CA1117120A - Oxydehydrogenation process for alkylaromatics and catalyst therefor - Google Patents
Oxydehydrogenation process for alkylaromatics and catalyst thereforInfo
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- CA1117120A CA1117120A CA000300424A CA300424A CA1117120A CA 1117120 A CA1117120 A CA 1117120A CA 000300424 A CA000300424 A CA 000300424A CA 300424 A CA300424 A CA 300424A CA 1117120 A CA1117120 A CA 1117120A
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- bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
ABSTRACT OF THE INVENTION
This invention relates to an improved process for the dehydrogenation of alkyl-substituted aromatic compounds to the corresponding, alkenyl-substituted aromatics in the presence of oxygen and in the presence of an improved metal phosphate catalyst composition.
This invention relates to an improved process for the dehydrogenation of alkyl-substituted aromatic compounds to the corresponding, alkenyl-substituted aromatics in the presence of oxygen and in the presence of an improved metal phosphate catalyst composition.
Description
BACKGROUND OF THE INVEN~ION
Curren-t commercial dehydrogenatlon practices as for example in the conversion of ethyl benzene to styrene, suEfer from -the disadvantages of low conversions, while hi~her conver-sion oxydehydrogenations quEfer from poor selectivities. Selec-tivity is especially important in this particular reaation since the starting materials for producing styrene comprise oVer 80,.
percent of its manufacturing costs. Thus there is a continuing search~for catalytic materials that are more efficient in mini-mizing side reactions and improving conversion rates.
A number of catalysts and catalytic systems have been disclosed utilizing various phosphates and pyrophosphates for the conVersion of alkyl aromatics to derivatives having ~ide~chain unsaturation. For example U.S. 3,923,916 claims nickel p~ro-phosphate as a superior catalyst for the oxydehydro~enation 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, respectively, as oxydehydrogenation catalysts for alkyl aromatics~
However catalyst compositions containing arsenic, antimony, bis-muth or cadmium phosphates which have demonstrated outstandin~
activity for the dehydrogenation reaction o~ the present inven-tion have hereto~ore not been disclosed. ~lthough U.S. 3,873,633 utilizes a cobalt-bismuth-phosphorus-ox~gen composition as a catalyst for the oxydehydrogenation of paraffinic hydrocarbons to J,~ 1- $
Curren-t commercial dehydrogenatlon practices as for example in the conversion of ethyl benzene to styrene, suEfer from -the disadvantages of low conversions, while hi~her conver-sion oxydehydrogenations quEfer from poor selectivities. Selec-tivity is especially important in this particular reaation since the starting materials for producing styrene comprise oVer 80,.
percent of its manufacturing costs. Thus there is a continuing search~for catalytic materials that are more efficient in mini-mizing side reactions and improving conversion rates.
A number of catalysts and catalytic systems have been disclosed utilizing various phosphates and pyrophosphates for the conVersion of alkyl aromatics to derivatives having ~ide~chain unsaturation. For example U.S. 3,923,916 claims nickel p~ro-phosphate as a superior catalyst for the oxydehydro~enation 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, respectively, as oxydehydrogenation catalysts for alkyl aromatics~
However catalyst compositions containing arsenic, antimony, bis-muth or cadmium phosphates which have demonstrated outstandin~
activity for the dehydrogenation reaction o~ the present inven-tion have hereto~ore not been disclosed. ~lthough U.S. 3,873,633 utilizes a cobalt-bismuth-phosphorus-ox~gen composition as a catalyst for the oxydehydrogenation of paraffinic hydrocarbons to J,~ 1- $
2~
monoolefins or diolefins, the use of -this type of catalyst for the conversion of alkyl aroma-tics to unsaturated side-chain derivatives has heretofore no-t been known.
SVM~IARY OF THE INVENTION
The present invention comprises the process for the oxydehydrogenation of alkyl-substituted aromatic compounds to the corresponding alken~l-substituted aromatics and the novel catalyst compositions thereEor. More specifically the invention comprises the oxydehydrogenation of alkyl aromatic compounds to form the corresponding unsaturated side-chain derivative wherein the alkyl aromatic contains at least one alkyl group ha~ing from two to six carbon atoms, and wherein the alkyl group is attached to only one aromatic ring. The aromatic may be a mononuclear or a condensed-ring dinuclear aromatic, or a corresponding nitrogen-containing heterocyclic aromatic.
The process comprises passing a gaseous mixture of molecular oxygen such as air and the alkyl aromatic compound in the presence or absence of a diluent such as steam, carbon dioxide, nitrogen, or an inert hydxocarbon, over a catalyst at a temperature of from about 300 to about 650C, said catalyst having a composition represented by the empirical formula:
Aa Mb M c M d Be Py x wherein A is an alkali metal anA or thallium;
; M is one or more of the elements of nickel, cobalt, copp~r, manganese, magnesium, zinc, calcium, niobium tantalum, strontium or bariumi l is one or more of the elements of iron, chromium, uranium, thorium, vanadium, titanium, lanthanum or the other rare earthsi Mll is one or more of the elements of tin, boxon, lead, germanium, aluminum, tungsten or molybdenum;
B is bismuth, telluxium, arsenic, antimony, cadmium, ox combinations thexeof;
P is phosphorus; and ~ 2 ~
wherein a through ~ have the ~ollowing values:
a = 0 to 20;
b = 0 to 20;
c ~ o to 20;
d = 0 to 4;
e = 0.1 to 20;
y ~ 8 to 16;
x , the number o~ oxygens required to satisfy the valence requirements of the other elements present; and wherein the sum of b ~ c + e is greater than 1.
Preferred in this invention are catalyst compositions wherein a = 0 to 2;
b = 4 to 12;
c = 0.2 to 4;
d = 0 to 2;
: : e = 0.5 to 5; and : y = lO to 14.
Contemplated within the scope of the present ~20 invention are the catalyst compositions represented by the empirical formula:
AaMbM CM dBePyOx ~: wherein A, M, Ml, Mll, B & P have the same compositions as has been hereinbefore designated, and wherein _ through y have the following values;
a = 0 to 5;
~ ~ .
b = 4 to 2:0, c = 0.1 to lO;
~ d = 0 to 4;
: 30 e = 0.1 to 12;
y = 8 to 16;
.
,~
monoolefins or diolefins, the use of -this type of catalyst for the conversion of alkyl aroma-tics to unsaturated side-chain derivatives has heretofore no-t been known.
SVM~IARY OF THE INVENTION
The present invention comprises the process for the oxydehydrogenation of alkyl-substituted aromatic compounds to the corresponding alken~l-substituted aromatics and the novel catalyst compositions thereEor. More specifically the invention comprises the oxydehydrogenation of alkyl aromatic compounds to form the corresponding unsaturated side-chain derivative wherein the alkyl aromatic contains at least one alkyl group ha~ing from two to six carbon atoms, and wherein the alkyl group is attached to only one aromatic ring. The aromatic may be a mononuclear or a condensed-ring dinuclear aromatic, or a corresponding nitrogen-containing heterocyclic aromatic.
