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Cobalt 2 3+ catalyst

Propagation and Chain Transfer Pathways/Theoretical Studies [Pg.127]

In an attempt to rationalize the experimental observations, a number of theoretical studies have been performed to probe the mode of propagation and chain transfer. As with oxidation state considerations for the active catalyst, uncertainty also exists about the precise electronic structure of the iron species. In an initial full ah initio study on the diisopropylphenyl Fe(II) catalysts derived from la, Gould and coworkers [132] determined the key structures operating for the first monomer insertion and showed that intermediates along the reaction coordinate have low spin (S = 0) configurations. Ziegler et al. have carried out density functional theory [Pg.128]

For the cobalt catalyst the story appears somewhat clearer. Both experiment and theory have been shown to be in agreement and support a stepwise pathway for the reaction of the cobalt(I) alkyl complexes with 1-alkenes, reacting by (3-hydride transfer via a cobalt hydride intermediate [135]. Such cobalt alkyls have also been shown to contain low-spin cobalt(II) antiferromagnetically coupled to a hgand radical anion. The lowest triplet state is thermaUy accessible and accounts for the observed H NMR chemical shifts at room temperature [66]. [Pg.129]


It was first described in 1608 when it was sublimed out of gum benzoin. It also occurs in many other natural resins. Benzoic acid is manufactured by the air oxidation of toluene in the liquid phase at 150°C and 4-6 atm. in the presence of a cobalt catalyst by the partial decarboxylation of phthalic anhydride in either the liquid or vapour phase in the presence of water by the hydrolysis of benzotrichloride (from the chlorination of toluene) in the presence of zinc chloride at 100°C. [Pg.56]

Carbon monoxide and excess steam are normally passed over a cobalt catalyst at about 250-300 C resulting in greater than 99% conversion of CO to COj. This conversion reaction is widely used in oil or solid fuel gasification processes for the production of town gas or substitute natural gas. ... [Pg.357]

Manufacture. Furan is produced commercially by decarbonylation of furfural in the presence of a noble metal catalyst (97—100). Nickel or cobalt catalysts have also been reported (101—103) as weU as noncatalytic pyrolysis at high temperature. Furan can also be prepared by decarboxylation of 2-furoic acid this method is usually considered a laboratory procedure. [Pg.81]

With various catalysts, butanediol adds carbon monoxide to form adipic acid. Heating with acidic catalysts dehydrates butanediol to tetrahydrofuran [109-99-9] C HgO (see Euran derivatives). With dehydrogenation catalysts, such as copper chromite, butanediol forms butyrolactone (133). With certain cobalt catalysts both dehydration and dehydrogenation occur, giving 2,3-dihydrofuran (134). [Pg.108]

Carbonylation of butyrolactone using nickel or cobalt catalysts gives high yields of glutaric acid [110-94-1] (163). [Pg.111]

Reduction. Hydrogenation of dimethyl adipate over Raney-promoted copper chromite at 200°C and 10 MPa produces 1,6-hexanediol [629-11-8], an important chemical intermediate (32). Promoted cobalt catalysts (33) and nickel catalysts (34) are examples of other patented processes for this reaction. An eadier process, which is no longer in use, for the manufacture of the 1,6-hexanediamine from adipic acid involved hydrogenation of the acid (as its ester) to the diol, followed by ammonolysis to the diamine (35). [Pg.240]

The cobalt catalyst can be introduced into the reactor in any convenient form, such as the hydrocarbon-soluble cobalt naphthenate [61789-51 -3] as it is converted in the reaction to dicobalt octacarbonyl [15226-74-17, Co2(CO)g, the precursor to cobalt hydrocarbonyl [16842-03-8] HCo(CO)4, the active catalyst species. Some of the methods used to recover cobalt values for reuse are (11) conversion to an inorganic salt soluble ia water conversion to an organic salt soluble ia water or an organic solvent treatment with aqueous acid or alkah to recover part or all of the HCo(CO)4 ia the aqueous phase and conversion to metallic cobalt by thermal or chemical means. [Pg.458]

