CA1100476A - Supported vanadia catalyst and use thereof for nitrile production - Google Patents
Supported vanadia catalyst and use thereof for nitrile productionInfo
- Publication number
- CA1100476A CA1100476A CA285,116A CA285116A CA1100476A CA 1100476 A CA1100476 A CA 1100476A CA 285116 A CA285116 A CA 285116A CA 1100476 A CA1100476 A CA 1100476A
- Authority
- CA
- Canada
- Prior art keywords
- support
- vanadia
- alkali metal
- catalyst
- supported
- 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.)
- Expired
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Classifications
-
- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
-
- 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
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
Abstract
Abstract of the Invention The invention relates to a vanadia catalyst supported on a silica-alumina or gamma-alumina support in an amount to provide a ratio of vanadia to support by weight ranging from about 0.3:1 to about 3:1 substantially entirely within the pores of the support.
The vanadia is placed in molten form substantially within the pores of a support having a surface area greater than about 50m2 gram and a porosity greater than about 0.4 cc/gram, which further includes an alkali metal, with the vanadium metal to alkali metal mole ratio being from 2:1 to 30:1. At least a portion of the alkali metal is preferably in the form of alkali metal vanadate. The catalyst is used for the production of nitriles from a compound containing at least one alkyl group.
The vanadia is placed in molten form substantially within the pores of a support having a surface area greater than about 50m2 gram and a porosity greater than about 0.4 cc/gram, which further includes an alkali metal, with the vanadium metal to alkali metal mole ratio being from 2:1 to 30:1. At least a portion of the alkali metal is preferably in the form of alkali metal vanadate. The catalyst is used for the production of nitriles from a compound containing at least one alkyl group.
Description
~ 7~
This invention relates to a supported vanadia catalyst and the use thereof for the production of nitriles.
United States Patent No. 3,963,645 discloses a supported vanadia catalyst wherein the vanadia is supported on a silica-alumina or gamma-alumina support in an amount to provide a ratio of metal oxide to support by weight ranging from about 0.3:1 to abou-t 3 1 substantially enti.rely wi-thin the pcres of the support. The vanadia is placed in molten form within the pores of the support which has a surace area greater than about SOm2/
gram and a porosity greater than about 0.4 cc/gram.
The present invention i.s directed to an improvement in the suppor-ted vanadia catalyst of the aforesaid patent, and the use of such an improved catalyst for the production of nitriles.
In accordance with the present invention, there is pro-vided a catalyst of vanadia supported on a porous support in an amount to provide a ratio vanadia to support by weight from about 0.3:1 to about 3:1 substantially entirely within the pores of the support, with ~.he vanadia having been placed . 20 in molten form substantially within the pores oE a support having a surface area greater than 50m2/gram and a porosity greater - than about 0.4 cc/gram, the catalyst further containing an alkali metal in an amount to increase the catalytic effect of the catalyst.
More particularly, the catalyst includes an alkali metal which is either lithium, sodium,~potassium. rubidium or cesium, in an amount to provide a mole ratio of vanadium metal to alkali metal from about 2:1 to 30:1~ and preferably from~about 8::L
to 20:1. The alkali metal is preferabl.y sodium.
The support on which the vanadium pentoxide is to ~e supported has a surface area grea-ter than about 50m2/gram and a porosity greater than about 0.4 cc/gram. In general, the surface area of is no greater than about 1.2 cc/gram. Supports having a surface area of about 200m2/gram have been found to provide particularly good results. As representative examples of preferred supports having such properties there may be mentioned: silica-alumina, zeolites and alumina, including microcrystalline and the ~ ;
and X modifications of alumina. The silica-alumlna and gamma-alumina supports are particularly preferred.
The fused supported vanadia catalyst which is promoted with an alkali metal may be conveniently prepared by mixing the support with an aqueous solutlon of the alkali metal hydroxide to provide the desired amount of alkali metal in the support. The support containing the alkali metal i9 then mixed with vanadia and heated to above the fusiorl point of the vanadia to draw the vanadia into the pores of the support treated wi~h the alkali metal.
Another method for preparing the supported vanadia catalyst is by a fuslon technique without initial treatment of the support with an alkali metal, followed by impregnation of the supported vanadia catalyst with an aqueous solution of the alkali metal hydroxide to provide the required amount of alkali metal, and heating to above the fusion point o vanadia.
Still another method :Eor preparing the supported vanadia ' catalyst is to pre-blend the vanadia and an alkali metal compound, such as the hydroxide or oxide, in the appropriate amouDts and to support the resulting blend on the support by fusion.
