CA1229352A - Process for oxydehydrogenation of ethane to ethylene - Google Patents
Process for oxydehydrogenation of ethane to ethyleneInfo
- Publication number
- CA1229352A CA1229352A CA000483431A CA483431A CA1229352A CA 1229352 A CA1229352 A CA 1229352A CA 000483431 A CA000483431 A CA 000483431A CA 483431 A CA483431 A CA 483431A CA 1229352 A CA1229352 A CA 1229352A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- ethylene
- ethanes
- water
- selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT
A process for the low temperature oxydehydrogenation of ethanes to ethylene uses a calcined oxide catalyst containing Mo, V, Nb, and Sb.
A process for the low temperature oxydehydrogenation of ethanes to ethylene uses a calcined oxide catalyst containing Mo, V, Nb, and Sb.
Description
~2~3~
PROCESS FOR OXYDEHYDROGENATION
. OF ETHANES TO ETHYLENE
Field of the Invention The invention relates to a process for low temperature oxydehydrogenation of ethanes to ethylene, and particularly to a process using an improved catalyst featuring good conversion and good selectivity.
Background of the Invention Low temperature oxydehydrogenation of ethanes to ethylene has become well known since the publication of "The Oxidative Dehydrogenation of Ethanes over Catalyst Containing Mixed Oxide of Molybdenum and Vanadium" by E. M. Thorsteinson, T. P. Wilson, F. G. Young and P. H. Casey, Journal of Catalysis 52, pp. 116-132 (1978). This article discloses mixed oxide catalysts containing molybdenum and vanadium together with another transition metal oxide (To, Or, MnJ Fe, Co, Nix Nub, Tax or Cue). The catalyst are active at temperatures as low as 200C for the oxydehydrogenation of ethanes to ethylene.
The effectiveness of the oxydehydrogenation of ethanes to ethylene is usually primarily determined by two parameters: conversion of ethanes and selectivity (efficiency) to ethylene. As used herein, these terms are defined as follows:
[Cakewalk I
conversion of ethanes = [Cakewalk [ 2 6 I
selectivity (efficiency) to ethylene =
I 4]
[CO]/2-~[C2]/2+[C2H4]
wherein: [] = relative moles of the component and the production ox acetic acid is negligible. The terms in the art are sometimes calculated differently but the values calculated either way are substantially the same.
Under certain reaction conditions, substantial amounts of acetic acid can be formed as a co-product and the effectiveness of the reaction to ethylene and acetic acid is calculated by the hollowing equations:
[CO] /2+[C02] /2+[C2H4~+[CH3COOH]
conversion of ethane=[cO]/2-~[co2~/2~[G2H4]~[c2H6] [ 3 selectivity efficiency to ethylene and acetic acid =
[C2H4]+[CH3COOH3 [CO~/2+[C02]/2~[C2H4]+[C2H6]+[CH3COOH]
US Patent No. 4,250,346 discloses catalytic oxydehydrogenation ox ethanes to ethylene at temperatures less than 550C in which the catalyst is a calcined composition comprising the elements Mow X, and Y in the ratio MoaXbYc wherein:
X = Or, My, Nub, Tax Tip V, and/or W
Y = Bit Cue, Co, Cut Fe, K, My, Nix P, Pub, SbJ Six Sun, To, and/or U
I
b = 0.05 to 1.0 c = 0 to 2 The numerical values of a, by and c represent the relative gram-atom ratios of the elements Mow X, and Y, respectively, which are present in the catalyst composition. The elements Mow X, and Y are present in the catalyst composition in combination with oxygen.
The patent discloses a wide variety of compositions; however, all of the examples of the patent which include antimony, examples 27, 28, and 41, disclosed very poor results. Example 27 had a catalyst having a composition V3Sbl2Cel and resulted in no selectivity for the formation of ethylene. Example 28 had catalyst having a composition Sb5VlNblBi5 and had an initial activity at 525C with a selectivity of only 26%.
Example 41 had a catalyst having a composition of Mol6V4Sb2 which provided a conversion of 6%
with a selectivity of 95% at 300C, and a conversion of 23% and a selectivity of 75% at 400C.
US. Patent No. 4,339,355 discloses a catalytic oxide of molybdenum, vanadium, niobium, and a fourth metal which is Co, Or, Cut Fe, In, My and/or Y. The patent discloses that the catalyst is suitable for the vapor phase catalytic oxidation of unsaturated aliphatic aldehydes to the corresponding saturated aliphatic carboxylic acid.
US. Patent No. 4,148,757 discloses catalysts for the oxidation and/or ammoxidation of olefins. The patent is particularly directed to a novel process for producing oxidation and/or ammoxidation catalysts and sets forth the following general formula for such catalyst:
[Mm Nun x]q [A) Cub Do Ed e' f Y
wherein:
M = Bit To, Sub, Sun, and/or Cut N = My and/or W
A = alkali, To, and/or Sum C = Nix Co, My, My, Be Cay Six Be, Zen, Cud, and/or Hug = Fe, Or, Cue, and/or V
E - P, As, B, Sub F = rare earth, Tip Or, Nub, Tax Rev Rut Ago A, Al, Gay In, Six Go, Pub, Thy and/or U
a = 0 to 4 b = 0 to 20 c = 0.01 to 20 d = 0 to 4 e = 0 to 8 f = 8 to 16 m 0.10 to 10 n = 0.1 to 30, and x and y aye numbers such that the valence requirements of the other elements for oxygen are satisfied; and the ratio q/p is 0.1 to 10.
None of the catalysts disclosed in US.
Patent No. 4,148,757 are disclosed as being suitable for the oxydehydrogenation of ethanes to ethylene.
Mortar, the suitability of the catalyst for olefins teaches away from the use of the catalysts I
for the oxydehydrogenation of ethanes to ethylene because it would be expected that the ethylene would be oxygenated.
Summary of the Invention The present invention relates to a process for the low temperature catalytic oxydehydrogenation of ethanes to ethylene in a gas phase and features the use of a catalyst having a calcined composition of MoaVbNbcSbd wherein:
a = 0.5 to 0.9 b = 0.1 to 0.4 c = 0.001 to 0.2 d = Or Owl to 0.1.
The values of a, b, c and d constitute relative gram-atoms of the elements Mow V, Nub and Sub, respectively, in the catalyst. The elements are present in combination with oxygen in a form of various oxides.
Discussion of the Invention The catalyst ox the invention can be used with or without a support. The choice of the compounds used as well as the specific procedures followed in preparing a catalyst can have a significant effect on the performance of a catalyst. The elements of the catalyst composition are in combination with oxygen as oxides.