The 0X0 and aldol reactions may be combined if the cobalt catalyst is modified by the addition of organic—soluble compounds of 2inc or other metals. Thus, propylene, hydrogen, and carbon monoxide give a mixture of aldehydes and 2-ethylhexenaldehyde [123-05-7] which, on hydrogenation, yield the corresponding alcohols. [Pg.460]

Goal Upgrading via Fischer-Tropsch. The synthesis of methane by the catalytic reduction of carbon monoxide and hydrogen over nickel and cobalt catalysts at atmospheric pressure was reported in 1902 (11). [Pg.79]

During World War II, nine commercial plants were operated in Germany, five using the normal pressure synthesis, two the medium pressure process, and two having converters of both types. The largest plants had capacities of ca 400 mr / d (2500 bbl/d) of Hquid products. Cobalt catalysts were used exclusively. [Pg.80]

Butane LPO conducted in the presence of very high concentrations of cobalt catalyst has been reported to have special character (2,205,217—219). It occurs under mild conditions with reportedly high efficiency to acetic acid. It is postulated to involve the direct attack of Co(III) on the substrate. Various additives, including methyl ethyl ketone, -xylene, or water, are claimed to be useful. [Pg.343]

A one-step LPO of cyclohexane directly to adipic acid (qv) has received a lot of attention (233—238) but has not been implemented on a large scale. The various versions of this process use a high concentration cobalt catalyst in acetic acid solvent and a promoter (acetaldehyde, methyl ethyl ketone, water). [Pg.344]

A thkd method utilizes cooxidation of an organic promoter with manganese or cobalt-ion catalysis. A process using methyl ethyl ketone (248,252,265—270) was commercialized by Mobil but discontinued in 1973 (263,264). Other promoters include acetaldehyde (248,271—273), paraldehyde (248,274), various hydrocarbons such as butane (270,275), and others. Other types of reported activators include peracetic acid (276) and ozone (277), and very high concentrations of cobalt catalyst (2,248,278). [Pg.344]

Reactions. The most important commercial reaction of cyclohexane is its oxidation (ia Hquid phase) with air ia the presence of soluble cobalt catalyst or boric acid to produce cyclohexanol and cyclohexanone (see Hydrocarbon oxidation Cyclohexanoland cyclohexanone). Cyclohexanol is dehydrogenated with 2iac or copper catalysts to cyclohexanone which is used to manufacture caprolactam (qv). [Pg.407]

Acetic acid is produced by direct carbonylation of methanol in the presence of a homogeneous rhodium or cobalt catalyst. [Pg.274]

Unmodified Cobalt Process. Typical sources of the soluble cobalt catalyst include cobalt alkanoates, cobalt soaps, and cobalt hydroxide [1307-86 ] (see Cobalt compounds). These are converted in situ into the active catalyst, HCo(CO)4, which is in equihbrium with dicobalt octacarbonyl... [Pg.466]

Because of its volatility, the cobalt catalyst codistills with the product aldehyde necessitating a separate catalyst separation step known as decobalting. This is typically done by contacting the product stream with an aqueous carboxyhc acid, eg, acetic acid, subsequently separating the aqueous cobalt carboxylate, and returning the cobalt to the process as active catalyst precursor (2). Alternatively, the aldehyde product stream may be decobalted by contacting it with aqueous caustic soda which converts the catalyst into the water-soluble Co(CO). This stream is decanted from the product, acidified, and recycled as active HCo(CO)4. [Pg.466]

