US3784485A - Oxidative dehydrogenation catalyst - Google Patents

Oxidative dehydrogenation catalyst Download PDF

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US3784485A
US3784485A US00244995A US3784485DA US3784485A US 3784485 A US3784485 A US 3784485A US 00244995 A US00244995 A US 00244995A US 3784485D A US3784485D A US 3784485DA US 3784485 A US3784485 A US 3784485A
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alkali metal
oxidative dehydrogenation
sodium
aluminum
reactor
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US00244995A
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E Tomezsko
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Atlantic Richfield Co
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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

Definitions

  • This invention relates to a novel catalytic method for the dehydrogenation of parafiins.
  • a gaseous mixture of a paraffin (alkane) having from 2 to 12 carbon atoms, preferably from 3 to 6 carbon atoms, together with molecular oxygen is passed through a bed of molten alkali metal hydroxide containing a soluble transition metal oxyanion dissolved therein and aluminum metal, thereby dehydrogenating the parafiin of the corresponding olefin. It is an object of this invention to provide an improved method for the oxidative dehydrogenation of parafiins.
  • the paraffin (alkane) feed to the process of the invention preferably has from 2 to 12 carbon atoms and is straight chain or branched chain, straight chain paraffins being somewhat more preferred. More preferably, the paraffin has from 3 to 6 carbon atoms and the most preferred paraffin is propane.
  • the molecular oxygen is introduced along with the paraffin feed and is preferably diluted with an inert gas such as nitrogen. It has been found that the optimum hydrocarbon to oxygen ratio is between about 1.8:1 and 5.021. In general, the volume ratio of oxygen to nitrogen can vary from about 1:2 to 1:6 but preferably it is about 1:4 since this provides a safety factor relative to the exice plosive limits of the hydrocarbon-oxygen mixture. Air has been found to be a satisfactory source of molecular oxygen.
  • the paraffin and molecular oxygen are continuously passed through a reactor containing molten alkali metal hydroxide.
  • the preferred alkali metal hydroxide is sodium hydroxide.
  • Aluminum metal is preferably included in the reactor, most preferably in the molten alkali metal hydroxide melt, and is preferably in the shape of small rings or irregular shapes in order to provide reaction surface while at the same time providing a packed condition which al lows the free passage of gases therethru.
  • the amount of aluminum need only be rather small, in general about 1 to 5 grams of aluminum per ml. of the molten sodium hydroxide is suificient 'but larger quantities can be employed within the scope of the invention.
  • the reaction may be carried out at temperatures ranging from about 390 C. to about 600 C.
  • the preferred reaction temperature is between about 425 C. and 500 C.
  • the most preferred range is between about 450 C. and 490 C.
  • Atmospheric pressure is preferred although higher pressures may be used consistent with flammability limits, in general, less than 100 psi.
  • the transition metal oxyanion is introduced into the melt as an alkali metal salt, having the formula [Q M O J wherein Q is an alkali metal, z is the valance of the transition metal oxyanion, M is the transition metal which is selected from Group III-B thru VIII of the Periodic Table, x and y are the number of atoms of M and 0 respectively in the anion, and w is a number from 1 to 6.
  • the transition metal oxyanion co-catalyst thus has the formula M,,O,, wherein M, x, y, and z are as defined above.
  • 2 has a value of 1 or 2
  • y has a value of 3 to 7
  • z has a value of 1 to 3.
  • Any compounds fitting this formula which are soluble in the alkali metal hydroxide melt are suitable.
  • the alkali 'but within the scope of the invention, are polymolybdates, polytungstates, and polyvanadates. 50
  • the alkali metal salt of the above formula is dissolved in the alkali metal hydroxide melt, and is present in a weight ratio range of from about 0.01% to 5% based upon the weight of the alkali metal hydroxide. It is most preferable that the compound be completely dissolved, and the solubility limits for each compound at varying temperatures are routinely determinable.
  • the gaseous hourly space velocity i.e., the volumes of gaseous feed per volume of molten sodium hydroxide per hour, is preferably from about 50 to 800 and preferably from 100 to 600.
  • the fresh reactor assembly is pre-oxidized by passing oxygen through the assembly for several hours, generally overnight or about 16 hours. Thereafter, the feed gas, consisting of the hydrocarbon, oxygen and nitrogen, is passed through the reactor for several additional hours before high conversions are attained.
  • EXAMPLE I The following runs were made with 200 grams of sodium hydroxide, 350 cubic centimeters of tabular alumina packing (4 x 8 mesh), and grams of aluminum rings at a reaction temperature of 490 C.
  • the feed gas composition is 40 mole percent propane, 12 mole percent oxygen, and 48 mole percent nitrogen.
  • Runs A and B are comparative and not within the present invention since no co-catalyst was used.
  • Run C is within the invention since there is further incorporated in the sodium hydroxide melt 0.1 weight percent of sodium metavanadate based on the weight of the sodium hydroxide.
  • Run A was carried out at a gaseous hourly space velocity of 101 and a conversion of 12.1.
  • the selectivity to propylene was 79.2 and the yield was 9.7.
  • Run B was carried out at a gaseous hourly space velocity of 102 with a conversion of 11.4, selectivity to propylene of 78.3, and a yield of 9.0.
  • Run C was carried out with the co-catalyst of the invention incorporated in the reactor under otherwise the same conditions except that the gaseous hourly space velocity was adjusted so as to provide equivalent conversion level.
  • the 4 gaseous hourly space velocity was 108 with a conversion of 20.9, a selectivity to propylene of 79.8, and a yield of 16.6.
  • Run D is comparative, that is, without the incorporation of sodium vanadate and had a gaseous hourly space velocity of 34 with a conversion of 30.9, selectivity of 63.0, and a yield of 19.5.
  • Run E is within the limits of the invention and is the same as Example D except that 0.1 weight percent sodium vanadate was incorporated in the melt.
  • the gaseous hourly space velocity was 72 while maintaining a conversion of 30.4, approximately equivalent to the conversion in Run D.
  • Selectivity increased slightly to 65.0 and yield to 19.8.
  • This example demonstrated that at twice the throughput (space velocity), equivalent conversions, selectivities, and yields can be obtained using the co-catalyst of the invention. That is, the use of this co-catalyst system essentially doubles the reaction rate.
  • Oxidative dehydrogenation catalyst composition comprising a solution of a compound having the formula (Q M O wherein Q is an alkali metal, M is a transition metal selected from Group III-B to VIII of the Periodic Table, x is 1 or 2, y is 3 to 7, w is 1 to 6 and z is 1 to 3 in molten alkali metal hydroxide, wherein said compound constitutes from about 0.01% to about 5% by weight of the composition.
  • the oxidative dehydrogenation catalyst composition of claim 1 wherein said compound is selected from the group consisting of sodium dichromate, sodium molyb date, sodium tungstate, sodium permanganate, and sodium metavanadate.

