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United States Patent [191 [11] Patent Number: 4,952,713 Lilga Et Al

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United States Patent [191 [11] Patent Number: 4,952,713 Lilga Et Al United States Patent [191 [11] Patent Number: 4,952,713 Lilga et al. [45] Date of Patent: Aug. 28, 1990 [54] BRIDGED TRANSITION-METAL Cobalt Complex, etc., Journal of American Chemistry COMPLEXES AND USES THEREOF FOR Soc., 101.16 (1979), pp. 4766-4768. HYDROGEN SEPARATION, STORAGE AND Collman et al., Principles and Applications of Organotran HYDROGENATION sition Metal Chemistry, Mill Valley, CA; University Science Books, 1980. [7's] Inventors: Michael A. Lily; Richard T. Hallen, Huheey, Inorganic Chemistry, New York; James E. both of Richland, Wash. Huheey, 1978. [73] Assignee: Battelle Memorial Institute, Primary Examiner-Pau1 F. Shaver Richland, Wash. Attorney, Agent, or Firm-Dellett, Smith-Hill and Bedell [21] Appl. No.: 202,097 [57] ABSTRACT [22] Filed: Jun. 2, 1988 The present invention constitutes a class of organome tallic complexes which reversibly react with hydrogen [51] Int. Cl.5 ....................... .. C07F 7/02; C07F 11/00; to form dihydrides and processes by which these com C07F 15/02; C07F 15/06 pounds can be utilized. The class includes bimetallic [52] U.S. Cl. ...................................... .. 556/60; 556/11; complexes in which two cyclopentadienyl rings are 556/31; 556/32; 556/41; 556/47; 556/48; bridged together and also separately ir-bonded to two 556/58; 556/142; 556/144; 556/145 transition metal atoms. The transition metals are be [58] Field of Search ................... .. 556/60, 142, 11, 47, lieved to bond with the hydrogen in forming the dihy 556/31, 32, 41, 48, 144, 145, 58 dride. Transition metals such as Fe, Mn or C0 may be [56] References Cited employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands U.S. PATENT DOCUMENTS such as C0 are bonded to the metal atoms in the com 3,064,024 11/1962 Wilkinson ........................... .. 556/60 plexes. Alkyl groups and the like may be substituted on 3,326,948 6/1967 Cais et a1. ........................... .. 556/60 the cyclopentadienyl rings. These organometallic com OTHER PUBLICATIONS pounds may be used in absorption/desorption systems and in facilitated transport membrane systems for stor Bitterwolf, Bis(cyclopentadienylthallium) Methane, ing and separating out H; from mixed gas streams such etc., Journal of Organometallic Chemistry, 312 (1986), as the produce gas from coal gasi?cation processes. pp. 197-206. Bryndza et al., Reaction of a Bridged Binuclear Dialkyl 5 Claims, 1 Drawing Sheet 4,952,713 1 2 number of such hydrogenation catalysts have included BRIDGED TRANSITION-METAL COMPLEXES transition metal organometallic complexes. AND USFB THEREOF FOR HYDROGEN For example, U.S. Pat. No. 4,645,849 issued Feb. 24, SEPARATION, STORAGE AND 1987 to Lewis describes a method for hydrogenating HYDROGENATION ole?ns and alkynes wherein the unsaturated hydrocar bon is reacted with H; in the presence of certain “cy This invention was made with government support clometallated” complexes in which a transition metal under contract number DE-AC06—76RLO 1830, such as palladium, platinum, cobalt or the like forms a awarded by the U.S. Department of Energy. The gov 4-6 membered ring system with a covalently bonded ernment has certain rights in the invention. carbon in a hydrocarbon chain and a ligand atom such as phosphorous, nitrogen, arsenic, oxygen or sulfur. BACKGROUND OF THE INVENTION Additionally, U.S. Pat. No. 4,670,621 issued June 2, This invention relates to reversible hydrogenation 1987 to Walker describes the use of certain cyclopenta reactions usable for H2 separation or storage or in chem dienyl transition metal complexes of iridium and os ical synthesis, and particularly to a class of bridged 15 mium as dehydrogenation catalysts in the conversion of bimetallic transition metal compounds that are useful as paraffms to ole?ns having a corresponding carbon skel catalysts for such reactions. eton. Also, U.S. Pat. No. 4,360,475 issued Nov. 23, 1982 The chemical reactions of molecular hydrogen have to Pruett, et a1 describes a class of bimetallic cluster use in the hydrogenation of unsaturated hydrocarbons compounds consisting of ruthenium carbide octahedra and similar compounds, and in processes for H2 separa 20 linked through a Group IIIA metal atom which may be tion and storage. In particular, the selective separation used for converting synthesis gas to hydrocarbons and or puri?cation of H; from the product gas of coal gasi? oxygenates. cation would be highly desirable. However, gas separa Several organometallic catalysts which have been tion has in the past been a dif?cult and energy intensive used for purposes other than hydrogenation (or dehy process. The development of new and innovative tech 25 drogenation) have employed the cyclopentadienyl niques for selectively and ef?ciently separating speci?c group as a ligand. For example, U.S. Pat. No. 4,423,276 gas components from mixed-gas streams