In accordance with a preferred embodiment of the present invention, a particularly active form of the catalyst is produced by providing a mixture of alkali metal hydro~ide and vanadia on the support and heating the supported mixture to the fusion temperature of the vanadia at a controlled heating rate. More particularly, the supported mlxture is heated to the vanadia fusion temperature at an average rate oE less than 20F/minute, preferably less than 15F/
minute, with a particularly preferred heating rate being 10F/minute or less. Thus, in general, the supported mixture is heated up to the fusion temperature over a time period of at least 1 hour, 5 with particularly good results being achieved over a period of 2 hours or more.
The supported mixture is maintained at or above the fusion temperature for a time sufficient to place the vanadia substantially entirely withln the pores of the support. In 10 general, the supported mixture is maintained at a temperature of from 1300F to 1450~F for a time period of from 1 to 10 hours.
In preparing the catalyst in accordance with the preferred procedure, i.e., controlled heating of vanadia and alkali metal hydroxide on the support, at least a portion of the 15 alkali metal is present in the final catalyst as -the alkali metal vanadate; preferably sodium vanadate. If the hea-tirlg to fusion temperature is effected at a more rapid rate, alkali metal vanadate is not formed and such~a catalyst has been found to be less selective for the production of nitriles, even -though it is 20 an improvement over the fused catalyst without the alkali metal.
Thus, in accordance with -the particularly preferred embodiment, the catalyst includes bo-th vanadia and alkali metal vanadate, preferably sodium vanadate. Preferably at least 106 by weight of the alkali metal is present as the vanadate.
The supported vanadia catalyst of the present invention is particularly suitable for the production of nitriles by oxidative ammonolysis (ammoxidation). The organic reactant employed as a starting material for the production of nitriles by ammoxldation is a co~lpound including at least one alkyl group;
namely, aromatic, aliphatic, alicyclic and heterocyclic compounds having at least one alkyl group.
q6 As representative examples of alkyl substituted aromatic hydrocarbons which are suitable as starting materials, there may be mentioned the alkyl substituted benzenes and naphthalenes, and in particular, benzene which may contain -two or more alkyl 5 groups in which case the resulting product is a polynitrile.
The alkyl group generally con-tains no more than 4 carbon atoms, preferably no more than 2 carbon atoms. As particular examples of suitable alkyl substituted aromatic hydrocarbons, there is:
toluene; various xylenes to produce the various phthalonitriles;
10 ethyl benzene, trimethyl benzenes, methyl-naphthalenes, durene and the like.
As representative examples of suitable aliphatic compounds, there may be mentioned: olefinic hydrocarbons having at least one alkyl group, such as propylene and isobutylene to produce 15 acrylonitrile and methacrylonitrile, respectively.
As representative examples of suitable alicyclic compounds, there may be mentioned: methylcyclopentane, methylcyclohexane, the alkyl substituted decalins, and the like.
Th~ heterocyclic compounds useful as starting materials 20 for producing nitriles by ammoxidation in accordance with ;the present invention include alkyl substituted furans, pyrroles, indoles, thiophenes, pyrazoles r imidazoles, thiazoles, oxazoles, pyrans, pyridines, quinolines, isoquinolines, pyrimidines, pyridazines, pyrazines and the llke. The preferred heterocyclic 25 compounds are the alkyl, preferably lower alkyl, substltuted pyridines, with pyridines having an alkyl group in a beta-positlon with respect to the heterocycllc nitrogen atom belng partlcularly preferred ln that such pyrldines can be converted to nicotinonitrile; in particular, 3-picoline, 2, 3-and 2,5-30 dimethylpyridlne, 2-methyl-5-ethylpyridlne and 3-ethylpyrldlne.
The starting material, con~aining at least one alkyl group is converted to a nitrile by contacting the starting material with ammonia, in the vapor phase, in the presence of the supported vanadia catalyst of the present invent:ion, either in the absence or presence of a gas containing free oxygen, preferably in the absence of a gas con~aining free oxygen. The contacting is generally effected at a temperature from about 300C to about 500C, preferably from about 375C to about 475C, with the contact time generally ranging from about 0.5 to about 15 seconds, preferably from about 2 to about 8 seconds. Reaction pressures generally range from about 1 to about 5 atmospheres. The mole ratio of ammonia to starting material generally ranges from about 2:1 to about 16:1, preferably from about 3:1 to about 8:1. If a gas containing free oxygen is employed in the feed, the gas is employed in an amount such that the quantity of oxygen and starting material in the feed is ou~side of the explosive range.
In accordance with the preferred embodiment of the invention, the starting material and ammonia are contacted with the supported vanadia catalyst of the present invention in the absence of oxygen, with the supported vanadia catalyst being periodically passed to another reactor and contacted therein with a gas con-.
taining free oxygen to effect regeneration of the catalyst, generally at a time period from about 2 to about 20 minutes.
