GB1598509A - Oxydehydrogenation process for alkylaromatics - Google Patents
Oxydehydrogenation process for alkylaromatics Download PDFInfo
- Publication number
- GB1598509A GB1598509A GB17230/78A GB1723078A GB1598509A GB 1598509 A GB1598509 A GB 1598509A GB 17230/78 A GB17230/78 A GB 17230/78A GB 1723078 A GB1723078 A GB 1723078A GB 1598509 A GB1598509 A GB 1598509A
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- United Kingdom
- Prior art keywords
- converted
- alkylaromatic
- catalyst
- elements
- aromatics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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)
Description
(54) OXYDEHYDROGENATION PROCESS FOR ALKYLAROMATICS
(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:
This invention relates to an improved process for the catalytic dehydrogenation of alkyl-substituted aromatic compounds to the corresponding alkenyl-substituted 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 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.
A number of catalysts and catalytic systems have been disclosed utilizing various phosphates and pyrophosphates for the conversion of alkylaromatics 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, respectively, as oxydehydrogenation catalysts for alkyl aromatics. However catalyst compositions containing arsenic, antimony, bismuth rellunum or cadmium phosphates which have demonstrated outstanding activity for the dehydrogenation reaction of the present invention have heretofore not been disclosed. Although U.S. 3,873,633 utilizes a cobalt-bismuth-phosphorus-oxygen composition as a catalyst for the oxydehydrogenation of paraffinic hydrocarbons to monoolefins or diolefins, the use of this type of catalyst for the conversion of alkylaromatics to unsaturated side-chain derivatives has heretofore not been known.
The present invention comprises a process for the catalytic oxydehydrogenation of alkyl-substituted aromatic compounds to the corresponding alkenyl-substituted aromatics.
More specifically the invention comprises the oxydehydrogenation of alkylaromatic compounds to form the corresponding unsaturated side-chain derivative wherein the alkylaromatic contains at least one alkyl group having 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 nitrogencontaining heterocyclic aromatic.
The invention therefore provides a process for the dehydrogenation of an alkylaromatic compound to the corresponding alkenylaromatic wherein said alkylaromatic 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 consisting of mononuclear, condensed-ring dinuclear aromatics and the corresponding nitrogen-containing heterocyclic aromatics, which comprises passing a gaseous mixture of the alkylaromatic, molecular oxygen and optionally a diluent gas over a catalyst at a temperature of from 300 to 6500C, in which the catalyst has a composition represented by the following empirical formula: AaMbMIcMlldXepyOx 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;
M1 is one or more of the elements of iron, chromium, uranium, thorium,
vanadium, titanium, lanthanum or the other rare earths; M11 is one or more of the elements of tin, boron, lead, germanium, aluminium,
tungsten or molybdenum;
X is tellurium, arsenic, antimony, cadmium or combinations thereof;
P is phosphorus; and wherein a to y have the following values:
a = 0 to 20;
b = 0 to 20;
c = 0 to 20;
d = O 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.
Preferred catalyst compositions in the process of the invention are those in which
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.
Catalyst compositions represented by the empirical formula: AaMbMICMl ldXePyOx in which A, M, X and P are as defined above,
M' represents one or more of the elements of iron, uranium, thorium, vanadium, titanium, lanthanum, or the other rare earths;
M" is one or more of the elements of tin, lead, germanium, aluminium or tungsten, and a to y have the following values;
a = 0 to 5;
b = 4 to 20;
c = 0.1 to 10;
d = 0 to 4;
e = 0.1 to 12;
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 2b + 3 (c + e) is greater than 9
and less than 3y, are particularly preferred for use in the process of the present
invention, and are described and claimed in our co-pending application No.
7938969 (Serial No. 1598510).
The catalysts used according to this invention are unexpectedly good oxydehydrogenation catalysts. For example in the dehydrogenation of ethylbenzene 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 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 with the carrier by coating, impregnation and coprecipitation.
The catalysts may be prepared by coprecipitation or by other methods known in the art.
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 but below a temperature deleterious to the catalyst.
