WO2008136857A1 - Procédé de production d'acides carboxyliques non aromatiques - Google Patents

Procédé de production d'acides carboxyliques non aromatiques Download PDF

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WO2008136857A1
WO2008136857A1 PCT/US2007/083925 US2007083925W WO2008136857A1 WO 2008136857 A1 WO2008136857 A1 WO 2008136857A1 US 2007083925 W US2007083925 W US 2007083925W WO 2008136857 A1 WO2008136857 A1 WO 2008136857A1
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combination
catalyst composition
reaction mixture
molybdenum
metal catalyst
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PCT/US2007/083925
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English (en)
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William H. Gong
Wayne P. Schammel
Victor A. Adamian
Chengxiang Zhou
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Bp Corporation North America Inc.
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Priority claimed from PCT/US2007/068268 external-priority patent/WO2007133976A2/fr
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Publication of WO2008136857A1 publication Critical patent/WO2008136857A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • This invention relates generally to the production of non-aromatic carboxylic acids and, more particularly, to a process for the production of at least one non-aromatic carboxylic acid by the bromine-free catalytic oxidation of non-alkylaromatic feedstock materials.
  • Adipic acid, acrylic acid and other non-aromatic carboxylic acids are commodity chemicals that are widely used in the manufacture of polymers.
  • Adipic acid is used in manufacturing plasticizer and lubricant components.
  • Adipic acid is also applied in making polyester polyols for polyurethane systems and it is used in the synthesis of nylon-6,6 fibers.
  • Acrylic acid is used in the manufacture of plastics, latex applications, floor polish, polymer solutions for coatings applications, emulsion polymers, paint formulations, leather finishings, and paper coatings.
  • Acrylic acid is also used as a chemical intermediate. The global demand for adipic acid and acrylic acid continues to grow at a rapid pace.
  • Adipic acid is currently made in a two-step process starting from cyclohexane.
  • cyclohexane is oxidized by contacting a reaction mixture containing a soluble, cobalt-salt catalyst with oxygen to produce cyclohexanone (ketone) and cyclohexanol (alcohol), known as "ketone and alcohol oil” or "KA oil,” at a low conversion.
  • Care is taken to avoid high conversion of cyclohexane since a significant oxidative degradation pathway for cyclohexane could occur and lead to higher manufacturing costs as a result of the cyclohexane being burned to carbon oxides, rather than converted to adipic acid.
  • the KA oil is separated from the first step mixture, and then it is oxidized in a second step by nitric acid to produce adipic acid and nitrous oxide as a byproduct.
  • Nitrous oxide poses a serious threat to the environment. It is classified as an ozone-depleting agent and it is a known greenhouse gas. Therefore, part of the process effort is to also capture and treat the nitrous oxide emission before it reaches the atmosphere.
  • KA oil is very difficult.
  • An ideal catalyst would be one that is insoluble in a highly soluble reaction mixture of both feedstock and final product. The insoluble catalyst could be removed by simply filtering the reaction mixture and then the filtered catalyst could be recycled for use again.
  • a direct, one- step process for the production of adipic acid from cyclohexane utilizing an insoluble catalyst would not only eliminate the need to isolate the KA oil, but also the need to use nitric acid and capture the ensuing nitrous oxide.
  • Bromine sources used with the catalyst and reaction products thereof formed during oxidation are corrosive.
  • process equipment including major equipment items, such as oxidation reactors are normally constructed using titanium or other expensive, corrosion-resistant metals or alloys.
  • the current process for acrylic acid is a high yielding, two-step process that starts with propylene as the feedstock.
  • Propylene is oxidized to acrolein at 320 - 330 0 C in an exothermic reaction. After the acrolein is isolated, it is subjected to another stage of oxidation with oxygen to produce acrylic acid at
  • the catalyst useful for the oxidation of propylene to acrolein is a mixed oxide containing molybdenum, antimony, or copper.
  • the catalytic systems are generally based on cobalt and nickel molybdates and vanadium phosphate mixed oxides. In both cases, tellurium is the modifier used to enhance the reaction.
  • the competitive product is acrolein, but the level of co- production of acrolein is dependent upon the compositional makeup of the catalyst.
