USRE32484E - Oxidation catalysts - Google Patents
Oxidation catalysts Download PDFInfo
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- USRE32484E USRE32484E US06/528,860 US52886083A USRE32484E US RE32484 E USRE32484 E US RE32484E US 52886083 A US52886083 A US 52886083A US RE32484 E USRE32484 E US RE32484E
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H3/00—Mechanisms for operating contacts
- H01H3/32—Driving mechanisms, i.e. for transmitting driving force to the contacts
- H01H3/40—Driving mechanisms, i.e. for transmitting driving force to the contacts using friction, toothed, or screw-and-nut gearing
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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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
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- C07C2527/19—Molybdenum
- C07C2527/192—Molybdenum with bismuth
Definitions
- the instant catalyst on the other hand, is particularly and unexpectedly effective in the conversion of isoamylenes, methyl butanols, or diisoamylene to isoprene, despite the presence of an alkali metal as an essential ingredient, and a relatively high content of Group VIII Fourth Period element.
- This invention relates to oxydehydrogenation catalysts consisting essentially of an alkali metal as an essential catalytic ingredient in combination with oxides of bismuth, molybdenum and iron.
- the instant alkali metal containing catalyst is an improvement over prior art catalysts in that it is particularly suited to the catalytic oxydehydrogenation of isoamylenes, methyl butanols or mixtures thereof to isoprene.
- a catalyst particularly effective in one oxydehydrogenation reaction is conspicuously unable to perform as well in another.
- an oxydehydrogenation catalyst containing the oxides of bismuth, molybdenum, iron and nickel is disclosed in U.S. Pat. No. 3,414,631, and it is particularly efficient in the oxydehydrogenation of butene to butadiene but significantly less effective in the conversion of isoamylenes to isoprene.
- This peculiar and unexplained preference of a catalyst for one reaction over another apparently analogous one is reflected and focused by the absence of examples disclosing analyses of the products of reaction in a number of prior art disclosures.
- the alkali metal oxide-bismuth oxide-molybdenum oxide-iron oxide base catalyst disclosed herein is referred to as a mixture of metal oxides, but this is not to be construed as meaning that the catalyst is composed either in whole or in part of only these compounds.
- the proportions of alkali metal, bismuth, molybdenum and the Group VIII Fourth Period element in the catalyst may vary within the ranges described hereinafter.
- Preferred alkali metals are potassium, cesium and rubidium.
- Preferred alkaline earth metals are magnesium, calcium, strontium and barium.
- the instant catalyst may include promoters from Group V and particularly phosphorus, arsenic and antimony.
- the unsupported catalyst of the instant invention gives excellent results.
- a catalyst support which may constitute from 3 percent to 99 percent, and preferably between 5 percent and 95 percent by weight of the finished catalyst.
- Any known catalyst support such as alumina, pumice, silicon carbide, zirconia, titania, silica, alumina-silica, and the inorganic phosphates, silicates, aluminates, borates and carbonates stable under the reaction conditions may be used.
- the metal oxides can be blended together or can be formed separately and then blended or formed separately or together in situ.
- Promoter oxides are preferably incorporated into the alkali metal-bismuth-molybdenum-iron base catalyst by blending into the gel before calcining or by blending into the oven-dried base catalyst before calcining.
- a preferred manner of incorporating promoter elements is by choosing a water-soluble salt of the promoter element, forming an aqueous solution of the salt, and mixing the solution with a solution or a suspension of the base elements or salts thereof.
- the promoter elements may be incorporated by the use of soluble complex salts or compounds with the desired base elements which upon calcination will yield the desired ratio of the elements in the finished catalyst.
- the alkali metal may be introduced into the catalyst as an oxide or as any salt which upon calcination will yield the oxide.
- Preferred salts are the nitrates which are readily available and easily soluble.
- Bismuth may be introduced into the catalyst as an oxide or as any salt which upon calcination will yield the oxide. Most preferred are the water-soluble salts which are easily dispersible within the catalyst and which form stable oxides upon heat-treating.
- the most preferred salt for introducing bismuth is bismuth nitrate.
- iron component may be any compound of iron which, upon calcination, will result in the oxides.
- water-soluble salts are preferred for the ease with which they may be uniformly dispersed within the catalyst.
- ferric nitrate Most preferred is ferric nitrate.
- Cobalt and nickel are similarly introduced.
- any molybdenum oxide such as the dioxide, trioxide, pentoxide, or sesquioxide may be used; more preferred is a hydrolyzable or decomposable molybdenum salt such as a molybdenum halide.
- a preferred starting material is ammonium heptamolybdate.
- the alkali or alkaline earth metals may be introduced into the catalyst in the form of water-soluble salts or insoluble carbonates, hydroxides and the like, which result in the oxides upon heat-treating.
- phosphorus When phosphorus is desired in the catalyst it may be introduced as phosphoric acid, or as an alkali or alkaline earth phosphate, particularly if it is desired to neutralize the solution and at the same time introduce the desired elements as phosphates.
- Arsenic may be introduced as orthoarsenic acid, and antimony may be introduced as a slurry of hydrous antimony oxide formed in situ from the metal in nitric acid, or by the action of boiling nitric acid on antimony oxide.
- promoter elements may be introduced, starting with the metal, oxidizing the metal with an oxidizing acid such as nitric acid, and then incorporating the nitrate into the catalyst.
- an oxidizing acid such as nitric acid
- the nitrates are readily available and form a very convenient starting material.
- any compounds containing the desired catalyst components may be used provided that they result, upon heating to a temperature within the range disclosed hereinafter, in the oxides of the instant catalyst.
- Proper selection of the promoter elements and the proportions of the elements present in the catalyst will influence the selectivity of particular oxydehydrogenation reactions.
