Alicyclic Patents (Class 562/543)
  • Patent number: 9533933
    Abstract: Cyclododecanone (CDON) is prepared by epoxidizing cyclododecene (CDEN) to epoxycyclododecane (CDAN epoxide), and rearranging the CDAN epoxide to CDON to obtain a mixture comprising said CDON and CDEN, wherein CDEN is separated from the CDON-containing mixture and sent to the epoxidation to CDAN epoxide in step a.
    Type: Grant
    Filed: July 31, 2015
    Date of Patent: January 3, 2017
    Assignee: EVONIK DEGUSSA GmbH
    Inventors: Kevin Micoine, Ralf Meier, Juergen Herwig, Martin Roos, Harald Haeger, Luca Cameretti, Jens Doering
  • Patent number: 9238608
    Abstract: Oxidation process can include: introducing small droplets of liquid reaction mixture having oxidizable reactant, catalyst, and solvent into a reaction zone containing oxygen and diluent gas; and oxidizing the reactant with the oxygen at a suitable reaction temperature and a suitable reaction pressure to produce an oxidized product. The liquid reaction mixture can have an aromatic feedstock having an oxidizable substituent as the oxidizable reactant. The oxidized product can include an aromatic compound having at least one carboxylic acid. For example, the aromatic feedstock can include a benzene ring having at least one oxidizable alkyl substituent, furan hetero-ring having at least one oxidizable alkyl substituent, a naphthalene poly-ring having at least one oxidizable alkyl substituent, derivatives thereof, and mixtures thereof.
    Type: Grant
    Filed: March 23, 2010
    Date of Patent: January 19, 2016
    Assignee: UNIVERSITY OF KANSAS
    Inventors: Bala Subramaniam, Daryle H. Busch, Fenghul Niu
  • Patent number: 9108121
    Abstract: A plant for the crystallization of adipic acid is described. A plant for the crystallization of adipic acid, some parts of which are made of a corrosion-resistant material, is also described. The corrosion-resistant material used can be a reference austenitic stainless steel of AISI 310L type, according to the AISI (USA) nomenclature, or X1 CrNi 25-21 (1.4335) type, according to the European nomenclature.
    Type: Grant
    Filed: November 24, 2009
    Date of Patent: August 18, 2015
    Assignee: RHODIA OPERATIONS
    Inventors: Philippe Carvin, Fabien Bellenger, Serge Crottier-Combe
  • Publication number: 20140179950
    Abstract: A method for direct synthesis of adipic acid (AA) adopting green catalytic oxidation route of cyclohexane (CH) using the bimetallic catalysts is described. The reaction to convert CH into AA in the presence of bimetallic catalyst is carried in an autoclave in the temperature range of 25 to 300° C. The CH conversion was over 21% with AA selectivity of 34% and ca. 63% selectivity of cyclohexanone and cyclohexanol together over Au—Pd/TiO2 bimetallic catalyst.
    Type: Application
    Filed: March 3, 2014
    Publication date: June 26, 2014
    Applicant: King Abdulaziz City for Science and Technology (KACST)
    Inventors: Ahmad S. ALSHAMMARI, Abdulaziz A. BAGABAS, Angela KÖCKRITZ, Venkata Narayana KALEVARU, Andreas MARTIN
  • Publication number: 20140107306
    Abstract: In this invention, a portion of the products from a pyrolysis reactor are reacted in a process to form one or more chemical intermediates.
    Type: Application
    Filed: October 17, 2013
    Publication date: April 17, 2014
    Inventors: Terry Mazanec, Eugene Schmelzer, Fred Pesa, Dennis McCullough, Ruozhi Song, Yu-Ting Cheng
  • Publication number: 20130296604
    Abstract: A bimetallic catalyst supported on a transition metal oxide is described. A method to make and use the bimetallic catalyst is also described. A method for preparing supported bimetallic catalysts of coinage group metal and a combination of a coinage group metal and a platinum metal group is described. A method for direct synthesis of adipic acid (AA) adopting green catalytic oxidation route of cyclohexane (CH) using the bimetallic catalysts is described. The reaction to convert CH into AA in the presence of bimetallic catalyst is carried in an autoclave in the temperature range of 25 to 300° C. The CH conversion was over 21% with AA selectivity of 34% and ca. 63% selectivity of cyclohexanone and cyclohexanol together over Au—Pd/TiO2 bimetallic catalyst.
    Type: Application
    Filed: May 4, 2012
    Publication date: November 7, 2013
    Applicant: King Absulaziz City for Science and Technology (KACST)
    Inventors: Ahmad S. ALSHAMMARI, Abdulaziz A. BAGABAS, Angela KÖCKRITZ, Venkata Narayana KALEVARU, Andreas MARTIN
  • Patent number: 8536374
    Abstract: The present invention relates to a method for preparing dicarboxylic acids from saturated and cycloaliphatic hydrocarbons by oxidation at a reaction temperature comprised in the range of 25 to 300° C. in an autoclave using a solid heterogeneous catalyst. More particularly, the method of the invention relates to a method for preparing adipic acid (AA) from cyclohexane (CH) by selective oxidation.