  • Propane would be a more preferable feedstock for the production of acrylic acid because propane is available in much higher volumes and lower costs than propylene.
  • the challenges for propane oxidation include the fact that the activation of the C-H bond of the methyl groups requires substantial energy, and that the oxygenated propane oxidation product is more active towards the oxidation of propane itself.
  • the over-oxidation of oxygenated propane leads to carbon oxides as the final products.
  • Three catalyst systems, namely vanadium phosphate catalysts, heteropoly acids and mixed metal oxides of transition metals, have been extensively examined for use in the oxidation of propane to acrylic acid, but have not been successful.
  • U.S. Patent No. 5,864,051 discloses a process for the selective oxidation of alkanes and alkenes using a catalyst which comprises a noble metal component, an antimony oxide component and optionally a modifier.
  • the selective oxidation occurs at a temperature in the range of about 300 0 C about 600 0 C and the resultant products are aldehydes.
  • the process of the invention in its embodiments and features, is directed to the production of at least one non-aromatic carboxylic acid by contacting a fluid reaction mixture comprising a non-alkylaromatic feedstock with oxygen in the presence of a bromine-free metal catalyst composition containing at least three metal or metalloid components, wherein the components comprise (a) palladium, (b) antimony, bismuth or a combination thereof, and (c) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof.
  • bromine-free means the absence of reactive bromine in both the metal catalyst composition and the fluid reaction mixture. Unlike some commercial processes for making non-aromatic carboxylic acids, such as adipic acid from cyclohexane, the inventive process is "bromine-free” in that it is effective in the substantial or complete absence of bromine sources. While the process, in some of its embodiments, is tolerant of bromine in minor amounts, the presence of bromine in proportions commonly used in conventional commercial processes poisons the catalysts in the inventive process, either deactivating them or shifting selectivity away from non- aromatic carboxylic acid products toward non-aromatic species with less fully- oxidized substituent groups.
  • the metal catalyst composition further comprises (d) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof, provided component (d) is not the same as component
  • the invention provides a process for the production of each of acrylic acid and acetic acid by contacting a gas reaction mixture comprising a non-alkylaromatic feedstock selected from the group consisting of propane, propylene and mixtures thereof with oxygen in the presence of a bromine-free metal catalyst composition containing at least three metal or metalloid components on an inert support selected from the group consisting of titanium dioxide, silicon dioxide, aluminum oxide and mixtures thereof, wherein the components comprise (a) palladium, (b) antimony, bismuth or a combination thereof, and (c) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof.
  • a gas reaction mixture comprising a non-alkylaromatic feedstock selected from the group consisting of propane, propylene and mixtures thereof with oxygen in the presence of a bromine-free metal catalyst composition containing at least three metal or metalloid components on an inert support selected from the group consisting of titanium dioxide, silicon dioxide, aluminum oxide and mixtures thereof, wherein
  • Another aspect of the invention is a process for the production of adipic acid comprising contacting a liquid reaction mixture comprising cyclohexane with oxygen in the presence of a bromine-free metal catalyst composition containing at least three metal or metalloid components on an inert support selected from the group consisting of titanium dioxide, silicon dioxide, aluminum oxide and mixtures thereof, wherein the components comprise (a) palladium, (b) antimony, bismuth or a combination thereof, and (c) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof.
  • the present invention efficiently and effectively produces non-aromatic carboxylic acids in a direct, one-step process whereby the use of an insoluble, bromine-free metal catalyst composition eliminates undesirable byproducts produced in commercial practice which are harmful to the environment, and provides enhanced catalyst and product separation, as well as process simplification.
  • the present invention is directed to a process for producing at least one non-aromatic carboxylic acid.
  • a fluid reaction mixture comprising a non-alkylaromatic feedstock is contacted with oxygen in the presence of a bromine-free metal catalyst composition comprising at least three metal or metalloid components, wherein the components comprise (a) palladium, (b) antimony, bismuth or a combination thereof, and (c) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof.