- one might use a relatively high amount of potassium and a lower amount of magnesium with a phosphorus promoter while in other cases one might use a minor quantity of a cesium promoter with a relatively high amount of barium without any phosphorus.
- the catalytic activity of the novel catalyst embodied in the present invention is enhanced by heating the catalyst at an elevated temperature.
- the catalyst mixture is dried and heated at a temperature of from 500° F. to 1250° F., more preferably at about 800° F. to 1150° F. for from 2 to 24 hours.
- the catalyst can be further heat-treated at a temperature above about 800° F. but below a temperature deleterious to the catalyst at which it is grossly decomposed, preferably in the range from about 800° F. to about 1400° F. for from 1 to 48 hours, in the presence of oxygen or an oxygen-containing gas such as air.
- activation temperature there appears to be no readily discernible correlation between activation temperature and the time required to effect activation.
- sufficiency of activation at any given set of conditions is ascertained by a spot test of a sample of the material for catalytic activity. Activation is best carried out in an open chamber, permitting circulation of air or oxygen, so that any oxygen consumed will be replaced.
- some of the instant catalysts can be further activated by subjecting heat-treated catalyst to a reducing atmosphere for a period of from about 1 hour to about 48 hours at a temperature in the range from about 400° F. to about 1250° F.
- This reducing treatment is conveniently accomplished by flowing a reducing gas such as ammonia, hydrogen or the like over the catalyst. It was found that catalysts treated with a reducing gas gave higher conversions to isoprene after some time, though during an initial short period of time, conversions were actually lower than those given by the same catalysts not subjected to the reducing treatment.
- the instant catalyst comprising an alkali metal as an essential catalytic ingredient with the combined oxides of bismuth, molybdenum and iron may be defined by the following formula:
- Q is an alkali metal
- R is an alkaline earth metal
- T is phosphorus, arsenic or antimony
- M is cobalt or nickel
- a, b and c are numbers in the range 0.1 to 12,
- d is a number from 0.1 to 8
- e is a number from 0 to 8
- f is a number from 0 to 6
- g is a number from 0 to 12
- x is a number determined by the valence requirements of the other elements present.
- the process of the instant invention is specifically concerned with the conversion of isoamylenes, methyl butanols or mixtures thereof to isoprene.
- This process involves passing a mixture of isoamylenes or any particular isomeric isoamylene, and a molecular oxygen-containing gas such as air, in the presence or absence of a diluent such as steam, carbon dioxide, nitrogen or other inert gas at relatively high temperatures over a catalyst of a composition described hereinabove.
- the above-described catalysts are active at temperatures in the range from about 500° F. to about 1000° F., and a preferred range for operation is between 650° F. and 900° F. In this temperature range the catalysts exhibit exceptional activity and selectivity.
- the pressure at which the instant process is usually conducted is about atmospheric, although pressures of from slightly below atmospheric up to and above 3 atmospheres are operable.
- the apparent contact time employed in the instant process may be within the range of 0.01 to 20 seconds, and for good selectivity and yields a contact of from 0.1 to 10 seconds is preferred.
- Molar ratios of isoamylenes to air may vary from about 1:1 to about 1:20. Ratios near the higher limit usually make for poor selectivity and ratios near the lower limit tend to decrease catalyst activity.
- the preferred molar ratio of isoamylenes to air is in the range of about 1:1 to 1:10. It may be advantageous to include gases such as steam, carbon dioxide or nitrogen in addition to the nitrogen contained in the air fed to the reactor. However, for economic reasons it is usually not desirable to add more than 10 volumes of diluent gas for each volume of isoamylene in the feed.
- the reactor employed for the conversion of isoamylenes, methyl butanols or mixtures thereof to isoprene in the instant invention may be a fixed-bed reactor, or a fluid-bed reactor. Changes in the physical characteristics of the catalyst described above, particularly to suit either the fluid-bed or the fixed-bed reactor, may be made according to known methods familiar to those skilled in the art.
- the particular reactor employed in the instant process for the examples appended hereto was a standard reactor with a fixed catalyst bed. The catalyst volume was about 20 cc., and the catalyst mesh size was 20-35 Tyler screen mesh. The gases were metered to the reactor with rotameters.
- reaction products were analyzed by means of a gas chromatograph
- the column employed was a one-fourth (1/4) inch diameter by 4 meter column packed with 20 percent orthonitrophenetole on Chromosorb W for hydrocarbons.
- Carbon dioxide and carbon monoxide were determined by means of a Fisher gas partitioner, using hexamethyl phosporamide and molecular sieve columns in series.
- Isoamylenes, methyl butanols and isoprene were analyzed by passing the reactor effluent gases over a solid drying agent and then into a gas sampling valve which was opened periodically for gas chromatographic analysis.
- a specific catalyst was made as follows: 36.4 grams bismuth nitrate, Bi(NO 3 ) 3 ⁇ 5H 2 O, were dissolved in 700 ml. dilute nitric acid taken in a large beaker. 7.6 grams potassium nitrate, KNO 3 , 120 grams cobaltous nitrate, Co(NO 3 ) 2 ⁇ 6H 2 O, and 182 grams ferric nitrate,
- Particular physical characteristics such as surface area, density, particle size, and the like may be obtained by a judicious choice of proportions of catalyst elements, the ratio of catalyst to catalyst support, and the manner in which catalyst is preliminarily calcined prior to its final heat treatment, all of which characteristics may be modified to suit the particular reactor and predetermined conditions of reaction in accordance with known skills, and none of which physical characteristics is specifically tabulated herein.
- Table II lists various promoted catalysts with and without a catalyst support under varying temperature of reaction, contact time, and air:nitrogen ratios.
