FI66129B - CATALYST ANVAENDBAR FOER OXIDERING AMMOXIDERING DEHYDROGENERING OCH OXIDEHYDROGENERING AV OLEFINER - Google Patents

Description

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Patani- och raglatorstyralsan 'f AmUkm »ud ^ d od> mUfcrtft— fbikmnd J 5 (31) (33) (31) H» * wr wottaw> «tW prtortm 28.07.77 USA (US) 819732 (71) The Standard Oil Company, Midland Building, Cleveland, Ohio Ml15, USA (72) Robert Karl Grasselli, Chagrin Falls, Ohio,

Dev Dhanaraj Suresh, Macedonia, Ohio,

Maria Strada Friedrich, Cleveland, Ohio,

David Allan Orndoff, Windsor, Ohio, USA (USM) 7M Oy Kolster Ab (5 * 0 Catalyst for Oxidation, Amoxidation, Dehydrogenation and Oxide Dehydrogenation of Olefins

Catalysts containing iron, bismuth, molybdenum and various additives have very advantageous catalytic properties for the oxidation and amoxidation of various olefins.

If catalysts for the oxidation, amoxidation and oxide dehydrogenation of olefins are already known (see, for example, U.S. Patents 3,642,930 and 3,414,631). In addition, reference is made to U.S. Patent Nos. 4,162,234 and 4,190,608. Although previously known catalysts are quite preferred, the catalysts of the present invention have significant advantages over these other catalysts.

The present invention is based on the finding that certain oxidation catalysts based on iron, bismuth and molybdenum, which additionally contain certain promoter substances, have excellent catalytic activity in various oxidation, amoxidation, dehydrogenation and oxide hydration of olefins. In particular, it has been found that certain catalyst compositions described later are particularly suitable for use in the preparation of acrylonitrile and methacrylonitrile by the oxidation of propylene and isobutene, respectively. In addition to being excellent amoxidation catalysts for the preparation of acrylonitrile or methacrylonitrile, these catalysts also have excellent catalytic activity in the conversion of olefins having four or more adjacent carbon atoms to the corresponding diolefins and oxides of olefins and diolefins.

According to the present invention, novel catalysts with improved catalytic properties are represented by the following empirical formula:

JaQbZcFedBieMo12 ° x where J is an alkali metal; Q is Co or Ni or a mixture thereof; Z is a system of two or more elements comprising the combination Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn, Mn + W, W + Sb, Cr + Sn, W + Sn, Ge + Sn, Sb + Sn, W + P, Sb + P, Cr + Cu,

Mn + Cu, Sb + Cu, Mn + P or a mixture thereof a is 0.01-0.5 b is 0.1 -20, c is 0.1 -9, d is 0.1 -20, and e is 0.1 -20.

and x has a value such that the Valens side oxygen requirements of the catalyst elements are satisfied.

In this catalyst composition, the Z component consists of systems of two or more elements. In these systems described above, each element of the system is present in an amount of at least 1 atomic percent, preferably at least 5 atomic percent based on the atoms in the selected system.

3 66129

Optimally, the elements are present in the following amounts: a is 0.03 to 0.5, b is 4 to 10, c is 0.5 to 7, d is 0.5 to 5, and e is 0.5 to 5.

In a particularly preferred embodiment, the above-mentioned preferred and optimal catalysts contain K, Rb and / or Cs and optionally Ni and / or Co.

It is also preferred that Z is selected so that the ratio of the amount of the first element in each system described above to the amount of the second element in the system is 1: 0.25 to 1: 0.75.

Of particular interest from the above catalysts is that in which the Z component is selected from the following elemental combinations: Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn and Mn + W, wherein those catalysts , where Z is one of the following: Ge + Sb, Cu + W, Cu + Sn, Ce + W and Pr + Mn are of particular note.

The catalysts of this invention can be prepared by any of the methods known in the art, such as using the various methods disclosed in the aforementioned patents. For example, catalysts can be prepared by forming an aqueous composition of the degradable salts and / or oxides of the metals contained in the catalyst, evaporating the water from this aqueous composition to form a thick paste, drying this thick paste and then calcining this paste at an elevated temperature in an oxidizing atmosphere. The technique for preparing catalysts of the type described herein is well known to those skilled in the art and it should not be difficult for one skilled in the art to prepare catalysts of the invention.