  • non-alkylaromatic means non-benzylic. It is recognized that in the oxidation of an alkylaromatic hydrocarbon, it is the benzylic carbon that undergoes the oxidative transformation. The benzylic carbon is any carbon atom attached to an aromatic ring. Electronic influences of the aromatic ring upon this carbon results in selective oxidation of the benzylic carbon. These influences do not occur on any carbon beyond the immediate benzylic carbon.
  • the benzylic carbon is sp 3 hybridized and, in addition to its attachment to the aromatic ring, it is also attached to three other hydrogen atoms.
  • sp 3 hybridized carbon atoms that are not benzylic which undergo oxidation.
  • These non-benzylic carbons reside among alkanes, are sp 3 hybridized, and are attached to at least two hydrogen atoms.
  • the non- alkylaromatic feedstocks which may be used include acyclic alkanes, cyclic alkanes, acyclic alkenes, cyclic alkenes, and mixtures thereof.
  • Preferable non- alkylaromatic feedstocks include, but are not limited to, methane, ethane, propane, butane, cyclohexane, propylene and mixtures thereof.
  • the current invention may be used to produce a variety of different non-aromatic carboxylic acids.
  • the non-aromatic carboxylic acids which are produced include acrylic acid, adipic acid and mixtures thereof.
  • the non-alkylaromatic feedstock is propane, propylene or a mixture thereof.
  • the non-alkylaromatic feedstock is cyclohexane.
  • the oxidation of an alkane feedstock can also produce desirable oxygenate byproducts, such as alcohols, ketones, aldehydes and carboxylic acids.
  • oxygenates are highly desirable in a "gas to liquids" process for light alkanes since liquid oxygenates are valuable as chemical feedstocks and solvents, and as fuel and/or additives.
  • the oxygenates can be easily and economically transported as liquids. The transportation of light alkanes as a compressed gas is much more expensive.
  • the oxygenates which may be produced by the oxidation of propane include, but are not limited to propionaldehyde (a.k.a. propanal), acetic acid, acetone, and propionic acid (a.k.a. propanoic acid).
  • the fluid reaction mixture comprises a non-alkylaromatic feedstock.
  • a "fluid" can be a liquid or a gas.
  • the non-alkylaromatic feedstock propane, propylene or a mixture thereof
  • the fluid reaction mixture is in the gas phase.
  • cyclohexane is utilized as the feedstock, then the fluid reaction mixture can be in either the gas or the liquid phase.
  • No solvent is required when the fluid reaction mixture is in the gas phase.
  • the cyclohexane can be oxidized in the gas phase by simply vaporizing it.
  • Preferred solvents which may be used when the fluid reaction mixture is in the liquid phase include water and low molecular weight carboxylic acids, such as acetic acid.
  • the bromine-free metal catalyst compositions which may be used according to aspects and embodiments of the invention are insoluble, heterogeneous catalysts.
  • the metal catalyst comprises at least three metal or metalloid components.
  • the metal catalyst composition comprises palladium, antimony and molybdenum.
  • the palladium which is employed is a metal in the reduced, i.e., zero, oxidation state.
  • metal or metalloid is used herein to refer collectively to metallic elements as well as semi-metallic and other elements not considered metals in a strict sense but having metal-like properties.
  • metals and metalloids as components of the catalyst composition, it will be understood that the terms are used in a broad sense to include the metals and metalloids as such, as well as their compounds, complexes, alloys and combinations in other forms. Significance of distinctions between metals and metalloids is not readily apparent for purposes of the invention.
  • the metal catalyst composition preferably comprises four metal or metalloid components.
  • the metal catalyst composition in addition to (a) palladium, (b) antimony, bismuth or a combination thereof, and (c) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof, the metal catalyst composition further comprises (d) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof, provided component (d) is not the same as component (c).
  • the metal catalyst composition comprises palladium, antimony, molybdenum and vanadium.
  • Proportions of the metal or metalloid components of the catalyst compositions can vary.
  • the components are present in amounts such that the weight ratio of (a) palladium to (b) antimony, bismuth or a combination thereof to (c) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof to (d) molybdenum, gold, niobium, vanadium, gallium, or a combination thereof, provided component (d) is not the same as component (c), is 1 :1 :1 :1 , 4:1 :1 :1 , 1 :1 :4:1 or 1 :1 :1 :4.
