GB1598510A

GB1598510A - Oxydehydrogenation catalyst

Info

Publication number: GB1598510A
Application number: GB38969/79A
Authority: GB
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1977-05-02
Filing date: 1978-05-02
Publication date: 1981-09-23
Also published as: PT67944B; JPS53135940A; CA1117120A; NL7804618A; IN148087B; BE866403A; EG13250A; NO781508L; IT7822880A0; GB1598509A; IT1094807B; CS199528B2; ES470908A1; JPH0154095B2; DE2816946A1; ES469145A1; FR2389590A1; BR7802706A; DD135897A5; PT67944A

Description

PATENT SPECIFICATION ( 11) 1 598 510

O ( 21) Application No 38969/79 ( 22) Filed 2 May 1978 ( 19) ( 62) Divided Out of No 1598509 ( 31) Convention Application No 792637 ( 32) Filed 2 May 1977 in t"' f Cbo ( 33) United States of America (US) U ( 44) Complete Specification Published 23 Sep 1981 -I ( 51) INT CL 3 BO 1 J 27/18 II CO 7 C 5/48 15/46 ( 52) Index at Acceptance Bl E 1123 1159 1197 1298 1301 1323 1342 1345 1351 1363 1371 1415 1433 1461 1462 1492 1497 1513 1514 1631 1634 1635 1702 1703 1714 1719 1721 1722 1729 1738 AA ( 72) Inventors: JOSEPH PETER BARTEK ROBERT KARL GRASSELLI ( 54) OXYDEHYDROGENATION CATALYST ( 71) We, THE STANDARD OIL COMPANY, a corporation organised under the laws of the State of Ohio, United States of America of Midland Building, Cleveland, Ohio 44115, United States of America do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: 5

This invention relates to a novel catalyst, which is of use particularly in the dehydrogenation of alkyl-substituted aromatic compounds to the corresponding alkenylsubstituted aromatics in the presence of oxygen.

Current commercial dehydrogenation practices as for example in the conversion of ethylbenzene to styrene, suffer from the disadvantages of low conversions, while higher 10 conversion oxydehydrogenations suffer from poor selectivities Selectivity is especially important in this particular reaction since the starting materials for producing styrene makes up over 80 percent of its manufacturing costs Thus there is a continuing search for catalytic materials that are more efficient in minimizing side reactions and improving conversion rates 15 A number of catalysts and catalytic systems have been disclosed utilizing various phosphates and pyrophosphates for the conversion of alkyl-aromatics to derivatives having side-chain unsaturation For example U S 3,923,916 claims nickel pyrophosphate as a superior catalyst for the oxydehydrogenation of alkyl aromatics U S 3,933, 932 and U S.

3,957,897 disclose the use of lanthanum, rare earth and alkaline earth phosphates, 20 respectively, as oxydehydrogenation catalysts for alkyl aromatics However the catalyst compositions of the present invention containing arsenic, antimony, bismuth, tellurium or cadmium phosphates which have demonstrated outstanding activity for this dehydrogenation reaction have heretofore not been disclosed.

The present invention therefore provides catalyst compositions represented by the 25 2 1 598 510 2 following empirical formula:

Aa Mb Mlc M 11 d XC Py Ox wherein A is an alkali metal and or thallium; M is one or more of the elements of nickel, cobalt, copper, manganese, magnesium, zinc, calcium, niobium, tantalum, strontium, or barium; 10 M' is one or more of the elements of iron, uranium, thorium, vanadium, titanium, lanthanum or the other rare earth metals MW' is one or more of the elements of tin, lead, germanium, aluminium or 15 tungsten; X is bismuth, tellurium, arsenic, antimony, cadmium or combinations thereof; 20 P is phosphorus; and wherein a to y have the following values:

a = O to 5; 25 b = 4 to 20; c = 0 1 to 10; 30 d = 0 to 4; e = 0 1 to 12; y = 8 to 16; 35 x = the number of oxygens required to satisfy the valence requirements of the elements present; and wherein the sum of 2 b + 3 (c + e) is greater than 9 and less than 3 y 40 A particularly preferred composition is one in which:

a is in the range of 0 1; 45 b is in the range of 4 to 12; c is in the range of 0 1 to 4; d is in the range of O to 2; 50 e is in the range of 0 1 to 4; and the sum of 2 b + 3 (c + e) is greater than 9 and less than 3 y.