Preferably, the catalyst is prepared from a solution of soluble compounds and/or complexes and/or compounds of each of the metals. The solution is preferably an aqueous system having a pi of l to 12 and more preferably a pi of 5 + 3, at a temperature of prom about 20C to about 100C.
Generally, a mixture of compounds containing the elements is prepared by dissolving sufficient quantities of soluble compounds and dispersing the insoluble compounds so as to provide a desired gram-atom ratios of the elements in the catalyst composition. The catalyst composition is then prepared by removing the water or other solvent from the mixture of the compounds in the solution system. The dried catalyst is calcined by heating to a temperature from about 220C to about SKYE in air or oxygen for a period of time from about one minute to about 24 hours to produce the desired catalyst composition. Generally, the higher the temperature the shorter the period of time required.
Suitable supports for the catalyst include silica, aluminum oxide silicon carbide, zircon, titanic, and mixtures thereof. When used on a support, the supported catalyst usually comprises from about 10 to 50% by eta of the catalyst composition, with the remainder being the support.
Preferably, the molybdenum is introduced into the solution in the form of ammonium salts such as ammonium paramolybdate, or organic acid salts of molybdenum such as acetates, oxalates, mandelates J
and glycolates. Some other partially water soluble molybdenum compound which may be used include molybdenum oxides, molybdic acid, and chlorides of molybdenum.
Preferably, the vanadium is introduced into the solution in the form of ammonium salts such as ammonium meta-vanadate and ammonium decavanadate, or organic acid salts of vanadium such as acetates, oxalates, and tart rates. Partially water soluble vanadium compounds such as vanadium oxides, and sulfates of vanadium can be used.
Preferably, the niobium is introduced into the solution in the form of oxalates. Other sources of this metal in soluble form include compounds in which niobium is coordinated, bonded or complexes to a beta-diketonate, carboxylic acid, and amine, and alcohol, or an alkanolamine.
Preferably, the antimony is introduced into solution in the form of antimony oxalate~ Other soluble and insoluble compounds of antimony can be used such as antimony oxide and antimony chloride.
Preferably, the catalyst is prepared by the following general procedure. The vanadium compound is mixed with water to form a first solution or suspension, the niobium and antimony compound are mixed with water to form a second solution or suspension, and molybdenum compound is mixed with water to form a third solution or suspension. The first and second solutions are heated separately and mixed for about fifteen minutes; and then combined and mixed with heating for about fifteen minutes.
The third solution is heated and mixed, and then added to the combined first and second solutions to form a combined solution. After mixing and heating of the combined solutions for about fifteen minutes, the combined solution is evaporated to dryness rapidly in air usually, but the drying could be carried out in an inert atmosphere.
I
When the catalyst is to be used with a support, it is believed desirable to filter the combined solution to remove the insoluble portion before impregnating the support. The filtering can be carried out using sistered glass, or a paper filter with or without suction.
It has been found that catalyst surface area and activity depend on the digestion time, i.e., the time taken to evaporate the combined solution to dryness. Compositions allowed to digest for relatively long periods of time, thirty minutes or more, before drying at 120C generally undergo particle growth with loss in surface area.
It is believed that the catalyst for the invention should have one or more of the metal components slightly below their highest possible oxidation states. The calcining is carried out with the flow of air or some other oxygen containing gas over the dry solids prepared from the solutions to control the reducing actions of reducing agents such as NH3 or organic reducing agents which are introduced into the solution system from which the catalysts are prepared. The rate of flow of the gas can be determined experimentally for the apparatus and the quantities of solids being used, for optimizing the properties of the catalyst being produced.
One or more of the tree valances of metals in the catalyst are occupied by one or more of oxide, hydroxyl, and COY.
In general, the catalyst supported or unsupported can be used in a fixed or flooded bed.
::~Lr~c3~
The raw material used as the source of the ethanes can be a gas stream which contains at least three volume percent ox` ethanes The gas stream can also contain minor amounts ox' hydrogen, carbon monoxide, and the C~-C4 alikeness and alikeness, less than jive volume percent ox each. The gas stream can also contain major amounts, more than jive volume percent, ox' nitrogen, methane, carbon dioxide, and water in the or ox steam.
The catalyst ox the invention is substantially limited to the oxydehydrogenation of ethanP to ethylene because the catalyst does not efficiently oxydehydrogenate propane, n-butane, and buttonhole, but predominantly burns these gases to carbon dioxide and other oxidized carbonaceous products.
The reaction mixture in carrying out the process is generally one mow ox ethanes 0.01 to 1.0 mow ox molecular oxygen either as pure oxygen or in the Norm ox air, and zero to 4.0 mow ox water in the form ox' steam. The water or steam is used as a reaction delineate and as a heat moderator or the reaction. Other gases may be used as reaction delineate or heat moderators such as nitrogen, helium, carbon dioxide, and methane.
During the course ox the reaction, one mow ox water is orbed or each mow ox ethanes that is oxydehydrogenated. 'Lowe water prom the reaction results in the oration ox some acetic acid. Under several atmospheres ox pressure, about 0.~5 to I
mow ox' acetic acid per mow ox' ethylene is orbed The water that is added to the teed stream will also cause the formation ox additional amounts of acetic acid, up to about 0.25 to 1.0 mow of acetic Audi per mow of ethylene that is formed.
The gaseous components of the reaction mixture include ethanes and oxygen, and possibly a delineate, and these components are uniformly admixed prior to being introduced into the reaction zone, The components may be preheated, individually or after being admixed, prior to being introduced into the reaction zone which should have temperature of from about 200C to about 450C, The reaction zone generally has a pressure of from about 1 to 30 atmospheres and preferably 1 to 20 atmospheres; a temperature of from about 150C
about to 450C, and preferably from about 200~C to about 400C; a contact time between the reaction mixture and the catalyst of from about 0.1 to about 100, and preferably from about 1 to 10 seconds; and a space velocity of from about 50 to 5000h 1, and preferably 200 to 3000h The contact time is defined as the ratio between the apparent volume of the catalyst bed and the volume of *he gaseous reaction mixture feed to the catalyst bed under the given reaction conditions in a unit of time.
The space velocity is calculated by determining total reactor outlet gas equivalent in liters of the total effluent evolved over a period of one hour divided by the liters of catalyst in the reactor. This room temperature volume is converted to the volume at 0C at 760mm Hug:
liters of outlet gas space velocity = equivalents Per hour oh-liters of catalyst in reactor ~2~33~
The reaction pressure is initially provided by the fee of the gaseous reactant and delineate and after the reaction has commenced, the pressure is maintained, preferably, by the use of suitable back-pressure controllers placed on the reactor outlet stream.