  • the most preferred weight ratio of the four components calculated as elements is 1 :1 :1 :1 .
  • Proportions of the metal and metalloid elements in various combinations can be determined and optimized for particular combinations and usages by persons skilled in catalytic oxidations for the manufacture of non-aromatic carboxylic acids guided by the description and examples appearing herein.
  • the heterogeneous catalyst also comprises an inert support capable of withstanding an acidic process environment without dissolving or significant loss of catalyst metals.
  • Preferred support materials are solids that are stable in the sense of maintaining physical integrity and catalyst metal loadings suitable to process operation over prolonged exposures to process conditions and use.
  • Carbons, high strength, acid stable silicon carbides and various metal oxides such as silicas, aluminas, titanias, including anatase and rutile phases thereof and mixed phase forms, and zirconia are examples of suitable support materials.
  • Preferable supports include titanium dioxide ("titania"), silicon dioxide (“silica”), aluminum oxide (“alumina”) and mixtures thereof.
  • the metal catalyst composition is also free of halogens other than bromine.
  • halogens other than bromine.
  • the absence of all halogens from the inventive process is preferred since halogens are known to cause undesirable corrosion and adversely affect the activity or selectivity of the metal catalyst compositions. Maximum benefit is achieved by eliminating the use of bromine and not replacing it with one or more other halogens.
  • Proportions of the non-alkylaromatic feedstock, catalyst and oxygen in oxidation are not critical and vary not only with choice of feed materials and intended product, but also choice of process equipment and operating factors. Oxygen or air or other mixtures of oxygen and nitrogen may be further introduced to contact the non-alkylaromatic feedstock and metal catalyst composition.
  • the rate of oxygen feed must be at least sufficient to fully oxidize all of the non-alkylaromatic feedstock to the non-aromatic carboxylic acid.
  • concentration of oxygen in any vapor phase of the process should be kept below about 12% by volume to prevent flammability of any non- alkylaromatic feedstock and oxygen mixtures.
  • Suitable oxidation reactors which may be used in the process include, but are not limited to slurry, CSTR, slurry bubble column, ebulating bed, fixed or packed bed, trickle bed and bubble column reactors.
  • the oxidation reaction may be staged in multiple reactors, if desired, with either feedstock, oxygen or both being introduced in one or more reactors by one or more inlet streams.
  • the intermediates and non-aromatic carboxylic acid products may be kept in solution or allowed to solidify in the process after formation. In either case, suitable means to separate products from catalyst and oxidation medium are employed to allow efficient recovery of non-aromatic carboxylic acid product.
  • the temperature, pressure and residence times are dependent upon the non-aromatic carboxylic acid being produced and can be determined and optimized by persons skilled in catalytic oxidations for the manufacture of non- aromatic carboxylic acids guided by the description and examples appearing herein.
  • the temperature of the fluid reaction mixture during oxidation should be maintained in the range of about 100 0 C to about 320 0 C and, preferably, in the range of about 160 0 C to about 280 0 C. Given the physical properties of the system components, these temperatures will result in a system pressure of about 1 bar absolute (bara) to about 100 bara.
  • the fluid reaction mixture is oxidized for about 0.01 hours to about 4 hours and, preferably, for about 0.5 hours to about 2 hours.
  • the process of the present invention effectively produces non-aromatic carboxylic acids, particularly adipic acid, acrylic acid and acetic acid, without undesirable byproducts, such as byproducts produced in current commercial practice which deplete the ozone layer and produce acid rain.
  • a fluid reaction mixture comprising a non-alkylaromatic feedstock with oxygen in the presence of a bromine-free catalyst composition comprising at least three metal or metalloid components, wherein the components comprise palladium; antimony, bismuth or a combination thereof; and molybdenum, gold, niobium, vanadium, gallium, or a combination thereof
  • the inventors have surprisingly discovered that non-aromatic carboxylic acids can be effectively produced in one step.
  • the catalysts were prepared from the metal precursors shown below in
  • the precursor solutions for Mo 1 Sb 1 and V were prepared by dissolving the metal salts in a warm (60 0 C) solution of citric acid and water, where the ratio of metal salt to citric acid was 1 :2 on a mass basis.