The process comprises passing a gaseous mixture of molecular oxygen such as air and the alkyl aromatic compound in the presence or absence of a diluent such as steam, carbon dioxide, nitrogen, or an inert hydxocarbon, over a catalyst at a temperature of from about 300 to about 650C, said catalyst having a composition represented by the empirical formula:
Aa Mb M c M d Be Py x wherein A is an alkali metal anA or thallium;
; M is one or more of the elements of nickel, cobalt, copp~r, manganese, magnesium, zinc, calcium, niobium tantalum, strontium or bariumi l is one or more of the elements of iron, chromium, uranium, thorium, vanadium, titanium, lanthanum or the other rare earthsi Mll is one or more of the elements of tin, boxon, lead, germanium, aluminum, tungsten or molybdenum;
B is bismuth, telluxium, arsenic, antimony, cadmium, ox combinations thexeof;
P is phosphorus; and ~ 2 ~
wherein a through ~ have the ~ollowing values:
a = 0 to 20;
b = 0 to 20;
c ~ o to 20;
d = 0 to 4;
e = 0.1 to 20;
y ~ 8 to 16;
x , the number o~ oxygens required to satisfy the valence requirements of the other elements present; and wherein the sum of b ~ c + e is greater than 1.
Preferred in this invention are catalyst compositions wherein a = 0 to 2;
b = 4 to 12;
c = 0.2 to 4;
d = 0 to 2;
: : e = 0.5 to 5; and : y = lO to 14.
Contemplated within the scope of the present ~20 invention are the catalyst compositions represented by the empirical formula:
AaMbM CM dBePyOx ~: wherein A, M, Ml, Mll, B & P have the same compositions as has been hereinbefore designated, and wherein _ through y have the following values;
a = 0 to 5;
~ ~ .
b = 4 to 2:0, c = 0.1 to lO;
~ d = 0 to 4;
: 30 e = 0.1 to 12;
y = 8 to 16;
.
,~
- 3 -.~' '~ .
. .
V
x , the number of oxygens required to satisfy the valence requirements of the other elements present;
and wherein the sum of 2b + 3 (c I e) is greater than 9 and less than 3y.
Preferred i5 the composition wherein:
a is in the range of O - l;
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;
e is in the range of 0.1 to 4; and the sum of 2b ~ 3 (c + e) is greater than 9 and less than 3y.
The catalysts of this invention are unexpectedly good oxydehydrogenation catalysts. For example in the dehydrogenation of ethyl-benzene to styrene, per pass conversions to styrene in the range of 70~ ard selectivi'ies of up to 90~ are ootained.
; , ,~
~ - 3a -, 7~
The catalysts use~ul in the instant process may be used alone o~ supported on a carri.er. Suitable carrier materials include silica, Alundum ~a trademark for a fused alumina), ti-tania and mullite and par-ticularly phosphate-type carriers such as zirconium phosphate, antimony phosphate, aluminum 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.
These catalysts may be prepared by coprecipitation or by other methods known in the art. Generally they a.re 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 physi-cal 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 250C but below a temperature deleterious to the catalyst.
Among the alkyl aromatics contemplated to be within the scope of the invention are the mono-substituted aromatics such as, for example, ethyl benzene, isopropyl benzene, secondary-butyl benzene; disubstituted aromatics such as ethyl toluene, diethyl benzene, t-butyl ethyl benzene; trisubstituted axomatics such as the ethyl xylenes; condensed ring aromatics such as ethyl naphthalene, methyl ethyl naphthalene, diethyl naphthalene;
and nitrogen-containing heterocyclic aromatics such as ethyl pyridine, methyl ethyl pyridine, ethyl quinollne, ethyl iso-quinoline, and the like. Particularly prefexred re~ctants inthis reaction are ethyl benzene which is readily converted to ~ -4-2~
styre~e, cliethyl benzene which i5 converted to mixtures of ethyl styrene and divinyl. benzene, ethyl pyridine and methyl e-thyl pyridine which are conver-ted to vi.ny.l pyridine and methyl vinyl pyridine, respectively.
The reaction may be conducted in a fixed-bed or a fluidized-bed reactor at temperatures as low as 300C, although optimum temperatures for -the dehydroyenation of the alkyl side-chains are in the range of from about ~00 to 600C, and there is no apparent ad~antage in operating at temperatures much in excess of 650C.
The pressure at ~hich the instant process is usually con-ducted is about atmospheric, al-though pressure of from slightly below atmospheric up -to and above 3 atmospheres are operable.
The apparent contact time employed in the instant pro-cess may be within the range of 0.1 to 50 seconds, and for good selectivity and yields a contact time of from 1 to 15 seconds is preferred.
The molar ratio of oxygen to alkyl aromatic compound fed to the reactor can range from about 0.5 to about 4 moles of oxygen per mole of alkyl aromatic compound, but a preferred range is from about 0.5 to about 1.5 moles of oxygen per mole of aromatic compound. The oxygen employed may be in the form of pure oxygen, ahtough the use of air is preferred for ~urposes of convenience.
Diluents such as steam~ carbon dioxide, nitrogen, inert hydrocarbons or other inert gases may also be used and amount of from 0 to 20 volumes of diluent per volume of alkyl aromatic compound are suitable.
The following examples ser~e to illustrate the feasi~
bility and the improvement obtained in the oxydehydxo~enation process utilizing catalysts of the present invention as compared with catalysts of the prior art.
"
L"i''L~
SPECIFIC_EM DlMENTS
Examples 1 - 26 are representative of the present inven-tion and Comparative Examples A - E are representative of prior art processes.
CATALYST PREPARATIONS
Comparative Examples A Ni2P2O7 Nickel nitrate hexahydrate (168.5g) was dissolved in 500 cc o water, and acidity was adjusted to a pH of 6.4 with a~monia.
Ammonium dihydrogen phosphate (77.7y) was dissolved in 250 cc of water, and the pH adjusted -to 6.8 with ammonia. The ~olutions were mixed and stirred at room temperature for 15 minutes, af-ter adjusting the pH to 6.0 with ammonia, then filtered. The light green precipi-tate was filtered, dried at 110C and heat-treated for 3 hours at 290C, 3 hours at 427C, and 2 hours at 550C to give a tan solid having a surface area of 14 m2/g.
Comparative Example B - Mg2P2O7 Magnesium nitrate hexahydrate (309.2g) was dissolved in 60 cc of water with heating. Ammonium dihydrogen phosphate (138.2g) was dissolved in 100 cc of water with heating. The solutions were mixed and stirred with heating until a white thick paste formed.
The paste was dried at 110C, heat-treated at 290C for 3 hours, 427C for 3 hours, and 550C for 16 hours in air to give a white solid having a surface area of 21.8m2/g.
Comparative Example C - La4 (P2~7) Lanthanum nitrate hexahydrate (trona code 548) (130~) waS dis-solved in 31.5 cc nitric acid and diluted to 250 cc with water.
Ammonium dihydrogen phosphate (57~lg) was dissol~ed in 25Q cc of water and acidified to a pH of 1 with 25 cc nitxic acid. ~n mixing the solutions with stirring, an opalescence foxmed~ ~ftex stirring 22 hours with heating a milky white precipitate formed.
~' .
On heatincJ to bo~ g, the gel thickened. The gel was filtered, dried a-t 110C, heat-treated a-t 290~C (3 hours), 427C (3 hours) and 550 C (16 hours) in air to give a white solid having a sur~ace area of 17 m /g.
Comparative Example D - Co7Fe3P12O41 5 Eerric nitrate nonahydrate (121.2g) and cobalk nitrate hexa-hydrate (203.8 g) were dissolved in 10 ml. of water w~th heating.
Ammonium dihydrogen phosphate (138.0g) was dissolved in 100 ml o~
water with heating. The solutions were mixed and stirred with heating unkil a thick paste formed. The paste was dried at 110C, then heat-treated at 290C (3 hours), 427C (3 hours) and 550C (3 hours) in air to give a blue solid with a surface area of 0.8 m /g.
Comparative Example E - Co2P2O7 Cobalt nitrate hexahydrate (349.1 g) was dissolved in 20 cc o~
water with heating. ~mmonium dihydrogen phosphate (138.0g) was dissolved in 100 cc of water with heating. The solutions were mixed and stirred with heating until a thick purple paste formed.