The reaction temperature is preferably provided by placing the catalyst bed within a tubular converter having walls immersed in a suitable heat transfer medium such as tetralin, molten salt mixtures, or other suitable heat transfer agents heated to the desired reaction temperature.
Generally, the process can be carried out in a single stage with all of the oxygen for the reaction being supplied along with an inert delineate. It is desirable to operate without a delineate to facilitate the isolation of the ethylene produced. When a delineate is not used this presents several problems because a large amount of oxygen can create a hazardous condition and the uncontrolled presence of water and acetic acid can adversely affect the production of ethylene.
Accordingly, it is believed that the use of multiple stages improves the process. Multiple stages allows the oxygen needed for the total reaction of the ethanes to be introduced at various stages and thereby avoid a potentially hazardous condition.
Surprisingly, the supply of oxygen in various stages rather than a supply of the total amount of the oxygen in the initial stage has no detrimental affect on the production of ethylene.
In addition the use of stages enables the control of the amount of water present in stages subsequent to the first stage. If desired, water can be withdrawn and thereby minimize the formation of acetic acid.
It is desirable to compare the performance of the instant catalysts with prior art catalysts.
Optimally, a comparison should be made for the same set of conditions and the same equipment. This is not always convenient or economically justified.
A reasonably good basis for comparing catalyst performance can be achieved by comparing selectivity to ethylene for the same conversion of ethanes This can be accomplished easily by taking advantage of the discovered substantially linear relationship between selectivity to ethylene and conversion of ethanes over the usable operating temperature range. Thus, it is unnecessary to actually operate at the conversion of ethanes being used for a comparison because one can interpolate or extrapolate to any desired set of values from two sets of data.
EXAMPLES
Several examples were carried out to demonstrate the invention and compare it to the prior art.
The process for the various catalysts were carried out in a tubular reactor under the following conditions:
Gas feed composition was 8% by volume ethanes 6.5% by volume oxygen, and 85.5% by volume helium. The space velocity was about 720 h 1 a a 33~
one atmosphere total pressure. rho reactor consisted of a 9 millimeter diameter stainless steel straight tube heated in an oven with a blower and at a temperature of from 3~0~C to 425~C. The reactor contained 2.5 grams of the catalyst. The reactor bed depth was about 6.0 centimeters so that the depth to cross section ratio was about seven. The liquid products, water and traces of acetic acid, were condensed in a trap and the gaseous products were analyzed for oxygen and carbon monoxide at 65C
on a em x 3mm column of A molecular sieve (60/80 mesh). An analysis at 6~C was carried out for carbon dioxide, ethylene, and ethanes on a 1.8 m x 3mm column of material sold under the trademark POROPAK Q (oboe mesh). in all cases, the conversion and selectivity calculations were based on the stoichiometry:
SHEA + 1/2 I _ SHEA + Ho SHEA + S/2 I KIWI + ~H20 SHEA I/2 2 2C02 + 3 HO
Example 1 A catalyst was prepared Jo have the following composition:
My 69V lob 07sbo~o3 Ammonium metavanadate in the amount of 14.5 grams (0~124 gram-atom of V) was added to 200ml of water and heated to ICKY with stirring or fifteen minutes. Niobium oxalate amounting to 51.~ grams of solution containing 10% by weight calculated as Nb205 (0.039 gram-atom of Nub) and antimony (III~
oxalate amounting to 4.7~ grams (0.019 gram-atom of Sub) was added to a second 200 ml of water and heated to 75C with stirring for fifteen minutes. The second mixture was combined with the first mixture and the combination was heated at 75C with stirring for fifteen minutes. To a third 200 ml ox water was added 70.6 grams (0.40 gram-atom of Mow of ammonium paramolybdate. This mixture was heated to 75C with stirring for fifteen minutes and then added to the combined mixtures. The final mixtures was heated at 75C and stirred for fifteen minutes.
The resulting mixture was evaporated to dryness in air with stirring in steam-heated stainless steel evaporating dish. The resulting solid was broken and sieved to an 8 x 30 mesh and dried additionally in an oven at 120C for sixteen hours. rho dried material was transferred to eight separate 50cc beakers and calcined in an oven equipped with a blower at a temperature of 350C.
The temperature was raised from room temperature to 350C over a period of twenty minutes and thereafter held at 350C for five hours.
The catalyst was tested according to the above described test and the results are shown in Table I.
Example 2 For comparison, the catalyst having a composition similar to the catalyst in Example 1 but without antimony was prepared and tested. The composition of this catalyst was:
My 71V 22Nb.o7 35~:
The catalyst was prepared in accordance with the procedure used in Example 1 except that antimony oxalate was not included. The result of the test with this catalyst is presented in Table I.
Example 3 A catalyst having the following composition was prepared:
My 70V 2lNb.07sb~o3 Ammonium metavanadate amounting to 7.24 grams (0.062 gram-atom of V) was added to loom of water and heated to 75C for fifteen minutes.
Niobium oxalate in the amount of 22.7 grams of a solution containing 11.3% by weight calculated as Nb2O5 (0.0192 gram-atom of Nub) and 1.36 grams of antimony (III) oxide (0.0093 gram-atom of Sub) were prepared in lo ml of water and heated to 75C with stirring for fifteen minutes. The second mixture was combined with the first mixture and the combined mixture was heated at 75C with stirring for twenty minutes. Ammonium paramolybdate amounting to 35.3 grams (.200 gram-atom of Mow was added to 200ml of water and this mixture was stirred and heated to 75C for fifteen minutes. Thereafter the two mixtures were combined and the resulting mixture was heated a 75C. and stirred for fifteen minutes. The drying, calcining, and evaluation were carried out as described in Example 1. The results are shown in Table 1.
Example 4 A catalyst having the following composition was prepared:
My 71V 21Nb 07Sb.015 35~
The procedures and amounts of the components were similar to what was carried out in Example 3 except that antimony (III) chloride (1.06 grams, 0.0047 gram-atom of Sub) was used. The results of the test with the catalyst is presented in Table I.
Example 5 A catalyst having the same composition as the catalyst in Example 2 was prepared using half the amounts of each of the compounds and half the amounts of water for each solution. In accordance with Example 2, the dried material was calcined at a temperature of 350C~ The results of the test with this catalyst are given in Table I.
sample 6 The catalyst of Example 5 was prepared except that the dried material was calcined at a temperature of 375C instead of 350C. The results of the test with the catalyst are given in Table I.
Example 7 The catalyst of Example 1 was prepared using the same procedure except that half the amount of the compounds and water were used. The dried solids were calcined at 350C and the results of tests with the catalyst are shown in Table I.
Example 8 Example 7 was reseated except that the dried solids were calclned at a temperature 370C
instead of 350C. The results of the test with the catalyst are given in Table I.