55 The catalyst according to this invention are unexpectedly good oxydehydrogenation catalysts For example in the dehydrogenation of ethlbenzene to styrene, per pass conversions to styrene in the range of 70 % and selectivities of up to 90 % are obtained.

The catalysts may be used alone or supported on a carrier Suitable carrier materials include silica, Alundum (Registered Trade Mark) titania and mullite and particularly 60 phosphate-type carriers such as zirconium phosphate, antimony phosphate, aluminium phosphate and especially boron phosphate In general, the support may be employed in amounts less than 95 % by weight of the final catalyst composition, and the catalyst may be incorporated in the carrier by coating, impregnation and coprecipitation.

The catalysts may be prepared by coprecipitation or by other methods known in the art 65 1 598 510 Generally they are prepared by mixing an aqueous solution of the metal nitrates with an aqueous solution of ammonium dihydrogen phosphate and drying the precipitate.

The catalyst may be calcined to produce desirable physical properties such as attrition resistance, optimum surface area and particle size It is generally preferred that the calcined catalyst be further heat-treated in the presence of oxygen at a temperature of above 250 C 5 but below a temperature deleterious to the catalyst.

A process for the dehydrogenation of an alkyl aromatic compound to the corresponding alkenyl aromatic compound, in the presence of catalyst compositions which include these catalyst compositions of the present invention which are bismuth-free is described and claimed in our co-pending application No 17230/78 (Serial No 1598509) 10 The invention will now be further illustrated by the following Examples.

EXAMPLES

Example 1

Co 7 Fe 3 Bio7 P 12043 15 Ammonium dihydrogen phosphate ( 138 g) was dissolved in 100 cc of water with heating.

A nitrate solution was made up by adding cobalt nitrate hexahydrate ( 203 8 g), ferric nitrate nonahydrate ( 121 2 g) and bismuth nitrate pentahydrate ( 35 lg) in order, to 10 cc of water, and the nitrate solution was added to the ammonium dihydrogen phosphate solution A slurry formed, which was heated with stirring to remove water, dried at 110 C, heat-treated 20 at 290 C ( 5 hours), 427 C ( 3 hours) and 550 C ( 3 hours) in air The resulting blue solid had a surface area of 7 7 m 2/g.

Example 2

50 % Co 7 Fe 3 Bi 1 P 1204350 % BPO 4 25 A nitrate solution was made up of cobalt nitrate hexahydrate ( 85 g), ferric nitrate nonahydrate ( 50 5 g) and bismuth nitrate pentahydrate ( 20 2 g) with 5 cc of water It was added to an ammonium dihydrogen phosphate solution ( 57 5 g) in 100 cc of water to which 53 g of boron phosphate was added The boron phosphate powder (-200 mesh) was made by mixing 121 g of 85 % H 3 PO 4 with 62 g H 3 BO 31 warming to 40 C for 5 hours, drying the 30 resulting paste at 110 C and calcining in air at 300 C ( 8 hours) After stirring and heating, the slurry was dried and calcined as in example 1 The resulting blue solid had a surface area of 11 9 m 2/g.

Example 3 35

Co 95 Fe 05 Bi P 12042 A nitrate solution was made up of cobalt nitrate hexahydrate ( 276 5 g), ferric nitrate nonahydrate ( 20 2 g) and bismuth nitrate pentahydrate ( 48 5 g) It was added to a solution of ammonium dihydrogen phosphate ( 138 g) in 100 cc of water, dried and heattreated as in Example 1 The resulting blue solid had a surface area of 12 6 m 2/g 40 Example 4

Mg 9 Fe Bi P 12042 A nitrate solution was made up of magnesium nitrate hexahydrate ( 115 4 g) , ferric nitrate nonahydrate ( 20 2 g) and bismuth nitrate pentahydrate ( 24 3 g) It was added to a solution of 45 ammonium dihydrogen phosphate ( 69 g) in 50 cc water, dried and heattreated as in Example 1.

