Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
  • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
  • C07C5/333—Catalytic processes
• • 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
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
  • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
  • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
  • C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds

Definitions

• This invention relates to processes for low temperature catalytic oxidation of
• the feed includes sulfur
• Patent 627,401 European Patent Application 480,594 and International Application
• WO 99/13980 describe catalysts and processes for the production of acetic acid from
• Oxidative dehydrogenation is a well known process for converting saturated or
• 3,970,697 include palladium and gold on supports such as zinc oxide, alumina and
• the catalyst is pre-treated with sulfur compound in moist air so that the
• concentration of sulfur-containing modifier is from about 0.05% to about 25% of the
• VAM vinyl acetate monomer
• the process of the present invention is a low temperature catalytic process for
• the invention relates to a low temperature catalytic process, where a reactant
• alkane C 2 ,C 3 ,C 4
• oxygen sulfur-containing compound
• a 1 to 5
• b is >0 to 0.1
• c 0.01 to 0.5
• d is >0 to 0.1.
• the numerical values a, b, c and d represent the relative gram-atom ratios of
• the elements Mo, V, Nb and Y, respectively, in the catalyst.
• the elements are
• composition is described in WO 99/13980 which is herein incorporated by reference.
• a 1 to 5
• b is 0 to 0.5
• c 0.01 to 0.5
• d is 0 to 0.045.
• the numerical values a, b, c and d represent the relative gram-atoms ratios of
• the elements Mo, V, Nb and Pd, respectively, in the catalyst.
• the elements are
• b 0.01 to 0.9
• c 0 > to 0.2
• d 0> to 0.2
• e is 0> to 0.2
• f is 0> to 0.3.
• the numerical values a, b, c , d, e and f represent the relative gram-atom ratios
• a 1 to 5
• b 0.01 to 0.9
• b 0.01 to 0.9
• d 0> to 0.2
• e is 0> to 0.2
• f is 0> to 0.5
• b 0.01 to 0.9
• d 0.0000001 to 0.2
• e is 0 to 0.2
• the catalysts of the invention can be used with or without a support. Suitable
• supports for the catalyst include porous materials such as micro/meso/nanoporous
• Support materials include, e.g., alumina, silica, titania, zirconia, zeolites, silicon carbide, carbon such as activated charcoal, Mo
• the supported catalyst When used on a support, the supported catalyst usually comprises from about 10 to
• Hydrocarbon feedstock is oxidized with molecular oxygen and co-feed sulfur-
• reaction mixture at a pressures of 1-50 bar, or 15 to 500 psi, for a contact time between reaction mixture
• the feed mixture includes from about 5% to about 95% by volume of lower
• hydrocarbons particularly C 2 to C 4 , more particularly, ethane, ethylene, propane,
• reaction mixture generally contains one mole of hydrocarbon (C j , C 3 , C 4 ), 0.01 to 2.0
• moles of molecular oxygen either as pure oxygen or in the form of air, and zero to 4.0
• Oxygen sources for the feed include purified
• the feed mixture can include molecular oxygen in an amount
• reaction can also be
• diluents such as inert gases, e.g., argon, helium, nitrogen, or steam.
• inert gas diluents can be used in an amount from about 5% to
• Steam can be used in an amount from zero up to about 40% by
• the ratio of hydrocarbons (C 2 -C 4 ) to diluents can be in the range 1/5 to 1/1.
• the water vapor or steam is used as a reaction diluent and as a heat moderator for the
• reaction diluent a gas which may be used as reaction diluent or heat
• moderators include, e.g., helium, nitrogen, and carbon dioxide.
• Sulfur containing compounds can act as a promoter and can be added to the
• reaction zone as a gas or liquid with water.
• compound can range from 0.05 to about 10 %, preferably about 0.05% to about 5%
• preferred sulfur compounds used in this invention have at least two oxygen atoms
• sulfur promoters include COS, SO 2 , SO 3 , H 2 SO 4 , sulfurous acids, sulfonic acid or
• the active sulfur species can be any inorganic and organic acid of sulfur.
• the active sulfur species can be any organic acid of sulfur.
• the active sulfur species can be any organic acid of sulfur.
• the active sulfur species can be any organic acid of sulfur.
• the active sulfur species can be any organic acid of sulfur.
• the active sulfur species can be any organic acid of sulfur.
• oxidizing agent such as mobile or adsorbed oxygen.
• the gaseous components of the reaction mixture include a non-explosive
• reaction zone are preferably uniformly admixed prior to being introduced into the reaction zone.
• the components may be preheated, individually or after being admixed, prior to being
• the reaction zone generally has a pressure of from 1 to 50 bar, preferably from 1 to 30 bar and a temperature of from about 150° C to
• a preferred pressure range in terms of psi is about 50 to about 500 psi.
• the liquid products of the reaction can be separated from the unreacted feed
• hydrocarbons by condensation or by scrubbing, usually with water or dilute acid.
• the process can be carried out in a single stage or in multiple stages of two or
• reaction conditions such as temperature and/or pressure can be adjusted.
• a mixture comprising ethane, steam,
• VAM monomer
• the first product mixture can be fed
• first product mixture can be adjusted by the addition of ethylene, acetic acid or oxygen. Moreover, the first product mixture can be subjected to temperature and/or
• Oxygen, nitrogen, H 2 S, COS and carbon monoxide were analyzed using a 3-mm by
• Al 0 226 was prepared and formulated into uniform particles of the 40-60
• Catalyst was evaluated at a temperature of 280° C / 200 psi with feed mixture containing ethane: oxygen: nitrogen: H 2 S: COS in a proportion of 40: 8: 52: 0:
• Pdo ⁇ .90e -o 4 Nb 0 125 Al 0226 was prepared and formulated into uniform particles of the 40-60
• Catalyst was evaluated at a temperature of 280° C / 200 psi with feed
• VAM monomer

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1999
  • 1999-09-17 US US09/399,275 patent/US6258992B1/en not_active Expired - Lifetime
• 2000
  • 2000-02-23 SA SA00201005A patent/SA00201005B1/ar unknown
  • 2000-09-11 JP JP2001524951A patent/JP4711582B2/ja not_active Expired - Fee Related
  • 2000-09-11 AT AT00962474T patent/ATE261925T1/de not_active IP Right Cessation
  • 2000-09-11 EP EP00962474A patent/EP1212276B1/en not_active Expired - Lifetime
  • 2000-09-11 WO PCT/EP2000/008889 patent/WO2001021570A1/en not_active Ceased
  • 2000-09-11 KR KR1020027003490A patent/KR100798183B1/ko not_active Expired - Fee Related
  • 2000-09-11 CN CNB008130280A patent/CN1213983C/zh not_active Expired - Fee Related
  • 2000-09-11 ES ES00962474T patent/ES2215724T3/es not_active Expired - Lifetime
  • 2000-09-11 DE DE60009092T patent/DE60009092T2/de not_active Expired - Lifetime

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