In general,the supported vanadia catalyst is not maintained on stream ~or a period greater than about 30 minutes, preferably from about 2 to about 10 minutes. The supported vanadia catalyst is then recycled to a nitrile productlon zone. It is believed -that the supported vanadia catalyst is reduced during the nitrile 30 production step and, consequently, periodic oxidation thereof is required to maintain the supported vanadia catalyst in the oxidized form necessary for the nitrile produc~lorl.
The invention wlll be further described with respect to the following examples:
EXAMPLE I
_ Catalyst A (Present Invention) 3000 g. of silica-alumina fluid bed catalyst suppor~ (Grace 135) was slurried in 4500 g. of 1% by weight of NaO~ and agitated for 30 minutes. After settling, the supernatant liquid was decanted and replaced with 4500 g. of water, and the mixture agitated for another 30 minutes. The mixture was again separated by decantation. After drying at 110C, the treated support contained 0.9 wt. % Na. This support was then blended with 2000 g. of powdered vanadia and heated at 1500F for 5 hours in a slowly rotating cylindrical kiln. After cooling, the catalyst was removed from the kiln and screened through a 40 mesh screen.
_atalyst B
3000 g. of a silica-a:Lumina fluid bed catalyst support (Grace 135) was blended with 2000 g. of powdered vanadia and heated at 1400F for 5 hours in a slowly rotating cylindrical kiln.
After cooling, the catalyst was removed from the kiln and screened through a 40 mesh screen.
Catalysts A and B were then employed for the production of isophthalonitrile under the following conditi.ons. The ammoxi-dation was effected in the absence of molecular oxygen, catalysts A and B being regenerated in a separate regenerator by contact with oxygen.
7~i T E I
Catalyst Type B A
Reactor Pressure, PSIG 10 10 Reactor Temp., E` 800 800 Regenerator Temp.,F 910-930 910-930 5 Catalyst circulation, gms/min. 56 53 Organic Feed Rate/cc/min. 3.3 3.4 Feed Composition m-xylene, wt.% 69 69 M-toluonitrile,w-t.% 31 31 10 NH3 in feed mol/mol. organic feed 9.1 8.8 Inert gas in feed mol/mol. organic feed 9.4 8.9 Conversion, mol% 52.5 41.5 15 Ultimate Yield of Isophthalonitrile Basis m-xylene, mol% 80.7 86.6 Basis ammonia, mol% 27 49 Improved results are obtained by using the catalyst of the present invention (Catalyst A) as evidenced by increased 20 ammonia and hydrocarbon yielcl.
EXAMPLE II
3000 g. of a silica-alumina fluid bed catalyst suppor~
(Grace 135) was slurried in 4500 g. of 1% by weight of NaOH
and agitated for 30 minutes. After settling, ~he supernatant liquid was decanted and replaced with 4500 g. of water, and the mixture agitated for another 30 minutes. The mixture was again separated by decantation. After drying at 110C, the treated support contained 0.9 wt. % Na. This support was then blended with 2000 g. of powdered vanadia and heated at the rate of 10F/
minute in a slowly rotating cylindrical kiln to a temperature of 1400F and maintained at such temperature for 5 hours. After cooling, the catalyst was removed from the kiln and screened through a 40 mesh screen.
Tabel II summarizes the results obtained when using this catalyst for the production of terephthalonitrile from p-xylene (Run 1) and the production of nicotinonitrile from beta-picoline (Run 2). The ammoxidation was effected in the absence of molecular oxygen, with catalysts being regenerated in a separate regenerator by contact with oxygen.
.
: :
~9_ _BLE II
Run 1 Run 2 Reactor Pressure, PSIG 25.0 15.0 Reactor Temp.,F 800 775 Regenerator Temp.,F 935-955 935-955 Catalyst circulation, yms/min. 112.8 73.8 Organic Feed Rate, cc/min. 6.7 8.0 NH3 in feed mol/mol. organic feed 7.8 5.0 Inert gas in feed mol/mol. oryanic feed 0.7 0.6 Conversion, mol% 50.67 30.05 In Run 1 the following selectivities and yields were achieved:
Selectivity mole %
Terephthalonitrile 93.53 p-tolunitrile 0.00 benzonitrile 0.04 carbon oxides 6.43 Yields, mole %
Ultimate Organic 93.53 Ammonia 65.71 In Run 2, the following selectivities and yields were achieved:
Selectivity, rnole %
Nicotinonitrile 89.66 Pyridine 0.74 Carbon Oxides 9.60 Yields, mole %
Ultimate Organic 89.66 Ammonia 66.70 EXAMPLE III
Two catalysts were prepared as described with reference to Example II, (40% vanadia and 1% sodium) except that one catalyst was heated at the rate of :lOF/min. and the second was heated at a rate of greater than 20Fimin.
Table III summarizes the results obtained when the catalysts were employed for producing isophthalonitrile from m-xylene. The amm~oxidatlon was effected in the absence of molecular oxygen, and the regeneration of the catalyst was effected on a cyclic basis rather than by continuous circulation of the catalyst, as in the previous Examples.