The resulting cream colored solid has a surface area of 12 0 m 2/g.

Example 5 50

Co 7 Lal 5 Bi P 12042 A nitrate solution was made up of cobalt nitrate hexahydrate ( 101 9 g), lanthanum nitrate hexahydrate ( 32 8 g), bismuth nitrate pentahydrate ( 48 5 g) and 7 cc of concentrated nitric acid It was added to a solution of ammonium dihydrogen phosphate ( 69 g) in 50 cc of water, dried and heat-treated as in Example 1, except that 550 C heat-treatment was extended to 55 16 hours The resultant blue solid had a surface area of 19 4 m 2/g.

Example 6

Co 8 Lao 5 Bi 2 P 12042 A nitrate solution was made up of cobalt nitrate hexahydrate ( 116 4 g), lanthanum nitrate 60 hexahydrate ( 10 9), bismuth nitrate pentahydrate ( 48 5 g), and 3 cc of concentrated nitric acid with 10 cc water It was added to ammonium dihydrogen phosphate ( 69 g) dissolved in cc water, then dried and heat-treated as in Example 5 The resulting solid had a surface area of 7 7 m 2/g.

1 598 510 Example 7

Co 9 Lai o Bi P 12042 A nitrate solution was made up of cobalt nitrate hexahydrate ( 131 g), lanthanum nitrate hexahydrate ( 217 g) and bismuth nitrate pentahydrate ( 24 3 g) with 10 cc of water It was S added to ammonium dihydrogen phosphate ( 69 g) dissolved in 50 cc of water The slurry was 5 dried and heat-treated as in Example 1 The resulting blue solid had a surface area of 10 5 m 2 ig.

Example 8

Ko O o Cog La 1 Bi Pl 2042 10 A nitrate solution was prepared as in Example 7 A 10 cc solution of potassium acetate ( 0.Sg/100 cc) was added to the mixed nitrates, and the nitrate solution was added to an ammonium dihydrogen phosphate solution as in Example 7 The slurry was dried and heat-treated as in Example 5 The resultant blue solid had a surface area of 19 0 m 2/g.

15 Example 9

Co 7 Zn 2 Las Bi P 12042 A nitrate solution was made up of cobalt nitrate hexahydrate ( 101 9 g), zinc nitrate hexahydrate ( 29 8 g) lanthanum nitrate hexahydrate ( 21 7 g) and bismuth nitrate pentahydrate ( 24 3 g) in 5 cc of water It was added to an ammonium dihydrogen phosphate ( 69 g) 20 solution in 50 cc of water After stirring and heating, the slurry was dried and heat-treated as in Example 5 The resultant blue solid had a surface area of 8 6 m 2/g.

Example 10

Cog Ce Bi P 13045 25 Ceric ammonium nitrate ( 27 4 g) was dissolved in 5 cc nitric acid (concentrated) and 100 cc of water Bismuth nitrate pentahydrate ( 24 3 g) and cobalt nitrate hexahydrate ( 131 g) were added to the ceric solution and dissolved The resultant solution was added to an ammonium dihydrogen phosphate ( 74 8 g) solution in 50 cc of water The resultant slurry was dried and heat-treated as in Example 1 The solid that formed had a surface area of 10 3 30 m 2/g.

Example 11

Mg 9 La Bi P 120 042 A nitrate solution was made up of magnesium nitrate hexahydrate ( 115 4 g) , lanthanum 35 nitrate hexahydrate ( 21 7 g) and bismuth nitrate pentahydrate ( 24 3 g) in 10 cc of water It was added to an ammonium dihydrogen phosphate ( 69 g) solution in 50 cc of water After stirring and heating, the slurry was dried and heat-treated as in Example 1 The resultant white solid had a surface area of 27 m 2/g.

40 Example 12

Co 9 DilBi PI 2042 "Didymium" oxide, mixed rare earths ( 16 5 g) (Trona Corp code 422) was dissolved in cc of concentrated nitric acid Bismuth nitrate pentahydrate ( 24 3 g) was added to the "didymium" solution which was then added to a solution of ammonium dihydrogen 45 phosphate ( 69 g) in 50 cc of water A cobalt nitrate hexahydrate ( 131 g) solution in 10 cc of water was then added The slurry was dried and heat-treated as in Example 1 The resultant blue solid had a surface area of 15 4 m 2/g.