The paste was dried at 110C, and heat=treated at 290C (3 hours), 427C (3 hours) and 550C (16 hours) to give a blue solid with a surface area of 12.2 m2/g.
Example 1 Bismuth nitrate pentahydrate (194g), 5 cc nitric acid (conc.) and 45 cc of water were warmed to 75C with stirring~ Ammonium di-hydrogen phosphate (69.0g) was added to 50 cc of water and warmed to 75C. The two solutions were mixed, then stirred and heated until a white paste formed. The paste was dried at 110C, heat-treated at 290C (5 hours), 427C (3 hours), and 550C (3 hours) in air. A white solid resulted with a surface area of 0.3 m2~g.
~ -7-Exam~le 2 25~Bi P O - 75%spo~
Bismuth nitrate pentahydrate (l9.~g) was di~olved in 1 cc of nitric acid (conc.) and 9 cc of water, with heating. Ammonium dihydrogen phosphate (6.9g) was dissolved in 25 cc of water. The solutions were combined, an~ 40.4 g boron phosphate were added.
The boron phosphate powder (-200 mesh) was made by mlxing 121g of 85~ ~3PO4 wi-th 62 y H3BO3, warminc3 to 40C for 5 hours, drying the resulting paste at 110C and calcining in air at 300~C ~8 hours). ~fter the BPO4-addltion the paste was dried at 110C
and heat-treated as in Example 1. A white solid having a surface area of 17 m2/g r~sulted.
Example 3 5~ ~ Cul 5siP5O15 5 95% 4 A boron phosphate powder was made from 45 g H3BO3 and 50 cc 85~
H3PO4 by refluxing H3BO3 in Eastman sec-butanol (350 cc), distil-ling off 170 cc alcohol-water azeotrope, then adding H3PO4. ~fter further distillation to remove water, the resultant gel was dried and calcined at 260C. Cupric nitrate hexahydrate (1.60 g) and bismuth nitrate pentahydrate (1.75g) were dissolved in 2.5 cc of nitric acid and 22.3 cc of water, and added to 25 g BPO4 powder~
The paste was dried at 110C and heat-treated as in Example 1.
The resultant light blue solid had a surface area of 63 m2/g.
Example 4 FelOBio 7Pl2o46 Ammonium dihydrogen phosphate (138g) was dissolved in 100 cc of water with heating. Ferric nitrate nonahydrate (404g) and bis-muth nitrate pentahydrate (35.1g) were added, in order, to 10 cc of water and heated. The resultant nitrate solution was added to the phosphate solution. A slurry formed which was heated with ~ -8-z`l~
stirring to remove water~ then dried and calcined as in Example 1.
The light tan solid obtained had a surface area of 3.8m2/g.
Example 5 colOBiO 7P1241 Ammonium dihydrogen phosphate (138g), cobalt nitrate hexahydrate (291.1g) and bismuth nitrate pentahydrate (35.1g) were dissolved and co~bined as in Example 4~ After heat-treatment as in Example 1, the resulting blue solid had a sur~ace area of 5.4 m2/g.
Example 6 C7Fe3Bio.7P12 43 A nitrate solution was made up of cobalt nitrate hexahydrate (203.8g), ferric nitrate nonahydrate (121.2g) and bismuth nitrate pentahydrate (35.1g) with 10 cc of water, and added to an ammo-nium dihydrogen phosphate (138.0g) solution as in Example 4.
After heat-trea-tment as in Example 1, the resulting blue solid had a surface area of 7.7 m2/g.
~ 7 50%Co7Fe3Bi]P12O43 50%BPO4 A nitrate solution was made up of cobalt nitrate hexahydrate (85g), ferric nitrate nonahydrate (50~5g) and bismuth nitrate pentahydrate ~20.2g) with 5 cc water. It was added to an ammo-nium dihydrogen phosphate solution (57.5g) in 100 cc of water to which 53g boron phosphate prepared as in Example 2, was added.
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 m2/g.
Example 8 CO9 .5Feo 5BiP1242 A nitrate solution was made up of cobalt nitrate hexahydrate (276.5g), ferric nitrate nonahydrate (20.2g) and bismuth nitrate ~ _g_ 2~3 pentahydrate (~8.5g). It was added to a solution of ammonium dihydrogen phosphate t138CJ) .in 100 cc of water, dried and heat-treated as in Example 1. The resulting blue solid had a surface area of 12.6 m /g.
Example 9 MggFeBiP12O42 A nitrate solution was made up of magnesium nitrate hexahydrate (115.4g), ferric nitrate nonahydrate (20.2g) and bismuth nitrate pentahydrate (24.3g). It was added to a solution of ammonium dihydrogen phosphate (69g) in 50 cc water, dried and heat-treated as in Example 1. The resulting cream colored solid had a sur-face area of 12.0 m /g.
Example 10 CogcrBipl2o42 .
A nitra-te solution was made up of cobalt nitrate hexahydrate (131g), chromium (III) nitrate nonahydrate (20g), bismuth nitrate pentahydrate (24.3g) and 5 cc of water. It was added to a solu-tion of ammonium dihydrogen phosphate (69g) in 50 cc of water, dried and heat-treated as in Example 1. The resulting blue solid had a surface area of 14.3 m2/g.
Example 11 Co7Lal 5Bi2Pl2o42 .
A nitrate solution was made up of cobalt nitrate hexahydrate (101.9g), lanthanum nitrate hexahydrate (32.8g), bismuth nitrate pentahydrate (48.5g) and 7 cc of concentrated nitric acid. It was added to a solution of ammonium dihydrogen phosphate (69g) in 50 cc of water, dried and heat-treated as in Example 1, except that 550C heat-treatment was extended to 16 hours. The resultant blue solid had a surface area of 19.4 m /g.
, , Z'3 Example 12 Co8LaO 5Bi2Pl2 42 A nitrate solution was made up of cobalt nitrate hexahydrate (116.4g), lanthanum nitrate hexahydrate (10.9g), bismuth nitrate pentahydrate (48.5g), and 3 cc o~ concentrated nitric acid with 10 cc water. It was added to ammonium dihydrogen phosphate (69g) dissolved in 50 cc water, then dried and heat-treated as in Example 11. The resulting blue solid had a surface area o~
7.7 m /g.
Example 13 CogLal oBilP124 A nitrate solution was made up of cobalt nitrate hexahydrate (131 g), lanthanum nitrate hexahydrate (21.7g) and bismuth nitrate pentahydrate (24.3g) with 10 cc of water. It was added to ammonium dihydrogen phosphate (69g) dissolved in 50 cc o~
water. The slurry was dried and heat-treated as in Example 1.
The resulting blue solid had a surface area of 10.5 m2/g.
Exam~le 14 Ko olco9LalBipl2o42 A nitrate solution was prepared as in Example 13. A 10 cc solu-tion o~ potassium acetate (0.5g/100 cc) was added to the mixed nitrates, and the nitrate solution ~as added to an ammonium di-hydrogen phosphate solution as in Example 13. The slurry was dried and heat-treated as in Example 11. The resultant blue solid had a surface area of 19.0 m /g.
Example 15 co7Zn2LalBiP1~042 A nitrate solution was made up o~ cobalt nitrate hexahydrate (101.9g), zinc nitrate hexahydrate (29.8~), lanthanum nitrate hexahydrate (21.7g) and bismuth nitrate pentahydrate (24.3g) in '/'P23 5 cc of water. It was aclded to an ammorlium dihydrogen phosphate (69y) solutlon in 50 cc o~ water. Af-ter stirriny and heatiny, the slurry was dri~d allcl heat-treated as in Example 11. The resultant blue solid had a surface area of 8.6 m2/g.