TA~LE III
~eating Rate for catalyst, F/min. > 20 10 Temperature, F 800 800 Catalyst Charge, g 400 400 Ca-t/Oil, g/cc 20.8 20 `
5 Pressure, psig 5 5 GHSV (STP),h 1 1040 1242 NH3/Organic, mol/mol 5.4 6 Selectivities, mol%
IPN 56.5 64.9 m-TN 33.9 22.3 BN - 1.7 CO~ 9.5 11.1 Conversion,% 37.2 47.4 Ultimate Yield,% 85.4 83.8 15 Space-Time Yield, g/gh 0.15 0~20 The catalyst produced by slow heating provides an lmproved selectivity in terms of conversion of methyl group to ni.trile.
The catalyst of the present inventi.on, when employed for the production of nitriles, provides improved hydrocarbon selectivity and ammonia yield over the catalyst described in U.S. Patent 3,963,645. While it is not intended to limit the scope of the invention, it is believed tha-t the improved catalytic effect results from a modification of the vanadia by reaction with the alkali metal at the fusion temperature.
This invention relates to a supported vanadia catalyst and the use thereof for the production of nitriles.
United States Patent No. 3,963,645 discloses a supported vanadia catalyst wherein the vanadia is supported on a silica-alumina or gamma-alumina support in an amount to provide a ratio of metal oxide to support by weight ranging from about 0.3:1 to abou-t 3 1 substantially enti.rely wi-thin the pcres of the support. The vanadia is placed in molten form within the pores of the support which has a surace area greater than about SOm2/
gram and a porosity greater than about 0.4 cc/gram.
The present invention i.s directed to an improvement in the suppor-ted vanadia catalyst of the aforesaid patent, and the use of such an improved catalyst for the production of nitriles.
In accordance with the present invention, there is pro-vided a catalyst of vanadia supported on a porous support in an amount to provide a ratio vanadia to support by weight from about 0.3:1 to about 3:1 substantially entirely within the pores of the support, with ~.he vanadia having been placed . 20 in molten form substantially within the pores oE a support having a surface area greater than 50m2/gram and a porosity greater - than about 0.4 cc/gram, the catalyst further containing an alkali metal in an amount to increase the catalytic effect of the catalyst.
More particularly, the catalyst includes an alkali metal which is either lithium, sodium,~potassium. rubidium or cesium, in an amount to provide a mole ratio of vanadium metal to alkali metal from about 2:1 to 30:1~ and preferably from~about 8::L
to 20:1. The alkali metal is preferabl.y sodium.
The support on which the vanadium pentoxide is to ~e supported has a surface area grea-ter than about 50m2/gram and a porosity greater than about 0.4 cc/gram. In general, the surface area of is no greater than about 1.2 cc/gram. Supports having a surface area of about 200m2/gram have been found to provide particularly good results. As representative examples of preferred supports having such properties there may be mentioned: silica-alumina, zeolites and alumina, including microcrystalline and the ~ ;
and X modifications of alumina. The silica-alumlna and gamma-alumina supports are particularly preferred.
The fused supported vanadia catalyst which is promoted with an alkali metal may be conveniently prepared by mixing the support with an aqueous solutlon of the alkali metal hydroxide to provide the desired amount of alkali metal in the support. The support containing the alkali metal i9 then mixed with vanadia and heated to above the fusiorl point of the vanadia to draw the vanadia into the pores of the support treated wi~h the alkali metal.
Another method for preparing the supported vanadia catalyst is by a fuslon technique without initial treatment of the support with an alkali metal, followed by impregnation of the supported vanadia catalyst with an aqueous solution of the alkali metal hydroxide to provide the required amount of alkali metal, and heating to above the fusion point o vanadia.
Still another method :Eor preparing the supported vanadia ' catalyst is to pre-blend the vanadia and an alkali metal compound, such as the hydroxide or oxide, in the appropriate amouDts and to support the resulting blend on the support by fusion.
In accordance with a preferred embodiment of the present invention, a particularly active form of the catalyst is produced by providing a mixture of alkali metal hydro~ide and vanadia on the support and heating the supported mixture to the fusion temperature of the vanadia at a controlled heating rate. More particularly, the supported mlxture is heated to the vanadia fusion temperature at an average rate oE less than 20F/minute, preferably less than 15F/
minute, with a particularly preferred heating rate being 10F/minute or less. Thus, in general, the supported mixture is heated up to the fusion temperature over a time period of at least 1 hour, 5 with particularly good results being achieved over a period of 2 hours or more.
The supported mixture is maintained at or above the fusion temperature for a time sufficient to place the vanadia substantially entirely withln the pores of the support. In 10 general, the supported mixture is maintained at a temperature of from 1300F to 1450~F for a time period of from 1 to 10 hours.