Example 13 50

Cog Fel Te P 12042 5 Tellurium dioxide ( 8 O g) was dissolved in 10 cc of nitric acid with warming This solution was added to a nitrate solution consisting of cobalt nitrate hexahydrate ( 131 g) and ferric nitrate nonahydrate ( 20 2 g) and 5 cc of water The nitrate solution was added to an ammonium dihydrogen phosphate ( 69 g) solution in 50 cc of water The slurry was dried at 55 C and heat-treated as in Example 1, with the final 550 C stage being performed in the stainless steel reactor The resultant blue solid had a surface area of 59 9 m 2/g.

Example 14

Co 8 Ba Fe Bi P 12042 60 A nitrate solution was made up of cobalt nitrate hexahydrate ( 116 4 g), bismuth nitrate pentahydrate ( 24 3 g), ferric nitrate nonahydrate ( 20 2 g) and 50 cc of water Barium hydroxide octahydrate ( 15 8 g) was acidified with 10 % solution of concentrated nitric acid in water to a p H of 1 5, then added to the nitrate The resultant slurry was added to an ammonium dihydrogen phosphate solution ( 69 g) in 50 cc of water The slurry was dried and 65 1 598 510 5 heat-treated as in Example 1, to give a solid with a surface area of 10 6 m 2/g.

The number of oxygen atoms in the catalysts in Examples 1 to 14 were estimated.

However, the number of oxygens may actually vary from 30 to 60, depending upon the reaction conditions.

Claims

WHAT WE CLAIM IS: 5

1 A catalyst composition represented by the formula:

Aa Mb M'c Ml d Xe Py Ox in which A is an alkali metal and or thallium; 10 M is one or more elements of nickel, cobalt, copper, manganese, magnesium, zinc, calcium, niobium, tantalum, strontium or barium; M' is one or more of the elements of iron, uranium, thorium, vanadium, 15 titanium, lanthanum or the other rare earth metals; MW' is one or more of the elements of tin, lead, germanium, aluminium or tungsten; 20 X is one or more of the elements of bismuth, tellurium, antimony, arsenic and cadmium; P is phosphorus; and 25 in which a to y have the following values:

a = 0 to 5; b = 4 to 20; 30 c = 0 1 to 10; d = 0 to 4; 35 e = 0 1 to 12; y = 8 to 16; x = the number of oxygens required to satisfy the valence requirements of the 40 other elements present; and wherein the sum of 2 b + 3 (c + e) is greater than 9 and less than 3 y.

2 A catalyst composition as claimed in claim 1 in which 45 a is in the range of 0 1; b is in the range of 4 to 12; 50 c is in the range of 0 1 to 4; d is in the range of 0 to 2; and e is in the range of 0 1 to 4 55 3 A catalyst composition as claimed in claim 1 or claim 2 in which M in the catalyst composition is cobalt, M' is lanthanum, and X is bismuth.

4 A catalyst composition as claimed in claim 1 or claim 2 in which M in the catalyst composition is cobalt, M' is iron and X is tellurium 60 A catalyst composition is claimed in claim 1 or claim 2 in which M in the catalyst composition is magnesium, M' is lanthanum and X is bismuth.

6 A catalyst composition as claimed in claim 1 substantially as herein described with reference to the Examples.

7 A method for the preparation of a catalyst composition as claimed in any of claims 1 65 6 1 598 510 6 to 6 in which the catalyst is prepared by coprecipitation of the catalyst components with subsequent calcination.

8 A method as claimed in claim 7 in which the catalyst is incorporated in a carrier by coprecipitation, coating or impregnation.

9 A method as claimed in claim 7 substantially as herein described with reference to 5 the Examples.

A catalyst when prepared by a method as claimed in any of claims 7 to 9.

ELKINGTON AND FIFE, Chartered Patent Agents, 10 High Holborn House, 52/54 High Holborn, London, WC 1 V 65 H Agents for the Applicants.

Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey 1981.

Published by The Patent Office 25 Southampton Buildings, London WC 2 A l AY, from which copies may be obtained.