Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
  • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8875—Germanium, tin or lead
• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/057—Selenium or tellurium; Compounds thereof
  • B01J27/0576—Tellurium; Compounds thereof
• • 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
• • 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 to the manufacture of unsaturated aliphatic carboxylic acids. More particularly, the invention pertains to the oxidation of propylene or isobutylene in the vapor phase with molecular oxygen to produce acrylic acid or methacrylic acid in a single step process.
• the major object of this invention is accordingly to provide a process for the manufacture of acrylic acid 3,475,488 Patented Oct. 28, 1969 or methacrylic acid in a single step processing from propylene or isobutylene in a considerably high order of yield, namely, in a high order of conversion and selectivity, substantially necessitating no recycling of the unreacted olefins and the intermediate aldehydes.
• the process of this invention for the manufacture of unsaturated aliphatic carboxylic acids comprises contacting in the vapor phase propylene or isobutylene with molecular oxygen in the presence of a catalyst of the formula:
• the present invention is based upon the discovery that the catalyst of the above formula enables the starting propylene or isobutylene to convert selectively in a single step to the corresponding unsaturated aliphatic carboxylic acids, acrylic acid or methacrylic acid, in a high order of selective conversion without recycling the unreacted u-olefins and the unsaturated aldehydes.
• the amount of the resultant unsaturated aldehydes and other byproducts is negligible, and the per pass yield of the desired unsaturated carboxylic acids is markedly improved.
• the catalyst employed in this invention consists of cobalt, tin, molybdenum, tellurium and oxygen in the order as disclosed in the aforesaid formula. Lack of any one element as specified in the formula results in a re duction in conversion and selectivity, so that the objects of this invention cannot be attained.
• the known catalyst consisting of cobalt, molybdenum, tellurim and oxygen invites a deterioration in conversion if selectivity is to be enhanced and vice versa, so that it is impracticable for said catalyst to improve the yield of the resultant unsaturated carboxylic acids in a single step.
• conversion and selectivity are both raised to a high order, producing in a single step the desired unsaturated carboxylic acids in high yields.
• conversion and selectivity as herein employed are defined as follows:
• the catalyst employed in this invention essentially consists of Co, Sn, Mo, Te and O in the atomic ratio of 1-16:1-5:12:O.1-6:20-82. Preferable effects are obtained in the atomic ratio of 3-11:1.2-4:12:0.5-3:2567, the most desirable ratio being 7 :1.7 212:2:54 or thereabout.
• the catalyst employed in this invention is prepared by any of the conventional processes, such as precipitation and evaporation to dryness or mixing oxides of each component metal.
• the procedures for preparing the catalyst of this invention will be described in more detail in the appended examples.
• the catalyst employed in this invention may be regarded as a mixture of oxides of each component metal or a mixture of a heteropoly acid salt and a metal oxide, such as a mixture of cobalt-tin-molybdate and tellurium oxide.
• Percent selectivity But the exact chemical structure of the catalyst is yet unknown. Whether the exact structure is known or not, however, it has been made clear for the first time in the art by the present inventors that the aforesaid catalyst has a property to produce the desired unsaturated aliphatic carboxylic acids in a markedly high order of per pass yield.
• the aforesaid catalyst of this invention may be employed singly or in conjunction with a suitable support, such as silica, diatomaceous earth, alumina, silicon carbide, titanium oxide or zirconium oxide.
• a suitable support such as silica, diatomaceous earth, alumina, silicon carbide, titanium oxide or zirconium oxide.
• the starting olefins employed in this invention are propylene and isobutylene.
• the starting u-olefins are oxidized into the corresponding aldehydes and the resultant aldehydes are subsequently converted to the desired corresponding unsaturated carboxylic acids.
• the catalyst of this invention can therefore be successfully applied to the oxidation of unsaturated aldehydes to produce the corresponding unsaturated carboxylic acids in high yields.
• olefins and aldehydes are respectively converted into the corresponding unsaturated aliphatic carboxylic acids, so that there can also be employed as a feed stock a-OlCfil'lS containing the corresponding unsaturated aldehydes in various proportions.
• a gas mixture of propylene and acrolein or a mixture of isobutylene and methacrolein is preferably employed to produce the corresponding acrylic acid or methacrylic acid in a yield as high as is the case with the single application of propylene or isobutylene.