TABLE I
Convert Select-soon of viny to Example Catalyst Tempt Ethanes Ethylene, _ No EN I % I/
MOE .21 byway .033575 3212 80 425 57` 72 .71V.22Nb.07 350 50 515 3 M.69V.21Nb.07Sb.03 3755 27 772 Moe 70V 21Nb,07$b.015 375 14 78 Mo~71V.22Nb.07375 54 52 6 My 71V 22Nb 07340 56 6562 7 Mo,69v,2lNb,07sb~o3 375 364 813 8 Mo,69V,2lNb.07~03 375 328 78 Examples 1, 3, 4, 7 and 8 are according to the invention while the remaining Examples 2, 5 and 6 are prior art. Using the data of Examples l, 3 and 4, the calculated selectivity to ethylene for a 50% conversion of ethanes is 75%, 63% and 66%, respectively. Examples 7 and 8 show that a 50%
conversion ox ethanes was measured to be selectivity of 76% and 75% respectively. It is economically highly advantageous to be able to obtain a selectivity of greater than 75% for a conversion to ethanes of YO-YO.
PROCESS FOR OXYDEHYDROGENATION
. OF ETHANES TO ETHYLENE
Field of the Invention The invention relates to a process for low temperature oxydehydrogenation of ethanes to ethylene, and particularly to a process using an improved catalyst featuring good conversion and good selectivity.
Background of the Invention Low temperature oxydehydrogenation of ethanes to ethylene has become well known since the publication of "The Oxidative Dehydrogenation of Ethanes over Catalyst Containing Mixed Oxide of Molybdenum and Vanadium" by E. M. Thorsteinson, T. P. Wilson, F. G. Young and P. H. Casey, Journal of Catalysis 52, pp. 116-132 (1978). This article discloses mixed oxide catalysts containing molybdenum and vanadium together with another transition metal oxide (To, Or, MnJ Fe, Co, Nix Nub, Tax or Cue). The catalyst are active at temperatures as low as 200C for the oxydehydrogenation of ethanes to ethylene.
The effectiveness of the oxydehydrogenation of ethanes to ethylene is usually primarily determined by two parameters: conversion of ethanes and selectivity (efficiency) to ethylene. As used herein, these terms are defined as follows:
[Cakewalk I
conversion of ethanes = [Cakewalk [ 2 6 I
selectivity (efficiency) to ethylene =
I 4]
[CO]/2-~[C2]/2+[C2H4]
wherein: [] = relative moles of the component and the production ox acetic acid is negligible. The terms in the art are sometimes calculated differently but the values calculated either way are substantially the same.
Under certain reaction conditions, substantial amounts of acetic acid can be formed as a co-product and the effectiveness of the reaction to ethylene and acetic acid is calculated by the hollowing equations:
[CO] /2+[C02] /2+[C2H4~+[CH3COOH]
conversion of ethane=[cO]/2-~[co2~/2~[G2H4]~[c2H6] [ 3 selectivity efficiency to ethylene and acetic acid =
[C2H4]+[CH3COOH3 [CO~/2+[C02]/2~[C2H4]+[C2H6]+[CH3COOH]
US Patent No. 4,250,346 discloses catalytic oxydehydrogenation ox ethanes to ethylene at temperatures less than 550C in which the catalyst is a calcined composition comprising the elements Mow X, and Y in the ratio MoaXbYc wherein:
X = Or, My, Nub, Tax Tip V, and/or W
Y = Bit Cue, Co, Cut Fe, K, My, Nix P, Pub, SbJ Six Sun, To, and/or U
I
b = 0.05 to 1.0 c = 0 to 2 The numerical values of a, by and c represent the relative gram-atom ratios of the elements Mow X, and Y, respectively, which are present in the catalyst composition. The elements Mow X, and Y are present in the catalyst composition in combination with oxygen.
The patent discloses a wide variety of compositions; however, all of the examples of the patent which include antimony, examples 27, 28, and 41, disclosed very poor results. Example 27 had a catalyst having a composition V3Sbl2Cel and resulted in no selectivity for the formation of ethylene. Example 28 had catalyst having a composition Sb5VlNblBi5 and had an initial activity at 525C with a selectivity of only 26%.
Example 41 had a catalyst having a composition of Mol6V4Sb2 which provided a conversion of 6%
with a selectivity of 95% at 300C, and a conversion of 23% and a selectivity of 75% at 400C.
US. Patent No. 4,339,355 discloses a catalytic oxide of molybdenum, vanadium, niobium, and a fourth metal which is Co, Or, Cut Fe, In, My and/or Y. The patent discloses that the catalyst is suitable for the vapor phase catalytic oxidation of unsaturated aliphatic aldehydes to the corresponding saturated aliphatic carboxylic acid.
US. Patent No. 4,148,757 discloses catalysts for the oxidation and/or ammoxidation of olefins. The patent is particularly directed to a novel process for producing oxidation and/or ammoxidation catalysts and sets forth the following general formula for such catalyst:
[Mm Nun x]q [A) Cub Do Ed e' f Y
wherein:
M = Bit To, Sub, Sun, and/or Cut N = My and/or W
A = alkali, To, and/or Sum C = Nix Co, My, My, Be Cay Six Be, Zen, Cud, and/or Hug = Fe, Or, Cue, and/or V
E - P, As, B, Sub F = rare earth, Tip Or, Nub, Tax Rev Rut Ago A, Al, Gay In, Six Go, Pub, Thy and/or U
a = 0 to 4 b = 0 to 20 c = 0.01 to 20 d = 0 to 4 e = 0 to 8 f = 8 to 16 m 0.10 to 10 n = 0.1 to 30, and x and y aye numbers such that the valence requirements of the other elements for oxygen are satisfied; and the ratio q/p is 0.1 to 10.
None of the catalysts disclosed in US.
Patent No. 4,148,757 are disclosed as being suitable for the oxydehydrogenation of ethanes to ethylene.
Mortar, the suitability of the catalyst for olefins teaches away from the use of the catalysts I
for the oxydehydrogenation of ethanes to ethylene because it would be expected that the ethylene would be oxygenated.
Summary of the Invention The present invention relates to a process for the low temperature catalytic oxydehydrogenation of ethanes to ethylene in a gas phase and features the use of a catalyst having a calcined composition of MoaVbNbcSbd wherein:
a = 0.5 to 0.9 b = 0.1 to 0.4 c = 0.001 to 0.2 d = Or Owl to 0.1.
The values of a, b, c and d constitute relative gram-atoms of the elements Mow V, Nub and Sub, respectively, in the catalyst. The elements are present in combination with oxygen in a form of various oxides.