In preparing the catalyst in accordance with the preferred procedure, i.e., controlled heating of vanadia and alkali metal hydroxide on the support, at least a portion of the 15 alkali metal is present in the final catalyst as -the alkali metal vanadate; preferably sodium vanadate. If the hea-tirlg to fusion temperature is effected at a more rapid rate, alkali metal vanadate is not formed and such~a catalyst has been found to be less selective for the production of nitriles, even -though it is 20 an improvement over the fused catalyst without the alkali metal.
Thus, in accordance with -the particularly preferred embodiment, the catalyst includes bo-th vanadia and alkali metal vanadate, preferably sodium vanadate. Preferably at least 106 by weight of the alkali metal is present as the vanadate.
The supported vanadia catalyst of the present invention is particularly suitable for the production of nitriles by oxidative ammonolysis (ammoxidation). The organic reactant employed as a starting material for the production of nitriles by ammoxldation is a co~lpound including at least one alkyl group;
namely, aromatic, aliphatic, alicyclic and heterocyclic compounds having at least one alkyl group.
q6 As representative examples of alkyl substituted aromatic hydrocarbons which are suitable as starting materials, there may be mentioned the alkyl substituted benzenes and naphthalenes, and in particular, benzene which may contain -two or more alkyl 5 groups in which case the resulting product is a polynitrile.
The alkyl group generally con-tains no more than 4 carbon atoms, preferably no more than 2 carbon atoms. As particular examples of suitable alkyl substituted aromatic hydrocarbons, there is:
toluene; various xylenes to produce the various phthalonitriles;
10 ethyl benzene, trimethyl benzenes, methyl-naphthalenes, durene and the like.
As representative examples of suitable aliphatic compounds, there may be mentioned: olefinic hydrocarbons having at least one alkyl group, such as propylene and isobutylene to produce 15 acrylonitrile and methacrylonitrile, respectively.
As representative examples of suitable alicyclic compounds, there may be mentioned: methylcyclopentane, methylcyclohexane, the alkyl substituted decalins, and the like.
Th~ heterocyclic compounds useful as starting materials 20 for producing nitriles by ammoxidation in accordance with ;the present invention include alkyl substituted furans, pyrroles, indoles, thiophenes, pyrazoles r imidazoles, thiazoles, oxazoles, pyrans, pyridines, quinolines, isoquinolines, pyrimidines, pyridazines, pyrazines and the llke. The preferred heterocyclic 25 compounds are the alkyl, preferably lower alkyl, substltuted pyridines, with pyridines having an alkyl group in a beta-positlon with respect to the heterocycllc nitrogen atom belng partlcularly preferred ln that such pyrldines can be converted to nicotinonitrile; in particular, 3-picoline, 2, 3-and 2,5-30 dimethylpyridlne, 2-methyl-5-ethylpyridlne and 3-ethylpyrldlne.
The starting material, con~aining at least one alkyl group is converted to a nitrile by contacting the starting material with ammonia, in the vapor phase, in the presence of the supported vanadia catalyst of the present invent:ion, either in the absence or presence of a gas containing free oxygen, preferably in the absence of a gas con~aining free oxygen. The contacting is generally effected at a temperature from about 300C to about 500C, preferably from about 375C to about 475C, with the contact time generally ranging from about 0.5 to about 15 seconds, preferably from about 2 to about 8 seconds. Reaction pressures generally range from about 1 to about 5 atmospheres. The mole ratio of ammonia to starting material generally ranges from about 2:1 to about 16:1, preferably from about 3:1 to about 8:1. If a gas containing free oxygen is employed in the feed, the gas is employed in an amount such that the quantity of oxygen and starting material in the feed is ou~side of the explosive range.
In accordance with the preferred embodiment of the invention, the starting material and ammonia are contacted with the supported vanadia catalyst of the present invention in the absence of oxygen, with the supported vanadia catalyst being periodically passed to another reactor and contacted therein with a gas con-.
taining free oxygen to effect regeneration of the catalyst, generally at a time period from about 2 to about 20 minutes.
In general,the supported vanadia catalyst is not maintained on stream ~or a period greater than about 30 minutes, preferably from about 2 to about 10 minutes. The supported vanadia catalyst is then recycled to a nitrile productlon zone. It is believed -that the supported vanadia catalyst is reduced during the nitrile 30 production step and, consequently, periodic oxidation thereof is required to maintain the supported vanadia catalyst in the oxidized form necessary for the nitrile produc~lorl.
