Abstract: A method for preparing acetic acid and/or methyl acetate by simultaneous isomerization and carbonylation reactions. A reaction mixture is provided containing at least one reagent which provides formyl radicals and at least one further reagent which provides methyl radicals, together with water in an amount of at most 5% by weight, carbon monoxide at a partial pressure between 0.1·105 Pa and 25·105 Pa, a solvent and a catalytic system which contains at least one halogenated promoter and at least one iridium-based compound. In a typical reaction mixture, methyl formate is isomerized to form acetic acid according to the reaction:
HCOOCH3CH3COOH
while methanol undergoes carbonylation to form acetic acid according to the reaction:
CH3OH+COCH3COOH
The reagent which provides the formyl radicals is kept at or below 20% by weight of the reaction mixture, while the molar ratio of methyl radicals to formyl radicals in the mixture is greater than 1.
Type:
Grant
Filed:
September 23, 1998
Date of Patent:
May 28, 2002
Assignee:
Acetex Chimie
Inventors:
Carl Patois, Robert Perron, Daniel Thiebaut
Abstract: The invention discloses pentenoic acid hydroxycarbonylation into adipic acid. More particularly, it concerns one pentenoic acid hydroxycarbonylation method involving reaction water and carbon monoxide, in the presence of a catalyst comprising at least rhodium and/or iridium and an iodinated or brominated catalytic promoter. In the method, the catalyst is derived at least in part from a previous pentenoic acid hydroxycarbonylation operation. The reaction is effected in the presence of an amount of branched carboxylic diacids having 6 carbon atoms not exceeding 200 grams per kilogram reaction mixture.
Type:
Grant
Filed:
March 17, 1999
Date of Patent:
April 16, 2002
Assignee:
Rhodia Fiber & Resin Intermediates
Inventors:
Jacques Brivet, Eric B. Henriet, Carl Patois, Robert Perron
Abstract: Enantiomerically pure &bgr;-hydroxy esters are prepared by a process in which &bgr;-keto esters are reacted with hydrogen in the presence of catalysts of the formula LRuX2 where
X is halogen, acetate, allyl, methallyl, 2-phenylallyl, perchlorate, trifluoroacetate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, hexafluoroarsenate or trichloroacetate,
L is a bidentate phospholane of the formula I
where
B=a bridging link with 1-5 carbon atoms between the two phosphorus atoms,
R1=H, C1-C6-alkyl, aryl, alkylaryl or SiR23,
R2=alkyl or aryl,
m=0 or 1,
R3=H or OR4, and
R4=R1,
with the proviso that if m=1 then R3=H and if m=0 then R3 ≠ H.
Abstract: A method for producing esters and carboxylic acids from lower alkyl alcohols, ethers, esters and ester-alcohol reactant mixtures and includes the step of contacting a vaporous mixture of the reactants, carbon monoxide and a halide with a supported catalyst under vapor-phase carbonylation conditions. The catalyst includes iridium and a second metal selected from group 4 (titanium, zirconium, hafnium) metals of the periodic table of elements. Desirably, the iridium and secondary metal are deposited on activated carbon as a support material. In a preferred aspect of the invention, the vapor phase carbonylation process is useful for preparing acetic acid, methyl acetate or a mixture thereof.
Type:
Grant
Filed:
August 25, 1999
Date of Patent:
March 12, 2002
Assignee:
Eastman Chemical Company
Inventors:
Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
Abstract: A solid supported catalyst suitable for the vapor phase carbonylation of lower aliphatic alcohols, ethers, ester, and ester-alcohol mixtures, and desirably, methanol, to produce acetic acid, methyl acetate and mixtures thereof. The solid supported catalyst includes an effective amount of iridium and at least one second metal selected from group metals of the periodic table of elements, their respective salts and mixtures thereof associated with a solid support material. Desirably, the support material is selected from carbon, activated carbon, pumice, alumina, silica, silica-alumina, magnesia, diatomaceous earth, bauxite, titania, zirconia, clay, magnesium silicate, silicon carbide, zeolites, ceramics and combinations thereof.