Discussion of the Invention The catalyst ox the invention can be used with or without a support. The choice of the compounds used as well as the specific procedures followed in preparing a catalyst can have a significant effect on the performance of a catalyst. The elements of the catalyst composition are in combination with oxygen as oxides.
Preferably, the catalyst is prepared from a solution of soluble compounds and/or complexes and/or compounds of each of the metals. The solution is preferably an aqueous system having a pi of l to 12 and more preferably a pi of 5 + 3, at a temperature of prom about 20C to about 100C.
Generally, a mixture of compounds containing the elements is prepared by dissolving sufficient quantities of soluble compounds and dispersing the insoluble compounds so as to provide a desired gram-atom ratios of the elements in the catalyst composition. The catalyst composition is then prepared by removing the water or other solvent from the mixture of the compounds in the solution system. The dried catalyst is calcined by heating to a temperature from about 220C to about SKYE in air or oxygen for a period of time from about one minute to about 24 hours to produce the desired catalyst composition. Generally, the higher the temperature the shorter the period of time required.
Suitable supports for the catalyst include silica, aluminum oxide silicon carbide, zircon, titanic, and mixtures thereof. When used on a support, the supported catalyst usually comprises from about 10 to 50% by eta of the catalyst composition, with the remainder being the support.
Preferably, the molybdenum is introduced into the solution in the form of ammonium salts such as ammonium paramolybdate, or organic acid salts of molybdenum such as acetates, oxalates, mandelates J
and glycolates. Some other partially water soluble molybdenum compound which may be used include molybdenum oxides, molybdic acid, and chlorides of molybdenum.
Preferably, the vanadium is introduced into the solution in the form of ammonium salts such as ammonium meta-vanadate and ammonium decavanadate, or organic acid salts of vanadium such as acetates, oxalates, and tart rates. Partially water soluble vanadium compounds such as vanadium oxides, and sulfates of vanadium can be used.
Preferably, the niobium is introduced into the solution in the form of oxalates. Other sources of this metal in soluble form include compounds in which niobium is coordinated, bonded or complexes to a beta-diketonate, carboxylic acid, and amine, and alcohol, or an alkanolamine.
Preferably, the antimony is introduced into solution in the form of antimony oxalate~ Other soluble and insoluble compounds of antimony can be used such as antimony oxide and antimony chloride.
Preferably, the catalyst is prepared by the following general procedure. The vanadium compound is mixed with water to form a first solution or suspension, the niobium and antimony compound are mixed with water to form a second solution or suspension, and molybdenum compound is mixed with water to form a third solution or suspension. The first and second solutions are heated separately and mixed for about fifteen minutes; and then combined and mixed with heating for about fifteen minutes.
The third solution is heated and mixed, and then added to the combined first and second solutions to form a combined solution. After mixing and heating of the combined solutions for about fifteen minutes, the combined solution is evaporated to dryness rapidly in air usually, but the drying could be carried out in an inert atmosphere.
I
When the catalyst is to be used with a support, it is believed desirable to filter the combined solution to remove the insoluble portion before impregnating the support. The filtering can be carried out using sistered glass, or a paper filter with or without suction.
It has been found that catalyst surface area and activity depend on the digestion time, i.e., the time taken to evaporate the combined solution to dryness. Compositions allowed to digest for relatively long periods of time, thirty minutes or more, before drying at 120C generally undergo particle growth with loss in surface area.
It is believed that the catalyst for the invention should have one or more of the metal components slightly below their highest possible oxidation states. The calcining is carried out with the flow of air or some other oxygen containing gas over the dry solids prepared from the solutions to control the reducing actions of reducing agents such as NH3 or organic reducing agents which are introduced into the solution system from which the catalysts are prepared. The rate of flow of the gas can be determined experimentally for the apparatus and the quantities of solids being used, for optimizing the properties of the catalyst being produced.
One or more of the tree valances of metals in the catalyst are occupied by one or more of oxide, hydroxyl, and COY.
In general, the catalyst supported or unsupported can be used in a fixed or flooded bed.
::~Lr~c3~
The raw material used as the source of the ethanes can be a gas stream which contains at least three volume percent ox` ethanes The gas stream can also contain minor amounts ox' hydrogen, carbon monoxide, and the C~-C4 alikeness and alikeness, less than jive volume percent ox each. The gas stream can also contain major amounts, more than jive volume percent, ox' nitrogen, methane, carbon dioxide, and water in the or ox steam.
The catalyst ox the invention is substantially limited to the oxydehydrogenation of ethanP to ethylene because the catalyst does not efficiently oxydehydrogenate propane, n-butane, and buttonhole, but predominantly burns these gases to carbon dioxide and other oxidized carbonaceous products.
The reaction mixture in carrying out the process is generally one mow ox ethanes 0.01 to 1.0 mow ox molecular oxygen either as pure oxygen or in the Norm ox air, and zero to 4.0 mow ox water in the form ox' steam. The water or steam is used as a reaction delineate and as a heat moderator or the reaction. Other gases may be used as reaction delineate or heat moderators such as nitrogen, helium, carbon dioxide, and methane.
During the course ox the reaction, one mow ox water is orbed or each mow ox ethanes that is oxydehydrogenated. 'Lowe water prom the reaction results in the oration ox some acetic acid. Under several atmospheres ox pressure, about 0.~5 to I
mow ox' acetic acid per mow ox' ethylene is orbed The water that is added to the teed stream will also cause the formation ox additional amounts of acetic acid, up to about 0.25 to 1.0 mow of acetic Audi per mow of ethylene that is formed.
The gaseous components of the reaction mixture include ethanes and oxygen, and possibly a delineate, and these components are uniformly admixed prior to being introduced into the reaction zone, The components may be preheated, individually or after being admixed, prior to being introduced into the reaction zone which should have temperature of from about 200C to about 450C, The reaction zone generally has a pressure of from about 1 to 30 atmospheres and preferably 1 to 20 atmospheres; a temperature of from about 150C
about to 450C, and preferably from about 200~C to about 400C; a contact time between the reaction mixture and the catalyst of from about 0.1 to about 100, and preferably from about 1 to 10 seconds; and a space velocity of from about 50 to 5000h 1, and preferably 200 to 3000h The contact time is defined as the ratio between the apparent volume of the catalyst bed and the volume of *he gaseous reaction mixture feed to the catalyst bed under the given reaction conditions in a unit of time.
The space velocity is calculated by determining total reactor outlet gas equivalent in liters of the total effluent evolved over a period of one hour divided by the liters of catalyst in the reactor. This room temperature volume is converted to the volume at 0C at 760mm Hug:
liters of outlet gas space velocity = equivalents Per hour oh-liters of catalyst in reactor ~2~33~
The reaction pressure is initially provided by the fee of the gaseous reactant and delineate and after the reaction has commenced, the pressure is maintained, preferably, by the use of suitable back-pressure controllers placed on the reactor outlet stream.