Example 16 9 _13 45 Ceric ammonium nitrate (27.4g) was dissolved in 5 cc nitric acid (concentrated) and 100 cc of wa-ter. Bismuth nitrate pentahydrate (24.3g) and cobalt nitrate hexahydrate (131g) were added to the ceric solution and dissolved. The resultant solution was added to an ammonium dihydrogen phosphate (74.8g) 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 m2/g.
Example 17 Mg9LalBipl2o42 A nitrate solution was made up of magnesium nitrate hexahydrate (115.4g), lanthanum nitrate hexahydrate (21.7g) and bismuth nitrate pentahydrate (24.3g) in 10 cc of water. It was added to an ammonium dihydrogen phosphate (69g) 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 m2/g.
Exam Cog"Dil BIPl2042 "Didymium" oxide, mixed rare earths (16.5g) (Trona Coxp. Code 422) was dissolved in 25 cc of concentrated nitric acid. Bismuth nitxate pentahydrate (24.3g) was added to the "didymium'l solution which was then added to a solution of ammonium dihydrogen phos-phate (69g) in 50 cc of water. A cobalt nltrate hexahydrate (131g) solution in 10 cc of water was then added. The slurry ~12-' was dried and heat-treated as in Example 1. The re~ultant blue solid had a surface area of 15.4 ~l2/g.
~ le 19 CogEelTepl2o42.5 Tellurium dioxide (8.0g) was dissolved in 10 cc of nitric acid with warming. This solution was added to a nitrate solution consisting of cobalt nitrate hexahydrate (131g) and ferric nitrate nonahydrate (20.2g) and 5 cc of water. The nitrate solu-tion was added to an ammonium dihydrogen phosphate (69y) solution in 50 cc of water. The slurry was dried at 110C and heat-treated as in Example 1, with the final 550C stage being per-formed in the stainless steel reactor. The resultant blue solid had a surface area of 59.9 m /g.
Example 20 cOloSb1 P1241-5 A slurry of Sb2O3 (14.6g) in 10 cc glacial acetic acid and 10 cc water was added to a solution of ammonium dihydrogen phosphate (69.0g) in 50 cc of water. A solution of cobalt nitrate hexa-hydrate (145.5g) in 10 cc of water was added. After heating and stirring, the slurry Was dried and heat-treated as in Example 1.
Example 21 ColOAslpl2o4l~5 ., A slurry of 9.9 g A~2O3 in 10 cc glacial acetic acid and 40 cc water was added to an ammonium dihydrogen phosphate solution (69.0g in 50 cc of water). The reminder o~ ~he preparation was the same as in Example 20.
Example 22 col.Ocd2Pl2ox Cobalt nitrate hexahydrate (145.5g) and cadmi~n nitrate tetra-hydrate (30.8g) were dissolved in 10 cc of water. This solution 1`~/'` -13-' ~13 ~
was added to an ammonium dlh~drogen phosphate solution (69g) in ~0 cc water. The resul-tant slurry was dried and heat-treated as in Example 1.
Example 23 cO8BaFeBipl2o42 A nitrate solution was made up of cobalt nitrate hexahydrate (116.4g), bismuth nitrate pentahydrate (24.3g), ferric nitrate nonahydrate (20.2g) and 50 cc of water. Barium hydroxide octa-hydrate (15.8g) was acidified with 10% solution of con~entrated nitric acid in water to a pH of 1.5, then added to the nitrate.
The resultant slurry was added to an ammonium dihydrogen phos-phate solution (69g) in 50 cc of water. The slurry was dried and heat-treated as in Example 1, to give a solid with a surface area of 10.6 m2/g.
Example 24 CogCeBipl2n45 __ ___ The same catalyst as Example 16 was regenerated by passing air over the catalyst at reaction temperature.
Example 25 MggLaBiP12O42 Same catalyst as Example 17 was regenerated by passing air over the catalyst at reaction temperature.
Example 26 Ko lco9crlBilpl2o42 This catalyst was prepared in the same manner as the catalyst of -Example 10 except for the addition of potassium acetate (0.49g) to the nitrate solution. The surface area was 15.2 m2/g.
rrhe num~er of ox~en atoms in -the catalysts in Examples 1 to 26 were es-timated. ~lowever, the numher of oxygens may actually vary from abou-t 30 to 60, depending upon the reaction conditions.
The above ca-talyst compositions were employed in the oxydehydrogenation of ethyl benzene to styrene, diethyl benzene to divinyl benzene and methyl ethyl pyridine to methyl vinyl pyridine in a fixed~bed reactox comprising a l/2-inch O.D. stain-less steel tube having a ca-talyst volume capacity of 15 cc.
A reac-tant mix-ture of air, aromatic compound and nitroyen were pre-mixed and fed to the reactor in a molar ratio of 5/1/2, respectively. The reactor was maintained at a temperature of 530-532C and at atmospheric pressure. The liquid hourly space velocity of the aromatic feed over the catalyst was 0.23 hours 1, and the contact time was 3.3 seconds. Particle size of the catalyst employed was 20-35 mesh. The percent per pass conver-sion to the desired alkenyl aromatic compound and the selectivity of the reactions reported in Tables 1 to 3 were calculated in the following manner:
Moles of alky~ aromatic converted 20 Percent Converslon ~ x 100 ~ Moles of alkyl aromatlc fed Moles of alkenyl aromatic obtained Percent Slngle Pass Yleld - - x 100 ~ Moles of alkyl aromatlc ~ed Percent Selectivity _ Moles,of alkenyl aromatic obtained x 100 Moles of alkyl aromatic converted TABLE I
OXYDEHYDROGENATION OF ETHYL BENZENE
TO STYRENE
Mole % Mole %
Conversion Per Pass Mole %
Example of Ethyl Yield Selectivity _ No Catalyst Benzene__to Styrene Comp. A N12 P2 7 55 43 79 Comp. B Mg2 P2 7 71 61 86 10 Comp. C La4 (P2O7)3 41 75 Comp. D Co7 Fe3P12O41.5 27 24 88 Comp. E CO2P2O7 47 37 78 1 BigP12O42 14 12.5 85 2 25~Bi8P12o42 75~BPO4 6 86 3 5%Cul.5Bi 515.5 95 51 42 82 BPO4 3 ~
. .
V
x , the number of oxygens required to satisfy the valence requirements of the other elements present;
and wherein the sum of 2b + 3 (c I e) is greater than 9 and less than 3y.
Preferred i5 the composition wherein:
a is in the range of O - l;
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;
e is in the range of 0.1 to 4; and the sum of 2b ~ 3 (c + e) is greater than 9 and less than 3y.
The catalysts of this invention are unexpectedly good oxydehydrogenation catalysts. For example in the dehydrogenation of ethyl-benzene to styrene, per pass conversions to styrene in the range of 70~ ard selectivi'ies of up to 90~ are ootained.
; , ,~
~ - 3a -, 7~
The catalysts use~ul in the instant process may be used alone o~ supported on a carri.er. Suitable carrier materials include silica, Alundum ~a trademark for a fused alumina), ti-tania and mullite and par-ticularly phosphate-type carriers such as zirconium phosphate, antimony phosphate, aluminum 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.
These catalysts may be prepared by coprecipitation or by other methods known in the art. Generally they a.re 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 physi-cal 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 250C but below a temperature deleterious to the catalyst.