    Type: Grant
    Filed: October 10, 2011
    Date of Patent: September 17, 2013
    Assignee: King Abdulaziz City for Science and Technology
    Inventors: Ahmad Alshammari, Narayana Venkata Kalevaru, Angela Koeckritz, Andreas Martin
  • Publication number: 20110137078
    Abstract: Provided is a catalyst which can prevent a lowering in selectivity for a target product in a gas phase catalytic reaction and has an excellent frictional resistance. A catalyst which is a supported catalyst comprising an inert support that is coated with a catalyst powder, characterized in that the inert support is ring-shaped and has an outer periphery that is curved in the lengthwise direction of the support, and the catalyst is produced by granulation in a moisten environment. The above described catalyst is useful in the gas phase oxidation of propylene, isobutylene, tertiary-butyl alcohol or methyl tertiary-butyl ether to thereby produce an unsaturated aldehyde corresponding thereto, or in the gas phase oxidation of such an unsaturated aldehyde as described above to thereby produce an unsaturated carboxylic acid.
    Type: Application
    Filed: May 25, 2009
    Publication date: June 9, 2011
    Applicant: NIPPON KAYAKU KABUSHIKI KAISHA
    Inventors: Masaki Nakahara, Hideki Sugi, Yoshimasa Seo, Tatsuhiko Kurakami, Hiroyuki Onoue
  • Patent number: 7803968
    Abstract: The present invention relates to a process for producing carboxylic acids. It relates more particularly to a process for producing carboxylic acids by oxidation of a hydrocarbon with oxygen or a gas containing oxygen, and even more particularly to the oxidation of cyclohexane to adipic acid. The invention relates to a process for producing carboxylic acids by oxidation with oxygen or a gas containing oxygen of a cycloaliphatic hydrocarbon in the presence of an oxidation catalyst and of a monocarboxylic oxidation solvent that is lipophilic in nature, comprising a step of extraction of the dicarboxylic acids formed in the oxidation step, consisting in carrying out, in liquid phase, an extraction of the diacids using water.
    Type: Grant
    Filed: October 28, 2003
    Date of Patent: September 28, 2010
    Assignee: Rhodia Polyamide Intermediates
    Inventors: Didier Bonnet, Daniel Amoros, Jean-Pierre Simonato, Frédéric Augier, Maria Ignez Broglio
  • Patent number: 7705179
    Abstract: The present invention relates to the oxidation with oxygen, or a gas containing it, of hydrocarbons to the corresponding carboxylic acids, alcohols and/or ketones or of alcohols and/or ketones to the corresponding carboxylic acids. More specifically, the invention consists of a process for oxidizing hydrocarbon, alcohol and/or ketone using oxygen or a gas containing it, in a liquid phase and in the presence of a catalyst dissolved in the reaction medium, characterized in that the catalyst comprises at least one soluble manganese and/or cobalt compound, at least one soluble chromium compound and at least one soluble iron compound.
    Type: Grant
    Filed: June 22, 2001
    Date of Patent: April 27, 2010
    Assignee: Rhodia Polyamide Intermediates
    Inventor: Eric Fache
  • Patent number: 7507856
    Abstract: The present invention relates to a process for the oxidation of hydrocarbons, in particular of branched or unbranched saturated aliphatic hydrocarbons, of cycloaliphatic or alkylaromatic hydrocarbons or of alcohols and/or ketones, to acid or polyacid compounds. It relates more particularly to the oxidation, by an oxidizing agent comprising molecular oxygen, of cyclohexane and/or of cyclohexanol and/or cyclohexanone to adipic acid, in the presence of an aromatic organic acid and a manganese-based catalyst. The yield and selectivity for adipic acid are of a high level with respect to those obtained with other solvents and catalysts.
    Type: Grant
    Filed: July 15, 2002
    Date of Patent: March 24, 2009
    Assignee: Rhodia Polyamide Intermediates
    Inventors: Didier Bonnet, Eric Fache, Jean-Pierre Simonato
  • Patent number: 7361622
    Abstract: Alkenes, unsaturated saturated carboxylic acids, saturated carboxylic acids and their higher analogues are prepared cumulatively from corresponding alkanes utilizing using a multi-staged catalyst system and a multi-stage process which comprises steam cracking of alkanes to corresponding alkenes at flame temperatures and at short contact times in combination with one or more oxidation catalysts for catalytically converting the corresponding alkenes to further corresponding oxygenated products using short contact time reactor conditions.
    Type: Grant
    Filed: November 8, 2005
    Date of Patent: April 22, 2008
    Assignee: Rohm and Haas Company
    Inventors: Abraham Benderly, Anne Mae Gaffney, Mark Anthony Silvano
  • Patent number: 7253312
    Abstract: The present invention relates to a process for producing carboxylic acids. It relates more particularly to a process for producing carboxylic acids by oxidation of a hydrocarbon with oxygen or a gas containing oxygen, and even more particularly to the oxidation of cyclohexane to adipic acid. It relates to a process comprising a step consisting of hydrolysis of the esters formed during the oxidation step.