- Table III is a comparison of a prior art catalyst and that of the instant invention. It will be noted that the latter contains an alkali metal as an essential catalytic ingredient.
- the effluent would preferably be cooled by indirect heat exchange with the incoming feed and then scrubbed with water or dilute caustic to neutralize traces of organic acids present, to inhibit the formation of oily polymeric by-products, and to condense and remove steam. If air is used to supply the oxygen, the remaining mixture is preferably compressed and scrubbed with oil to separate the hydrocarbons from the nitrogen, carbon dioxide and carbon monoxide.
- the hydrocarbon may be stripped from the oil and subjected to an extractive distillation or a copper ammonium acetate treatment in the known manner to separate and recover the diolefin. Unreacted isoamylenes would be recycled to the reactor from the recovery section, and it is not essential that the recycle stream be pure isoamylenes. It can contain carbon dioxide, carbon monoxide, nitrogen and steam since these gases would serve only as diluents.
- the term “consisting essentially of” is meant to include the main elements, namely, alkali metal, bismuth, molybdenum and iron, and the specified promoters where applicable, but is not meant to exclude small amounts of other elements, the presence of which may be incident to the quality, origin or particular processing of raw materials used to manufacture the instant catalyst. It will be apparent to thse skilled in the catalytic oxidation art that embodiments of the invention, other than those specifically described for illustrative purposes, may be evolved and that modifications in these specific embodiments may be made without departing from the spirit and scope of the invention as expressed above and as defined in the appended claims.
Abstract
A vapor phase catalytic oxydehydrogenation process for the conversion of a steam of mixed isomeric isoamylenes, methyl butanols or mixtures thereof to isoprene with relatively short contact times at a reactor temperature in the range of 500° F. to 1100° F. at from 0.5 to about 10 atmospheres pressure. The catalysts comprise an alkali metal as an essential catalytic ingredient.
Description
.Iadd.This is a continuation of application Ser. No. 713,024, filed Aug. 9, 1976, now abandoned. .Iaddend.
This application is a continuation-in-part of our copending and now abandoned application Ser. No. 794,469 filed Dec. 30, 1968.
The catalytic oxydehydrogenation of olefins for the production of butadiene and isoprene has been the subject of continued interest for many years. The prior art encompasses catalysts consisting of elements which appear to cover the entire spectrum of the Periodic Table. Particular oxydehydrogenation catalysts are disclosed in U.S. Pat. Nos. 2,991,321; 2,991,322; 3,067,272; 3,110,746; 3,119,111. An all-important requirement in the commercial production of any chemical by catalytic oxidation is that the catalyst exhibit not only high conversion but extremely high selectivity for long periods of time. The foregoing patents, drawn to oxydehydrogenation catalysts, are disclosed to be generally effective in several reactions. The instant catalyst on the other hand, is particularly and unexpectedly effective in the conversion of isoamylenes, methyl butanols, or diisoamylene to isoprene, despite the presence of an alkali metal as an essential ingredient, and a relatively high content of Group VIII Fourth Period element.
This invention relates to oxydehydrogenation catalysts consisting essentially of an alkali metal as an essential catalytic ingredient in combination with oxides of bismuth, molybdenum and iron. The instant alkali metal containing catalyst is an improvement over prior art catalysts in that it is particularly suited to the catalytic oxydehydrogenation of isoamylenes, methyl butanols or mixtures thereof to isoprene.
It is noteworthy that, in general, a catalyst particularly effective in one oxydehydrogenation reaction is conspicuously unable to perform as well in another. For example, an oxydehydrogenation catalyst containing the oxides of bismuth, molybdenum, iron and nickel is disclosed in U.S. Pat. No. 3,414,631, and it is particularly efficient in the oxydehydrogenation of butene to butadiene but significantly less effective in the conversion of isoamylenes to isoprene. This peculiar and unexplained preference of a catalyst for one reaction over another apparently analogous one, is reflected and focused by the absence of examples disclosing analyses of the products of reaction in a number of prior art disclosures. In any event, there is significant utility of the instant invention in the catalytic oxidation of olefins to unsaturated aldehydes and acids, and for the catalytic ammoxidation of olefins to unsaturated nitriles.
The alkali metal oxide-bismuth oxide-molybdenum oxide-iron oxide base catalyst disclosed herein is referred to as a mixture of metal oxides, but this is not to be construed as meaning that the catalyst is composed either in whole or in part of only these compounds. The proportions of alkali metal, bismuth, molybdenum and the Group VIII Fourth Period element in the catalyst may vary within the ranges described hereinafter. Preferred alkali metals are potassium, cesium and rubidium. Preferred alkaline earth metals are magnesium, calcium, strontium and barium. Additionally, the instant catalyst may include promoters from Group V and particularly phosphorus, arsenic and antimony.
The unsupported catalyst of the instant invention gives excellent results. In a commercial reactor, for economic reasons, it might be desirable to use a catalyst support which may constitute from 3 percent to 99 percent, and preferably between 5 percent and 95 percent by weight of the finished catalyst. Any known catalyst support such as alumina, pumice, silicon carbide, zirconia, titania, silica, alumina-silica, and the inorganic phosphates, silicates, aluminates, borates and carbonates stable under the reaction conditions may be used.
In the preparation of the promoted catalysts useful in this invention, the metal oxides can be blended together or can be formed separately and then blended or formed separately or together in situ. Promoter oxides are preferably incorporated into the alkali metal-bismuth-molybdenum-iron base catalyst by blending into the gel before calcining or by blending into the oven-dried base catalyst before calcining. A preferred manner of incorporating promoter elements is by choosing a water-soluble salt of the promoter element, forming an aqueous solution of the salt, and mixing the solution with a solution or a suspension of the base elements or salts thereof. Optionally, the promoter elements may be incorporated by the use of soluble complex salts or compounds with the desired base elements which upon calcination will yield the desired ratio of the elements in the finished catalyst.