Among the alkyl aromatics contemplated to be within the scope of the invention are the mono-substituted aromatics such as, for example, ethyl benzene, isopropyl benzene, secondary-butyl benzene; disubstituted aromatics such as ethyl toluene, diethyl benzene, t-butyl ethyl benzene; trisubstituted axomatics such as the ethyl xylenes; condensed ring aromatics such as ethyl naphthalene, methyl ethyl naphthalene, diethyl naphthalene;
and nitrogen-containing heterocyclic aromatics such as ethyl pyridine, methyl ethyl pyridine, ethyl quinollne, ethyl iso-quinoline, and the like. Particularly prefexred re~ctants inthis reaction are ethyl benzene which is readily converted to ~ -4-2~
styre~e, cliethyl benzene which i5 converted to mixtures of ethyl styrene and divinyl. benzene, ethyl pyridine and methyl e-thyl pyridine which are conver-ted to vi.ny.l pyridine and methyl vinyl pyridine, respectively.
The reaction may be conducted in a fixed-bed or a fluidized-bed reactor at temperatures as low as 300C, although optimum temperatures for -the dehydroyenation of the alkyl side-chains are in the range of from about ~00 to 600C, and there is no apparent ad~antage in operating at temperatures much in excess of 650C.
The pressure at ~hich the instant process is usually con-ducted is about atmospheric, al-though pressure of from slightly below atmospheric up -to and above 3 atmospheres are operable.
The apparent contact time employed in the instant pro-cess may be within the range of 0.1 to 50 seconds, and for good selectivity and yields a contact time of from 1 to 15 seconds is preferred.
The molar ratio of oxygen to alkyl aromatic compound fed to the reactor can range from about 0.5 to about 4 moles of oxygen per mole of alkyl aromatic compound, but a preferred range is from about 0.5 to about 1.5 moles of oxygen per mole of aromatic compound. The oxygen employed may be in the form of pure oxygen, ahtough the use of air is preferred for ~urposes of convenience.
Diluents such as steam~ carbon dioxide, nitrogen, inert hydrocarbons or other inert gases may also be used and amount of from 0 to 20 volumes of diluent per volume of alkyl aromatic compound are suitable.
The following examples ser~e to illustrate the feasi~
bility and the improvement obtained in the oxydehydxo~enation process utilizing catalysts of the present invention as compared with catalysts of the prior art.
"
L"i''L~
SPECIFIC_EM DlMENTS
Examples 1 - 26 are representative of the present inven-tion and Comparative Examples A - E are representative of prior art processes.
CATALYST PREPARATIONS
Comparative Examples A Ni2P2O7 Nickel nitrate hexahydrate (168.5g) was dissolved in 500 cc o water, and acidity was adjusted to a pH of 6.4 with a~monia.
Ammonium dihydrogen phosphate (77.7y) was dissolved in 250 cc of water, and the pH adjusted -to 6.8 with ammonia. The ~olutions were mixed and stirred at room temperature for 15 minutes, af-ter adjusting the pH to 6.0 with ammonia, then filtered. The light green precipi-tate was filtered, dried at 110C and heat-treated for 3 hours at 290C, 3 hours at 427C, and 2 hours at 550C to give a tan solid having a surface area of 14 m2/g.
Comparative Example B - Mg2P2O7 Magnesium nitrate hexahydrate (309.2g) was dissolved in 60 cc of water with heating. Ammonium dihydrogen phosphate (138.2g) was dissolved in 100 cc of water with heating. The solutions were mixed and stirred with heating until a white thick paste formed.
The paste was dried at 110C, heat-treated at 290C for 3 hours, 427C for 3 hours, and 550C for 16 hours in air to give a white solid having a surface area of 21.8m2/g.
Comparative Example C - La4 (P2~7) Lanthanum nitrate hexahydrate (trona code 548) (130~) waS dis-solved in 31.5 cc nitric acid and diluted to 250 cc with water.
Ammonium dihydrogen phosphate (57~lg) was dissol~ed in 25Q cc of water and acidified to a pH of 1 with 25 cc nitxic acid. ~n mixing the solutions with stirring, an opalescence foxmed~ ~ftex stirring 22 hours with heating a milky white precipitate formed.
~' .
On heatincJ to bo~ g, the gel thickened. The gel was filtered, dried a-t 110C, heat-treated a-t 290~C (3 hours), 427C (3 hours) and 550 C (16 hours) in air to give a white solid having a sur~ace area of 17 m /g.
Comparative Example D - Co7Fe3P12O41 5 Eerric nitrate nonahydrate (121.2g) and cobalk nitrate hexa-hydrate (203.8 g) were dissolved in 10 ml. of water w~th heating.
Ammonium dihydrogen phosphate (138.0g) was dissolved in 100 ml o~
water with heating. The solutions were mixed and stirred with heating unkil a thick paste formed. The paste was dried at 110C, then heat-treated at 290C (3 hours), 427C (3 hours) and 550C (3 hours) in air to give a blue solid with a surface area of 0.8 m /g.
Comparative Example E - Co2P2O7 Cobalt nitrate hexahydrate (349.1 g) was dissolved in 20 cc o~
water with heating. ~mmonium dihydrogen phosphate (138.0g) was dissolved in 100 cc of water with heating. The solutions were mixed and stirred with heating until a thick purple paste formed.
The paste was dried at 110C, and heat=treated at 290C (3 hours), 427C (3 hours) and 550C (16 hours) to give a blue solid with a surface area of 12.2 m2/g.
Example 1 Bismuth nitrate pentahydrate (194g), 5 cc nitric acid (conc.) and 45 cc of water were warmed to 75C with stirring~ Ammonium di-hydrogen phosphate (69.0g) was added to 50 cc of water and warmed to 75C. The two solutions were mixed, then stirred and heated until a white paste formed. The paste was dried at 110C, heat-treated at 290C (5 hours), 427C (3 hours), and 550C (3 hours) in air. A white solid resulted with a surface area of 0.3 m2~g.
~ -7-Exam~le 2 25~Bi P O - 75%spo~
Bismuth nitrate pentahydrate (l9.~g) was di~olved in 1 cc of nitric acid (conc.) and 9 cc of water, with heating. Ammonium dihydrogen phosphate (6.9g) was dissolved in 25 cc of water. The solutions were combined, an~ 40.4 g boron phosphate were added.
The boron phosphate powder (-200 mesh) was made by mlxing 121g of 85~ ~3PO4 wi-th 62 y H3BO3, warminc3 to 40C for 5 hours, drying the resulting paste at 110C and calcining in air at 300~C ~8 hours). ~fter the BPO4-addltion the paste was dried at 110C
and heat-treated as in Example 1. A white solid having a surface area of 17 m2/g r~sulted.
Example 3 5~ ~ Cul 5siP5O15 5 95% 4 A boron phosphate powder was made from 45 g H3BO3 and 50 cc 85~
H3PO4 by refluxing H3BO3 in Eastman sec-butanol (350 cc), distil-ling off 170 cc alcohol-water azeotrope, then adding H3PO4. ~fter further distillation to remove water, the resultant gel was dried and calcined at 260C. Cupric nitrate hexahydrate (1.60 g) and bismuth nitrate pentahydrate (1.75g) were dissolved in 2.5 cc of nitric acid and 22.3 cc of water, and added to 25 g BPO4 powder~
The paste was dried at 110C and heat-treated as in Example 1.
The resultant light blue solid had a surface area of 63 m2/g.
Example 4 FelOBio 7Pl2o46 Ammonium dihydrogen phosphate (138g) was dissolved in 100 cc of water with heating. Ferric nitrate nonahydrate (404g) and bis-muth nitrate pentahydrate (35.1g) were added, in order, to 10 cc of water and heated. The resultant nitrate solution was added to the phosphate solution. A slurry formed which was heated with ~ -8-z`l~
stirring to remove water~ then dried and calcined as in Example 1.