The invention wlll be further described with respect to the following examples:
EXAMPLE I
_ Catalyst A (Present Invention) 3000 g. of silica-alumina fluid bed catalyst suppor~ (Grace 135) was slurried in 4500 g. of 1% by weight of NaO~ and agitated for 30 minutes. After settling, the supernatant liquid was decanted and replaced with 4500 g. of water, and the mixture agitated for another 30 minutes. The mixture was again separated by decantation. After drying at 110C, the treated support contained 0.9 wt. % Na. This support was then blended with 2000 g. of powdered vanadia and heated at 1500F for 5 hours in a slowly rotating cylindrical kiln. After cooling, the catalyst was removed from the kiln and screened through a 40 mesh screen.
_atalyst B
3000 g. of a silica-a:Lumina fluid bed catalyst support (Grace 135) was blended with 2000 g. of powdered vanadia and heated at 1400F for 5 hours in a slowly rotating cylindrical kiln.
After cooling, the catalyst was removed from the kiln and screened through a 40 mesh screen.
Catalysts A and B were then employed for the production of isophthalonitrile under the following conditi.ons. The ammoxi-dation was effected in the absence of molecular oxygen, catalysts A and B being regenerated in a separate regenerator by contact with oxygen.
7~i T E I
Catalyst Type B A
Reactor Pressure, PSIG 10 10 Reactor Temp., E` 800 800 Regenerator Temp.,F 910-930 910-930 5 Catalyst circulation, gms/min. 56 53 Organic Feed Rate/cc/min. 3.3 3.4 Feed Composition m-xylene, wt.% 69 69 M-toluonitrile,w-t.% 31 31 10 NH3 in feed mol/mol. organic feed 9.1 8.8 Inert gas in feed mol/mol. organic feed 9.4 8.9 Conversion, mol% 52.5 41.5 15 Ultimate Yield of Isophthalonitrile Basis m-xylene, mol% 80.7 86.6 Basis ammonia, mol% 27 49 Improved results are obtained by using the catalyst of the present invention (Catalyst A) as evidenced by increased 20 ammonia and hydrocarbon yielcl.
EXAMPLE II
3000 g. of a silica-alumina fluid bed catalyst suppor~
(Grace 135) was slurried in 4500 g. of 1% by weight of NaOH
and agitated for 30 minutes. After settling, ~he supernatant liquid was decanted and replaced with 4500 g. of water, and the mixture agitated for another 30 minutes. The mixture was again separated by decantation. After drying at 110C, the treated support contained 0.9 wt. % Na. This support was then blended with 2000 g. of powdered vanadia and heated at the rate of 10F/
minute in a slowly rotating cylindrical kiln to a temperature of 1400F and maintained at such temperature for 5 hours. After cooling, the catalyst was removed from the kiln and screened through a 40 mesh screen.
Tabel II summarizes the results obtained when using this catalyst for the production of terephthalonitrile from p-xylene (Run 1) and the production of nicotinonitrile from beta-picoline (Run 2). The ammoxidation was effected in the absence of molecular oxygen, with catalysts being regenerated in a separate regenerator by contact with oxygen.
.
: :
~9_ _BLE II
Run 1 Run 2 Reactor Pressure, PSIG 25.0 15.0 Reactor Temp.,F 800 775 Regenerator Temp.,F 935-955 935-955 Catalyst circulation, yms/min. 112.8 73.8 Organic Feed Rate, cc/min. 6.7 8.0 NH3 in feed mol/mol. organic feed 7.8 5.0 Inert gas in feed mol/mol. oryanic feed 0.7 0.6 Conversion, mol% 50.67 30.05 In Run 1 the following selectivities and yields were achieved:
Selectivity mole %
Terephthalonitrile 93.53 p-tolunitrile 0.00 benzonitrile 0.04 carbon oxides 6.43 Yields, mole %
Ultimate Organic 93.53 Ammonia 65.71 In Run 2, the following selectivities and yields were achieved:
Selectivity, rnole %
Nicotinonitrile 89.66 Pyridine 0.74 Carbon Oxides 9.60 Yields, mole %
Ultimate Organic 89.66 Ammonia 66.70 EXAMPLE III
Two catalysts were prepared as described with reference to Example II, (40% vanadia and 1% sodium) except that one catalyst was heated at the rate of :lOF/min. and the second was heated at a rate of greater than 20Fimin.
Table III summarizes the results obtained when the catalysts were employed for producing isophthalonitrile from m-xylene. The amm~oxidatlon was effected in the absence of molecular oxygen, and the regeneration of the catalyst was effected on a cyclic basis rather than by continuous circulation of the catalyst, as in the previous Examples.
TA~LE III
~eating Rate for catalyst, F/min. > 20 10 Temperature, F 800 800 Catalyst Charge, g 400 400 Ca-t/Oil, g/cc 20.8 20 `
5 Pressure, psig 5 5 GHSV (STP),h 1 1040 1242 NH3/Organic, mol/mol 5.4 6 Selectivities, mol%
IPN 56.5 64.9 m-TN 33.9 22.3 BN - 1.7 CO~ 9.5 11.1 Conversion,% 37.2 47.4 Ultimate Yield,% 85.4 83.8 15 Space-Time Yield, g/gh 0.15 0~20 The catalyst produced by slow heating provides an lmproved selectivity in terms of conversion of methyl group to ni.trile.