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

Abstract

METHOD FOR THE OXIDATIVE DEHYDROGENATION OF PARAFFINS TO PRODUCE OLEFINS BY CONTACTING THE PARAFFINS WITH MOLECULAR OXYGEN IN THE PRESENCE OF MOLTEN ALKALI METAL HYDROXIDES, ALUMINUM, AND A SOLUBLE TRANSITION METAL OXYANION INCLUDED IN THE MOLTEN ALKALI METAL HYDROXIDE.

Description

United States Patent US. Cl. 252-467 Claims ABSTRACT OF THE DISCLOSURE Method for the oxidative dehydrogenation of parafiins to produce olefins by contacting the parafiins with molecular oxygen in the presence of molten alkali metal hydroxides, aluminum, and a soluble transition metal oxyanion included in the molten alkali metal hydroxide.
RELATED APPLICATIONS This application is a divisional application of US. Ser. No. 124,979, filed Mar. 16, 1971, and now US. Pat. 3,697,614.
BACKGROUND OF THE INVENTION Field of the invention This invention relates to a novel catalytic method for the dehydrogenation of parafiins.
Prior art US. Ser. No. 844,608, filed July 24, 1969, now US. Pat. 3,586,733, discloses a method for the oxidative dehydrogenation of parafiins to produce olefins by contacting the paraffins with molecular oxygen in the presence of molten alkali metal hydroxides, and aluminum metal or activated alumina.
SUMMARY OF THE INVENTION In accordance with this invention a gaseous mixture of a paraffin (alkane) having from 2 to 12 carbon atoms, preferably from 3 to 6 carbon atoms, together with molecular oxygen is passed through a bed of molten alkali metal hydroxide containing a soluble transition metal oxyanion dissolved therein and aluminum metal, thereby dehydrogenating the parafiin of the corresponding olefin. It is an object of this invention to provide an improved method for the oxidative dehydrogenation of parafiins.
It is another object of this invention to provide a method for the oxidative dehydrogenation of paraflins to olefins utilizing molecular oxygen. It is a further object of this invention to provide a method for the oxidative dehydrogenation of parafiins to olefins using molecular oxygen, molten alkali metal hydroxide, aluminum metal, and a transition metal oxyanion dissolved in the melt.
Other objects of this invention will become apparent from the following description of the invention.
DETAILED DESCRIPTION OF THE INVENTION The paraffin (alkane) feed to the process of the inventionpreferably has from 2 to 12 carbon atoms and is straight chain or branched chain, straight chain paraffins being somewhat more preferred. More preferably, the paraffin has from 3 to 6 carbon atoms and the most preferred paraffin is propane.
The molecular oxygen is introduced along with the paraffin feed and is preferably diluted with an inert gas such as nitrogen. It has been found that the optimum hydrocarbon to oxygen ratio is between about 1.8:1 and 5.021. In general, the volume ratio of oxygen to nitrogen can vary from about 1:2 to 1:6 but preferably it is about 1:4 since this provides a safety factor relative to the exice plosive limits of the hydrocarbon-oxygen mixture. Air has been found to be a satisfactory source of molecular oxygen. The paraffin and molecular oxygen are continuously passed through a reactor containing molten alkali metal hydroxide. The preferred alkali metal hydroxide is sodium hydroxide.
Aluminum metal is preferably included in the reactor, most preferably in the molten alkali metal hydroxide melt, and is preferably in the shape of small rings or irregular shapes in order to provide reaction surface while at the same time providing a packed condition which al lows the free passage of gases therethru.
The amount of aluminum need only be rather small, in general about 1 to 5 grams of aluminum per ml. of the molten sodium hydroxide is suificient 'but larger quantities can be employed within the scope of the invention.
The reaction may be carried out at temperatures ranging from about 390 C. to about 600 C. The preferred reaction temperature is between about 425 C. and 500 C. The most preferred range is between about 450 C. and 490 C.
Atmospheric pressure is preferred although higher pressures may be used consistent with flammability limits, in general, less than 100 psi.