  • the starting Pd nitrate solution (35.34% Pd nitrate) was diluted with water to obtain a solution of 0.25 g Pd-nitrate/mL solution.
  • Two gram samples were prepared by mixing the supports with the necessary amount of the precursor solutions to obtain catalyst compositions having the desired weight ratio of components. Since sufficient solution volume is required to obtain homogeneous distribution of the precursor solutions upon mixing with the support, extra water was added to obtain a homogeneous slurry.
  • the samples Prior to the final, reduction step, the samples were ground to a powder in a mortar.
  • the ground samples were transferred to crucibles for reduction under a flow of 100 mL 7% H 2 and 93% N 2 .
  • the temperature was first kept at room temperature for one hour, and then heated to 250 0 C at a rate of 1 °C/min.
  • the samples were kept at 250 0 C for 5 hours.
  • the catalysts for the propane and propylene oxidation studies were further processed for gas- phase primary screening. The reduced catalysts were then shaped, crushed and sieved to a particle size ranging from 200 to 400 microns.
  • the 160 catalyst compositions were examined at 140 0 C and 180 0 C for the liquid phase oxidation of cyclohexane. This resulted in a total of 320 experiments. Additionally, 16 experiments were "blanks" and replicates, bringing the total to 336.
  • High temperature-high pressure batch reactors were used to conduct the experiments.
  • the reactors each had a volume of 8 ml_, of which the ideal working volume was 1 -1 .5 mL, and were stirred magnetically.
  • the reaction mixture was heated in the heating zone to provide a maximum operating temperature of approximately 220 0 C.
  • the heterogeneous catalyst was weighed into a disposable Teflon insert containing a magnetic stir bar.
  • the starting cyclohexane feedstock (800 ⁇ ) was dispensed and weighed before the reactors were closed and pressurized to 60 bar with 40% O 2 and 60% N 2 at room temperature.
  • the upper part of the reactor block was set at a temperature that was 15 0 C lower than the desired reaction temperature, with 160 0 C as the upper limit.
  • the temperature of the heating block was set to reach a temperature of 140 0 C or 180 0 C in the reaction mixture.
  • Example No. 2C when a higher concentration of palladium was used so that the Pd/Sb/V/Ga ratio was 4:1 :1 : 1 on the same silica support as Example No. 2C, the oxidation produced a conversion of cyclohexane, but no detectable levels of any cyclohexanol and cyclohexanone (see Example No. 2D). Similarly, individual increases in the level of V (Example No. 2E) or Ga (Example No. 2F) also resulted in lower concentrations of cyclohexanol than the Comparative
  • the most effective catalyst composition at 140 0 C was Example No. 2B, where Pd/Sb/Au/V was used at 1 :1 :1 :1 ratio on silica.
  • the support was changed to titania (Example No. 2G)
  • the resulting cyclohexane conversion, and concentrations of cyclohexanol and cyclohexanone were lower.
  • an effective and efficient catalyst composition contains palladium, antimony and vanadium. Table 3
  • Example 3 Catalyst compositions containing palladium, antimony or bismuth, and vanadium in a 1 :1 :1 :1 ratio were analyzed by gas chromatography to quantify cyclohexanol and cyclohexanone, as well as adipic acid. (ADA). The results are shown below in Table 4. These experiments were conducted twice at 180 0C, so the results for the cyclohexane conversion, cyclohexanol and cyclohexanone produced are averages of both experiments. The adipic acid concentration, however, was only measured for the duplicated experiment. A comparison of Example Nos. 3B and 3C indicates that antimony had a stronger influence on the production of adipic acid than bismuth. Antimony produced twice the concentration of adipic acid as bismuth. Also, the catalyst composition of Pd/Sb/Mo/V in Example No. 3E produced the highest concentration of adipic acid at 0.0793 wt%.
  • Cobalt 1000 ppmw based on feedstock
  • cobalt (II) naphthenate a more hydrocarbon-soluble cobalt catalyst
  • cobalt(ll) acetate tetrahydrate was used when acetic acid (HOAc) or water was employed as the solvent.
  • the metals were fixed at a 1 :1 :1 :1 ratio with palladium and all other metals at 1.5 wt% loading on the support.