    Type: Grant
    Filed: October 8, 2003
    Date of Patent: August 7, 2007
    Assignee: Rhodia Polyamides Intermediates
    Inventors: Didier Bonnet, Tania Ireland, Jean-Pierre Simonato
  • Patent number: 7081549
    Abstract: A process for the production of acetic acid, which process comprises contacting ethane and/or ethylene with a molecular oxygen-containing gas in a fluid bed reactor in the presence of a microspheroidal fluidised particulate solid oxidation catalyst, wherein at least 90% of said catalyst particles are less than 300 microns.
    Type: Grant
    Filed: March 5, 2001
    Date of Patent: July 25, 2006
    Assignee: BP Chemicals Limited
    Inventors: John Cook, Brian Ellis, Philip Howard, Michael David Jones, Simon James Kitchen
  • Patent number: 7041848
    Abstract: The present invention relates to a process for oxidizing hydrocarbons, in particular branched or unbranched saturated aliphatic hydrocarbons, cycloaliphatic or alkylaromatic hydrocarbons to acidic or polyacidic compounds. The invention relates more particularly to the oxidation, with an oxidizing agent containing molecular oxygen, of cyclohexane to adipic acid, in the presence of organic acid of lipophilic nature and in the absence of adipic acid. The separation and recycling of the unoxidized cyclohexane, the oxidation intermediates and the catalysts are easier than in the presence of acetic acid.
    Type: Grant
    Filed: March 7, 2001
    Date of Patent: May 9, 2006
    Assignee: Rhodia Polymide Intermediates
    Inventor: Eric Fache
  • Patent number: 7015355
    Abstract: A method for the selective production of acetic acid from a gas-phase feed of ethane, ethylene, or mixtures thereof and oxygen at elevated temperatures. The gas-phase feed is brought into contact with a catalyst, containing the elements Mo, Pd, X and Y in the gram atom ratios a:b:c: in combination with oxygen according to formula (I): MOaPdbXcYd. The symbols X and Y have the following meanings: X=one or several elements chosen from the group Cr, Mn, Nb, Ta, Ti, V, Te and W; Y=one or several elements chosen from the group B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Au, Fe, Fu, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Ti and U: the indices a, b, c, d and x=the gram atom ration for the corresponding elements, where: a=1; b—0.0001 to 0.01; c=0.4 to 1; and d=0.005 to 1, wherein the space-time yield for the above oxidation to yield acetic acid is 470 kg/(hm3) and the selectivity of the oxidative reaction of ethane and/or ethylene to give acetic acid is, in particular, ?70 mol %.
    Type: Grant
    Filed: May 3, 2001
    Date of Patent: March 21, 2006
    Assignee: Celanese International Corporation
    Inventors: Sabine Zeyss, Uwe Dingerdissen
  • Patent number: 7015356
    Abstract: A carboxylic acid is produced by oxidative cleavage of a cycloalkane with oxygen and performs a reaction in the presence of a catalyst including an imide compound and a metallic compound, the imide compound having a cyclic imide skeleton represented by the following Formula (I): wherein X is an oxygen atom or an —OR group, and wherein R is a hydrogen atom or a hydroxyl-protecting group, under conditions of a reaction temperature of 80° C. or higher and a concentration of the cycloalkane of 21% by weight or more.
    Type: Grant
    Filed: December 7, 2001
    Date of Patent: March 21, 2006
    Assignee: Daicel Chemical Industries, Ltd.
    Inventors: Yasutaka Ishii, Yasuteru Kajikawa
  • Patent number: 7012155
    Abstract: Aliphatic carboxylic acids of formulae (Ib) R1—COOH(Ia) and R2—COOH wherein R1 is tertiary C4-20-alkyl and R2 together are —(CH2)n— with n=3 to 10, are produced by oxidizing an aliphatic or alicyclic ketone of the formula (II): wherein R1 and R2 are as defined above, with molecular oxygen in the presence of a soluble manganese (II) compound. The process has a high selectivity and is carried out under very mild conditions. It is especially useful for the production of dicarboxylic acids, such as, adipic acid, from cyclic ketones.
    Type: Grant
    Filed: May 11, 2001
    Date of Patent: March 14, 2006
    Assignee: Lonza S.p.A.
    Inventors: Carlo Fumagalli, Francesco Minisci, Roberto Pirola
  • Patent number: 6958414
    Abstract: Organic compounds are prepared by heterogeneously catalyzed partial gas-phase oxidation of precursor compounds by a process in which a portion of the reaction gas starting mixture is brought from a low initial pressure to a higher final pressure by means of a radial compressor.