The reaction temperature is preferably provided by placing the catalyst bed within a tubular converter having walls immersed in a suitable heat transfer medium such as tetralin, molten salt mixtures, or other suitable heat transfer agents heated to the desired reaction temperature.
Generally, the process can be carried out in a single stage with all of the oxygen for the reaction being supplied along with an inert delineate. It is desirable to operate without a delineate to facilitate the isolation of the ethylene produced. When a delineate is not used this presents several problems because a large amount of oxygen can create a hazardous condition and the uncontrolled presence of water and acetic acid can adversely affect the production of ethylene.
Accordingly, it is believed that the use of multiple stages improves the process. Multiple stages allows the oxygen needed for the total reaction of the ethanes to be introduced at various stages and thereby avoid a potentially hazardous condition.
Surprisingly, the supply of oxygen in various stages rather than a supply of the total amount of the oxygen in the initial stage has no detrimental affect on the production of ethylene.
In addition the use of stages enables the control of the amount of water present in stages subsequent to the first stage. If desired, water can be withdrawn and thereby minimize the formation of acetic acid.
It is desirable to compare the performance of the instant catalysts with prior art catalysts.
Optimally, a comparison should be made for the same set of conditions and the same equipment. This is not always convenient or economically justified.
A reasonably good basis for comparing catalyst performance can be achieved by comparing selectivity to ethylene for the same conversion of ethanes This can be accomplished easily by taking advantage of the discovered substantially linear relationship between selectivity to ethylene and conversion of ethanes over the usable operating temperature range. Thus, it is unnecessary to actually operate at the conversion of ethanes being used for a comparison because one can interpolate or extrapolate to any desired set of values from two sets of data.
EXAMPLES
Several examples were carried out to demonstrate the invention and compare it to the prior art.
The process for the various catalysts were carried out in a tubular reactor under the following conditions:
Gas feed composition was 8% by volume ethanes 6.5% by volume oxygen, and 85.5% by volume helium. The space velocity was about 720 h 1 a a 33~
one atmosphere total pressure. rho reactor consisted of a 9 millimeter diameter stainless steel straight tube heated in an oven with a blower and at a temperature of from 3~0~C to 425~C. The reactor contained 2.5 grams of the catalyst. The reactor bed depth was about 6.0 centimeters so that the depth to cross section ratio was about seven. The liquid products, water and traces of acetic acid, were condensed in a trap and the gaseous products were analyzed for oxygen and carbon monoxide at 65C
on a em x 3mm column of A molecular sieve (60/80 mesh). An analysis at 6~C was carried out for carbon dioxide, ethylene, and ethanes on a 1.8 m x 3mm column of material sold under the trademark POROPAK Q (oboe mesh). in all cases, the conversion and selectivity calculations were based on the stoichiometry:
SHEA + 1/2 I _ SHEA + Ho SHEA + S/2 I KIWI + ~H20 SHEA I/2 2 2C02 + 3 HO
Example 1 A catalyst was prepared Jo have the following composition:
My 69V lob 07sbo~o3 Ammonium metavanadate in the amount of 14.5 grams (0~124 gram-atom of V) was added to 200ml of water and heated to ICKY with stirring or fifteen minutes. Niobium oxalate amounting to 51.~ grams of solution containing 10% by weight calculated as Nb205 (0.039 gram-atom of Nub) and antimony (III~
oxalate amounting to 4.7~ grams (0.019 gram-atom of Sub) was added to a second 200 ml of water and heated to 75C with stirring for fifteen minutes. The second mixture was combined with the first mixture and the combination was heated at 75C with stirring for fifteen minutes. To a third 200 ml ox water was added 70.6 grams (0.40 gram-atom of Mow of ammonium paramolybdate. This mixture was heated to 75C with stirring for fifteen minutes and then added to the combined mixtures. The final mixtures was heated at 75C and stirred for fifteen minutes.
The resulting mixture was evaporated to dryness in air with stirring in steam-heated stainless steel evaporating dish. The resulting solid was broken and sieved to an 8 x 30 mesh and dried additionally in an oven at 120C for sixteen hours. rho dried material was transferred to eight separate 50cc beakers and calcined in an oven equipped with a blower at a temperature of 350C.
The temperature was raised from room temperature to 350C over a period of twenty minutes and thereafter held at 350C for five hours.
The catalyst was tested according to the above described test and the results are shown in Table I.
Example 2 For comparison, the catalyst having a composition similar to the catalyst in Example 1 but without antimony was prepared and tested. The composition of this catalyst was:
My 71V 22Nb.o7 35~:
The catalyst was prepared in accordance with the procedure used in Example 1 except that antimony oxalate was not included. The result of the test with this catalyst is presented in Table I.
Example 3 A catalyst having the following composition was prepared:
My 70V 2lNb.07sb~o3 Ammonium metavanadate amounting to 7.24 grams (0.062 gram-atom of V) was added to loom of water and heated to 75C for fifteen minutes.
Niobium oxalate in the amount of 22.7 grams of a solution containing 11.3% by weight calculated as Nb2O5 (0.0192 gram-atom of Nub) and 1.36 grams of antimony (III) oxide (0.0093 gram-atom of Sub) were prepared in lo ml of water and heated to 75C with stirring for fifteen minutes. The second mixture was combined with the first mixture and the combined mixture was heated at 75C with stirring for twenty minutes. Ammonium paramolybdate amounting to 35.3 grams (.200 gram-atom of Mow was added to 200ml of water and this mixture was stirred and heated to 75C for fifteen minutes. Thereafter the two mixtures were combined and the resulting mixture was heated a 75C. and stirred for fifteen minutes. The drying, calcining, and evaluation were carried out as described in Example 1. The results are shown in Table 1.
Example 4 A catalyst having the following composition was prepared:
My 71V 21Nb 07Sb.015 35~
The procedures and amounts of the components were similar to what was carried out in Example 3 except that antimony (III) chloride (1.06 grams, 0.0047 gram-atom of Sub) was used. The results of the test with the catalyst is presented in Table I.
Example 5 A catalyst having the same composition as the catalyst in Example 2 was prepared using half the amounts of each of the compounds and half the amounts of water for each solution. In accordance with Example 2, the dried material was calcined at a temperature of 350C~ The results of the test with this catalyst are given in Table I.
sample 6 The catalyst of Example 5 was prepared except that the dried material was calcined at a temperature of 375C instead of 350C. The results of the test with the catalyst are given in Table I.