Incorporated in the alkali metal hydroxide melt in accordance with my invention is a soluble transition metal oxyanion co-catalyst which has been found to cause an increase in the rate of the oxidative dehydrogenation reaction as well as an improvement in selectivity to the desired olefin. The transition metal oxyanion is introduced into the melt as an alkali metal salt, having the formula [Q M O J wherein Q is an alkali metal, z is the valance of the transition metal oxyanion, M is the transition metal which is selected from Group III-B thru VIII of the Periodic Table, x and y are the number of atoms of M and 0 respectively in the anion, and w is a number from 1 to 6. The transition metal oxyanion co-catalyst thus has the formula M,,O,, wherein M, x, y, and z are as defined above. In the above formula, 2: has a value of 1 or 2, y has a value of 3 to 7, and z has a value of 1 to 3. Any compounds fitting this formula which are soluble in the alkali metal hydroxide melt are suitable. The alkali 'but within the scope of the invention, are polymolybdates, polytungstates, and polyvanadates. 50
Preferably, the alkali metal salt of the above formula is dissolved in the alkali metal hydroxide melt, and is present in a weight ratio range of from about 0.01% to 5% based upon the weight of the alkali metal hydroxide. It is most preferable that the compound be completely dissolved, and the solubility limits for each compound at varying temperatures are routinely determinable.
The gaseous hourly space velocity, i.e., the volumes of gaseous feed per volume of molten sodium hydroxide per hour, is preferably from about 50 to 800 and preferably from 100 to 600.
In the following examples runs were carried out utilizing a vertical tubular reactor composed of high purity alumina which measured about 40 inches in length by 1.5 inches in outside diameter. The reactor is provided with a concentric ceramic feed tube about A-inch outside diameter which extended to the bottom of the reactor and was provided with apertures at the bottom of the tube to provide a distribution means for the gaseous charge. The gaseous charge was passed downwardly through the feed tube and upwardly through a bed located in the annular space between the feed tube and the inner wall of the reactor. The bed consisted of a bottom layer of aluminum metal rings obtained by cutting an aluminum tube about y -inch outside diameter by As-inch inside diameter to about %-ll'1Ch ring lengths. Above the rings there was provided a layer of tabular alumina (8-14 mesh). When activated alumina was used, the aluminum rings were replaced by the activated alumina. In this reactor 100 ml. of molten caustic filled the space between the rings and between the particles of packing and extended upwardly in the tube in the annular space. The co-catalyst is incorporated with the aluminum and the molten caustic. In some instances suflicient packing was utilized so that the packing extended above the layer of the molten caustic while in other runs smaller amounts of packing were used so that the molten caustic layer was above the top of the packing layer. The outside of the reactor tube was surrounded with three heaters so that the temperature of the reaction could be controlled uniformly to the desired level throughout the reaction zone. The top of the reactor tube is provided with conventional fittings to remove the reaction products. In the runs shown in the following examples a reaction temperature of 490 C. was utilized in order to make comparisons of the other variables. Runs have been made in the broad temperature range and in the preferred temperature range with the preferred and most preferred temperatures giving the best results.
It has been found that there is an induction period required to start up the reaction. The fresh reactor assembly is pre-oxidized by passing oxygen through the assembly for several hours, generally overnight or about 16 hours. Thereafter, the feed gas, consisting of the hydrocarbon, oxygen and nitrogen, is passed through the reactor for several additional hours before high conversions are attained.
In the following examples, runs are shown utilizing the apparatus described. These runs illustrate specific embodiments of the invention and show the preferred conditions for carrying out the reaction of this invention, and should not be construed as limiting the invention.