    Type: Grant
    Filed: September 23, 2003
    Date of Patent: October 25, 2005
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Schliephake, Ulrich Hammon, Ernst Lang, Carl-Ludwig Krüger, Jürgen Schröder, Klaus Joachim Müller-Engel
  • Patent number: 6933407
    Abstract: A process prepares methacrylic acid from isobutane by subjecting isobutane to a partial catalytic dehydrogenation in the gas phase and charging an oxidation zone with the isobutenic product gas mixture after the components other than isobutane and isobutene have been substantially removed from the product gas mixture. The oxygen required to charge the oxidation zone is introduced accompanied by nitrogen.
    Type: Grant
    Filed: June 28, 2002
    Date of Patent: August 23, 2005
    Assignee: BASF Aktiengesellschaft
    Inventors: Silke Berndt, Klaus Joachim Müller-Engel, Götz-Peter Schindler, Frank Rosowski, Jochen Petzoldt
  • Patent number: 6927311
    Abstract: A method for producing an oxygenated compound from a cycloalkane compound which method is characterized in that a cycloalkane compound is contacted with oxygen in the presence of a cobalt compound and a ruthenium compound.
    Type: Grant
    Filed: March 26, 2003
    Date of Patent: August 9, 2005
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Nobuhiro Tani, Shuzo Murata
  • Patent number: 6927307
    Abstract: This invention provides a method of reactivating a catalyst for methacrylic acid production, which catalyst is used in production of methacrylic acid through vapor-phase oxidation of methacrolein or vapor-phase oxidative dehydrogenation of isobutyric acid, contains P and Mo, and exhibits reduced activity. The process comprises treating the catalyst, whose activity level has dropped (deteriorated catalyst), with a gas containing a nitrogen-containing heterocyclic compound (e.g., pyridine, piperidine, piperazine, quinoline).
    Type: Grant
    Filed: August 28, 2003
    Date of Patent: August 9, 2005
    Assignee: Sumitomo Chemical Co., Ltd.
    Inventors: Hiroto Kasuga, Eiichi Shiraishi
  • Patent number: 6858754
    Abstract: Acrylic acid is prepared by heterogeneously catalyzed partial oxidation of propane by a process in which the steam content of the reaction gas starting mixture is reduced in the course of the process.
    Type: Grant
    Filed: May 2, 2002
    Date of Patent: February 22, 2005
    Assignee: BASF Aktiengesellschaft
    Inventor: Frieder Borgmeier
  • Patent number: 6833473
    Abstract: Kits are provided for use in the screening of the risk for, the diagnosis, management and research of atherosclerosis and coronary heart disease comprising means for isolating LDL from a serum or plasma sample for the preparation of a LDL fraction, and means for separating the lipids from the LDL fraction to obtain a lipid fraction. The kit can further include a means for use in the determination of the level of conjugated dienes (LDL-BDC) in the lipid fraction. The invention also relates to a kit for in the above mentioned purpose including means for isolating LDL from a serum or plasma sample for the preparation of a LDL fraction, and means for use in the determination of the antioxidant potential of LDL in the sample.
    Type: Grant
    Filed: March 15, 1999
    Date of Patent: December 21, 2004
    Assignee: Oy Aboatech AB
    Inventor: Markku Ahotupa
  • Publication number: 20040242922
    Abstract: The present invention relates to a process for the oxidation of hydrocarbons, in particular of branched or unbranched saturated aliphatic hydrocarbons, of cycloaliphatic or alkylaromatic hydrocarbons or of alcohols and/or ketones, to acid or polyacid compounds.
    Type: Application
    Filed: July 8, 2004
    Publication date: December 2, 2004
    Inventors: Didier Bonnet, Eric Fache, Jean-Pierre Simonato
  • Patent number: 6787669
    Abstract: The present invention relates to the treatment of the reaction mixtures resulting from an oxidation reaction of cyclohexane to adipic acid and more particlarly to the separation of the various constituents of the said mixtures and to the purification of the adipic acid.
    Type: Grant
    Filed: November 8, 2000
    Date of Patent: September 7, 2004
    Assignee: Rhodia Fiber & Resin Intermediates
    Inventors: Michel Costantini, Eric Fache, Philippe Leconte
  • Patent number: 6762319
    Abstract: The present invention relates to the oxidation, by means of oxygen or a gas containing it, of hydrocarbons to the corresponding carboxylic acids, alcohols and/or ketones or of alcohols and/or ketones to the corresponding carboxylic acids. It consists more precisely in a process for oxidizing hydrocarbon, alcohol and/or ketone, using oxygen or a gas containing it, in liquid phase and in the presence of a catalyst dissolved in the reaction medium, characterized in that the catalyst comprises a soluble manganese compound and at least one soluble chromium compound.
    Type: Grant
    Filed: April 16, 2002
    Date of Patent: July 13, 2004
    Assignee: Rhodia Polyamide Intermediates
    Inventors: Eric Fache, Michel Costantini
  • Publication number: 20040092767
    Abstract: Process for producing an aqueous solution comprising adipic acid, hydroxyhexanoic acid and oligomers thereof.