Prior to 1975, reaction of mixed butenes with syn gas required high temperatures (160—180°C) and high pressures 20—40 MPa (3000—6000 psi), in the presence of a cobalt catalyst system, to produce / -valeraldehyde and 2-methylbutyraldehyde. Even after commercialization of the low pressure 0x0 process in 1975, a practical process was not available for amyl alcohols because of low hydroformylation rates of internal bonds of isomeric butenes (91,94). More recent developments in catalysts have made low pressure 0x0 process technology commercially viable for production of low cost / -valeraldehyde, 2-methylbutyraldehyde, and isovaleraldehyde, and the corresponding alcohols in pure form. The producers are Union Carbide Chemicals and Plastic Company Inc., BASF, Hoechst AG, and BP Chemicals. [Pg.374]

High temperature hydrogenation with a cobalt catalyst gives pyrroHdine, (27) + (19) (72). Under dehydrating conditions, 2-pyrrohdinone... [Pg.361]

Benzoic Acid. Ben2oic acid is manufactured from toluene by oxidation in the liquid phase using air and a cobalt catalyst. Typical conditions are 308—790 kPa (30—100 psi) and 130—160°C. The cmde product is purified by distillation, crystallization, or both. Yields are generally >90 mol%, and product purity is generally >99%. Kalama Chemical Company, the largest producer, converts about half of its production to phenol, but most producers consider the most economic process for phenol to be peroxidation of cumene. Other uses of benzoic acid are for the manufacture of benzoyl chloride, of plasticizers such as butyl benzoate, and of sodium benzoate for use in preservatives. In Italy, Snia Viscosa uses benzoic acid as raw material for the production of caprolactam, and subsequendy nylon-6, by the sequence shown below. [Pg.191]

The basic process usually consists of a large reaction vessel in which air is bubbled through pressuri2ed hot Hquid toluene containing a soluble cobalt catalyst as well as the reaction products, a system to recover hydrocarbons from the reactor vent gases, and a purification system for the ben2oic acid product. [Pg.53]

With a cobalt catalyst at 250°C, methanethiol (methyl mercaptan [74-93-1]) results ... [Pg.28]

The original catalysts for this process were iodide-promoted cobalt catalysts, but high temperatures and high pressures (493 K and 48 MPa) were required to achieve yields of up to 60% (34,35). In contrast, the iodide-promoted, homogeneous rhodium catalyst operates at 448—468 K and pressures of 3 MPa. These conditions dramatically lower the specifications for pressure vessels. Yields of 99% acetic acid based on methanol are readily attained (see Acetic acid Catalysis). [Pg.51]

Eatty amines are made by dehydration of amides to nitriles at 280—330°C, followed by hydrogenation of the nitrile over nickel or cobalt catalysts ... [Pg.85]

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). [Pg.94]

Conventional Transportation Fuels. Synthesis gas produced from coal gasification or from natural gas by partial oxidation or steam reforming can be converted into a variety of transportation fuels, such as gasoline, aviation turbine fuel (see Aviation and other gas turbine fuels), and diesel fuel. A widely known process used for this appHcation is the Eischer-Tropsch process which converts synthesis gas into largely aHphatic hydrocarbons over an iron or cobalt catalyst. The process was operated successfully in Germany during World War II and is being used commercially at the Sasol plants in South Africa. [Pg.277]

Medium Pressure Synthesis. Pressures of 500—2000 kPa (5—20 atm) were typical for the medium pressure Fischer-Tropsch process. Cobalt catalysts similar to those used for the normal pressure synthesis were typically used at temperatures ranging from 170 to 200°C ia tubular "heat exchanger" type reactors. [Pg.290]

During World War II German scientists developed a method of hydrogenating soHd fuels to remove the sulfur by using a cobalt catalyst (see Coal CONVERSION processes). Subsequently, various American oil refining companies used the process in the hydrocracking of cmde fuels (see CATALYSIS SuLFUR REMOVAL AND RECOVERY). Cobalt catalysts are also used in the Fisher-Tropsch method of synthesizing Hquid fuels (21—23) (see Fuels, synthetic). [Pg.372]