The catalysts of the present invention can be used without a support or using various conventional supports such as SiO 2, Al 2 O 2, ZrCl 2 / TiCl 2, BPO 2, SbPO 4, MgO, montmorillonite or the like. They can be used in solid layers or fluidized bed reactions as desired. When these catalysts are used, they simply replace the catalysts previously used and the reaction is carried out under essentially the same conditions.

4 66129

For example, when the catalysts of the invention are used in the amoxidation of propylene and isobutene to form acrylonitrile or methacrylonitrile, respectively, the reacting olefin together with oxygen and ammonia in conventional proportions is contacted with the catalyst at elevated temperature, usually about 200-600 ° C. time to effect an appropriate amoxidation reaction. Similarly, when the catalysts of the invention are used to catalyze other known reactions, the reaction conditions used are conventional.

Specific embodiments

Comparative Example A

804 K0.1Ni2,5Co4,5re3BlP0,5Mo12 ° X * 208 Si ° 2

A solution of 127.1 g of ammonium heptamolybdate (NH 4) g Mo7024.4H 2 O and water was prepared. To this solution were added 6.9 g of a 42.5% H 2 PO 4 solution and 102.7 g of Nalco-silicic acid sol (40%) to form a slurry. Separately, an aqueous solution containing 72.7 g of ferrin nitrate Fe (NO 2) 3 · 9H 2 O was prepared; 29.1 g bismuth nitrate Bi (NO 2) 3.5H 2 O; 78.6 g of cobalt nitrate Co (NO 2) 2 · 6Η20; 43.6 g nickel nitrate Ni (NO 2) 2 · 6H 2 O; and 6.1 g of a 10% potassium nitrate solution. The metal nitrate solution was slowly added to the slurry. The resulting slurry was evaporated to dryness and the resulting solid composition was heat treated at 290 ° C for three hours, at 425 ° C for three hours and at 550 ° C for 16 hours.

Examples 1-7

In the same manner as described in Comparative Example A, the catalysts listed in Table I below were prepared. The catalytic activity of each of these catalysts as well as Catalyst A was tested in the amoxidation of propylene to acrylonitrile. In this test, each catalyst was charged to a 5 cm solid bed reactor. The feed of propylene / ammonia / oxygen / nitrogen / steam in the amount of 1.8 / 2.2 / 3.6 / 2.4 / 6 was fed to the reactor so that the WWH was 0.1 g of propylene per gram of catalyst per hour and the contact time was three seconds. The reaction temperature was maintained at 420 ° C. The results obtained and the results obtained with comparative catalyst A are shown in Table I.

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The parentheses used in Table I and in Table II below have no meaning other than to clarify the differences between the different catalysts.

Examples 8-10 Using various catalysts prepared as described above, additional experiments were performed in which propylene was amoxidized to acrylonitrile. These additional experiments were performed using the same procedure as in Examples 1-7 except that the reaction temperature was 430 ° C, the contact time was 6 seconds, and the catalyst support was 50% SiO 2. The results obtained are shown in the following Table II: 7 66129 Λ! <υ

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Claims (1)

Catalyst for oxidation, amoxidation, dehydrogenation and oxide dehydrogenation of olefins, characterized in that it has the formula WcFeaBieMo12 ° x wherein J is an alkali metal; Q is Co or Ni or a mixture thereof; Z is a system of two or more elements comprising the combination Ge + Sb, Cu + W, Cu + Sn, Ce + W, Pr + Mn, Sn + Mn, Mn + W, W + Sb, Cr + Sn, W + Sn, Ge + Sn, Sb + Sn, W + P, Sb + P, Cr + Cu, Mn + Cu, Sb + Cu, Mn + P or a mixture thereof, and where 0.01 <a <0.5 0, 1 <b <20 0.1 <c <9 0.1 <d <20 0.1 <e <20, and xs has a value such that the Valens requirements for the oxygen of the catalyst elements are satisfied; wherein each element of said two or more elemental systems is present in an amount of at least 1 atomic% based on the atoms in the system.