    Type: Application
    Filed: November 7, 2002
    Publication date: May 13, 2004
    Inventors: Luis A. Chu, Ludovic Fodor, David L. Valdez
  • Publication number: 20040024248
    Abstract: A process of the present invention produces a corresponding dicarboxylic acid by oxidative cleavage of a cycloalkane with oxygen and performs a reaction in the presence of a catalyst including an imide compound and a metallic compound, the imide compound having a cyclic imide skeleton represented by following Formula (I): 1
    Type: Application
    Filed: June 11, 2003
    Publication date: February 5, 2004
    Inventors: Yasutaka Ishii, Yasuteru Kajikawa
  • Publication number: 20030166967
    Abstract: The present invention relates to a process for oxidizing hydrocarbons, in particular branched or unbranched saturated aliphatic hydrocarbons, cycloaliphatic or alkylaromatic hydrocarbons to acidic or polyacidic compounds.
    Type: Application
    Filed: December 2, 2002
    Publication date: September 4, 2003
    Inventor: Eric Fache
  • Patent number: 6563001
    Abstract: The present invention relates to an improved process for processing the reaction mixture from the direct oxidation of hydrocarbon into carboxylic acid, using molecular oxygen or a gas containing it, in the liquid phase, in a solvent and in the presence of a catalyst dissolved in the reaction medium, characterized in that the said process comprises: when the composition of the reaction mixture allows it, a decantation into two liquid phases: a nonpolar upper phase and a polar lower phase; a distillation of the said lower phase or, where appropriate, of all of the reaction mixture, thus separating, on the one hand, a distillate and, on the other hand, the distillation residue comprising the acids formed, the catalyst, the heavy compounds, at least some of the solvent and, if any, the reaction intermediates and side products; a purification treatment by oxidation, using molecular oxygen or a gas containing it or using oxygen donors, of the distillation residue obtained above, a distillation of the reaction s
    Type: Grant
    Filed: June 12, 2001
    Date of Patent: May 13, 2003
    Assignee: Rhodia Fiber & Resin Intermediates
    Inventors: Michel Costantini, Eric Fache, Gilbert Marin
  • Patent number: 6521789
    Abstract: The present invention relates to an improved process for the preparation of adipic acid. More particularly, the present invention relates to an environmental-friendly, clean process for the preparation of adipic acid through oxidation of cyclohexanol, cyclohexanone or a mixture thereof with oxygen or oxygen-containing gas, in the presence of an oxidation initiator, a polar solvent and an organometallic &mgr;3-oxo-bridged Co/Mn cluster complex catalyst.
    Type: Grant
    Filed: December 21, 2001
    Date of Patent: February 18, 2003
    Assignee: Council of Scientific and Industrial Research
    Inventors: Darbha Srinivas, Suhas Arunkumar Chavan, Paul Ratnasamy
  • Patent number: 6515172
    Abstract: Process for the preparation of perfluorocarboxylic acids of the formula RF—COOH, salts thereof and esters thereof from perfluoroalkyl iodides of the formula RF′—I, in which RF and RF′ are cyclic, branched or linear, saturated or unsaturated perfluoroalkyl radicals, by activating the perfluoroalkyl iodides in the presence of oxygen and in organic solvents.
    Type: Grant
    Filed: July 10, 2001
    Date of Patent: February 4, 2003
    Assignee: Clariant GmbH
    Inventors: Ralf Grottenmüller, Wolfgang Knaup, Anton Probst, Klaus Dullinger
  • Patent number: 6433220
    Abstract: This invention relates to methods of controlling the oxidation of cyclohexane to adipic acid in the presence of a monobasic acid solvent, by extracting the catalyst from the reaction mixture, outside the reaction zone. Substantially all the unreacted cyclohexane, the majority of adipic acid, and preferably substantially all the monobasic acid solvent are removed from the reaction product. In the case that substantially all the monobasic acid solvent is removed, protic solvent, is added intermittently or continuously in the reaction mixture during the removal of the monobasic acid solvent, preferably by distillation, thus preventing solids precipitation. Dipolar aprotic solvent is then added in the presence of an adequate amount of the protic solvent (the total of dipolar aprotic solvent and the protic solvent constituting a novel combination solvent) to maintain a single liquid phase, followed by a step of extracting substantially all the catalyst in protic solvent.
    Type: Grant
    Filed: June 30, 1999
    Date of Patent: August 13, 2002
    Assignee: RPC Inc.
    Inventors: Douglas J. Dudgeon, David C. DeCoster, Mark W. Dassel, Eustathios Vassiliou, Ader M. Rostami
  • Patent number: 6433221
    Abstract: This invention relates to methods of controlling the oxidation of cyclohexane to adipic acid in the presence of a monobasic acid solvent, by separating the catalyst from the reaction mixture, outside the reaction zone. Substantially all the unreacted cyclohexane, the majority of adipic acid, and substantially all the monobasic acid solvent are preferably removed. A protic solvent, may be added intermittently or continuously in the reaction mixture during the removal of the monobasic acid solvent, preferably by distillation, for preventing solids precipitation. A dipolar aprotic solvent is then added in the presence of an adequate amount of the protic solvent to maintain a single liquid phase, followed by a step of formation of two liquid phases, a solids-free protic liquid phase containing substantially all the catalyst, and a solids-free aprotic liquid phase containing at least the majority of ingredients of the reaction mixture.