The light tan solid obtained had a surface area of 3.8m2/g.
Example 5 colOBiO 7P1241 Ammonium dihydrogen phosphate (138g), cobalt nitrate hexahydrate (291.1g) and bismuth nitrate pentahydrate (35.1g) were dissolved and co~bined as in Example 4~ After heat-treatment as in Example 1, the resulting blue solid had a sur~ace area of 5.4 m2/g.
Example 6 C7Fe3Bio.7P12 43 A nitrate solution was made up of cobalt nitrate hexahydrate (203.8g), ferric nitrate nonahydrate (121.2g) and bismuth nitrate pentahydrate (35.1g) with 10 cc of water, and added to an ammo-nium dihydrogen phosphate (138.0g) solution as in Example 4.
After heat-trea-tment as in Example 1, the resulting blue solid had a surface area of 7.7 m2/g.
~ 7 50%Co7Fe3Bi]P12O43 50%BPO4 A nitrate solution was made up of cobalt nitrate hexahydrate (85g), ferric nitrate nonahydrate (50~5g) and bismuth nitrate pentahydrate ~20.2g) with 5 cc water. It was added to an ammo-nium dihydrogen phosphate solution (57.5g) in 100 cc of water to which 53g boron phosphate prepared as in Example 2, was added.
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 m2/g.
Example 8 CO9 .5Feo 5BiP1242 A nitrate solution was made up of cobalt nitrate hexahydrate (276.5g), ferric nitrate nonahydrate (20.2g) and bismuth nitrate ~ _g_ 2~3 pentahydrate (~8.5g). It was added to a solution of ammonium dihydrogen phosphate t138CJ) .in 100 cc of water, dried and heat-treated as in Example 1. The resulting blue solid had a surface area of 12.6 m /g.
Example 9 MggFeBiP12O42 A nitrate solution was made up of magnesium nitrate hexahydrate (115.4g), ferric nitrate nonahydrate (20.2g) and bismuth nitrate pentahydrate (24.3g). It was added to a solution of ammonium dihydrogen phosphate (69g) in 50 cc water, dried and heat-treated as in Example 1. The resulting cream colored solid had a sur-face area of 12.0 m /g.
Example 10 CogcrBipl2o42 .
A nitra-te solution was made up of cobalt nitrate hexahydrate (131g), chromium (III) nitrate nonahydrate (20g), bismuth nitrate pentahydrate (24.3g) and 5 cc of water. It was added to a solu-tion of ammonium dihydrogen phosphate (69g) in 50 cc of water, dried and heat-treated as in Example 1. The resulting blue solid had a surface area of 14.3 m2/g.
Example 11 Co7Lal 5Bi2Pl2o42 .
A nitrate solution was made up of cobalt nitrate hexahydrate (101.9g), lanthanum nitrate hexahydrate (32.8g), bismuth nitrate pentahydrate (48.5g) and 7 cc of concentrated nitric acid. It was added to a solution of ammonium dihydrogen phosphate (69g) in 50 cc of water, dried and heat-treated as in Example 1, except that 550C heat-treatment was extended to 16 hours. The resultant blue solid had a surface area of 19.4 m /g.
, , Z'3 Example 12 Co8LaO 5Bi2Pl2 42 A nitrate solution was made up of cobalt nitrate hexahydrate (116.4g), lanthanum nitrate hexahydrate (10.9g), bismuth nitrate pentahydrate (48.5g), and 3 cc o~ concentrated nitric acid with 10 cc water. It was added to ammonium dihydrogen phosphate (69g) dissolved in 50 cc water, then dried and heat-treated as in Example 11. The resulting blue solid had a surface area o~
7.7 m /g.
Example 13 CogLal oBilP124 A nitrate solution was made up of cobalt nitrate hexahydrate (131 g), lanthanum nitrate hexahydrate (21.7g) and bismuth nitrate pentahydrate (24.3g) with 10 cc of water. It was added to ammonium dihydrogen phosphate (69g) dissolved in 50 cc o~
water. The slurry was dried and heat-treated as in Example 1.
The resulting blue solid had a surface area of 10.5 m2/g.
Exam~le 14 Ko olco9LalBipl2o42 A nitrate solution was prepared as in Example 13. A 10 cc solu-tion o~ potassium acetate (0.5g/100 cc) was added to the mixed nitrates, and the nitrate solution ~as added to an ammonium di-hydrogen phosphate solution as in Example 13. The slurry was dried and heat-treated as in Example 11. The resultant blue solid had a surface area of 19.0 m /g.
Example 15 co7Zn2LalBiP1~042 A nitrate solution was made up o~ cobalt nitrate hexahydrate (101.9g), zinc nitrate hexahydrate (29.8~), lanthanum nitrate hexahydrate (21.7g) and bismuth nitrate pentahydrate (24.3g) in '/'P23 5 cc of water. It was aclded to an ammorlium dihydrogen phosphate (69y) solutlon in 50 cc o~ water. Af-ter stirriny and heatiny, the slurry was dri~d allcl heat-treated as in Example 11. The resultant blue solid had a surface area of 8.6 m2/g.
Example 16 9 _13 45 Ceric ammonium nitrate (27.4g) was dissolved in 5 cc nitric acid (concentrated) and 100 cc of wa-ter. Bismuth nitrate pentahydrate (24.3g) and cobalt nitrate hexahydrate (131g) were added to the ceric solution and dissolved. The resultant solution was added to an ammonium dihydrogen phosphate (74.8g) 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 m2/g.
Example 17 Mg9LalBipl2o42 A nitrate solution was made up of magnesium nitrate hexahydrate (115.4g), lanthanum nitrate hexahydrate (21.7g) and bismuth nitrate pentahydrate (24.3g) in 10 cc of water. It was added to an ammonium dihydrogen phosphate (69g) 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 m2/g.
Exam Cog"Dil BIPl2042 "Didymium" oxide, mixed rare earths (16.5g) (Trona Coxp. Code 422) was dissolved in 25 cc of concentrated nitric acid. Bismuth nitxate pentahydrate (24.3g) was added to the "didymium'l solution which was then added to a solution of ammonium dihydrogen phos-phate (69g) in 50 cc of water. A cobalt nltrate hexahydrate (131g) solution in 10 cc of water was then added. The slurry ~12-' was dried and heat-treated as in Example 1. The re~ultant blue solid had a surface area of 15.4 ~l2/g.
~ le 19 CogEelTepl2o42.5 Tellurium dioxide (8.0g) was dissolved in 10 cc of nitric acid with warming. This solution was added to a nitrate solution consisting of cobalt nitrate hexahydrate (131g) and ferric nitrate nonahydrate (20.2g) and 5 cc of water. The nitrate solu-tion was added to an ammonium dihydrogen phosphate (69y) solution in 50 cc of water. The slurry was dried at 110C and heat-treated as in Example 1, with the final 550C stage being per-formed in the stainless steel reactor. The resultant blue solid had a surface area of 59.9 m /g.
Example 20 cOloSb1 P1241-5 A slurry of Sb2O3 (14.6g) in 10 cc glacial acetic acid and 10 cc water was added to a solution of ammonium dihydrogen phosphate (69.0g) in 50 cc of water. A solution of cobalt nitrate hexa-hydrate (145.5g) in 10 cc of water was added. After heating and stirring, the slurry Was dried and heat-treated as in Example 1.