The alkali metal may be introduced into the catalyst as an oxide or as any salt which upon calcination will yield the oxide. Preferred salts are the nitrates which are readily available and easily soluble.
Bismuth may be introduced into the catalyst as an oxide or as any salt which upon calcination will yield the oxide. Most preferred are the water-soluble salts which are easily dispersible within the catalyst and which form stable oxides upon heat-treating. The most preferred salt for introducing bismuth is bismuth nitrate.
To introduce the iron component into the catalyst one may use any compound of iron which, upon calcination, will result in the oxides. As with the other elements, water-soluble salts are preferred for the ease with which they may be uniformly dispersed within the catalyst. Most preferred is ferric nitrate. Cobalt and nickel are similarly introduced.
To introduce the molybdenum component, any molybdenum oxide such as the dioxide, trioxide, pentoxide, or sesquioxide may be used; more preferred is a hydrolyzable or decomposable molybdenum salt such as a molybdenum halide. A preferred starting material is ammonium heptamolybdate.
The alkali or alkaline earth metals may be introduced into the catalyst in the form of water-soluble salts or insoluble carbonates, hydroxides and the like, which result in the oxides upon heat-treating. When phosphorus is desired in the catalyst it may be introduced as phosphoric acid, or as an alkali or alkaline earth phosphate, particularly if it is desired to neutralize the solution and at the same time introduce the desired elements as phosphates. Arsenic may be introduced as orthoarsenic acid, and antimony may be introduced as a slurry of hydrous antimony oxide formed in situ from the metal in nitric acid, or by the action of boiling nitric acid on antimony oxide. Other promoter elements may be introduced, starting with the metal, oxidizing the metal with an oxidizing acid such as nitric acid, and then incorporating the nitrate into the catalyst. Generally, the nitrates are readily available and form a very convenient starting material.
Other variations in starting materials will suggest themselves to one skilled in the art, particularly when the preferred starting materials mentioned hereinabove are unsuited to the economics of large-scale manufacture. In general, any compounds containing the desired catalyst components may be used provided that they result, upon heating to a temperature within the range disclosed hereinafter, in the oxides of the instant catalyst. Proper selection of the promoter elements and the proportions of the elements present in the catalyst will influence the selectivity of particular oxydehydrogenation reactions. Thus, in some cases one might use a relatively high amount of potassium and a lower amount of magnesium with a phosphorus promoter, while in other cases one might use a minor quantity of a cesium promoter with a relatively high amount of barium without any phosphorus.
The catalytic activity of the novel catalyst embodied in the present invention is enhanced by heating the catalyst at an elevated temperature. Preferably the catalyst mixture is dried and heated at a temperature of from 500° F. to 1250° F., more preferably at about 800° F. to 1150° F. for from 2 to 24 hours. If the activity-selectivity relationship is not satisfactory, the catalyst can be further heat-treated at a temperature above about 800° F. but below a temperature deleterious to the catalyst at which it is grossly decomposed, preferably in the range from about 800° F. to about 1400° F. for from 1 to 48 hours, in the presence of oxygen or an oxygen-containing gas such as air.
There appears to be no readily discernible correlation between activation temperature and the time required to effect activation. The sufficiency of activation at any given set of conditions is ascertained by a spot test of a sample of the material for catalytic activity. Activation is best carried out in an open chamber, permitting circulation of air or oxygen, so that any oxygen consumed will be replaced.
It has also been found that some of the instant catalysts can be further activated by subjecting heat-treated catalyst to a reducing atmosphere for a period of from about 1 hour to about 48 hours at a temperature in the range from about 400° F. to about 1250° F. This reducing treatment is conveniently accomplished by flowing a reducing gas such as ammonia, hydrogen or the like over the catalyst. It was found that catalysts treated with a reducing gas gave higher conversions to isoprene after some time, though during an initial short period of time, conversions were actually lower than those given by the same catalysts not subjected to the reducing treatment.
The instant catalyst comprising an alkali metal as an essential catalytic ingredient with the combined oxides of bismuth, molybdenum and iron may be defined by the following formula:
Bi.sub.a Fe.sub.b Mo.sub.c Q.sub.d R.sub.e T.sub.f M.sub.g O.sub.x
wherein
Q is an alkali metal,
R is an alkaline earth metal,
T is phosphorus, arsenic or antimony,
M is cobalt or nickel; and
wherein
a, b and c are numbers in the range 0.1 to 12,
d is a number from 0.1 to 8,
e is a number from 0 to 8,
f is a number from 0 to 6,
g is a number from 0 to 12,
x is a number determined by the valence requirements of the other elements present.
The process of the instant invention is specifically concerned with the conversion of isoamylenes, methyl butanols or mixtures thereof to isoprene. This process involves passing a mixture of isoamylenes or any particular isomeric isoamylene, and a molecular oxygen-containing gas such as air, in the presence or absence of a diluent such as steam, carbon dioxide, nitrogen or other inert gas at relatively high temperatures over a catalyst of a composition described hereinabove.
It is a noteworthy feature of the instant process that a mixed stream of isomeric isoamylenes and methyl butanols, without regard to the molar balance of isomers and methyl butanols, may be fed to the reactor with substantially the same results in conversion. In all of the example appended hereto, the more easily converted 3-methyl butene-1 was deliberately excluded from the feed, which consisted of a mixture of 2-methyl butene-1 and 2-methyl butene-2. The alcohol utilized in the examples was t-amyl alcohol although 2-methyl butanol-3,3-methyl butanol-1, and 2-methyl butanol-1 can also be converted.