  • the reaction temperature was set at 180 0 C for three hours.
  • Example No. 4A used cobalt as the reference catalyst in the oxidation of cyclohexane and water. Most of the catalysts used in this set of experiments produced no detectable levels of adipic acid. The only two catalysts that produced adipic acid were Example
  • Nos. 4D and 4F namely Pd/Sb/Mo/V and Pd/Sb/Au/V on a titania support.
  • the cobalt reference catalyst When water was replaced by acetic acid in the oxidation of cyclohexane, the cobalt reference catalyst produced detectable levels of adipic acid. Differences in the effectiveness of the support under these acetic acid-based conditions were noted.
  • the titania and alumina support for the catalyst Pd/Sb/Nb/V generated equivalent adipic acid, so this catalyst was not sensitive to the support.
  • the titania support that was more effective than the alumina support (Example No. 4L). This same trend was seen in the Pd/Sb/Au/V catalyst where the titania support (Example No.
  • titania was an effective support for the Pd/Sb/Nb/V and Pd/Sb/Mo/V catalysts.
  • the Pd/Sb/Nb/V catalyst When water was replaced by acetic acid, the Pd/Sb/Nb/V catalyst was insensitive to the support with regard to the adipic acid produced (Example Nos. 4BB and 4CC). However, when Pd/Sb/Mo/V was examined, the alumina support produced the highest concentration of adipic acid (Example No. 4EE) in comparison to the titania support in Example No. 4DD. This trend was reversed when the Pd/Sb/Au/V catalyst was examined. In this case, the titania supported catalyst in Example No. 4FF outperformed the alumina supported catalyst in Example No. 4GG.
  • Examples Nos. 4HH through 4MM examined the catalyst compositions in the oxidation of cyclohexanol with no solvent. In all cases, the catalysts that performed well were those that were supported on alumina. Thus, these experiments illustrate that catalytic performance is dependent on what feedstock and solvent (if any) are used. The experiments also demonstrate that the oxidation catalyst is not deactivated by acetic acid or water, and that it can perform in the absence of any solvent. Table 5
  • Catalyst screening experiments were performed in an experimental set-up known as a "continuous oxidation system" that consisted of four blocks, each containing 16 micro fixed bed reactors with a manifold that was fed by two feed lines. The manifold distributed a gaseous feed to each of the 16 reactors of each of the blocks from each of the feed lines going to the manifold. Because each block was independently heated, it was possible for four separate temperatures to be examined for the continuous, gas-phase oxidations of propane and propylene (IUPAC name propene). For the investigation of these catalyst compositions, one feed line contained either propane or propylene plus molecule oxygen, a diluent gas such as nitrogen, and helium, which was used as an internal standard. A second feed line delivered water.
  • a back pressure regulator device for each of the blocks to control gas exit in order to contain a set pressure for each of these blocks.
  • selection valves which were computer controlled to direct the exit gaseous stream to one of two gas chromatographs designed to quantify the anticipated propane or propylene oxygenation products, byproducts and carbon oxides, as well as helium.
  • a catalyst volume of 50, 100 or 200 microliters was loaded into the reactor.
  • a diluent guard bed 25 microliters of zirblast, inert ceramic beads was added at the top of the catalyst bed.
  • the catalyst compositions for the propane and propylene oxidations were then sieved and those having a particle size in the range of 200 to 400 microns were tested.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention se rapporte à un procédé de production d'au moins un acide carboxylique non aromatique en mettant en contact un mélange réactionnel fluide comprenant une charge non alkylaromatique avec de l'oxygène en présence d'une composition catalytique métallique sans brome comprenant au moins trois composants métalliques ou métalloïdes, les composants comprenant du palladium, de l'antimoine, du bismuth ou une combinaison de ceux-ci ; et du molybdène, de l'or, du niobium, du vanadium, du gallium ou une combinaison de ceux-ci. Ce procédé produit avec efficacité des acides carboxyliques non aromatiques en une étape, élimine les sous-produits indésirables générés dans les produits du commerce, et permet d'obtenir une meilleure séparation du catalyseur et du produit.