Alkylaromatics which may be oxydehydrogenated acording to the process of the invention include the mono-substituted aromatics such as, for example, ethylbenzene, isopropylbenzene, secondary-butylbenzene; disubstituted aromatics such as ethyltoluene, diethylbenzene, t-butyl-ethyl-benzene; trisubstituted aromatics such as the ethylxylenes; condensed ring aromatics such as ethylnaphthalene, methyl ethylnaphthalene, diethylnaphthalene; and nitrogen-containing heterocyclic aromatics such as ethylpyridine, methylethylpyridine, ethylquinoline and ethylisoquinoline. Particularly preferred alkylaromatics are ethylbenzene which is readily converted to styrene, diethylbenzene which is converted to mixtures of ethylstyrene and divinylbenzene, ethylpyridine and methylethylpyridine which are converted to vinylpyridine and methylvinylpyridine, respectively.
The reaction may be conducted in a fixed-bed or a fluidized-bed reactor at temperatures as low as 300"C, although optimum temperatures for the dehydrogenation of the alkyl side-chains are in the range of from 400" to 6000C, and there is no apparent advantage in operating at temperatures much in excess of 650"C.
The pressure at which the process is usually conducted is approximately atmospheric, although pressure of from slightly below atmospheric up to and above 3 atmospheres may be used.
The apparent contact time employed in the process of the invention 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 alkylaromatic compound fed to the reactor can vary from 0.5 to 5 moles of oxygen per mole of alkyl aromatic compound, but a preferred range is from 0.5 to 1.5 moles of oxygen per mole of aromatic compound. The oxygen employed may be in the form of pure oxygen, although the use of air is preferred for purposes 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 alkylaromatic compound are suitable.
The following examples serve to illustrate the feasibility and the improvement obtained in the oxydehydrogenation process utilizing catalysts used according to the present invention as compared with catalysts of the prior art.
SPECIFIC EMBODIMENTS
Examples 1-4 are representative of the present invention and Comparative Examples A - E are representative of prior art processes.
CATALYST PREPARATIONS
Comparative Example A Ni2P207
Nickel nitrate hexahydrate (168.5g) was dissolved in 500 cc of water, and acidity was adjusted to a pH of 6.4 with ammonium. Ammonium dihydrogen phosphate (77.7 g) was dissolved in 250 cc of water, and the pH adjusted to 6.8 with ammonia. The solutions were mixed and stirred at room temperature for 15 minutes, after adjustment of the pH to 6.0 with ammonia, then filtered. The light green precipitate was filtered, dried at 1100C and heat-treated for 3 hours at 2900C, 3 hours at 4270C, and 2 hours at 5500C to give a tan solid having a surface area of 14m2/g.
Comparative Example B-Mg2P207 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 110 C, heat-treated at 290 C for 3 hours, 427 C for 3 hours, and 550 C for 16 hours in air to give a white solid having a surface area of 21.8m/kg.
Comparative Example C - La4(P20,) Lanthanum nitrate hexahydrate (Trona code 548) (130g) was dissolved in 31.5 cc nitric acid and diluted to 250 cc with water. Ammonium dihydrogen phosphate (57.1g) was dissolved in 250 cc of water and acidified to a pH of 1 with 25 cc nitric acid. On mixing the solutions with stirring, an opalescence formed. After stirring 22 hours with heating a milky white precipitate formed. On heating to boiling, the gel thickened. The gel was filtered, dried at llO"C, heat-treated at 290"C (3 hours), (427"C (3 hours) and 550 C (16 hours) in air to give a white solid having a surface area of 17 m'/g.
Comparative Example D - Co7Fe3Pl204ss Ferric nitrate nonahydrate (121.2g) and cobalt nitrate hexahydrate (203.8g) were dissolved in 10 ml. of water with heating. Ammonium dihydrogen phosphate (138.0g) was dissolved in 100 ml. of water with heating. The solutions were mixed and stirred with heating until a thick paste formed. The paste was dried at 110 C, then heat-treated at 290 C (3 hours), 427 C (3 hours) and 550 C (3 hours) in air to give a blue solid with a surface area of 0.8 m/g.
Comparative Example E - Co2P207 Cobalt nitrate hexahydrate (349.1 g) was dissolved in 20 cc of water with heating.