There are currentiy no commercial producers of C-19 dicarboxyhc acids. During the 1970s BASF and Union Camp Corporation offered developmental products, but they were never commercialized (78). The Northern Regional Research Laboratory (NRRL) carried out extensive studies on preparing C-19 dicarboxyhc acids via hydroformylation using both cobalt catalyst and rhodium complexes as catalysts (78). In addition, the NRRL developed a simplified method to prepare 9-(10)-carboxystearic acid in high yields using a palladium catalyst (79). [Pg.63]

C-19 dicarboxyhc acid can be made from oleic acid or derivatives and carbon monoxide by hydroformylation, hydrocarboxylation, or carbonylation. In hydroformylation, ie, the Oxo reaction or Roelen reaction, the catalyst is usually cobalt carbonyl or a rhodium complex (see Oxo process). When using a cobalt catalyst a mixture of isomeric C-19 compounds results due to isomerization of the double bond prior to carbon monoxide addition (80). [Pg.63]

The nickel or cobalt catalyst causes isomerization of the double bond resulting in a mixture of C-19 isomers. The palladium complex catalyst produces only the 9-(10)-carboxystearic acid. The advantage of the hydrocarboxylation over the hydroformylation reaction is it produces the carboxyUc acids in a single step and obviates the oxidation of the aldehydes produced by hydroformylation. [Pg.63]

Prepa.ra.tlon, There are several methods described in the Hterature using various cobalt catalysts to prepare syndiotactic polybutadiene (29—41). Many of these methods have been experimentally verified others, for example, soluble organoaluminum compounds with cobalt compounds, are difficult to reproduce (30). A cobalt compound coupled with triphenylphosphine aluminum alkyls water complex was reported byJapan Synthetic Rubber Co., Ltd. (fSR) to give a low melting point (T = 75-90° C), low crystallinity (20—30%) syndiotactic polybutadiene (32). This polymer is commercially available. [Pg.530]

The physical properties of low melting point (60—105°C) syndiotactic polybutadienes commercially available from JSR are shown in Table 1. The modulus, tensile strength, hardness, and impact strength all increase with melting point. These properties are typical of the polymer made with a cobalt catalyst modified with triphenylphosphine ligand. [Pg.531]


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1-Decene catalysts, cobalt complexes