• the range of amount of oxygen to be fed to the reactor varies widely, but good results are obtained when oxygen is employed in the order of from 0.1 to 20 moles, preferably from 3 to 12 moles, per mole of the starting a-olefin or the starting mixture of an a-olefin and the corresponding aldehyde.
• the reaction gas of the starting organic compound and oxygen may be diluted, where desirable, with an inert gas, such as carbon dioxide, nitrogen, saturated hydrocarbon or steam, so that air is advantageously used as an oxygen source from the economic point of view.
• the most desirable diluent is steam as conversion and selectivity are still more increased when the reaction gas is diluted with steam.
• the range of amount of steam to be applied is very wide.
• steam is employed in the order of from 1 to 60 moles, preferably from 5 to 30 moles, per mole of the starting u-olefin or the starting mixture of an a-olefin and the corresponding aldehyde.
• the reaction temperature employed in this invention ranges from 200 to 500 C., preferably from 250 to 400 C. There is no appreciable effect of pressure on reaction. Hence the reaction may be carried out under normal, increased or reduced pressure, but normal atmospheric pressure is preferred.
• the time of contact of the gas mixture with the catalyst can be varied widely. Satisfactory results, however, are obtained in the range of from 0.1 to 20 seconds, preferably from 1 to seconds.
• the term contact time as employed herein is defined as follows:
• EXAMPLE 1 In 1,800 cc. of hot water were dissolved With stirring 494 grams of ammonium paramolybdate of a formula (NH Mo O -4H O and heated to boil the solution. To the resultant boiling mixture were added 107 grams of ammonium chloride dissolved in a small amount of warm water. There were then added dropwise 126 grams of stannic chloride of a formula SnCl -3H O dissolved in 100 cc. of water. The mixture was heated with stirring for further 10 minutes, and the precipitate was filtered, washed with water and dried.
• EXAMPLE 2 The pellet catalyst of Example 1 was employed under the reaction conditions identical to those employed in Example 1, except the contact time was reduced to 6 seconds. Results obtained were as follows:
• EXAMPLE 3 40 cc. of the pellet catalyst of Example 1 were placed in a U-shaped stainless reactor, 25 mm. in internal diameter, and the reactor was dipped in a nitrate bath heated to 305 C. Into this reactor was introduced a gas mixture of 1.1 percent by volume of isobutylene, 60.9 percent by volume of air, and 38 percent by volume of steam, and reacted by contact for 2.7 seconds. Results obtained were as follows:
• EXAMPLE 4 60 cc. of the pellet catalyst of Example 1 were placed in a U-shaped stainless steel reactor, 25 mm. in internal diameter, and the reactor was dipped in a nitrate bath heated to 360 C. Into this reactor was introduced a gas mixture of 1.2 percent by volume of propylene, 40 percent by volume of air, and 58.8 percent by volume of nitrogen, and reacted by contact for 4.8 seconds. Results obtained were as follows:
• Acrylic acid 31.3 40.4 59.1 70.3 51.8 43.1 Aceticacid- 1.0 1.2 1.2 1.4 5.2 7.3 Acrolem- 50.4 38.0 20.4 9.8 6.3 5.2 Carbondsoxrde..- 10.3 10.5 10.9 11.6 19.9 25.3 Carbon monoxlde 5.2 5.0 5.8 6.1 13.1 15.5 Others 1.8 4.9 2.6 0.8 3.7 3.6
• Acrylic acid 77.2 moles, acetic acid: 1.3 moles, acrolein: 2.5 moles, carbon dioxide: 11.0 moles, carbon monoxide: 6.3 moles, others: 1.7 moles.
• EXAMPLE 10 A still another series of runs were conducted employing the catalyst of Example 1 in which the amount of cobalt nitrate, stannic chloride and metal tellurium was varied as specified in the subsequent table.
• a process for the manufacture of an unsaturated aliphatic carboxylic acid comprising reacting in the vapor phase at a temperature ranging from 200 to 500 C. an a-olefin selected from the group consisting of propylene and isobutylene with molecular oxygen in the presence of a catalyst of the following formula:
• reaction gas to be fed contains molecular oxygen in the range of from 0.1 to 20 moles per mole of the starting a-olefin.
• reaction gas to be fed contains molecular oxygen in the range of from 0.1 to 20 moles per mole of the starting gas mixture of an a-olefin and the corresponding e -unsaturated aldehyde.
• reaction gas contains steam as diluent in the range of from 1 to moles per mole of the starting u-olefin.
• reaction gas contains steam as diluent in the range of from 1 to 60 moles per mole of the starting gas mixture of an a-olefin and the corresponding a,;3-unsaturated aldehyde.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (5)

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Citations (1)

• 1964
  • 1964-11-25 GB GB47966/64A patent/GB1035147A/en not_active Expired
  • 1964-12-11 DE DE1964N0025964 patent/DE1468429A1/de not_active Withdrawn
• 1965
  • 1965-01-11 FR FR1446A patent/FR1443901A/fr not_active Expired
• 1968
  • 1968-01-23 US US699763A patent/US3475488A/en not_active Expired - Lifetime

Patent Citations (1)

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