acetylenes into the corresponding butenes, with little loss of butenes, thereby obtaining the butene fraction substantially free from said Q-diolefins and C,-acetylenes.
• the conventional hydrogenation catalysts such as palladium, platinum and nickel, used for such selective hydrogenation processes possess the disadvantage of promoting double bond migration in addition to the desired hydrogenation of the unsaturated bonds. Accordingly, conventionally practiced selective hydrogenation employing such catalysts are inevitably accompanied by double bond migration of mono-olefinic hydrocarbons.
• C -diolefins e.g., l,3butadiene, methyl allene
• C -acetylenes e.g., dimethyl acetylene, ethyl acetylene, vinyl acetylene
• both the selective hydrogenation reaction of C -diolefins and/or C acetylenes into butenes and the double bond migration of l-butene into Z-butene take place simultaneously under the same reaction condition.
• the greater part of the l-butene is lost.
• Another object of the present invention is to provide a method of effectively preventing the double bond migration of mono-olefinic hydrocarbons during the selective hydrogenation of polyunsaturated hydrocarbons by the use of a small amount of carbon monoxide.
• Still another object of the present invention is to provide a process for the selective hydrogenation of polyunsaturated hydrocarbons containing mono-olefinic hydrocarbons, each of said polyunsaturated hydrocarbons and mono-olefinic hydrocarbons having at least four carbon atoms, in the absence of the usual accompanying double bond migration.
• Still another object of the present invention is to provide a method of inhibiting only the isomerization (double bond migration) activity of conventional hydrogenation catalysts being employed for the selective hydrogenation of polyunsaturated hydrocarbons coexisting with mono-olefinic hydrocarbons, each of said polyunsaturated hydrocarbons and monoolefinic hydrocarbons having at least four carbon atoms.
• the polyunsaturated hydrocarbons coexisting with the mono-olefinic hydrocarbons, each of which hydrocarbons having at least four carbon atoms, are selectively hydrogenated in the presence of hydrogen and 1-50 mo]. during the initial stage of the reaction and thereafter 005-] mol. of carbon monoxide, respectively based on the hydrogen, by the use of a Irunw: rvnn copper-free palladium or nickel catalyst.
• said polyunsaturated hydrocarbons are selectively hydrogenated and thus eliminated, and the double bond migration of said mono-olefinic hydrocarbons is effectively prevented.
• a hydrocarbon feed utilized in the selective hydrogenation of the present invention comprises a mixture of mono-olefinic hydrocarbon and a polyunsaturated hydrocarbon, each having at least four carbon atoms.
• the hydrocarbon feed may contain hydrocarbons having up to 16 carbon atoms.
• the said polyunsaturated hydrocarbons are polyolefinic hydrocarbons (e.g., diolefins, triolefins and the like) and/or acetylenic hydrocarbons (e.g., alkynes, alkenynes).
• the content of the polyunsaturated hydrocarbons in the hydrocarbon feed is preferably less than about 50 mol.
• Feeds containing greater amounts of polyunsaturated hydrocarbons may, however, be employed within the scope of the invention.
• the hydrocarbon feed may contain paraffinic hydrocarbons, such as n-butane, pentane, hexane, etc.; inert gases such as hydrogen, nitrogen, etc; and occasionally a small amount of C polyunsaturated hydrocarbon, such as methyl acetylene and allene.
• the hydrogen to be used in this invention may be either pure hydrogen or hydrogen-containing gases, such as natural gas, reformer off-gas, etc.
• the rest of the hydrogen being required for the selective hydrogenation of this invention may be supplied from an external source.
• the amount of hydrogen employed in the present invention will vary depending upon the contents of the polyunsaturated hydrocarbon in the hydrocarbon feed. It is necessary to use more than the stoichiometric amount of hydrogen needed for hydrogenating the polyunsaturated hydrocarbons into corresponding mono-olefinic hydrocarbons. in general, l-20,000 moles of hydrogen per total mole of polyunsaturated hydrocarbons may be employed for the selective hydrogenation.
• the hydrogenation catalyst to be used in the present inven tion is a copper-free hydrogenation catalyst containing palladium or nickel.
• Suitable hydrogenation catalysts are palladium or nickel metals, or the sulfides or oxides of these metals, or such metals or compounds supported on known carriers, such as alumina, silica-alumina, magnesia, titania, diatomaceous earth, etc., by conventional treatment.
• Preferable catalysts are palladium supported on carrier (Pd cont. 0.005-3 weight or nickel on a supported carrier (Ni cont. 1-40 weight
• the hydrogen in the reaction system must contain l-50 mol, preferably 5-30 mol.
• the carbon monoxide may be introduced to the reaction system in any manner as long as hydrogen is also present. in practical operation, it is convenient to previously mix the carbon monoxide with hydrogen in a specific ratio and then to bring the resultant carbon monoxide-hydrogen mixture into contact with the hydrocarbon feed.
• the content of carbon monoxide is thereafter (after the initial stage) lowered to a later (following the initial stage) range, i.e. 0.05-l mol. (based on the hydrogen present) at once, stepwise or continuously.
• Said later content of carbon monoxide in an amount of less than 0.05 mol. is not desirable, since double bond migration will also take place along with the selective hydrogenation. If the later content of carbon monoxide is more than 1 mol. the double bond migration does not take place in the selective hydrogenation.
• said process wherein the amount of carbon monoxide is more than 1 mol. is shown in our copending application as mentioned above.