1.3- Butadiene, 1-phenylhydrogenation catalysts, cobalt complexes

Acetic acid cobalt catalysts

Activity cobalt catalyst solutions

Adipic acid cobalt catalysts

Alkanes cobalt catalysts

Alkenes cobalt catalysts

Alumina-supported cobalt catalysts, hydrogen

Aryl bromides catalysts, cobalt complexes

Atomic-Scale Structure of the Cobalt-Promoted Catalyst

Benzene, alkyloxidation cobalt catalysts

Benzil catalysts, cobalt complexes

Benzil cobalt catalysts

Benzils cobalt catalysts

Benzoic acid cobalt catalysts

Benzyl halides catalysts, cobalt complexes

Butadiene catalysts, cobalt complexes

By Cobalt Carbonyl Catalysts

By Cobalt Catalysts

Calcined catalysts cobalt oxide species

Carbene catalysts cobalt

Carbenoids cobalt catalysts

Carbided cobalt catalysts

Carbon deactivation, cobalt catalysts

Carbon monoxide hydrogenation cobalt catalysts

Carbon monoxide oxidation cobalt oxide catalyst

Carbon number support effects, cobalt catalysts

Catalyst cobalt-molybdate (COMO

Catalyst cobalt-salen

Catalyst cobalt/silica

Catalyst cobalt/zinc oxide

Catalysts Other than Cobalt and Rhodium

Catalysts cobalt modified

Catalysts copper-cobalt based

Catalysts, supported cobalt

Catalytic methanol carbonylation cobalt iodide catalyst

Classification of Carbon Types on Cobalt FTS Catalysts

Cobalt -molybdenum-sulfur catalysts

Cobalt -molybdenum-sulfur catalysts mechanism

Cobalt -molybdenum-sulfur catalysts preparation

Cobalt FT catalyst

Cobalt Fischer-Tropsch catalyst

Cobalt Fischer-Tropsch catalysts, preparation

Cobalt Schiff-base catalysts

Cobalt acetylacetonate catalyst

Cobalt alloy synthesis catalysts

Cobalt as catalyst

Cobalt based drying catalysts

Cobalt carbonyl as catalyst

Cobalt carbonyl catalysts

Cobalt catalyst alkali-activated

Cobalt catalyst for Fischer-Tropsch

Cobalt catalyst ligand

Cobalt catalyst products from

Cobalt catalyst promoters

Cobalt catalyst surface area

Cobalt catalysts Fischer-Tropsch synthesis rates, metal

Cobalt catalysts activation

Cobalt catalysts active sites generation

Cobalt catalysts applications

Cobalt catalysts behavior

Cobalt catalysts carbon number distribution

Cobalt catalysts catalyst

Cobalt catalysts catalyst

Cobalt catalysts catalytic properties

Cobalt catalysts characterization studies

Cobalt catalysts concentrations

Cobalt catalysts conjugation reactions

Cobalt catalysts containing cationic

Cobalt catalysts coordination polymers

Cobalt catalysts distribution

Cobalt catalysts effect

Cobalt catalysts experiment

Cobalt catalysts hydroformylation, Fischer-Tropsch

Cobalt catalysts hydrogen reduction, surface

Cobalt catalysts metal-free polymers

Cobalt catalysts poly derivatives

Cobalt catalysts preparation

Cobalt catalysts pressure

Cobalt catalysts reaction products

Cobalt catalysts structure

Cobalt catalysts supported, selectivity

Cobalt catalysts synthesis

Cobalt catalysts, chiral

Cobalt catalysts, heterogeneous

Cobalt catalysts, hydrosilylation using

Cobalt catalysts, product distribution

Cobalt chloride catalyst

Cobalt complex catalysts

Cobalt complex catalysts hydroformylation

Cobalt complex catalysts hydrogenation

Cobalt complex, modified hydroformylation catalyst

Cobalt complex, unmodified hydroformylation catalyst

Cobalt complexes as catalysts

Cobalt complexes oxidation catalysts

Cobalt doped catalysts

Cobalt hydrides catalysts

Cobalt hydrocarbon synthesis catalysts

Cobalt hydrocarbonyl catalyst

Cobalt hydrocarbonyl catalyst preparation

Cobalt hydrocarbonyl catalyst reactions

Cobalt hydrogenation catalysts

Cobalt increases catalyst activity

Cobalt intermetallic catalysts

Cobalt modified synthesis catalyst

Cobalt molybdate catalysts

Cobalt molybdates, hydrodesulfurization catalysts

Cobalt naphthenate catalyst

Cobalt naphthenate crosslinking catalyst

Cobalt oxidation catalysts

Cobalt oxidation catalysts thiol

Cobalt oxide catalyst

Cobalt oxide catalyst, ammonia oxidation

Cobalt oxide, dehydrogenation catalyst