PCT/US2007/083925 2007-05-04 2007-11-07 Procédé de production d'acides carboxyliques non aromatiques WO2008136857A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
USPCT/US2020/07/68268 2007-05-04
USPCT/US2020/07/68274 2007-05-04
PCT/US2007/068268 WO2007133976A2 (fr) 2006-05-08 2007-05-04 Procédé de production d'acides carboxyliques aromatiques dans de l'eau
USPCT/US2020/07/68261 2007-05-04
PCT/US2007/068274 WO2007133978A2 (fr) 2006-05-08 2007-05-04 Procédé et catalyseur pour l'oxydation de composés aromatiques
PCT/US2007/068261 WO2007133973A2 (fr) 2006-05-08 2007-05-04 Procédé et catalyseur pour oxyder des composés aromatiques

Publications (1)

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WO2008136857A1 true WO2008136857A1 (fr) 2008-11-13

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Country Link
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017184496A1 (fr) * 2016-04-21 2017-10-26 Rohm And Haas Company Procédés d'utilisation de matériaux inertes macroporeux dans la production de monomères

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DE19630832A1 (de) * 1996-07-31 1998-02-05 Hoechst Ag Verfahren zur selektiven Herstellung von Essigsäure
DE19745902A1 (de) * 1997-10-17 1999-04-22 Hoechst Ag Verfahren zur selektiven Herstellung von Essigsäure durch katalytische Oxidation von Ethan
WO2000029106A1 (fr) * 1998-11-16 2000-05-25 Saudi Basic Industries Corporation Catalyseurs pour l'oxydation catalytique du propane en acide acrylique, et ses procedes d'obtention et d'utilisation
EP1113238A2 (fr) * 1999-12-28 2001-07-04 Nippon Shokubai Co., Ltd. Echangeur de chaleur à tubes et calandre
US20050131255A1 (en) * 2003-11-18 2005-06-16 Abraham Benderly Catalyst systems for converting alkanes to alkenes and to their corresponding oxygenated products
WO2007133973A2 (fr) * 2006-05-08 2007-11-22 Bp Corporation North America Inc. Procédé et catalyseur pour oxyder des composés aromatiques

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19630832A1 (de) * 1996-07-31 1998-02-05 Hoechst Ag Verfahren zur selektiven Herstellung von Essigsäure
DE19745902A1 (de) * 1997-10-17 1999-04-22 Hoechst Ag Verfahren zur selektiven Herstellung von Essigsäure durch katalytische Oxidation von Ethan
WO2000029106A1 (fr) * 1998-11-16 2000-05-25 Saudi Basic Industries Corporation Catalyseurs pour l'oxydation catalytique du propane en acide acrylique, et ses procedes d'obtention et d'utilisation
EP1113238A2 (fr) * 1999-12-28 2001-07-04 Nippon Shokubai Co., Ltd. Echangeur de chaleur à tubes et calandre
US20050131255A1 (en) * 2003-11-18 2005-06-16 Abraham Benderly Catalyst systems for converting alkanes to alkenes and to their corresponding oxygenated products
WO2007133973A2 (fr) * 2006-05-08 2007-11-22 Bp Corporation North America Inc. Procédé et catalyseur pour oxyder des composés aromatiques
WO2007133976A2 (fr) * 2006-05-08 2007-11-22 Bp Corporation North America Inc Procédé de production d'acides carboxyliques aromatiques dans de l'eau
WO2007133978A2 (fr) * 2006-05-08 2007-11-22 Bp Corporation North America Inc. Procédé et catalyseur pour l'oxydation de composés aromatiques

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017184496A1 (fr) * 2016-04-21 2017-10-26 Rohm And Haas Company Procédés d'utilisation de matériaux inertes macroporeux dans la production de monomères
CN109153627A (zh) * 2016-04-21 2019-01-04 罗门哈斯公司 在单体生产中使用大孔惰性材料的方法
US10577299B2 (en) 2016-04-21 2020-03-03 Rohm And Haas Company Methods for using macroporous inert materials in monomer production
CN109153627B (zh) * 2016-04-21 2022-08-02 罗门哈斯公司 在单体生产中使用大孔惰性材料的方法

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