中科微点-全球专利检索

  1. Login
  2. Sign Up

Search Results

651 records (took 0.022 seconds)

    Method of treating spontaneously combustible catalysts
    262.
    发明授权
    Method of treating spontaneously combustible catalysts 失效
    处理自燃可燃催化剂的方法

    公开(公告)号：US5681787A

    公开(公告)日：1997-10-28

    申请号：US430522

    申请日：1995-04-27

    Applicant: James Dallas Seamans ,  John Alexander Partin ,  Edward Roy Samonte

    Inventor： James Dallas Seamans ,  John Alexander Partin ,  Edward Roy Samonte

    IPC: B01J23/85 ,  B01J31/02 ,  B01J33/00 ,  B01J37/02 ,  B01J37/12 ,  B01J37/20 ,  C10G49/02 ,  B01J20/34

    CPC classification number: B01J23/883 ,  B01J23/85 ,  B01J33/00 ,  B01J37/0203 ,  B01J37/12 ,  B01J37/20 ,  C10G49/02 ,  B01J31/0201

    Abstract: Self-heating characteristics of a spontaneously combustible catalyst are reduced by treating spontaneously combustible catalysts with oxygen-containing hydrocarbons having at least 12 carbon atoms. The treatment is particularly suitable for reducing the self-heating characteristics of sulfidable metal oxide(s)-containing catalysts, presulfurized catalysts, presulfided catalysts or reduced catalysts. When applied to sulfur-containing catalysts, the treatment gives a catalyst that has suppressed self-heating properties without substantially compromising sulfur retention or activity. Further, a method of safely unloading a catalyst from a reactor is provided where the catalyst in the reactor is treated with a liquid mixture containing oxygen-containing hydrocarbon having at least 12 carbon atoms to wet the catalyst.

    Abstract translation: 通过用具有至少12个碳原子的含氧烃处理可自燃的催化剂来减少自发燃烧的催化剂的自加热特性。 该处理特别适用于降低含硫化金属氧化物催化剂，预硫化催化剂，预硫化催化剂或还原催化剂的自热特性。 当应用于含硫催化剂时，该处理产生抑制自热性能而不显着损害硫保留或活性的催化剂。 此外，提供了一种从反应器中安全卸载催化剂的方法，其中用含有至少12个碳原子的含氧烃的液体混合物处理反应器中的催化剂以润湿催化剂。

    Separation of molybdenum
    263.
    发明授权
    Separation of molybdenum 失效
    分离钼

    公开(公告)号：US5232559A

    公开(公告)日：1993-08-03

    申请号：US793902

    申请日：1991-11-18

    Applicant: William A. Smith ,  David L. Miller ,  Robert A. Meyer

    Inventor： William A. Smith ,  David L. Miller ,  Robert A. Meyer

    IPC: B01J31/40 ,  B01J37/34 ,  B01J38/48 ,  B01J38/68 ,  C25C1/22

    CPC classification number: B01J31/0201 ,  B01J31/0202 ,  B01J31/0239 ,  B01J31/34 ,  B01J31/4015 ,  B01J31/4076 ,  B01J37/348 ,  B01J38/48 ,  B01J38/68 ,  C25C1/22 ,  B01J2231/72

    Abstract: An organic solution of a soluble molybdenum compound is ammonated with ammonia, ammonium hydroxide and/or an ammonium salt in order to significantly reduce the electrical resistance of the solution and a direct electric current is passed therethrough in order to collect a significant amount of the molybdenum in solid form at the negative electrode. Preferably, an epoxidation reaction product formed by the molybdenum catalyzed reaction of propylene with tertiary butyl hydroperoxide to provide propylene oxide and tertiary butyl alcohol is separated by distillation into a propylene fraction, a propylene oxide fraction, a tertiary butyl alcohol fraction and a heavy liquid distillation fraction containing substantially all of the dissolved molybdenum catalyst, the heavy liquid distillation fraction is saturated with ammonia to precipitate the molybdenum therefrom, the precipitated molybdenum is removed from the ammonated heavy distillation fraction and a direct electric current is passed through the remaining liquid portion of the ammonated fraction in an electrolytic cell in order to collect a significant portion of the remaining molybdenum residually dissolved therein at the cathode.