Cobalt oxide-supported metal catalysts

Cobalt phosphine catalyst

Cobalt polysulfide hydrogenation catalyst

Cobalt powders catalyst

Cobalt precipitation catalysts

Cobalt resinate catalysts

Cobalt salophen complex catalyst

Cobalt salts catalysts

Cobalt skeletal catalyst, preparation

Cobalt standard catalyst

Cobalt sulfide catalyst

Cobalt sulfide phase structure catalysts

Cobalt sulfides, hydrogenation catalyst

Cobalt tetracarbonyl anion catalyst

Cobalt zeolite catalysts

Cobalt, bis catalyst

Cobalt, bis catalyst partial reduction of pyridinium salts

Cobalt, fuel cell oxygen reduction catalysts

Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts

Cobalt-alumina catalyst

Cobalt-aluminum hydroxide catalyst

Cobalt-based catalyst, fischer-Tropsch

Cobalt-based catalyst, fischer-Tropsch selectivity

Cobalt-based catalyst, fischer-Tropsch synthesis

Cobalt-based catalysts

Cobalt-based hydrogenation catalysts

Cobalt-chromium oxide catalysts

Cobalt-containing catalysts

Cobalt-copper-manganese catalyst

Cobalt-manganese oxide-copper catalyst

Cobalt-molybdenum catalysts

Cobalt-molybdenum catalysts EXAFS

Cobalt-molybdenum catalysts activity

Cobalt-molybdenum catalysts catalyst activity

Cobalt-molybdenum catalysts preparation

Cobalt-molybdenum catalysts promoter atoms

Cobalt-molybdenum catalysts sulfided

Cobalt-molybdenum catalysts unsupported

Cobalt-molybdenum catalysts, role

Cobalt-molybdenum hydrotreating catalysts

Cobalt-molybdenum sulfide catalyst

Cobalt-molybdenum-alumina catalysts

Cobalt-nickel catalysts

Cobalt-promoted catalyst

Cobalt-ruthenium catalysts

Cobalt/bismuth, oxidation catalysts

Cobalt/rhodium catalysts

Cobalt/rhodium catalysts amidocarbonylations

Cobaltous chloride, catalyst

Cobaltous oxide catalysts

Cobaltous oxide catalysts characterization

Cobaltous oxide catalysts reduction

Cobaltous oxide catalysts sulfidation

Copper-cobalt based catalysts performances

Cyclohexane cobalt catalysts

Cyclohexene catalysts, cobalt complexes

Cyclohexene cobalt catalysts

Cyclopentadiene catalysts, cobalt complexes

Cyclopentenes cobalt carbonyl catalyst

Cyclopropanation cobalt catalysts

Diamines cobalt catalysts

Dienes catalysts, cobalt complexes

Domino cobalt catalysts

Eight cobalt catalysts

Electron microscopy cobalt catalysts

Ethers, allyl propargyl use of cobalt complexes catalysts

Fischer-Tropsch cobalt-thoria catalyst

Flavonols cobalt catalysts

High surface area cobalt-on-alumina catalyst

Hydrocarbons cobalt catalysts

Hydroesterification catalysts, cobalt complexes

Hydroformylation cobalt catalysts

Hydroformylation, Fischer-Tropsch synthesis cobalt catalysts

Hydrosilylation cobalt catalysts used

Indole cobalt catalysts

Iron-cobalt carbonyl catalyst

Lanthanum cobaltate catalysts

Ligands cobalt catalyst stability

Magnetite Catalyst Containing Cobalt

Metal supported cobalt catalysts from

Metal supported cobalt-rhodium catalysts

Metal supported cobalt-ruthenium catalysts

Nitric oxide calcination, silica-supported cobalt catalysts

Nitriles cobalt catalysts

Organic modification, cobalt catalysts

Oxidative addition cobalt halide catalysts

Oxidative cleavage cobalt catalysts

Phenols cobalt catalysts

Phosphine-Modified Cobalt Catalysts

Polymerisation cobalt catalyst

Propene cobalt-nitro complex catalysts

Propylene catalysts, cobalt complexes

Pyridine, 2-vinylhydroesterification catalysts, cobalt complexes

Raney cobalt, hydrogenation catalyst

Raney type nickel-cobalt catalyst

Raney-Cobalt catalyst

Reduction cobalt halide catalysts

Rhodium-cobalt complex catalyst

Rich cobalt catalysts

Ruthenium-cobalt catalysts, iodide

Ruthenium-cobalt catalysts, iodide production

Silica-supported cobalt catalysts, nitric oxide

Styrene cobalt catalysts

Terephthalic acid cobalt catalysts

Triphenylphosphine-cobalt bromide, catalyst

Unmodified Cobalt Catalysts

Water-soluble cobalt catalyst

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