The above-described catalysts are active at temperatures in the range from about 500° F. to about 1000° F., and a preferred range for operation is between 650° F. and 900° F. In this temperature range the catalysts exhibit exceptional activity and selectivity.
The pressure at which the instant process is usually conducted is about atmospheric, although pressures of from slightly below atmospheric up to and above 3 atmospheres are operable.
The apparent contact time employed in the instant process may be within the range of 0.01 to 20 seconds, and for good selectivity and yields a contact of from 0.1 to 10 seconds is preferred.
Molar ratios of isoamylenes to air may vary from about 1:1 to about 1:20. Ratios near the higher limit usually make for poor selectivity and ratios near the lower limit tend to decrease catalyst activity. The preferred molar ratio of isoamylenes to air is in the range of about 1:1 to 1:10. It may be advantageous to include gases such as steam, carbon dioxide or nitrogen in addition to the nitrogen contained in the air fed to the reactor. However, for economic reasons it is usually not desirable to add more than 10 volumes of diluent gas for each volume of isoamylene in the feed.
The reactor employed for the conversion of isoamylenes, methyl butanols or mixtures thereof to isoprene in the instant invention may be a fixed-bed reactor, or a fluid-bed reactor. Changes in the physical characteristics of the catalyst described above, particularly to suit either the fluid-bed or the fixed-bed reactor, may be made according to known methods familiar to those skilled in the art. The particular reactor employed in the instant process for the examples appended hereto was a standard reactor with a fixed catalyst bed. The catalyst volume was about 20 cc., and the catalyst mesh size was 20-35 Tyler screen mesh. The gases were metered to the reactor with rotameters. The reaction products were analyzed by means of a gas chromatograph The column employed was a one-fourth (1/4) inch diameter by 4 meter column packed with 20 percent orthonitrophenetole on Chromosorb W for hydrocarbons. Carbon dioxide and carbon monoxide were determined by means of a Fisher gas partitioner, using hexamethyl phosporamide and molecular sieve columns in series. Isoamylenes, methyl butanols and isoprene were analyzed by passing the reactor effluent gases over a solid drying agent and then into a gas sampling valve which was opened periodically for gas chromatographic analysis.
A specific catalyst was made as follows: 36.4 grams bismuth nitrate, Bi(NO3)3 ·5H2 O, were dissolved in 700 ml. dilute nitric acid taken in a large beaker. 7.6 grams potassium nitrate, KNO3, 120 grams cobaltous nitrate, Co(NO3)2 ·6H2 O, and 182 grams ferric nitrate,
Fe(NO.sub.3).sub.3 ·9H.sub.2 O
were all added to the solution and also dissolved. 8.65 grams phosphoric acid (85 percent) were added to the solution while it was continuously stirred. 159 grams ammonium molybdate, (NH4)6 Mo7 O24 ·4H2 O, were dissolved in a small quantity of water and slowly added to the foregoing acidic solution. Precipitation wes instantaneous. The solution was constantly stirred and heated over a hot plate until the entire mass gelled. The gel was spooned out into trays and dried in a conventional convection oven at 130° C. for 16 hours. The dried mass was then calcined in air at 800° F. for 16 hours. A final heat-treatment in air at 1000° F. for 3 hours was given the catalyst prior to loading into the reactor.
Other catalyst compositions were prepared in a similar manner using, for convenience, water-soluble salts of the elements desired in the final composition, though as has been disclosed hereinbefore, the use of water-soluble salts is not essential.
In Table I appended hereto, various catalysts, prepared in a manner similar to that described in Example 1 above, are effective in the manufacture of isoprene under the tabulated process conditions. All runs in Table I were made in a fixed-bed reactor at 750° F. with a feed consisting of a mixture of 2-methyl butene-1 and 2-methyl butene-2 diluted with nitrogen, and the molar ratio of air:isoamylenes:nitrogen was about 4:1:4. Particular physical characteristics such as surface area, density, particle size, and the like may be obtained by a judicious choice of proportions of catalyst elements, the ratio of catalyst to catalyst support, and the manner in which catalyst is preliminarily calcined prior to its final heat treatment, all of which characteristics may be modified to suit the particular reactor and predetermined conditions of reaction in accordance with known skills, and none of which physical characteristics is specifically tabulated herein.
The appended Table II lists various promoted catalysts with and without a catalyst support under varying temperature of reaction, contact time, and air:nitrogen ratios.
The appended Table III is a comparison of a prior art catalyst and that of the instant invention. It will be noted that the latter contains an alkali metal as an essential catalytic ingredient.
The appended Table IV lists runs utilizing the instant catalyst on some preferred supports.
In the appended Table V, two runs are shown utilizing a catalyst consisting of 60 percent Fe9 Bi3 PMo12 Ox ·K2 SO4 and 40 percent TiO2, wherein x is a number taken to satisfy the oxygen requirements of the elements in the catalyst. The reactor was a fixed bed, and the contact time was 4 seconds. In one case a t-amyl alcohol feed was used, while in the other an equimolor mixture of t-amyl alcohol and 2-methyl butene-2 was used.
In all of the examples tabulated in the tables hereinbelow, small quantities of by-products are formed which are not specifically identified (or quantified in the tables) and have been disregarded in the calculations. These by-products may be oxidation products such as the aldehydes and acids and are usually present as relatively high molecular weight condensation products with an oily appearance.