    Abstract translation: 可溶性钼化合物的有机溶液用氨，氢氧化铵和/或铵盐氨化，以显着降低溶液的电阻，并且直流电流通过其中以收集显着量的钼 在固体形式的负极。 优选地，通过丙烯与叔丁基过氧化氢的钼催化反应形成环氧丙烷和叔丁醇形成的环氧化反应产物通过蒸馏分离成丙烯馏分，环氧丙烷馏分，叔丁醇馏分和重液体蒸馏 馏分含有基本上所有的溶解的钼催化剂，重液体蒸馏馏分用氨饱和，从中沉淀出钼，从氨化的重馏分中除去沉淀的钼，直流电流通过 在电解池中的氨化部分，以便在阴极收集残留的钼的很大部分。

    Process for the production of formates
    264.
    发明授权
    Process for the production of formates 失效
    生产甲酸盐的方法

    公开(公告)号：US4734525A

    公开(公告)日：1988-03-29

    申请号：US533981

    申请日：1983-09-20

    Applicant: Michael J. Green

    Inventor： Michael J. Green

    IPC: B01J31/02 ,  C07C53/02 ,  C07C67/36 ,  C07C69/06

    CPC classification number: B01J31/0201 ,  B01J31/0251 ,  C07C53/02 ,  C07C67/36

    Abstract: An alkyl ester of formic acid is prepared by reacting carbon monoxide with an alcohol in the presence, as catalyst, of (a) a guanidine or (b) an amidine and an epoxide.The amidine or guanidine structure can by cyclic. The process can be operated in the liquid phase at pressures from 20 to 120 bars and temperatures from 40.degree. to 150.degree. C. with excess carbon monoxide over that required for conversion of the alcohol to the formate ester.

    Abstract translation: 在（a）胍或（b）脒和环氧化物作为催化剂存在下，使一氧化碳与醇反应制备甲酸的烷基酯。 脒或胍结构可以循环。 该方法可以在液相中在20至120巴的压力和40至150℃的温度下操作，过量的一氧化碳超过将醇转化为甲酸酯所需的量。

    Processes for regenerating dispersions of ligand-stabilized, palladium(II) halide complexes used in carbonylation catalysts
    266.
    发明授权
    Processes for regenerating dispersions of ligand-stabilized, palladium(II) halide complexes used in carbonylation catalysts 失效
    用于羰基化催化剂中的配位体稳定的卤化钯（II）配合物再分散的方法

    公开(公告)号：US4048093A

    公开(公告)日：1977-09-13

    申请号：US635995

    申请日：1975-11-28

    Applicant: John F. Knifton

    Inventor： John F. Knifton

    IPC: B01J31/40 ,  B01J27/32 ,  C07C51/00 ,  C11C3/02

    CPC classification number: B01J31/0234 ,  B01J31/0239 ,  B01J31/0268 ,  B01J31/1895 ,  B01J31/2404 ,  B01J31/26 ,  B01J31/4038 ,  B01J2231/321 ,  B01J2231/34 ,  B01J2531/824 ,  B01J27/10 ,  B01J31/0201