Example 7 The catalyst of Example 1 was prepared using the same procedure except that half the amount of the compounds and water were used. The dried solids were calcined at 350C and the results of tests with the catalyst are shown in Table I.
Example 8 Example 7 was reseated except that the dried solids were calclned at a temperature 370C
instead of 350C. The results of the test with the catalyst are given in Table I.
TABLE I
Convert Select-soon of viny to Example Catalyst Tempt Ethanes Ethylene, _ No EN I % I/
MOE .21 byway .033575 3212 80 425 57` 72 .71V.22Nb.07 350 50 515 3 M.69V.21Nb.07Sb.03 3755 27 772 Moe 70V 21Nb,07$b.015 375 14 78 Mo~71V.22Nb.07375 54 52 6 My 71V 22Nb 07340 56 6562 7 Mo,69v,2lNb,07sb~o3 375 364 813 8 Mo,69V,2lNb.07~03 375 328 78 Examples 1, 3, 4, 7 and 8 are according to the invention while the remaining Examples 2, 5 and 6 are prior art. Using the data of Examples l, 3 and 4, the calculated selectivity to ethylene for a 50% conversion of ethanes is 75%, 63% and 66%, respectively. Examples 7 and 8 show that a 50%
conversion ox ethanes was measured to be selectivity of 76% and 75% respectively. It is economically highly advantageous to be able to obtain a selectivity of greater than 75% for a conversion to ethanes of YO-YO.
Claims (3)
1. In a low temperature process for converting ethane to ethylene by catalytically oxydehydrogenating ethane exothermically at a temperature of less than 450°C in the gas phase, the improvement comprises using a calcined catalyst containing MoaVbNbcSbd in the form of oxides wherein:
a - 0.5 to 0.9 b = 0.1 to 0.4 c = 0.001 to 0.2 d = 0.001 to 0.1
a - 0.5 to 0.9 b = 0.1 to 0.4 c = 0.001 to 0.2 d = 0.001 to 0.1
2. The process of claim 1, wherein the selectivity to ethylene is greater than 63% for a 50% conversion of ethane.
3. The process of claim 1, wherein the selectivity to ethylene is greater than 75% for a 50% conversion of ethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/625,778 US4568790A (en) | 1984-06-28 | 1984-06-28 | Process for oxydehydrogenation of ethane to ethylene |
| US625,778 | 1984-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229352A true CA1229352A (en) | 1987-11-17 |
Family
ID=24507552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000483431A Expired CA1229352A (en) | 1984-06-28 | 1985-06-07 | Process for oxydehydrogenation of ethane to ethylene |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4568790A (en) |
| EP (1) | EP0166438B1 (en) |
| JP (1) | JPS6118729A (en) |
| KR (1) | KR860000234A (en) |
| AU (1) | AU588814B2 (en) |
| BR (1) | BR8503105A (en) |
| CA (1) | CA1229352A (en) |
| DE (1) | DE3561010D1 (en) |
| MX (1) | MX167426B (en) |
| NO (1) | NO160917C (en) |
| YU (1) | YU108085A (en) |
| ZA (1) | ZA854884B (en) |
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|---|---|---|---|---|
| GB8915410D0 (en) * | 1989-07-05 | 1989-08-23 | Bp Chem Int Ltd | Chemical process |
| US4524236A (en) * | 1984-06-28 | 1985-06-18 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
| US4899003A (en) * | 1985-07-11 | 1990-02-06 | Union Carbide Chemicals And Plastics Company Inc. | Process for oxydehydrogenation of ethane to ethylene |
| US4769357A (en) * | 1986-02-27 | 1988-09-06 | Mitsubishi Petrochemical Company Limited | Process for producing composite oxide catalyst |
| US5162578A (en) * | 1987-06-12 | 1992-11-10 | Union Carbide Chemicals & Plastics Technology Corporation | Acetic acid from ethane, ethylene and oxygen |
| US4777319A (en) * | 1987-07-01 | 1988-10-11 | Northwestern University | Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons |
| US5260250A (en) * | 1989-07-05 | 1993-11-09 | Bp Chemicals Limited | Catalyst for the production of ethylene and acetic acid |
| US5210293A (en) * | 1989-07-05 | 1993-05-11 | Bp Chemicals Limited | Process and catalyst for the production of ethylene and acetic acid |
| US5472925A (en) * | 1991-08-08 | 1995-12-05 | Mitsubishi Chemical Corporation | Catalyst for the production of nitriles |
| US5527979A (en) * | 1993-08-27 | 1996-06-18 | Mobil Oil Corporation | Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen |
| WO1996033152A1 (en) * | 1995-04-17 | 1996-10-24 | Mobil Oil Corporation | Catalytic dehydrogenation of alkanes with simultaneous oxidation of hydrogen |
| US6013597A (en) * | 1997-09-17 | 2000-01-11 | Saudi Basic Industries Corporation | Catalysts for the oxidation of ethane to acetic acid processes of making same and, processes of using same |
| US6030920A (en) | 1997-12-24 | 2000-02-29 | Saudi Basic Industries Corporation | Catalysts for producing acetic acid from ethane oxidation, processes of making same and method of using same |
| GB9807142D0 (en) * | 1998-04-02 | 1998-06-03 | Bp Chem Int Ltd | Catalyst and process utilising the catalyst |
| US6087297A (en) * | 1998-06-29 | 2000-07-11 | Saudi Basic Industries Corporation | Catalysts for gas phase production of acetic acid from ethane, processes of making the same and methods of using same |
| US6028221A (en) | 1998-06-29 | 2000-02-22 | Saudi Basic Industries Corporation | Catalyst systems for the one step gas phase production of acetic acid from ethylene and methods of making and using the same |
| CN1166452C (en) * | 1998-08-28 | 2004-09-15 | 旭化成株式会社 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| US6060421A (en) * | 1998-12-23 | 2000-05-09 | Saudi Basic Industries Corporation | Catalysts for the oxidation of ethane to acetic acid, methods of making and using the same |
| US6017846A (en) * | 1999-01-11 | 2000-01-25 | Saudi Basic Industries Corporation | Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same |
| US6037304A (en) * | 1999-01-11 | 2000-03-14 | Saudi Basic Industries Corporation | Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same |
| US6417422B1 (en) * | 1999-02-22 | 2002-07-09 | Symyx Technologies, Inc. | Ni catalysts and methods for alkane dehydrogenation |
| US6355854B1 (en) * | 1999-02-22 | 2002-03-12 | Symyx Technologies, Inc. | Processes for oxidative dehydrogenation |