Ammonium 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 110 C, and heat-treated at 290 C (3 hours), 427 C (3 hours) and 550 C (16 hours) to give a blue solid with a surface area of 12.2 m/g.
Example 1 - CogFelTePl20425 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 solution was added to an ammonium dihydrogen phosphate (69g) solution in 50 cc of water. The slurry was dried at 110 C and heat-treated at 290 C (5 hours), 427 C (3 hours) and 550 C (3 hours) in air with the final 550 C stage being performed in the stainless steel reactor. The resultant blue solid had a surface area of 59.9 m2/g.
Example 2- CosoSbl P12041.5 A slurry of Sb203 (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 hexahydrate (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 3 - COIDASIPI1041 5 A slurry of 9.9 g AS203 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 remainder of the preparation was the same as in Example 2.
Example 4 - COi0Cd2Pi2Ox Cobalt nitrate hexahydrate (145.5g) and cadmium nitrate tetrahydrate (30.8g) were dissolved in 10 cc of water. This solution was added to an ammonium dihydrogen phosphate solution (69g) in 80 cc water. The resultant slurry was dried and heat-treated as in Example 1.
The number of oxygen atoms in the catalysts in Examples 1 to 4 were estimated.
However, the number of oxygens may actually vary from 30 to 60, depending upon the reaction conditions.
The above catalyst compositions were employed in the oxydehydrogenation of ethylbenzene to styrene, diethylbenzene to divinylbenzene and methylethylpyridine to methylvinylpyridine in a fixed-bed reactor comprising a 1/2-inch O.D. stainless steel tube having a catalyst volume capacity of 15 cc.
A reactant mixture of air, aromatic compound and nitrogen 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 530-532"C 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 conversion to the desired alkenyl-aromatic compound and the selectivity of the reactions reported in the following Table were calculated in the following manner: Moles of alkylaromatic converted
Percent Conversion = x 100
Moles of alkylaromatic fed
Moles of alkenylaromatic obtained
Percent Single Pass Yield = x 100
Moles of alkylaromatic fed
Moles of alkenyl aromatic obtained
Percent Selectivity = x 100
Moles of alkylaromatic converted TABLE
Oxydehydrogenation of Ethylbenzene to Styrene
Mole % per Mole %
Mole % Conversion Pass Yield Selectivity
Example No. Catalyst of Ethylbenzene to Styrene to Styrene
Comp. A Ni2 P2 O7 55 43 79
Comp. B Mg2 P2 O7 71 61 86
Comp. C La4 (P2O7)3 55 41 75
Comp. D Co7 Fe3P12O41.5 27 24 88
Comp. E Co2P2O7 47 37 78 1 Co9Fe1TeP12O42.5 60 50 83 2 Co10Sb1P12O41.5 58 46 80 3 Co10As1P12O41.5 52 43 83 4 Co10Cd2P12O42 49 42 87
Claims (13)
1. A process for the dehydrogenation of an alkylaromatic compound to the corresponding alkenylaromatic wherein said alkylaromatic 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 consisting of mononuclear, condensed-ring dinuclear aromatics and the corresponding nitrogen-containing heterocyclic aromatics, which comprises passing a gaseous mixture of the alkylaromatic, molecular oxygen and optionally a diluent gas over a catalyst at a temperature of from 300 to 6500C, in which the catalyst has a composition represented by the following empirical formula: AaMbMlCMlldXepyOx 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 of iron, chromium, uranium, thorium,
vanadium, titanium, lanthanum or the other rare earths;
M11 is one or more of the elements of tin, boron, lead, germanium, aluminium,
tungsten or molybdenum;
X is, tellurium, arsenic, antimony, cadmium or combinations thereof;
P is phosphorus; and wherein a to 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. A process as claimed in claim 1 in which the catalyst composition is one in which 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.
3. A process as claimed in claim 1 or claim 2 in which ethylbenzene is converted to styrene.
4. A process as claimed in claim 1 or claim 2 in which diethylbenzene is converted to divinylbenzene.
5. A process as claimed in claim 1 or claim 2 in which ethyltoluene is converted to vinyltoluene.
6. A process as claimed in claim 1 or claim 2 in which methylethylpyridine is converted
to methylvinylpyridine.