    Type: Grant
    Filed: June 30, 1999
    Date of Patent: August 13, 2002
    Assignee: RPC Inc.
    Inventors: Ader M. Rostami, Douglas J. Dudgeon, David C. DeCoster, Mark W. Dassel, Eustathios Vassiliou
  • Patent number: 6392093
    Abstract: The present invention relates to an improved process for the oxidation of cyclohexane to adipic acid using air as an oxidant and a solid organotransition metal complex as a catalyst. The process comprises comprises reacting cyclohexane with air in the presence of a solid catalyst containing an encapsulated salen or substituted salen metal complex wherein some of the hydrogen atoms of the said organomanganese complex have been substituted by one or more electron withdrawing groups, at a temperature in the range of 20 to 120° C., at a pressure in the range of 50 to 1000 psi, in the presence or absence of solvents, with or without a promoter and isolating the adipic acid formed by conventional methods, such as filtration and centrifugation.
    Type: Grant
    Filed: November 17, 2000
    Date of Patent: May 21, 2002
    Assignee: Council of Scientific & Industrial Research
    Inventors: Puthusseril Varkey Saji, Chandra Ratnasamy, Sarada Gopinathan
  • Patent number: 6359173
    Abstract: Methods and devices for controlling the reaction of a hydrocarbon to an acid by making phase-related adjustments are disclosed. In order to improve reaction rate and reactivity of the oxidation, a single phase at the operating temperature is attained and maintained by adjusting one or more of gaseous oxidant flow rate, pressure in the reaction zone, temperature in the reaction zone, feed rate of hydrocarbon, feed rate of solvent, feed rate of water if water is being fed, feed rate of the catalyst and other parameters. Methods and devices are also disclosed, wherein a hydrocarbon is reacted at a steady state with a gaseous oxidant to form an acid in a liquid mixture. The amount of water is maintained between a maximum level of water, over which maximum level the substantially single liquid phase is transformed to two liquid phases, and a minimum level under which catalyst precipitates.
    Type: Grant
    Filed: December 12, 1997
    Date of Patent: March 19, 2002
    Assignee: RPC Inc.
    Inventors: Sharon M. Aldrich, David C. DeCoster, Eustathios Vassiliou, Mark W. Dassel, Ader M. Rostami
  • Patent number: 6307100
    Abstract: Disclosed are catalysts useful for catalyzing the synthesis of adipic acid from cyclohexane and oxygen. Also disclosed are methods of making the catalysts, methods of using the catalysts to catalyze the production of adipic acid from cyclohexane and oxygen, and kits containing the catalysts.
    Type: Grant
    Filed: August 18, 2000
    Date of Patent: October 23, 2001
    Assignee: University of Florida Research Foundation
    Inventors: David Richardson, Cheng Xu, Khalil Abboud, Garry K. Weakley
  • Patent number: 6288274
    Abstract: Methods and devices for controlling the reaction rate and/or reactivity of a hydrocarbon to an intermediate oxidation product, such as an acid, within predetermined limits, are disclosed. Control of the reaction rate and/or reactivity within predetermined limits is achieved by monitoring and controlling the oxidant consumption rate. According to the present invention, examples of ways to determine the oxidant consumption rate include, but are not limited to, monitoring the flow rates of incoming and outgoing oxidant, monitoring pressure differentials after temporarily ceasing entry and exit of gases, and monitoring the flow rates of incoming and outgoing gases, and monitoring the rates of incoming and outgoing hydrocarbon.
    Type: Grant
    Filed: February 19, 1999
    Date of Patent: September 11, 2001
    Assignee: RPC Inc.
    Inventors: David C. DeCoster, Eustathios Vassiliou, Mark W. Dassel, Sharon M. Aldrich, Ader M. Rostami
  • Patent number: 6288270
    Abstract: Methods for controlling the reaction rate of a hydrocarbon to an acid by making phase-related adjustments are disclosed. In order to improve reaction rate of the oxidation, a single phase at the operating temperature is attained and maintained by adjusting one or more of gaseous oxidant flow rate, pressure in the reaction zone, temperature in the reaction zone, feed rate of hydrocarbon, feed rate of solvent, feed rate of water if water is being fed, feed rate of the catalyst. The preferred hydrocarbon is cyclohexane, the preferred acid is adipic acid, the preferred solvent is acetic acid, and the preferred catalyst is cobalt acetate. Other hydrocarbons include, but are not limited to, methylated benzene, methylated structures involving two benzene rings, and methylated naphthalene.
    Type: Grant
    Filed: March 6, 1997
    Date of Patent: September 11, 2001
    Assignee: RPC Inc.