would signi? issued Dec. 27, 1983 to Johnson describes a class of cantly reduce the cost and complexity of product gas cyclopentadienyl tantalum compounds useful for ole?n production and processing. For example, ef?cient H2 30 isomerization, i.e., the switching of an internal double separation from synthesis gas could help to make coal bond to a terminal double bond. The process seems to an attractive future source of Hg for use as a fuel or be peculiar to the Ta atom. Similarly, U.S. Pat. No. chemical feedstock. In addition, this technology could 4,153,576 issued May 8, 1979 to Karol, et al relates to have a signi?cant impact on processes not directly asso the preparation of cyclopentadienyl chromium alkyl/a ciated with coal gasi?cation in which H2 is lost in waste 35 ryl oxides and siloxides, for use primarily as catalysts in streams. These processes may include ammonia manu the polymerization of ethylene but also for use in scav facture, reduction of metallic oxide ores, and the hydro enging oxygen and volatile sulfur compounds from genation of fats and oils. Thus, wide-ranging applica various liquid and gaseous streams. However, these tions exist for H2 separation and recovery technologies compounds must be used on a silicon support and acti However, the chemical reactions used either for sepa 40 vated with a silane. U.S. Pat. No. 4,086,408 issued Apr. ration or puri?cation of H2 must be highly reversible 25, 1978 to Karol, et al further describes the modi?ca and selective in order to be commercially attractive. tion of bis-cyclopentadienyl chromium [II] compounds The reactions that are currently used for such purposes used as supported catalysts on an inorganic oxide. These tend to be either inef?cient or non-selective. For exam complexes are modi?ed by addition thereto of oxygen ple, the recovery of H2 from Pressure Swing Adsorp 45 containing compounds such as ethers in order to im tion (PSA) is on the order of only 80%. Furthermore, prove the impact strength and toughness of ethylene PSA is ineffective with feeds containing less than 50% polymers made therewith. Also, Japanese Pat. No. J6 of H2. Membrane separation systems are inherently 0092-297-A describes a catalyst for the synthesis of energy efficient, but existing commercial systems such pyridine derivatives from alkynes and nitriles which as PRISM cannot separate Hz from streams containing 50 may be produced by the reaction of eta 5-substituted gases such as C02. cyclopentadienyl cobalt monohalides with polyenes A signi?cant factor in determining the ef?ciency and having l-16 carbon atoms. yield of any process for storing or recovering hydrogen _ In reactions with molecular hydrogen, the use of is the type of catalyst employed. For example, U.S. Pat. bimetallic complexes as catalysts has sometimes been No. 4,695,446 issued Sept. 22, 1987 to Bogdanovic, 55 preferred. For example, U.S. Pat. No. 4,605,751 issued describes a method of separating H2 from a hydrogen Aug. 12, 1986 to Curtis, et al describes a class of poor gas mixtures by contacting the mixture with a type heterobimetallic cluster compositions usable for the of “active” magnesium which has been doped with a selective hydrogenation of carbon monoxide. The com transition metal. The active magnesium reacts with plex includes sulfur directly bonded into the cluster, a hydrogen from the mixture to form magnesium hydride. metal from the group consisting of Cr, Co and W, an Hydrogen may then be recovered by thermally dehy other metal from the group Fe, Co and Ni and two or drogenating the magnesium hydride. However, it is more cyclopentadienyl groups. The catalyst is sup preferred to use homogeneous catalytic processes in ported on a refractory base such as alumina. Also, U.S. order to provide commercially acceptable rates of reac Pat. No. 4,656,299 issued Apr. 7, 1987 to Fujii, et al tion. 65 describes a class of substituted cyclopentadienyl cobalt The bulk of the research with respect to hydrogena complexes including certain bimetallics that are usable tion catalysts has related to chemical synthesis and espe as catalysts in the preparation of pyridine homologues. cially the hydrogenation of unsaturated compounds. A The bimetallic form of this complex has two cobalt 4,952,713 3 4 atoms bonded directly together and further connected carry out reactions involving hydrogen does not seem through a metallocyclic ring. to have been previously investigated. It has been dis U.S. Pat. No. 4,361,497 issued Nov. 30, 1982 to Boldt, covered that by bridging together of two unsaturated et al represents one instance in which catalysts of the ring systems such as cyclopentadienyl groups and by cyclopentadienyl metal carbonyl type have been used forming bimetallic complexes therewith, compounds for hydrogenation. However, these have been poly have been produced which have surprising selectivity, meric catalysts in which the metal complex is bound to reactivity and reversibility when reacted with molecu a polymer carrier, either directly through the cyclopen lar hydrogen.
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