Example 21 ColOAslpl2o4l~5 ., A slurry of 9.9 g A~2O3 in 10 cc glacial acetic acid and 40 cc water was added to an ammonium dihydrogen phosphate solution (69.0g in 50 cc of water). The reminder o~ ~he preparation was the same as in Example 20.
Example 22 col.Ocd2Pl2ox Cobalt nitrate hexahydrate (145.5g) and cadmi~n nitrate tetra-hydrate (30.8g) were dissolved in 10 cc of water. This solution 1`~/'` -13-' ~13 ~
was added to an ammonium dlh~drogen phosphate solution (69g) in ~0 cc water. The resul-tant slurry was dried and heat-treated as in Example 1.
Example 23 cO8BaFeBipl2o42 A nitrate solution was made up of cobalt nitrate hexahydrate (116.4g), bismuth nitrate pentahydrate (24.3g), ferric nitrate nonahydrate (20.2g) and 50 cc of water. Barium hydroxide octa-hydrate (15.8g) was acidified with 10% solution of con~entrated nitric acid in water to a pH of 1.5, then added to the nitrate.
The resultant slurry was added to an ammonium dihydrogen phos-phate solution (69g) in 50 cc of water. The slurry was dried and heat-treated as in Example 1, to give a solid with a surface area of 10.6 m2/g.
Example 24 CogCeBipl2n45 __ ___ The same catalyst as Example 16 was regenerated by passing air over the catalyst at reaction temperature.
Example 25 MggLaBiP12O42 Same catalyst as Example 17 was regenerated by passing air over the catalyst at reaction temperature.
Example 26 Ko lco9crlBilpl2o42 This catalyst was prepared in the same manner as the catalyst of -Example 10 except for the addition of potassium acetate (0.49g) to the nitrate solution. The surface area was 15.2 m2/g.
rrhe num~er of ox~en atoms in -the catalysts in Examples 1 to 26 were es-timated. ~lowever, the numher of oxygens may actually vary from abou-t 30 to 60, depending upon the reaction conditions.
The above ca-talyst compositions were employed in the oxydehydrogenation of ethyl benzene to styrene, diethyl benzene to divinyl benzene and methyl ethyl pyridine to methyl vinyl pyridine in a fixed~bed reactox comprising a l/2-inch O.D. stain-less steel tube having a ca-talyst volume capacity of 15 cc.
A reac-tant mix-ture of air, aromatic compound and nitroyen were pre-mixed and fed to the reactor in a molar ratio of 5/1/2, respectively. The reactor was maintained at a temperature of 530-532C and at atmospheric pressure. The liquid hourly space velocity of the aromatic feed over the catalyst was 0.23 hours 1, and the contact time was 3.3 seconds. Particle size of the catalyst employed was 20-35 mesh. The percent per pass conver-sion to the desired alkenyl aromatic compound and the selectivity of the reactions reported in Tables 1 to 3 were calculated in the following manner:
Moles of alky~ aromatic converted 20 Percent Converslon ~ x 100 ~ Moles of alkyl aromatlc fed Moles of alkenyl aromatic obtained Percent Slngle Pass Yleld - - x 100 ~ Moles of alkyl aromatlc ~ed Percent Selectivity _ Moles,of alkenyl aromatic obtained x 100 Moles of alkyl aromatic converted TABLE I
OXYDEHYDROGENATION OF ETHYL BENZENE
TO STYRENE
Mole % Mole %
Conversion Per Pass Mole %
Example of Ethyl Yield Selectivity _ No Catalyst Benzene__to Styrene Comp. A N12 P2 7 55 43 79 Comp. B Mg2 P2 7 71 61 86 10 Comp. C La4 (P2O7)3 41 75 Comp. D Co7 Fe3P12O41.5 27 24 88 Comp. E CO2P2O7 47 37 78 1 BigP12O42 14 12.5 85 2 25~Bi8P12o42 75~BPO4 6 86 3 5%Cul.5Bi 515.5 95 51 42 82 BPO4 3 ~
4 FeloBio.7pl2o46 28 ~ 72 Col0Bio 7Pl2o4l 48 86 6 Co7Fe3Bio.7pl2o42~5 85 7 50~c7Fe3BilPl2 43 62 53 85 20 8 Cog 5Fe0 sBiP12424 75 64 87 g MggFelBipl2o42 65 55 84 CogCrBiP12O42 74 65 89 11 Co7Lal sBi2P12O42 65 87 12 Co8La0 5Bi2Pl2o42 69 60 87 13 CogLaBiP12O42 79 71 90 14 Ko olco9LalBipl2o42 Co7Zn2LalBipl2o42 66 90 16 CogCeBIP13O45 77 69 90 17 MggLalBipl2o42 78 70 90 3018 CogllDi lBiP12O42 63 51 82 19 CogFelTepl2o42.5 60 50 83 Col0SblP12O41 5 58 46 80 21 Col0AslP12O41.5 52 43 83 22 Col0cd2Pl2O42 42 87 ~16-'L2~3 ~O~ ~ ~ ~ N
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Claims (31)
1. A process for the dehydrogenation of an alkyl aro-matic compound to the corresponding alkenyl aromatic wherein said alkyl aromatic contains at least one alkyl group of from 2 to 6 carbon atoms which is attached to a single aromatic ring, and wherein the aromatic group is selected from the group con-sisting of mononuclear aromatics condensed-ring dinuclear aro-matics, pyridine, quinoline and isoquinoline, the process com-prising passing a gaseous mixture of the alkyl aromatic, molecu-lar oxygen and optionally a diluent gas over a catalyst at a temperature of from about 300 to 650°C, said catalyst having the composition represented by the following empirical formula:
AaMbMlcM11dBePyOx 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;
M is one or more of the elements or iron, chromi.um, uranium, thorium, vanadium, titanium, lanthanum or the other rare earths;
M11 is one or more of the elements of tin, boron, lead, germanium, aluminum, tungsten or molybdenum;
B is bismuth, tellurium, arsenic, antimony, or combinations thereof;
P is phosphorus; and wherein a through y have the following values:
a = 0 to 20;
b = 0 to 20;
c = 0 to 20;
d = 0 to 4;
e = 0.1 to 20;
y = 8 to 16;
x = the number of oxygens required to satisfy the valence requirements of the other elements present; and wherein the sum of b + c + e is greater than 1.
AaMbMlcM11dBePyOx 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;
M is one or more of the elements or iron, chromi.um, uranium, thorium, vanadium, titanium, lanthanum or the other rare earths;
M11 is one or more of the elements of tin, boron, lead, germanium, aluminum, tungsten or molybdenum;
B is bismuth, tellurium, arsenic, antimony, or combinations thereof;
P is phosphorus; and wherein a through y have the following values:
a = 0 to 20;
b = 0 to 20;
c = 0 to 20;
d = 0 to 4;
e = 0.1 to 20;
y = 8 to 16;
x = the number of oxygens required to satisfy the valence requirements of the other elements present; and wherein the sum of b + c + e is greater than 1.
2. The process in claim 1 wherein in the catalyst composition a = 0 to 2;
b = 4 to 12;
c = 0.2 to 4;
d = 0 to 2;
e = 0.5 to 5; and y = 10 to 14.
b = 4 to 12;
c = 0.2 to 4;
d = 0 to 2;
e = 0.5 to 5; and y = 10 to 14.