    Inventors: Mark William Dassel, Eustathios Vassiliou, David Cole DeCoster, Ader Meherban Rostami, Sharon Marie Aldrich
  • Patent number: 6258981
    Abstract: Disclosed are catalysts useful for catalyzing the synthesis of adipic acid from cyclohexane and oxygen. Also disclosed are methods of making the catalysts, methods of using the catalysts to catalyze the production of adipic acid from cyclohexane and oxygen, and kits containing the catalysts.
    Type: Grant
    Filed: February 17, 2000
    Date of Patent: July 10, 2001
    Assignee: University of Florida
    Inventors: David Richardson, Cheng Xu, Khalil Abboud
  • Patent number: 6235932
    Abstract: The present invention relates to one-step oxidation process for preparation of cyclohexane to adipic acid, using molecular oxygen, in liquid phase, in the presence of catalyst, containing either cobalt or cobalt and iron. The catalyst is activated outside the reactor and molecular oxygen is used as an oxidant. The use of molecular oxygen as oxidant along with preactivated catalyst in the reactor and also by restricting the conversion of cyclohexane between 20-30% with catalyst in the reactor results in enhanced selectivity to adipic acid. The reaction mixture of cyclohexane and preactivated catalyst is subjected to oxidation by bubbling pure molecular oxygen while stirring the homogenous mixture while bubbling the oxygen at a predetermined temperature, pressure and space velocity conditions. The product selectivity to form adipic acid is found to be at least 5% better than the maximum attainable using the conventional processes.
    Type: Grant
    Filed: September 9, 1999
    Date of Patent: May 22, 2001
    Assignee: Chemintel (India) Private Ltd.
    Inventors: Sanjib Mall, Sreeramagiri Siva Kumar
  • Patent number: 6232495
    Abstract: This invention relates to methods and reactor devices for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a cobalt catalyst and a monobasic acid, such as acetic acid, by treating the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. In one preferred embodiment, the catalyst is reduced to contain, preferably predominantly and more preferably substantially, cobalt ions in valence II, and at least partially precipitated by de-watering and/or thermal treatment. In a different preferred embodiment, the catalyst in the reaction mixture is first oxidized or maintained, preferably predominantly and more preferably substantially, at valence III, the reaction mixture is de-watered, the catalyst is reduced, preferably predominantly and more preferably substantially, to valence II, causing precipitation either spontaneously at a predetermined temperature or after further thermal treatment.
    Type: Grant
    Filed: February 4, 1999
    Date of Patent: May 15, 2001
    Assignee: RPC Inc.
    Inventors: Eustathios Vassiliou, Mark W. Dassel, Ader M. Rostami, Douglas J. Dudgeon, David C. DeCoster
  • Patent number: 6218573
    Abstract: This invention relates to methods of controlling the oxidation of cyclohexane to adipic acid in the presence of a monobasic acid solvent, by removing the catalyst from the reaction mixture, outside the reaction zone. Substantially all the unreacted cyclohexane along with at least the majority of the monobasic acid solvent are removed. A substantially non-solvent for the catalyst (first constituent), and water are added into the resulting mixture, in such amounts as to maintain one solids-free single liquid phase. This process is highly facilitated in the presence of considerable amounts of adipic acid. The catalyst may then be extracted with water from the solids-free single liquid phase. A water phase containing dissolved catalyst may also be formed by addition of small amounts of a solvent which is substantially non-solvent for the catalyst and substantially non-solvent for the dibasic acids (second constituent), and/or dropping the temperature.
    Type: Grant
    Filed: June 30, 1999
    Date of Patent: April 17, 2001
    Assignee: RPC Inc.
    Inventors: Eustathios Vassiliou, Mark W. Dassel, Ader M. Rostami, Douglas J. Dudgeon, David C. DeCoster
  • Patent number: 6147256
    Abstract: Carboxylic acids, e.g., adipic acid, are more selectively prepared by oxidizing cyclohexane with oxygen or an oxygen-containing gas, in liquid phase, in a solvent reaction medium which comprises a polar protic or aprotic solvent, and also in the presence of a catalytically effective amount of catalyst values dissolved in said solvent reaction medium, the catalyst values comprising at least one solvent-soluble cobalt compound and at least one solvent-soluble chromium compound.
    Type: Grant
    Filed: April 10, 1998
    Date of Patent: November 14, 2000
    Assignee: Rhodia Fiber and Resin Intermediates
    Inventors: Michel Costantini, Eric Fache
  • Patent number: 6129875
    Abstract: This invention relates to methods for controlling the oxidation of hydrocarbons to dibasic acids, in the presence of a catalyst and a monobasic acid, by removing the catalyst from the reaction mixture, outside the oxidation zone, after the oxidation has taken place at least partially. Initially, the catalyst is partially precipitated and removed by reducing the water level in the reaction mixture and/or subjecting the reaction mixture to a temperature, at which or over which catalyst precipitates. After the initial partial precipitation of the catalyst, the remaining catalyst is subjected to a thermal treatment, during which at least part of the monobasic acid is removed leaving behind molten dibasic acids, in which, at least a major part of the remaining catalyst is precipitated, and it is removed. A minor part of remaining catalyst is removed by methods, which include but are not limited to ion exchange, precipitation with a base or appropriate salt, and electrodialysis.