| US6436871B1 (en) | 1999-02-22 | 2002-08-20 | Symyx Technologies, Inc. | Catalysts for oxidative dehydrogenation |
| GB9907704D0 (en) * | 1999-04-01 | 1999-05-26 | Bp Chem Int Ltd | Catalyst and process utilising the catalyst |
| US6235678B1 (en) | 1999-06-11 | 2001-05-22 | Saudi Basic Industries Corporation | Catalyst system for oxidative dehydrogenation of paraffins |
| US6258992B1 (en) | 1999-09-17 | 2001-07-10 | Saudi Basic Industries Corporation | Gas phase catalytic oxidation of hydrocarbons to carboxylic acids and dehydrogenated products |
| US6627571B1 (en) | 2000-03-01 | 2003-09-30 | Symyx Technologies, Inc. | Method and system for the situ synthesis of a combinatorial library of supported catalyst materials |
| US6486091B1 (en) | 2000-03-14 | 2002-11-26 | Saudi Basic Industries Corporation | Process for making highly active and selective catalysts for the production of unsaturated nitriles |
| US6444845B1 (en) * | 2000-04-28 | 2002-09-03 | Saudia Basic Industries Corporation | Process for the oxidation of unsaturated aldehydes to produce carboxylic acids using Mo-V based catalysts |
| US6531631B1 (en) | 2000-04-28 | 2003-03-11 | Saudi Basic Industries Corporation | Oxidation of ethane to acetic acid and ethylene using molybdenum and vanadium based catalysts |
| KR100407528B1 (en) * | 2000-09-18 | 2003-11-28 | 아사히 가세이 가부시키가이샤 | Process for producing an oxide catalyst for oxidation or ammoxidation |
| US6677497B2 (en) * | 2001-03-22 | 2004-01-13 | Symyx Technologies, Inc. | Ni catalysts and methods for alkane dehydrogenation |
| ES2192983B1 (en) * | 2002-01-31 | 2004-09-16 | Universidad Politecnica De Valencia. | A CATALYST FOR OXIDATIVE DEHYDROGENATION FROM ETANO TO ETENO. |
| US7145051B2 (en) * | 2002-03-22 | 2006-12-05 | Exxonmobil Chemical Patents Inc. | Combined oxydehydrogenation and cracking catalyst for production of olefins |
| US7122492B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| US7122494B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| US7125817B2 (en) * | 2003-02-20 | 2006-10-24 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| EP1622719A1 (en) * | 2003-02-05 | 2006-02-08 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| US7122493B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| RU2412145C2 (en) * | 2005-06-01 | 2011-02-20 | Селаниз Интернэшнл Корпорейшн | Method for selective oxidation of ethane to ethylene |
| US20080132723A1 (en) * | 2006-12-04 | 2008-06-05 | Celanese International Corporation | Process for the production of ethylene, acetic acid and carbon monoxide from ethane |
| EP2165997A1 (en) * | 2008-09-18 | 2010-03-24 | Rohm and Haas Company | Improved process for the oxidative dehydrogenation of ethane |
| CA2828727A1 (en) * | 2011-03-02 | 2012-09-07 | Mark Allen Nunley | Methods for integrated natural gas purification and products produced therefrom |
| US9409156B2 (en) | 2012-10-19 | 2016-08-09 | Instituto Mexicano Del Petroleo | Oxidative dehydrogenation of ethane to ethylene and preparation of multimetallic mixed oxide catalyst for such process |
| US20140275619A1 (en) | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Process for Producing Acetic Acid and/or Ethanol By Methane Oxidation |
| WO2018118440A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Research And Engineering Company | Upgrading ethane-containing light paraffins streams |
| US10464864B2 (en) | 2016-12-20 | 2019-11-05 | Exxonmobil Research And Engineering Company | Upgrading ethane-containing light paraffins streams |
| CA3044680A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Research And Engineering Company | Upgrading ethane-containing light paraffins streams |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE790275A (en) * | 1971-11-19 | 1973-04-19 | Inst Francais Du Petrole | CATALYST USED IN PARTICULAR FOR THE DEHYDROGENATION OF SATURATED HYDROCARBONS |
| US4339355A (en) * | 1975-10-09 | 1982-07-13 | Union Carbide Corporation | Catalytic oxide of molybdenum, vanadium, niobium and optional 4th metal |
| US4148757A (en) * | 1977-08-10 | 1979-04-10 | The Standard Oil Company | Process for forming multi-component oxide complex catalysts |
| US4250346A (en) * | 1980-04-14 | 1981-02-10 | Union Carbide Corporation | Low temperature oxydehydrogenation of ethane to ethylene |
| JPS56161841A (en) * | 1980-05-19 | 1981-12-12 | Mitsubishi Petrochem Co Ltd | Manufacture of composite oxide catalyst |
| US4524236A (en) * | 1984-06-28 | 1985-06-18 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
-
1984
- 1984-06-28 US US06/625,778 patent/US4568790A/en not_active Expired - Lifetime
-
1985
- 1985-06-07 CA CA000483431A patent/CA1229352A/en not_active Expired
- 1985-06-27 JP JP60139259A patent/JPS6118729A/en active Granted
- 1985-06-27 MX MX205796A patent/MX167426B/en unknown
- 1985-06-27 EP EP85107947A patent/EP0166438B1/en not_active Expired
- 1985-06-27 DE DE8585107947T patent/DE3561010D1/en not_active Expired
- 1985-06-27 YU YU01080/85A patent/YU108085A/en unknown
- 1985-06-27 NO NO852593A patent/NO160917C/en unknown
- 1985-06-27 KR KR1019850004582A patent/KR860000234A/en not_active Application Discontinuation
- 1985-06-27 ZA ZA854884A patent/ZA854884B/en unknown
- 1985-06-27 BR BR8503105A patent/BR8503105A/en unknown
- 1985-06-28 AU AU44290/85A patent/AU588814B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO160917B (en) | 1989-03-06 |
| KR860000234A (en) | 1986-01-27 |
| EP0166438A3 (en) | 1986-04-23 |
| ZA854884B (en) | 1986-02-26 |
| JPS6118729A (en) | 1986-01-27 |
| JPH0456808B2 (en) | 1992-09-09 |
| US4568790A (en) | 1986-02-04 |
| YU108085A (en) | 1987-10-31 |
| BR8503105A (en) | 1986-03-18 |
| MX167426B (en) | 1993-03-22 |
| AU4429085A (en) | 1986-01-02 |
| AU588814B2 (en) | 1989-09-28 |
| EP0166438B1 (en) | 1987-11-19 |
| NO852593L (en) | 1985-12-30 |
| DE3561010D1 (en) | 1987-12-23 |
| NO160917C (en) | 1989-06-14 |
| EP0166438A2 (en) | 1986-01-02 |
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