Type:
Grant
Filed:
August 25, 1999
Date of Patent:
March 12, 2002
Assignee:
Eastman Chemical Company
Inventors:
Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
Abstract: The present invention provides a process for preparing a pentenoic ester, comprising heating a 3-, 4-formylvaleric ester or mixtures thereof at 50° C. to 400° C. in the presence of a supported noble metal catalyst. The noble metal catalyst is supported on a mixed oxide (M1)a(M2)b(M3)cPdAle SiOx, wherein M1 is an alkali metal, M2 is an alkaline earth metal, M3 is a Group IVB metal, a=0.5˜1.5, b=0.2˜0.8, c=0.2˜0.8, d=2˜8, e=3˜10, and x is the stoichiometric value. By means of the specific supported catalyst of the present invention, the selectivity of the 3- and 4-pentenoic esters can be increased and that of the 2-pentenoic ester can be greatly decreased.
Type:
Grant
Filed:
January 31, 2000
Date of Patent:
March 12, 2002
Assignees:
Industrial Technology Research Institute, Acelon Chemicals & Fiber Corporation
Abstract: A method for producing esters and carboxylic acids from lower alkyl alcohols, ethers, esters and ester-alcohol reactant mixtures and includes the step of contacting a vaporous mixture of the reactants, carbon monoxide and a halide with a supported catalyst under vapor-phase carbonylation conditions. The catalyst includes iridium and a second metal selected from group 5 (vanadium, niobium, tantalum) metals of the periodic table of elements. Desirably, the iridium and secondary metal are deposited on activated carbon as a support material. In a preferred aspect of the invention, the vapor phase carbonylation process is useful for preparing acetic acid, methyl acetate or a mixture thereof.
Type:
Grant
Filed:
August 25, 1999
Date of Patent:
March 5, 2002
Assignee:
Eastman Chemical Company
Inventors:
Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
Abstract: This invention relates to an improvement for the preparation of bis(3-hydroxypropyl) dicarboxylate monomers using 1,3-propanediol and a dialkyl dicarboxylate in the presence of a catalytic amount of such yttrium and/or samarium compounds as yttrium/samarium acetylacetonate or tris(2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium/samarium which act as a catalyst for the transesterification reaction
Abstract: A catalyst for the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid comprising a porous support on the porous surfaces of which is deposited catalytically effective amounts of metallic palladium and gold, said catalyst having been prepared by steps comprising impregnating a porous support, the porous surfaces of which contain a catalytically effective amount of a prereduced metallic palladium, with a solution of potassium aurate, and reducing the potassium aurate to a catalytically effective amount of metallic gold. Alternate embodiments are also disclosed.
Abstract: In a process for production of vinyl acetate in which ethylene, liquid acetic acid and an oxygen-containing gas are fed to a fluid bed reactor containing a catalyst comprising a Group VIII metal, a promoter and a co-promoter, stickiness of the catalyst is reduced by limiting the amount of co-promoter to up to 6% by weight of the catalyst.
Type:
Grant
Filed:
July 29, 1999
Date of Patent:
February 26, 2002
Assignee:
BP Chemicals Limited
Inventors:
Simon James Kitchen, George Frederick Salem, Bruce Leo Williams
Abstract: A catalyst system capable of catalyzing the carbonylation of ethylene and a process which uses such a system wherein the catalyst system is obtainable by combining a metal of Group VIII, e.g., palladium, or a compound thereof and a bidentate phosphine, e.g. bis(di-t-butyl phospino)-o-xylene, according to the equation C2H4+CO+ROH→C2H5CO2R,.
Type:
Grant
Filed:
October 13, 1999
Date of Patent:
February 19, 2002
Assignee:
Imperial Chemical Industries PLC
Inventors:
Xiao Lan Wang, Robert Paul Tooze, Keith Whiston, Graham Ronald Eastham
Abstract: The present invention is relative to a method for the homogeneous, catalytic, enantioselective hydrogenation of compounds of the general formula (I)
with the aid of compounds of the general formula (II)
The use of the hydrogenated derivatives in organic synthesis.
Type:
Grant
Filed:
June 18, 1999
Date of Patent:
February 19, 2002
Assignee:
Degussa-Huls AG
Inventors:
Paul Knochel, Juan Jose Almena Perea, Karlheinz Drauz, Ingo Klement
Abstract: A carboxylic acid ester is prepared by a process comprising:
reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen as indicated by the following reaction:
RCHO+R′OH+O2→RCOOR′+H2O
in the presence of a catalyst comprising at least palladium and an element X, wherein X is bismuth, lead or a combination thereof, supported on a carrier, wherein the catalyst has an acid strength, pKa, of more than 4.8 and shows an ammonia chemical adsorption amount at 0° C. of 0-150 &mgr;mol/g-catalyst.