    Type: Grant
    Filed: February 4, 1999
    Date of Patent: October 10, 2000
    Assignee: RPC Inc.
    Inventors: Mark W. Dassel, Ader M. Rostami, Douglas J. Dudgeon, David C. DeCoster, Eustathios Vassiliou
  • Patent number: 6114274
    Abstract: The aliphatic carboxylic acids, e.g., acetic acid, are selectively prepared, even on an industrial scale, by controlledly oxidizing the corresponding alkanes, e.g., ethane, with a source of oxygen, in the presence of a catalytically effective amount of an advantageously supported heteropolyacid catalyst having the formula (I):[A.sub.a B.sub.b ].sub.f [C.sub.c D.sub.d E.sub.e O.sub.x ].sup.f-(I)in which A is at least one monovalent cation selected from among hydrogen, an alkali metal, or the ammonium ion; B is VO.sup.2 +, VO.sup.3 +, an alkaline earth metal ion, or an ion of a metal of Groups VII A, VIII, I B, IV B and V B of the Periodic Table; C is Mo and/or W; D is phosphorus, arsenic, antimony, silicon, germanium and/or boron; E is vanadium, optionally in combination with at least one metal of Groups V A, VII A and VIII of the Periodic Table or chromium; f=a+.alpha.b wherein .alpha.
    Type: Grant
    Filed: May 18, 1995
    Date of Patent: September 5, 2000
    Assignee: Rhone-Poulenc Chimie
    Inventors: Elisabeth Bordes, Michel Gubelmann, Laurent Tessier
  • Patent number: 6063958
    Abstract: A method of recovering adipic acid and 6-hydroxycaproic acid from the waste solution of alkali metal salts of organic acids coming from the process of cyclohexane oxidation, which comprises:(i) basifying the reaction mixture coming from cyclohexane oxidation with an aqueous solution of an alkali-metal base so that the organic acids essentially comprising adipic acid and 6-hydroxycaproic acid therein, are saponified, extracting the formed alkali metal salts of organic acids from the mixture with water, then acidifying the aqueous extract comprising the alkali metal salts of organic acids to a pH value of 3 or lower with an aqueous solution of a protic inorganic acid, as a result, said aqueous extract is separated into an oily layer and an aqueous layer;(ii) extracting the organic acid from said oily layer obtained from the step (i) with an aqueous solution of a protic inorganic acid, to obtain an aqueous extract;(iii) extracting the organic acid from the aqueous layer obtained from the step (i) with an organic
    Type: Grant
    Filed: December 22, 1998
    Date of Patent: May 16, 2000
    Assignee: China Petrochemical Development Corporation
    Inventors: Kuang-Ruei Chen, Jih-Dar Hwang, Shu-Hui Chen
  • Patent number: 6039902
    Abstract: This invention relates to methods of recycling catalyst in oxidations of hydrocarbons, such as cyclohexane for example, to respective intermediate oxidation products, such as adipic acid for example, by a direct process. The catalyst remains in solution despite removal of water from the composition, since the water removal is controlled at such temperatures and such remaining water levels that prevent catalyst from precipitating. The water removal is preferably conducted before removal of the intermediate oxidation product. Also, preferably, some, and more preferably all steps of the process are conducted in a single liquid phase region.
    Type: Grant
    Filed: September 18, 1997
    Date of Patent: March 21, 2000
    Assignee: RPC Inc.
    Inventors: Ader M. Rostami, David C. DeCoster, Eustathios Vassiliou, Mark W. Dassel
  • Patent number: 6037491
    Abstract: This invention relates to methods and devices of preparing acids, such as adipic acid for example, by oxidizing a hydrocarbon, such as cyclohexane for example, with a gas containing an oxidant, preferably oxygen. A respective hydrocarbon is reacted, preferably at a steady state, with a gaseous oxidant to form an acid in a liquid mixture which preferably contains a solvent, a catalyst, water, and an initiator. The ratio of solvent to hydrocarbon may be controlled in a manner to maintain in the reaction zone maximum reaction rate and/or reactivity, or reaction rate and/or reactivity within a desired range, or reaction rate and/or reactivity directed toward a desired range. In addition, the ratio of solvent to hydrocarbon is controlled in a manner to maintain in the reaction zone substantially maximum selectivity and/or yield, or selectivity and/or yield within a desired range, or selectivity and/or yield directed toward a desired range.
    Type: Grant
    Filed: July 25, 1997
    Date of Patent: March 14, 2000
    Assignee: RPC Inc.
    Inventors: Eustathios Vassiliou, Mark W. Dassel, Sharon M. Aldrich, Ader M. Rostami, David C. DeCoster