    Abstract: This invention concerns processes for the regeneration of carbonylation catalysts consisting of dispersions of ligand-stabilized palladium(II) halide complexes in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermanate(II) using organic peroxides as the regenerating agent.STATEMENT OF THE INVENTIONThis invention pertains to the art of regenerating spent palladium carbonylation catalysts useful for the carbonylation of olefins.More particularly, this invention concerns the regeneration of certain carbonylation catalysts consisting of dispersions of ligand-stabilized palladium(II) halide complexes in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermanate(II) using substantially anhydrous organic peroxide reagents.BACKGROUND OF THE INVENTIONThis invention concerns a process for regenerating certain palladium catalysts used in the carbonylation of olefins. Carbonylation refers here to the reaction of .alpha.-olefins with carbon monoxide and active-hydrogen-containing compounds selected from the group consisting of alkanols or water. The major products of carbonylation are fatty(carboxylic) acids and their esters.The preparation of the fatty acids or fatty acid esters using metal carbonyls or carbonyl precursors to catalyze the carbonylation of olefins is old in the literature, originally involving Reppe and his coworkers and contemporaries. Reviews by C.W. Bird [Chem. Rev.62, 283 (1962)] document this work. Unfortunately, many of these carbonyl or carbonyl-type catalysts have the disadvantages of inherent toxicity, they require stringent reaction conditions which in turn lead to competing side reactions such as olefin isomerization, polymerization and reduction, and they exhibit poor selectivity to the desired linear acid ester.Recently, more acceptable homogeneous catalyst systems have been developed which offer substantially improved selectivity in converting olefins to primarily linear fatty acids or linear fatty esters, in good yield, under moderate reaction conditions of temperature and pressure.As is usually the case, after much more extensive usage, certain drawbacks in the catalysts have become more evident. These include difficulty in maintaining high conversions, high selectivities and high yields after recycling the catalyst several times. These problems are due to catalyst degradation as well as catalyst decomposition, mechanical losses and further catalyst decomposition during the separation of the products from the homogeneous catalysts and the inert solvents of the reaction mixture. Thermal instability of the catalyst is particularly troublesome in the recovery and working-up of certain ligand-stabilized homogeous palladium catalyst reaction mixtures.In order to avoid or minimize these problems, the use of molten quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermanate (II) as both solvent and part of the catalytic entity has been disclosed, particularly in the two U.S. patents of G.W. Parshall, U.S. Pat. Nos. 3,657,368 and 3,565,823, which are known in the art as well as in applicant's Ser. No. 526,867 filed 11/25/74 in the U.S. Patent Office. More recently, two procedures, involving distillation and solvent extraction, for isolating product fatty acids/esters from palladium carbonylation catalysts consisting of dispersions of ligand-stabilized palladium(II) halides in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermante(II) have been set forth in Ser. No. 581,320 and Ser. No. 581,395 both filed May 27, 1975. Following the separation of the catalyst and fatty acid ester products by these methods the palladium catalyst is suitable for recycle with fresh olefin/alcohol feed. Claims to the regeneration of the same palladium catalysts after multiple cycling by chlorination or treatment with mineral acid are also set forth in the above two applications. Each of these applications also discloses that a useful carbonylation must have:1. A simple and efficient means of separating catalysts from the products,2. The ability to recycle the catalyst without its substantial deactivation. This is particularly important since the palladium catalysts are thermally sensitive, and3. A capability of operating at high concentrations of catalyst in the feed stream, thereby minimizing capital costs.DESCRIPTION OF THE INVENTIONThe innovative and claimed aspect of this application is the discovery that the loss of catalytic activity of the above mentioned spent palladium carbonylation dispersion catalysts, can be restored by treatment of the catalysts with substantially anhydrous organic peroxides. The use of the latter (alternatively referred to as hydroperoxides) reagents