In the examples listed hereinbelow, the following definitions are employed: ##EQU1##
From the foregoing description of the manner in which the experimental runs were made, it will be apparent that there were no provisions for many process steps which would be engineered into a commercial unit. For example, in a commercial reactor, the effluent would preferably be cooled by indirect heat exchange with the incoming feed and then scrubbed with water or dilute caustic to neutralize traces of organic acids present, to inhibit the formation of oily polymeric by-products, and to condense and remove steam. If air is used to supply the oxygen, the remaining mixture is preferably compressed and scrubbed with oil to separate the hydrocarbons from the nitrogen, carbon dioxide and carbon monoxide. The hydrocarbon may be stripped from the oil and subjected to an extractive distillation or a copper ammonium acetate treatment in the known manner to separate and recover the diolefin. Unreacted isoamylenes would be recycled to the reactor from the recovery section, and it is not essential that the recycle stream be pure isoamylenes. It can contain carbon dioxide, carbon monoxide, nitrogen and steam since these gases would serve only as diluents.
In the claims below, the term "consisting essentially of" is meant to include the main elements, namely, alkali metal, bismuth, molybdenum and iron, and the specified promoters where applicable, but is not meant to exclude small amounts of other elements, the presence of which may be incident to the quality, origin or particular processing of raw materials used to manufacture the instant catalyst. It will be apparent to thse skilled in the catalytic oxidation art that embodiments of the invention, other than those specifically described for illustrative purposes, may be evolved and that modifications in these specific embodiments may be made without departing from the spirit and scope of the invention as expressed above and as defined in the appended claims.
TABLE I
__________________________________________________________________________
Contact
Percent per pass
Total
time,
conversion to
percent
Selectivity,
Example
Catalyst secs.
Isoprene
CO.sub.2
CO conversion
percent
__________________________________________________________________________
1 KFe.sub.4 BiMo.sub.12 Co.sub.5.5 O.sub.x
3.2 50.2 6.26
1.30
57.7 87.0
2 K.sub.0.28 Fe.sub.4 Bi.sub.3 PMo.sub.12 O.sub.x
3.8 33.8 5.53
1.03
43.0 78.6
3 KFe.sub.4 Bi.sub.3 PMo.sub.12 O.sub.x
3.8 44.6 6.33
1.04
53.4 83.5
4 K.sub.2 Fe.sub.9 Bi.sub.3 ; PMo.sub.12 O.sub.x
3.5 50.7 6.73
1.40
60.7 83.4
5 K.sub.3 Fe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.7 47.5 6.42
0.92
57.5 82.7
6 K.sub.4.5 Fe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.8 33.0 7.77
1.12
41.8 78.9
7 K.sub.6 Fe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.7 18.5 5.13
0.61
24.7 74.8
8 RbFe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.7 53.6 3.95
0.90
61.5 87.2
9 Li.sub.0.1 Fe.sub.4 Bi.sub.3 PMo.sub.12 O.sub.x
3.9 36.0 7.38
1.32
45.5 79.1
10 Li.sub.2 Fe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.8 34.5 7.08
1.30
42.8 80.5
11 K.sub.3 Fe.sub.9 Bi.sub.2 PMo.sub.12 O.sub.x
3.6 51.1 5.78
0.85
59.9 85.3
12 CsFe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.6 52.4 5.17
0.82
61.5 85.2
13 CsFe.sub.4 Bi.sub.3 PMo.sub.12 O.sub.x
3.5 60.4 5.95
1.00
71.5 84.4
14 K.sub.2 Fe.sub.4 BiPMo.sub.12 O.sub.x
3.4 53.2 7.28
1.29
61.8 86.2
15 K.sub.4 Fe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
3.6 43.7 6.98
1.09
53.1 82.4
16 K.sub.2 Fe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x
0.2 54.1 6.7
1.5
57.7 87.0
17 NaFe.sub.4 Bi.sub.3 PMo.sub.12 O.sub.x
2.5 32.9 6.2
1.3
40.4 81.5
18 K.sub.0.1 Fe.sub.2 Bi.sub.0.5 Sb.sub.0.8 Mo.sub.6 O.sub.x
.5 49.8 5.7
1.4
56.9 88.0
__________________________________________________________________________
TABLE II
__________________________________________________________________________
Ex- Air/N.sub.2 *
Contact Total
Percent
am- Temp.,
mole time,
Percent conversion
con-
selec-
ple
Catalyst °F.
ratio
secs.
Isoprene
CO CO.sub.2
version
tivity
__________________________________________________________________________
700 6/2.5
4 6.0 0.3
1.8
8.1
74
19 82.5% KCo.sub.2 Ni.sub.0.5 Fe.sub.0.5 Bi.sub.0.5 AsMo.sub.12 O.sub.x.17
.5% SiO.sub.2 750 6/2.6
4 24.3 1.7
9.0
32.0
76
support 800 6/2.6
4 35.2 1.8
12.0
49.0
71.9
650 6/2.6
4 7.5 1.8
8.0
17.3
43.4
20 82.5% KNi.sub.10.5 FeBi.sub.0.5 Sb.sub.0.5 Mo.sub.12 O.sub.x.17.5%
SiO.sub.2 support 700 6/2.5
4 32.3 3.0
11.8
47.1
68.5
750 6/2.6
4 36.4 2.8
11.8
51.0
71.3
700 6.2/3.7
1 15.2 1.1
5.4
21.7
70.0
21 100% KNi.sub. 10.5 FeBi.sub.0.5 Sb.sub.0.5 Mo.sub.12 O.sub.x
750 6.3/3.8
1 31.7 2.0
10.4
44.1
71.9
800 6.6/3.9
1 33.2 1.8
12.6
47.6
69.7
700 5.4/3.2
1 9.6 0.8
3.4
13.8
69.6
22 80% KCo.sub.0.5 Fe.sub.4 BiPMo.sub.12 O.sub.x.20% Al.sub.2 O.sub.3
support
750 5.6/3.4
1 31.7 3.6
8.3
43.6
72.6
__________________________________________________________________________
*Per mole isoamylene.
TABLE III
__________________________________________________________________________
Contact
Percent per pass
Total
Percent
Molar ratio
Temp.
time conversion to-
con-
selec-
Example
Catalyst air/N.sub.2.sup.1
(°F.)