The catalyst of the present inventi.on, when employed for the production of nitriles, provides improved hydrocarbon selectivity and ammonia yield over the catalyst described in U.S. Patent 3,963,645. While it is not intended to limit the scope of the invention, it is believed tha-t the improved catalytic effect results from a modification of the vanadia by reaction with the alkali metal at the fusion temperature.
Claims (19)
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A catalyst of vanadia supported on a porous support is an amount to provide a ratio by weight of vanadia to support from 0.3:1 to 3:1 substantially entirely within the pores of the support, said vanadia having been placed in molten form substantially within the pores of the support, the support having a surface area greater than 50m2/gram and a porosity greater than 0.4 cc/gram, said catalyst containing an alkali metal in an amount to provide a mole ratio of vanadium metal to alkali metal of from 2:1 to 30:1.
2. The catalyst claimed in Claim 1, wherein the support is silica-alumina.
3. The catalyst claimed in Claim 1 or Claim 2 wherein the alkali metal is sodium.
4. The catalyst claimed in Claim 1, wherein mole ratio of vanadium metal to alkali metal is from 8:1 to 20:1.
5. The catalyst claimed in Claim 1, wherein the support is gamma-alumina.
6. The catalyst of Claim 1, wherein at least 10% by weight of the alkali metal is present as alkali metal vanadate.
7. A process for the catalytic ammoxidation of a compound containing at least one alkyl group to a nitrile, which comprises effecting said ammoxidation with the catalyst of Claim 1.
8. The process claimed in Claim 7, wherein the compound is benzene substituted with at least one alkyl group.
9. The process claimed in Claim 7, wherein the compound is a pyridine substituted with at least one alkyl group which is in a beta-position with respect to the heterocyclic nitrogen.
10. A process for producing a supported vanadia catalyst, comprising:
treating a porous support having a surface area greater than 50 meters square per gm. and a porosity greater than 0.4 cc per gm. with an aqueous solution of an alkali metal hydroxide, and heating the treated support and vanadia on the support to above the vanadia fusion temperature, said vanadia and alkali A
metal hydroxide being employed in an amount to provide a ratio of vanadia to support by weight from 0.3:1 to 3:1 substantially entirely within the pores of the support and a mole ratio of vanadium metal to alkali metal of from 2:1 to 30:1.
treating a porous support having a surface area greater than 50 meters square per gm. and a porosity greater than 0.4 cc per gm. with an aqueous solution of an alkali metal hydroxide, and heating the treated support and vanadia on the support to above the vanadia fusion temperature, said vanadia and alkali A
metal hydroxide being employed in an amount to provide a ratio of vanadia to support by weight from 0.3:1 to 3:1 substantially entirely within the pores of the support and a mole ratio of vanadium metal to alkali metal of from 2:1 to 30:1.
11. The process claimed in Claim 10, wherein the support is treated with said alkali metal hydroxide prior to placing vanadia on the support.
12. The process claimed in Claim 10, wherein the support is treated with the aqueous solution of alkali metal hydroxide subsequent to placing said vanadia on the support.
13. The process claimed in Claim 10, wherein the support is treated with said alkali metal hydroxide simultaneously with placing said vanadia on said support.
14. The process claimed in Claim 10, wherein said alkali metal hydroxide is sodium hydroxide.
15. The process of Claim 22 wherein said support is gamma-alumina.
16. The process of Claim 22, wherein said support is silica-alumina.
17. The process claimed in Claim 10, which comprises heating a mixture of an alkali metal hydroxide and vanadia supported on a porous support having a surface area greater than 50 meters square per gram and a porosity greater than 0.4 cc per gram to the fusion temperature of vanadia at an average rate of less than 20°F per minute, said vanadia and alkali metal hydroxide being employed in an amount to provide a ratio of vanadia to support by weight of from 0.3:1 to 3:1 substantially entirely within the pores of the support and a mole ratio of vanadium metal to alkali metal of from 2:1 to 30:1; and maintaining the supported mixture at vanadia fusion temperature to place the vanadia substantially entirely within the pores of the support.