is exemplified in Example 1, described infra. Here the octene, ethanol mixture is carbonylated by the procedure described, the ethyl nonanoate ester recovered by distillation, and after five cycles, the solid catalyst regenerated as follows:1. The recovered catalyst is treated with organic peroxide reagent, preferably in the presence of an inert solvent, and the mixture heated under an inert atmosphere.2. Excess liquid is removed by distillation under reduced pressure.3. Additional stabilizing ligand, such as triphenylphosphine, is added to the cooled melt catalyst after peroxide treatment in the mole ratio of 1-10 mole ligand per mole Pd. The regenerated catalyst is then ready for recycle to the carbonylation reactor with fresh olefin/alcohol feed.Generally speaking, a wide range of peroxide and hydroperoxide reagents may be employed to regenerate said palladium carbonylation catalysts, Suitable hydroperoxide reagents include tert-butylhydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide and 2,5-dimethylhexyl-2,5-dihydroperoxide. Suitable peroxide reagents include carprylyl peroxide, lauroyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl peracetate, t-butyl perbenzoate, and methyl ethyl ketone peroxide.At least a stoichiometric amount of peroxide reagent should be added to the spent palladium catalyst in order to achieve satisfactory regeneration, that is at least one mole of peroxide regent per gram atom of palladium present in the catalyst. Preferably, an excess of peroxide reagent should be employed, from 1 to 10.sup.4 moles of peroxide reagent per gram atom of palladium. Regeneration is judged to have occurred when a sample of treated catalyst delivers a selectivity to the desired linear fatty (carboxylic) acid or ester of between 70 and 95%, and a yield of total ester of from 20 to 95%.The peroxide or hydroperoxide regenerating reagents may be added to the spent catalyst neat, but preferably they are added in dilute form in the presence of a dried, inert solvent. Suitable inert solvents include among others, paraffinic solvents such as petroleum ethers, heptane, hexane and n-octane etc., ketones such as methyl isobutyl ketone, acetone and methyl ethyl ketone, chlorinated solvents such as o-dichlorobenzene, methylene chloride, and chloronaphthalenes, sulphones such as dimethylsulphone, aromatics such as benzene, toluene and xylenes, and mixtures thereof.The quatity of solvent used to dilute the organic peroxide or hydroperoxide reagent is not critical as to volume, for convenience sake about 0.1 parts by volume to 10.sup.4 parts by volume of inert solvent may be employed for each volume part of peroxide reagent. Likewise the time and temperature of regeneration are not initial, and temperatures of 20.degree. to 150.degree. C may be employed for 0.01 to 48 hours, according to the choice of palladium catalyst to be regenerated, and the choice of peroxide reagent.Catalyst regeneration is normally carried out in the presence of an inert atmosphere. This may be nitrogen, helium, argon, neon, carbon dioxide, or mixtures thereof, or the regeneration may be carried out in vacuo.Regeneration of palladium carbonylation catalysts with peroxide reagents is exemplified infra in Example 1 for the melt complex [(C.sub.2 H.sub.5).sub.4 N][SnCl.sub.3 ]-PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2. Other palladium carbonylation catalysts beyond [(C.sub.2 H.sub.5).sub.4 N] [SnCl.sub.3 ]-PdCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.2 may also be generated by this technique. These catalysts generally consist of ligand-stabilized palladium(II) halide complexes dispersed in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermanate(II). They are illustrated, but not limited by, the carbonylation catalysts described in Examples 8 to 14.Other substrate mixtures beyond the 1-octene, ethanol used in Example 1 may also be carbonylated by the regenerated palladium carbonylation catalysts. Some typical examples are given in Examples 15 to 20, described infra. Generally, for the carbonylation of .alpha.-olefins, as exemplified in equation 1, R.sub.1 and R.sub.2, individually, may by hydrogen, alkyl up to 12 carbon atoms, alkenyl up to 12 carbon atoms, or aryl up to 12 carbon atoms, or mixed alklaryl or arylalkyl groups. Suitable alkanols (ROH) ##STR1## include primary and secondary alcohols of 1 to 12 carbon atoms, phenols, substituted alcohols and polyols. The major products of the carbonylation reaction are fatty (carboxylic) acids and their esters.

    Abstract translation: 本发明涉及使用有机过氧化物作为再生剂，由配位体稳定的卤化钯（II）配合物在三卤代锇酸酯（II）和三卤代（II）的季铵，鏻和ium盐中的分散体组成的羰基化催化剂的再生方法。

Patent Agency Ranking