EXAMPLE I The following runs were made with 200 grams of sodium hydroxide, 350 cubic centimeters of tabular alumina packing (4 x 8 mesh), and grams of aluminum rings at a reaction temperature of 490 C. The feed gas composition is 40 mole percent propane, 12 mole percent oxygen, and 48 mole percent nitrogen. Runs A and B are comparative and not within the present invention since no co-catalyst was used. Run C is within the invention since there is further incorporated in the sodium hydroxide melt 0.1 weight percent of sodium metavanadate based on the weight of the sodium hydroxide. Run A was carried out at a gaseous hourly space velocity of 101 and a conversion of 12.1. The selectivity to propylene was 79.2 and the yield was 9.7. Run B was carried out at a gaseous hourly space velocity of 102 with a conversion of 11.4, selectivity to propylene of 78.3, and a yield of 9.0. Run C was carried out with the co-catalyst of the invention incorporated in the reactor under otherwise the same conditions except that the gaseous hourly space velocity was adjusted so as to provide equivalent conversion level. In Run C the 4 gaseous hourly space velocity was 108 with a conversion of 20.9, a selectivity to propylene of 79.8, and a yield of 16.6. Thus it can be seen from a comparison of these runs that incorporation of 0.1 weight percent sodium vanadate at approximately equal gaseous hourly space velocity results in much higher conversions at equal selectivities.
EXAMPLE II The conditions of Example I were repeated. Run D is comparative, that is, without the incorporation of sodium vanadate and had a gaseous hourly space velocity of 34 with a conversion of 30.9, selectivity of 63.0, and a yield of 19.5. Run E is within the limits of the invention and is the same as Example D except that 0.1 weight percent sodium vanadate was incorporated in the melt. The gaseous hourly space velocity was 72 while maintaining a conversion of 30.4, approximately equivalent to the conversion in Run D. Selectivity increased slightly to 65.0 and yield to 19.8. This example demonstrated that at twice the throughput (space velocity), equivalent conversions, selectivities, and yields can be obtained using the co-catalyst of the invention. That is, the use of this co-catalyst system essentially doubles the reaction rate.
While I have described my invention with great detail, various modifications, improvements, and variations should become readily apparent without departing from the spirit and scope thereof.
I claim:
1. Oxidative dehydrogenation catalyst composition comprising a solution of a compound having the formula (Q M O wherein Q is an alkali metal, M is a transition metal selected from Group III-B to VIII of the Periodic Table, x is 1 or 2, y is 3 to 7, w is 1 to 6 and z is 1 to 3 in molten alkali metal hydroxide, wherein said compound constitutes from about 0.01% to about 5% by weight of the composition.
2. The oxidative dehydrogenation catalyst composition of claim 1 wherein said compound is selected from the group consisting of sodium dichromate, sodium molyb date, sodium tungstate, sodium permanganate, and sodium metavanadate.
3. The oxidative dehydrogenation catalyst composition of claim 2 wherein said compound is sodium metavanadate.
4. The oxidative dehydrogenation catalyst composition of claim 1 wherein said compound is sodium metavanadate and said alkali metal hydroxide is sodium hydroxide.
5. The oxidative dehydrogenation catalyst composition of claim 1 wherein Q is sodium.
References Cited UNITED STATES PATENTS 3,692,860 9/1972 Boutry et al. 260683.3 X
DANIEL E. WYMAN, Primary Examiner W. J. SHINE, Assistant Examiner U.S. Cl. X.R.
US00244995A 1971-03-16 1972-04-17 Oxidative dehydrogenation catalyst Expired - Lifetime US3784485A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482646A (en) * 1983-04-21 1984-11-13 Phillips Petroleum Company Oxidative dehydrogenation of paraffins
US5071815A (en) * 1989-09-01 1991-12-10 British Columbia Research Corporation Method for producing catalysts
US5086032A (en) * 1989-01-18 1992-02-04 Norsolor Catalyst for oxidative dehydrogenation of propane
EP2399865A1 (en) * 2009-01-20 2011-12-28 Yasuo Ishikawa Catalyst for hydrogen generation, method for generating hydrogen, and hydrogen generator
US9376317B2 (en) 2010-01-06 2016-06-28 Yasuo Ishikawa Method of generating hydrogen