(secs.)
Isoprene
CO.sub.2
CO version
tivity
__________________________________________________________________________
23 Bi.sub.2 FeMo.sub.4.5 O.sub.x.sup.2
4.02/3.8
750 2 25.9 8.73
1.38
36.01
72.0
24 K.sub.0.378 Bi.sub.2 Fe.sub.1 Mo.sub.4.5 O.sub.x
4/4 750 2 50.0 6.24
1.03
59.90
83.4
25 Bi.sub.0.5 Fe.sub.1 Mo.sub.1.34 O.sub.x.sup.2
4/4 750 2 28.2 8.57
1.40
38.70
72.8
26 K.sub.0.1 Bi.sub.0.5 Fe.sub.3 Mo.sub.1.34 O.sub.x
4/4 750 2 54.5 5.42
1.00
64.00
85.1
__________________________________________________________________________
.sup.1 Per mole isoamylenes.
TABLE IV
__________________________________________________________________________
Molar Contact
Percent per
Total
Percent
ratio,
Temp.
time conversion to-
Con-
selec-
Example
Catalyst and support air/N.sub.2.sup.2
(°F.)
(secs.)
Isoprene
CO.sub.2
CO version
tivity
__________________________________________________________________________
27 65% KFe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x.35% Illinois mineral
(1160).sup.2 4/4 750 4 46.4 6.7
1.3
55.3
82.5
28 80% KFe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x.20% pumice
4/4 750 4 49.6 7.0
1.3
60.0
82.7
29 80% KFe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x.20% Aluminum
4/4sphate
750 4 41.8 6.2
1.3
54.0
77.4
30 20% KFe.sub.9 Bi.sub.3 PMo.sub.12 O.sub.x.80% Alundum
4/4 750 4 36.2 8.8
0.7
44.8
79.5
__________________________________________________________________________
.sup.1 Per mole isoamylenes.
.sup.2 99% amorphous silica.
TABLE X
______________________________________
Example 32
1/1 (molar)
Example 31
t-amyl alcohol
t-amyl 2-methyl
Feed alcohol butene-2
______________________________________
Air/feed mole ratio
3.87 3.74
Products, percent carbon basis:
2-methyl butene-1 14.4 16.6
2-methyl butene-2 40.3 45.9
Isoprene 41.4 31.2
CO.sub.2 5.3 5.5
CO 0.9 0.8
Conversion, carbon basis
45.3 37.6
Selectivity 91.4 83.1
t-Amyl alcohol conversion, percent
100 100
______________________________________
Note-
Contact time: 4 seconds: 60% Fe.sub.4 Bi.sub.3 Mo.sub.12 O.sub.x.K.sub.2
SO and 40% TiO.sub.3.
Claims (9)
- isoprene..]. .[.2. The process of claim 1 wherein said molecular oxygen-containing gas is air..]. .[.3. The process of claim 2 wherein the molar ratio of isoamylenes, methyl butanols or mixtures thereof to air is from 1:0.5 to 1:30..]. .[.4. The process of claim 1 wherein nitrogen is included in the feed stream to said reaction zone..]. .[.5. The process of
- claim 1 wherein said catalyst is supported on a catalyst support..]. 6. A catalyst composition consisting essentially of an activated catalytic oxide complex of an alkali metal, bismuth, iron and molybdenum as essential catalytic ingredients, and defined by the following formula:
Bi.sub.a Fe.sub.b Mo.sub.c Q.sub.d R.sub.e T.sub.f M.sub.g O.sub.x
whereinQ is an alkali metal,R is an alkaline earth metal,T is phosphorus, arsenic or antimony,M is cobalt .Iadd.and .Iaddend.or nickel, andwhereina, b and c are numbers in the range 0.1 to 12,d is a number from 0.1 to 8,e is a number from 0 to 8,f is a number from 0 to 6,g is a number from 0 to 12, andx is a number determined by the valence requirements of the other elements - present. 7. The composition of claim 6 wherein Q is potassium. 8. The
- catalyst composition of claim 7 containing phosphorus. 9. The composition
- of claim 8 containing cobalt. 10. The composition of claim 8 containing
- nickel. 11. The composition of claim 6 supported on a catalyst support present in a range from 5 percent to 95 percent by weight of the supported
- catalyst. 12. The composition of claim 7 containing cobalt and nickel. .Iadd.13. The composition of claim 7 containing Nickel. .Iaddend. .Iadd.14. The composition of claim 7 containing cobalt. .Iaddend. .Iadd.15. The composition of claim 6 wherein Q is potassium and M is cobalt, and wherein e equals 0, f equals 0, and g is a number larger than 0. .Iaddend. .Iadd.16. The composition of claim 7 containing antimony. .Iaddend. .Iadd.17. The composition of claim 7 containing arsenic. .Iaddend. .Iadd.18. The composition of claim 14 wherein said catalyst is
- supported on silica. .Iaddend. .Iadd.19. The composition of claim 6 wherein Q is cesium. .Iaddend. .Iadd.20. The composition of claim 19 containing nickel. .Iaddend. .Iadd.21. The composition of claim 19 containing cobalt. .Iaddend. .Iadd.22. The composition of claim 19 containing arsenic. .Iaddend. .Iadd.23. The composition of claim 19 containing phosphorous. .Iaddend. .Iadd.24. The composition of claim 19 containing antimony. .Iaddend. .Iadd.25. The composition of claim 19 wherein said catalyst is supported on silica. .Iaddend. .Iadd.26. The composition of claim 6 wherein Q is rubidium. .Iaddend. .Iadd.27. The composition of claim 26 containing nickel. .Iaddend. .Iadd.28. The composition of claim 26 containing cobalt. .Iaddend. .Iadd.29. The composition of claim 26 containing antimony. .Iaddend. .Iadd.30. The composition of claim 26 containing phosphorous. .Iaddend. .Iadd.31. The composition of claim 26 containing arsenic. .Iaddend. .Iadd.32. The composition of claim 26 wherein said catalyst is supported on silica.