Abstract: The invention relates to a catalyst which contains palladium and/or compounds thereof, cadmium compounds, alkali metal compounds and at least one lanthanoid metal. The invention also relates to the utilization of the catalyst in order to produce vinyl acetate from acetic acid, ethylene and oxygen or gases containing oxygen.
Type:
Grant
Filed:
July 20, 2000
Date of Patent:
February 12, 2002
Assignees:
Celanese Chemicals Europe GmbH, Celanese International Corporation
Inventors:
Bernhard Herzog, Tao Wang, Ioan Nicolau
Abstract: A process for producing methacrolein and methacrylic acid by catalytically oxidizing isobutylene or tertiary butanol in the presence of a catalyst comprising a compound oxide containing molybdenum, bismuth and iron as the essential components, wherein a catalytic oxidation reaction is started at a temperature of (T−3)° C. or lower wherein T° C. is defined as the boundary temperature of activation energy of a reaction for obtaining methacrolein and methacrylic acid from isobutylene using said catalyst, the reaction is continued while the reaction temperature is increased as the activity of the catalyst decreases, and an activation treatment is conducted for the catalyst at least once before the reaction temperature exceeds the boundary temperature of activation energy.
Abstract: A metal oxide catalyst which can produce acrylic acid by a vapor phase catalytic oxidation of propane in high yield and has excellent abrasion resistance is disclosed. The metal oxide catalyst comprises Mo, V, Sb, A (A represents Nb or Ta) and optionally other metals, and is prepared through the following steps (1) and (2):
(1) Step of reacting V+5 and Sb+3 at a temperature of 70° C. or higher in the presence of Mo+6 in an aqueous medium, and bubbling an oxygen-containing gas into the reaction solution during or after the reaction; and
(2) Step of adding to the reaction product obtained in step (1) a solution containing a compound comprising A and an aqueous solution of nitric acid or ammonium nitrate, uniformly stirring these components, and then calcining the resulting mixture.
Abstract: The invention concerns a method consisting in making a mixed (meth)acrylic anhydride of formula (I) by reacting an alkaline (meth)acrylate of formula (II) and a chloroformate of formula (III), carrying out said reaction in an aqueous medium and in the absence of amines, the mol ratio chloroformate (III)/alkaline (meth)acrylate (II) being at least equal to 1.15. R1 represents H or CH3; R2 represents an alkyl, alkenyl, aryl, alkaryl or aralkyl residue; and M is an alkaline metal.
Abstract: In a process for production of vinyl acetate by the reaction of ethylene, acetic acid and oxygen, ethylene is recovered from the gases withdrawn from the reactor and recycled such that the amount of ethylene in the combined feed to the reactor is at least 60 mol %.
Type:
Grant
Filed:
July 29, 1999
Date of Patent:
January 29, 2002
Assignee:
BP Chemicals Limited
Inventors:
Bruce Leo Williams, Robert William Clarke, Timothy Crispin Bristow, Michael James Baker
Abstract: There is disclosed a process for producing an unsaturated ester of the formula (3):
wherein R1, R2 and R3 independently represent hydrogen, halogen, alkyl, alkenyl and the like and R5 represents alkyl which may be substituted and the like, which process is characterized by subjecting an unsaturated ester of the formula (1):
wherein R1, R2 and R3 have the same meaning as previously defined and R4 represents alkyl or phenyl and the like, to a transesterification reaction with a hydroxy compound of the formula (2):
R5OH (2)
wherein R5 has the same meaning as previously defined, in the presence of a lanthanoide metal alkoxide.
Abstract: Methods for preparing substituted aromatic carboxylic acid esters are described. In particular, the invention relates a method for preparing a nitro-substituted aromatic carboxylic acid ester:
Additionally the invention relates to a method for preparing a thioether-substituted aromatic carboxylic acid ester:
Such aryl esters are useful in the preparation of various agrochemicals and agrochemical intermediates.
Type:
Grant
Filed:
April 9, 1999
Date of Patent:
January 8, 2002
Assignee:
Eastman Chemical Co.
Inventors:
Neil W. Boaz, M. Todd Coleman, Timothy R. Hightower