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482646A (en) * 1983-04-21 1984-11-13 Phillips Petroleum Company Oxidative dehydrogenation of paraffins
US5086032A (en) * 1989-01-18 1992-02-04 Norsolor Catalyst for oxidative dehydrogenation of propane
US5071815A (en) * 1989-09-01 1991-12-10 British Columbia Research Corporation Method for producing catalysts
EP2399865A1 (en) * 2009-01-20 2011-12-28 Yasuo Ishikawa Catalyst for hydrogen generation, method for generating hydrogen, and hydrogen generator
CN102369155A (en) * 2009-01-20 2012-03-07 石川泰男 Catalyst for hydrogen generation, method for generating hydrogen, and hydrogen generator
EP2399865A4 (en) * 2009-01-20 2012-10-24 Yasuo Ishikawa Catalyst for hydrogen generation, method for generating hydrogen, and hydrogen generator
US8845998B2 (en) 2009-01-20 2014-09-30 Yasuo Ishikawa Catalyst for generating hydrogen, method of generating hydrogen and apparatus for generating hydrogen
CN102369155B (en) * 2009-01-20 2016-01-27 石川泰男 Hydrogen produces catalyzer, hydrogen production method, hydrogen generation apparatus
US9376317B2 (en) 2010-01-06 2016-06-28 Yasuo Ishikawa Method of generating hydrogen

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