3. The process in claim 1 wherein ethyl benzene is converted to styrene.
4. The process in claim 1 wherein diethyl benzene is converted to divinyl benzene.
5. The process in claim 1 wherein ethyl toluene is converted to vinyl toluene.
6. The process in claim 1 wherein methyl ethyl pyridine is converted to methyl vinyl pyridine,
7. The process in claim 1 wherein ethyl pyridine is converted to vinyl pyridine,
8. The process in claim 1 wherein the molar ratio of oxygen to alkyl aromatic is in the range of from about 0.5 to 4.
9. The process in claim 8 wherein the reaction temperature is in the range of from about 400° to 600°C.
10. The process in claim 9 wherein the apparent con-tact time is from about 1 to 15 seconds.
11. The process in claim 10 wherein M in the catalyst composition is cobalt, M1 is lanthanum, and B is bismuth.
12. The process in claim 10 wherein M in the catalyst composition is cobalt, M1 is iron and B is tellurium.
13. The process in claim 10 wherein M in the catalyst composition is magnesium, M1 is lanthanum and B is bismuth,
14. The process in claim 1 wherein the catalyst composi-tion a = 0 - 5;
b = 4 - 20;
c = 0.1 - 10;
d = 0 - 4;
e = 0.1 - 12; and y = 8 - 16.
b = 4 - 20;
c = 0.1 - 10;
d = 0 - 4;
e = 0.1 - 12; and y = 8 - 16.
15. The process of claim 1 wherein M is one or more of the elements of nickel, copper, manganese, magnesium, zinc, calcium, niobium, tantalum, strontium, or barium.
16. The process of claim 15 wherein B is tellurium, arsenic, antimony, or combinations thereof.
17. The process of claim 1 wherein a is greater than zero.
18. The process of claim 17 wherein b is greater than zero.
19. The process of claim 17 wherein c is greater than zero.
20. The process of claim 17 wherein d is greater than zero.
21. The process of claim 1 wherein b is greater than zero.
22. The process of claim 21 wherein c is greater than zero.
23. The process of claim 21 wherein d is greater than zero.
24. The process of claim 1 wherein c is greater than zero.
25. The process in claim 24 wherein d is greater than zero.
26. The process of claim 24 wherein the catalyst contains bismuth.
27. The process of claim 24 wherein the catalyst contains at least one of cobalt, magnesium and zinc.
28. The process of claim 24 wherein M1 is selected from the group consisting of iron, chromium and lanthanum.
29. The process of claim 1 wherein d is greater than zero.
30. The process of claim 29 wherein M11 is boron.
31. The process of claim 29 wherein the catalyst con-tains bismuth.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79263777A | 1977-05-02 | 1977-05-02 | |
| US792,637 | 1991-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117120A true CA1117120A (en) | 1982-01-26 |
Family
ID=25157563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000300424A Expired CA1117120A (en) | 1977-05-02 | 1978-04-04 | Oxydehydrogenation process for alkylaromatics and catalyst therefor |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS53135940A (en) |
| BE (1) | BE866403A (en) |
| BR (1) | BR7802706A (en) |
| CA (1) | CA1117120A (en) |
| CS (1) | CS199528B2 (en) |
| DD (1) | DD135897A5 (en) |
| DE (1) | DE2816946A1 (en) |
| EG (1) | EG13250A (en) |
| ES (2) | ES469145A1 (en) |
| FR (1) | FR2389590A1 (en) |
| GB (2) | GB1598509A (en) |
| IN (1) | IN148087B (en) |
| IT (1) | IT1094807B (en) |
| NL (1) | NL7804618A (en) |
| NO (1) | NO781508L (en) |
| PT (1) | PT67944B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2849715A1 (en) * | 1978-11-16 | 1980-05-29 | Hoechst Ag | CARRIER CATALYST AND METHOD FOR THE PRODUCTION THEREOF |
| DE2849637A1 (en) * | 1978-11-16 | 1980-05-29 | Hoechst Ag | CARRIER CATALYST AND METHOD FOR THE PRODUCTION THEREOF |
| ATE7861T1 (en) * | 1980-07-18 | 1984-06-15 | Mitsubishi Chemical Industries Limited | CATALYTIC COMPOSITION, PROCESS FOR ITS PREPARATION AND ITS USE. |
| US4777313A (en) * | 1983-08-12 | 1988-10-11 | Atlantic Richfield Company | Boron-promoted reducible metal oxides and methods of their use |
| JPH0764763B2 (en) * | 1987-03-05 | 1995-07-12 | 東ソー株式会社 | Method for producing methylstyrene |
| DE19530454A1 (en) * | 1995-08-18 | 1997-02-20 | Manfred Prof Dr Baerns | Economical continuous oxidative dehydrogenation of propane to propene in high yield |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3641180A (en) * | 1969-12-29 | 1972-02-08 | Dow Chemical Co | Method of dehydrogenating compounds |
| US3925499A (en) * | 1971-11-01 | 1975-12-09 | Phillips Petroleum Co | Oxidative dehydrogenation using group IA or IIA metal Sn/P/O catalyst |
| JPS5146299B2 (en) * | 1972-08-15 | 1976-12-08 | ||
| US3935126A (en) * | 1974-05-28 | 1976-01-27 | The Dow Chemical Company | Catalyst and method of oxydehydrogenation of alkyl aromatic compounds |
| US3957897A (en) * | 1974-05-28 | 1976-05-18 | The Dow Chemical Company | Method of oxydehydrogenation of alkyl aromatic compounds |
-
1978
- 1978-04-04 CA CA000300424A patent/CA1117120A/en not_active Expired
- 1978-04-13 IN IN270/DEL/78A patent/IN148087B/en unknown
- 1978-04-19 DE DE19782816946 patent/DE2816946A1/en not_active Withdrawn
- 1978-04-20 JP JP4717478A patent/JPS53135940A/en active Granted
- 1978-04-24 PT PT67944A patent/PT67944B/en unknown
- 1978-04-25 FR FR7812199A patent/FR2389590A1/fr not_active Withdrawn
- 1978-04-26 ES ES469145A patent/ES469145A1/en not_active Expired
- 1978-04-26 BE BE187127A patent/BE866403A/en unknown
- 1978-04-28 BR BR7802706A patent/BR7802706A/en unknown
- 1978-04-28 DD DD78205104A patent/DD135897A5/en unknown
- 1978-04-28 NL NL7804618A patent/NL7804618A/en not_active Application Discontinuation
- 1978-04-28 NO NO781508A patent/NO781508L/en unknown
- 1978-04-28 IT IT22880/78A patent/IT1094807B/en active
- 1978-04-29 EG EG280/78A patent/EG13250A/en active
- 1978-05-02 CS CS782795A patent/CS199528B2/en unknown
- 1978-05-02 GB GB17230/78A patent/GB1598509A/en not_active Expired
- 1978-05-02 GB GB38969/79A patent/GB1598510A/en not_active Expired
- 1978-06-19 ES ES470908A patent/ES470908A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO781508L (en) | 1978-11-03 |
| ES470908A1 (en) | 1979-02-01 |
| IT1094807B (en) | 1985-08-10 |
| PT67944A (en) | 1978-05-01 |
| PT67944B (en) | 1979-11-14 |
| GB1598509A (en) | 1981-09-23 |
| IN148087B (en) | 1980-10-18 |
| JPS53135940A (en) | 1978-11-28 |
| IT7822880A0 (en) | 1978-04-28 |
| DE2816946A1 (en) | 1978-11-09 |
| BE866403A (en) | 1978-08-14 |
| NL7804618A (en) | 1978-11-06 |
| EG13250A (en) | 1981-03-31 |
| FR2389590A1 (en) | 1978-12-01 |
| DD135897A5 (en) | 1979-06-06 |
| ES469145A1 (en) | 1978-11-16 |
| JPH0154095B2 (en) | 1989-11-16 |
| BR7802706A (en) | 1979-01-23 |
| CS199528B2 (en) | 1980-07-31 |
| GB1598510A (en) | 1981-09-23 |
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