18. The process claimed in Claim 17, wherein the average heating rate is no greater than 10°F/min.
19. The process claimed in Claim 17, wherein the supported mixture is maintained at a temperature of 1300°F for a period of from 1 to 10 hours.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72706076A | 1976-09-27 | 1976-09-27 | |
| US727,060 | 1976-09-27 | ||
| US819,771 | 1977-07-28 | ||
| US05/819,771 US4092271A (en) | 1976-09-27 | 1977-07-28 | Supported vanadia catalyst for nitrile production and process for preparing the catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100476A true CA1100476A (en) | 1981-05-05 |
Family
ID=27111443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA285,116A Expired CA1100476A (en) | 1976-09-27 | 1977-08-19 | Supported vanadia catalyst and use thereof for nitrile production |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPS5342193A (en) |
| AR (1) | AR218264A1 (en) |
| AU (1) | AU513349B2 (en) |
| BR (1) | BR7706375A (en) |
| CA (1) | CA1100476A (en) |
| CH (1) | CH641156A5 (en) |
| CS (1) | CS216248B2 (en) |
| DD (1) | DD132785A5 (en) |
| DE (1) | DE2741625B2 (en) |
| DK (1) | DK157663C (en) |
| ES (1) | ES462675A1 (en) |
| FI (1) | FI63867C (en) |
| FR (1) | FR2365372A2 (en) |
| GB (1) | GB1539366A (en) |
| IE (1) | IE45969B1 (en) |
| NL (1) | NL178313C (en) |
| NO (1) | NO150146C (en) |
| PL (1) | PL119446B1 (en) |
| PT (1) | PT67087B (en) |
| RO (1) | RO73289A (en) |
| SE (1) | SE434706B (en) |
| YU (1) | YU40012B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0065704A1 (en) * | 1981-05-12 | 1982-12-01 | Ashland Oil, Inc. | Redox catalyst plus promoter for oxidation of hydrocarbons |
| DE3401676A1 (en) * | 1984-01-19 | 1985-07-25 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PRODUCING A V (ARROW DOWN) 2 (ARROW DOWN) O (ARROW DOWN) 5 (ARROW DOWN) AND ALKALISULFATE-CONTAINING CATALYST FOR THE OXIDATION OF SO (ARROW DOWN) 2 (ARROW DOWN) (ARROW DOWN) DOWN) |
| EP0253360B1 (en) * | 1986-07-15 | 1993-12-01 | Koei Chemical Co., Ltd. | Process for preparing nitriles |
| JPS63116465U (en) * | 1987-01-22 | 1988-07-27 | ||
| EP0556489A1 (en) * | 1992-02-19 | 1993-08-25 | Shell Internationale Researchmaatschappij B.V. | Process for the dehydrogenation of hydrocarbons |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1357675A (en) * | 1963-02-11 | 1964-04-10 | Aquitaine Petrole | New catalyst for the recovery of gaseous sulfur compounds contained in low concentrations in waste gases and flue gases, and their transformation into sulfur trioxide and process using such a catalyst |
| DE1290125C2 (en) * | 1963-11-06 | 1974-04-11 | PROCESS FOR THE PREPARATION OF BENZONITRILE | |
| US3963645A (en) * | 1969-02-27 | 1976-06-15 | The Lummus Company | Supported metal oxides |
| DE1930880B2 (en) * | 1969-06-18 | 1980-02-21 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of iso- and / or terephthalic acid dinitriles |
-
1977
- 1977-08-19 CA CA285,116A patent/CA1100476A/en not_active Expired
- 1977-08-25 AU AU28236/77A patent/AU513349B2/en not_active Expired
- 1977-08-26 FI FI772543A patent/FI63867C/en not_active IP Right Cessation
- 1977-09-08 AR AR269136A patent/AR218264A1/en active
- 1977-09-09 NL NLAANVRAGE7709953,A patent/NL178313C/en not_active IP Right Cessation
- 1977-09-15 DE DE2741625A patent/DE2741625B2/en not_active Withdrawn
- 1977-09-16 NO NO773192A patent/NO150146C/en unknown
- 1977-09-19 JP JP11251977A patent/JPS5342193A/en active Pending
- 1977-09-19 GB GB39031/77A patent/GB1539366A/en not_active Expired
- 1977-09-23 BR BR7706375A patent/BR7706375A/en unknown
- 1977-09-23 FR FR7728700A patent/FR2365372A2/en active Granted
- 1977-09-26 DD DD7700201203A patent/DD132785A5/en unknown
- 1977-09-26 CS CS776227A patent/CS216248B2/en unknown
- 1977-09-26 SE SE7710757A patent/SE434706B/en not_active IP Right Cessation
- 1977-09-26 PL PL1977201050A patent/PL119446B1/en unknown
- 1977-09-26 CH CH1172277A patent/CH641156A5/en not_active IP Right Cessation
- 1977-09-27 PT PT67087A patent/PT67087B/en unknown
- 1977-09-27 IE IE1974/77A patent/IE45969B1/en unknown
- 1977-09-27 DK DK427177A patent/DK157663C/en not_active IP Right Cessation
- 1977-09-27 RO RO7791679A patent/RO73289A/en unknown
- 1977-09-27 ES ES462675A patent/ES462675A1/en not_active Expired
- 1977-09-27 YU YU2287/77A patent/YU40012B/en unknown
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