7. A process as claimed in claim 1 or claim 2 in which ethylpyridine is converted to vinyl
pyridine.
8. A process as claimed in any of claims 1 to 7 in which the molar ratio of oxygen to
alkylaromatic is within the range of 0.5 to 5.
9. A process as claimed in claim 8 in which the reaction temperature is in the range of
from 400 to 6000C.
10. A process as claimed in claim 9 in which the apparent contact time is from about 1 to
15 seconds.
11. A process as claimed in claim 10 in which M in the catalyst composition is cobalt, M1 is iron and X is tellurium.
12. A process as claimed in claim 1 substantially as herein described with reference to the Examples.
13. Alkenylaromatic compounds when prepared by a process as claimed in any of claims 1 to 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79263777A | 1977-05-02 | 1977-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1598509A true GB1598509A (en) | 1981-09-23 |
Family
ID=25157563
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB38969/79A Expired GB1598510A (en) | 1977-05-02 | 1978-05-02 | Oxydehydrogenation catalyst |
| GB17230/78A Expired GB1598509A (en) | 1977-05-02 | 1978-05-02 | Oxydehydrogenation process for alkylaromatics |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB38969/79A Expired GB1598510A (en) | 1977-05-02 | 1978-05-02 | Oxydehydrogenation catalyst |
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) | GB1598510A (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 |
|---|---|---|---|---|
| DE2849637A1 (en) * | 1978-11-16 | 1980-05-29 | Hoechst Ag | CARRIER CATALYST AND METHOD FOR THE PRODUCTION THEREOF |
| DE2849715A1 (en) * | 1978-11-16 | 1980-05-29 | Hoechst Ag | CARRIER CATALYST AND METHOD FOR THE PRODUCTION THEREOF |
| EP0044875B1 (en) * | 1980-07-18 | 1984-06-13 | Mitsubishi Kasei Corporation | Catalytic composition, method 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 | ||
| US3957897A (en) * | 1974-05-28 | 1976-05-18 | The Dow Chemical Company | Method of oxydehydrogenation of alkyl aromatic compounds |
| US3935126A (en) * | 1974-05-28 | 1976-01-27 | The Dow Chemical Company | Catalyst and 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 BE BE187127A patent/BE866403A/en unknown
- 1978-04-26 ES ES469145A patent/ES469145A1/en not_active Expired
- 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
- 1978-04-28 BR BR7802706A patent/BR7802706A/en unknown
- 1978-04-28 DD DD78205104A patent/DD135897A5/en unknown
- 1978-04-29 EG EG280/78A patent/EG13250A/en active
- 1978-05-02 GB GB38969/79A patent/GB1598510A/en not_active Expired
- 1978-05-02 CS CS782795A patent/CS199528B2/en unknown
- 1978-05-02 GB GB17230/78A patent/GB1598509A/en not_active Expired
- 1978-06-19 ES ES470908A patent/ES470908A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2389590A1 (en) | 1978-12-01 |
| IT7822880A0 (en) | 1978-04-28 |
| IN148087B (en) | 1980-10-18 |
| JPS53135940A (en) | 1978-11-28 |
| DD135897A5 (en) | 1979-06-06 |
| PT67944A (en) | 1978-05-01 |
| PT67944B (en) | 1979-11-14 |
| BE866403A (en) | 1978-08-14 |
| EG13250A (en) | 1981-03-31 |
| NO781508L (en) | 1978-11-03 |
| BR7802706A (en) | 1979-01-23 |
| CS199528B2 (en) | 1980-07-31 |
| ES469145A1 (en) | 1978-11-16 |
| CA1117120A (en) | 1982-01-26 |
| NL7804618A (en) | 1978-11-06 |
| ES470908A1 (en) | 1979-02-01 |
| JPH0154095B2 (en) | 1989-11-16 |
| GB1598510A (en) | 1981-09-23 |
| IT1094807B (en) | 1985-08-10 |
| DE2816946A1 (en) | 1978-11-09 |
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| PCNP | Patent ceased through non-payment of renewal fee |