• the content of carbon monoxide is lowered from the initial range, i.e. 1-50 mol. to the later range, i.e. 0.05-1 mol. after the hydrogenation catalyst has been treated with a requisite amount of carbon monoxide under a high content (1-50 mol. of carbon monoxide during the initial stage of hydrogenation reaction.
• the content of carbon monoxide may usually be lowered to the later range of 005-1 mol. after the total amount of carbon monoxide added to the reaction system comes to at least 0.05 moles per gram of the hydrogenation catalyst.
• the content of carbon monoxide can be lowered to the later range after the total amount of carbon monoxide comes to preferably at least 0.l20 moles, most preferably at least 0.2l0 moles, per gram of the catalyst.
• new carbon monoxide is not added to the reaction system during the decrease of carbon monoxide content from the initial range l50 mol. to the later range (0.05-l mol.
• new carbon monoxide begins to be introduced into the reaction system along with hydrogen.
• the content of carbon monoxide is enough in the later range (0.05-l mol. provided that the catalyst is treated in the initial range with l-5O mol. of carbon monoxide at least once.
• the selective hydrogenation of the present invention is preferably carried out at a temperature of 20-250 C. under the pressure of about atmospheric to 50 kg/cm. Under such a relatively mild reaction condition, skeletal isomerization of the mono-olefinic hydrocarbons will not occur in any substantial amount during the selective hydrogenation.
• the milder reaction conditions e.g., to lower the temperature of hydrogenation reaction as shown in the examples. Said milder reaction conditions are chosen to prevent excessive hydrogenation. In this case, the double bond migration can be effectively prevented even though hydrogenation temperature is or is not lowered.
• the hydrocarbon feed is introduced as either an upflow or downflow to a reactor packed with the hydrogenation catalyst at a liquid hourly space velocity (L.H.S.V.) of 0. and is selectively hydrogenated therein.
• L.H.S.V. liquid hourly space velocity
• the selective hydrogenation may be carried out in either a batch, semicontinuous or continuous operation.
• a sulfur compound such as hydrogen sulfide, mercaptan or carbon disulfide together with carbon monoxide to the reaction system for the purpose of avoiding excessive hydrogenation in the process of this invention.
• the sulfur compound itself has no ability to prevent the double bond migration as mentioned above.
• the present invention is particularly useful in carrying out the selective hydrogenation of butenes containing Q-diolefins and/or C -acetylenes without lowering the l-butene content, and also in obtaining l-butene, or a fraction rich in l-butene, from l-butene mixtures with C -diolefins and/or C -acetylenes by selective hydrogenation.
• the field of the application of the present invention is not limited only to these specific examples.
• EXAMPLE 1 The hydrocarbon feed employed was a butene-containing feed having the composition shown in Table I. Said butene feed is a raffinate extracted from a C fraction produced by naphtha steam cracking.
• the hydrogenation catalyst employed was a commercial palladium catalyst (PGC-C" produced by Englehard Industries, Ltd.) containing 0.1 by weight of palladium supported on alumina.
• a vertically disposed reactor of 50 mm inner diameter was packed with 200 m1 of the palladium catalyst.
• the butene feed at the rate of 600 ml/hr (L.H.S.V. 3.0) and hydrogen containing 25 mol. carbon monoxide at the rate of 60 liters (N.T.P.)/hr, at a temperature of 90 C. and pressure of 25 kg/cm to effect the selective hydrogenation.
• the hydrogenated product thus obtained was analyzed by gas chromatography.
• Example 2 The procedure of Example 1 was repeated except that the hydrocarbon feed employed was a C -fraction having the composition shown in Table 3, which was produced by naphtha steam cracking. The reaction was carried out at a temperature of 80 C. under a pressure of 25 kglcm and the rate of hydrogen containing 5 mol. carbon monoxide was 500 liters (N.T.P. )/hr.
• composition of product thus obtained is also given under Product D in Table 3.
• Example 3 The procedure of Example 1 was repeated except that the reaction was carried out at a temperature of C. under a pressure of 15 kglcm and the rate of hydrogen containing 5 mol. carbon monoxide was 50 liters (N.T.P.)/hr. A nickelcontaining hydrogenation catalyst containing 1.0 by weight of nickel supported on alumina was used in place of palladium-alumina catalyst.
• compositions of the former and the latter product are given under Product H and Product K, respectively, in Table 5': I
• a process for the selective hydrogenation of at least one member, having at least four carbon atoms in the molecule, selected from the group consisting of a polyolefm, an alkyne, and alkenyne, and mixtures thereof in a hydrocarbon mixture containing at least one mono-olefin having at least four carbon atoms in the molecule which comprises contacting said hydrocarbon mixture with a copper-free hydrogenation catalyst com rising a member selected from the hgroup consistmg of palla rum and nickel under selective ydrogenation conditions in the presence of hydrogen and carbon monoxide of 1-50 mol. based on the hydrogen, during the initial stage of the reaction and thereafter lowering the content of carbon monoxide to a range of 0.05-l mol. based on the hydrogen, said process preventing double bond migration of the monoolefin.
• liquid hourly space velocity of the hydrocarbon feed ranges from 0.1 to 40.0.

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Citations (5)

• 1970
  • 1970-01-26 JP JP45006333A patent/JPS4928163B1/ja active Pending
• 1971
  • 1971-01-07 GB GB869/71A patent/GB1272728A/en not_active Expired
  • 1971-01-22 US US109051A patent/US3674886A/en not_active Expired - Lifetime
  • 1971-01-25 FR FR717102366A patent/FR2077619B2/fr not_active Expired
  • 1971-01-26 DE DE2103574A patent/DE2103574C3/de not_active Expired

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