- .Iaddend. .Iadd.33. The composition of claim 6 containing nickel. .Iaddend. .Iadd.34. The composition of claim 6 containing cobalt. .Iaddend. .Iadd.35. The composition of claim 6 wherein Q is sodium. .Iaddend. .Iadd.36. A catalyst composition of claim 6 wherein c is 12. .Iaddend. .Iadd.37. A catalyst composition of claim 15 wherein c is 12. .Iaddend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/528,860 USRE32484E (en) | 1968-12-30 | 1983-09-02 | Oxidation catalysts |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79446968A | 1968-12-30 | 1968-12-30 | |
| US06/528,860 USRE32484E (en) | 1968-12-30 | 1983-09-02 | Oxidation catalysts |
Related Parent Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US79446968A Continuation-In-Part | 1968-12-30 | 1968-12-30 | |
| US86793469A Reissue | 1968-12-30 | 1969-10-20 | |
| US05713024 Continuation | 1976-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE32484E true USRE32484E (en) | 1987-08-25 |
Family
ID=27062855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/528,860 Expired - Lifetime USRE32484E (en) | 1968-12-30 | 1983-09-02 | Oxidation catalysts |
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Cited By (4)
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|---|---|---|---|---|
| US4965393A (en) * | 1988-03-03 | 1990-10-23 | Nitto Chemical Industry Co., Ltd. | Process for producing acrylonitrile |
| US5840955A (en) * | 1997-11-25 | 1998-11-24 | Sockell; Edward J. | Waste minimization and product recovery process |
| US6596897B1 (en) * | 1997-09-03 | 2003-07-22 | China Petro-Chemical Corporation | Catalyst for producing acrylonitrile |
| US20100099936A1 (en) * | 2008-10-17 | 2010-04-22 | Chae-Ho Shin | Complex oxide catalyst of bi/mo/fe for the oxidative dehydrogenation of 1-butene to 1,3-butadiene and process thereof |
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| US3405172A (en) * | 1962-12-19 | 1968-10-08 | Distillers Co Yeast Ltd | Preparation of acrylic acid with the prevention of formation of acrylic polymers |
| US3328315A (en) * | 1963-05-09 | 1967-06-27 | Standard Oil Co | Promoted catalysts for the oxidation of olefins |
| US3454630A (en) * | 1964-10-06 | 1969-07-08 | Nippon Kayaku Kk | Process for the oxidation of olefins to aldehydes and acids |
| US3414631A (en) * | 1965-06-10 | 1968-12-03 | Standard Oil Co | Oxydehydrogenation process |
| US3338952A (en) * | 1965-11-15 | 1967-08-29 | Standard Oil Co | Process for the catalytic ammoxidation of olefins to nitriles |
| US3522299A (en) * | 1965-11-17 | 1970-07-28 | Nippon Kayaku Kk | Process for the oxidation of olefins to aldehydes and acids and catalyst therefor |
| US3595911A (en) * | 1966-02-26 | 1971-07-27 | Distillers Co Yeast Ltd | Production of unsaturated carboxylic acids |
| US3415886A (en) * | 1967-02-07 | 1968-12-10 | Du Pont | Heat treated bismuth molybdate on silica catalysts |
| US3551470A (en) * | 1967-12-20 | 1970-12-29 | Standard Oil Co | Process for the ammoxidation of olefins to unsaturated nitriles |
| US3666822A (en) * | 1967-12-20 | 1972-05-30 | Standard Oil Co Ohio | Uranium-molybdenum oxidation catalysts |
| US3621072A (en) * | 1967-12-23 | 1971-11-16 | Sumitomo Chemical Co | Process for producing isoprene |
| US3497461A (en) * | 1968-02-02 | 1970-02-24 | Du Pont | Bismuth molybdate on silica catalysts |
| US3766092A (en) * | 1970-01-31 | 1973-10-16 | Asahi Chemical Ind | Catalyst for preparation of unsaturated nitriles |
| GB1319190A (en) * | 1970-10-30 | 1973-06-06 | Standard Oil Co | Process for the manufacture of acrylonitrile and methacrylonitrile |
| US3907713A (en) * | 1973-02-02 | 1975-09-23 | Standard Oil Co Ohio | Superior catalyst prepared by impregnation of preformed matrix |
| US3984477A (en) * | 1973-12-11 | 1976-10-05 | Daicel, Ltd. | Catalyst for production of α,β-unsaturated aldehydes |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965393A (en) * | 1988-03-03 | 1990-10-23 | Nitto Chemical Industry Co., Ltd. | Process for producing acrylonitrile |
| US6596897B1 (en) * | 1997-09-03 | 2003-07-22 | China Petro-Chemical Corporation | Catalyst for producing acrylonitrile |
| US5840955A (en) * | 1997-11-25 | 1998-11-24 | Sockell; Edward J. | Waste minimization and product recovery process |
| US20100099936A1 (en) * | 2008-10-17 | 2010-04-22 | Chae-Ho Shin | Complex oxide catalyst of bi/mo/fe for the oxidative dehydrogenation of 1-butene to 1,3-butadiene and process thereof |
| US8420878B2 (en) * | 2008-10-17 | 2013-04-16 | Korea Kumho Petrochemical Co., Ltd. | Complex oxide catalyst of Bi/Mo/Fe for the oxidative dehydrogenation of 1-butene to 1,3-butadiene and process thereof |
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