CA1229351A - Process for oxydehydrogenation of ethane to ethylene - Google Patents
Process for oxydehydrogenation of ethane to ethyleneInfo
- Publication number
- CA1229351A CA1229351A CA000479614A CA479614A CA1229351A CA 1229351 A CA1229351 A CA 1229351A CA 000479614 A CA000479614 A CA 000479614A CA 479614 A CA479614 A CA 479614A CA 1229351 A CA1229351 A CA 1229351A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- ethylene
- compounds
- ethane
- ore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- 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
- 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
- B01J23/30—Tungsten
-
- 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
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- 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
-
- 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 ethane to ethylene uses calcined oxide catalyst containing Mo, V, Nb, Sb, and at least one metal from a given group of metals.
A process for the low temperature oxydehydrogenation of ethane to ethylene uses calcined oxide catalyst containing Mo, V, Nb, Sb, and at least one metal from a given group of metals.
Description
AL
PROCESS FOR OXYDEHYDROGENATION
OF ETHANES TO ETHYLENE
Field of the Invention The invention relates to a process for low temperature oxydehydrogena~ion of ethanes to ethylene, end particularly to process using on improved catalyst featuring good conversion and good selectivity.
Background of the Invention Low temperature oxydehydrogenation of eth~ne to ethylene his become well known since the publication of "The Oxidative Dehydrogenation of Ethanes over Catalyst Containing Mixed Oxide of Molybdenum and Vanadium" by Ho M. Thorsteinson, T. P. Wilson, F. G. Young end P. H. K~sai, Journal of C~talysls 52, pp. 116-132 (1978~. This article discloses mixed oxide catalysts containing molybdenum end van~dlum together with another transition metal oxide (To, Or, My, Fe, Co, Nix Nub, Tax or Cue). The catalysts are active at temperatures us low as 200C for the oxydehydro~enation of ethanes to ethylene.
The effectiveness of the oxydehydrogena~ion of eth~ne Jo ethylene is usually primarily determined by two parameters conversion of eth3ne, end select$vlty efficiency to ethylene. As used herein these terms ore defined as follows:
owe] 1~2+[C2] /2+~C2H4]
nver~i~n ox thin = coequal [ 2
PROCESS FOR OXYDEHYDROGENATION
OF ETHANES TO ETHYLENE
Field of the Invention The invention relates to a process for low temperature oxydehydrogena~ion of ethanes to ethylene, end particularly to process using on improved catalyst featuring good conversion and good selectivity.
Background of the Invention Low temperature oxydehydrogenation of eth~ne to ethylene his become well known since the publication of "The Oxidative Dehydrogenation of Ethanes over Catalyst Containing Mixed Oxide of Molybdenum and Vanadium" by Ho M. Thorsteinson, T. P. Wilson, F. G. Young end P. H. K~sai, Journal of C~talysls 52, pp. 116-132 (1978~. This article discloses mixed oxide catalysts containing molybdenum end van~dlum together with another transition metal oxide (To, Or, My, Fe, Co, Nix Nub, Tax or Cue). The catalysts are active at temperatures us low as 200C for the oxydehydro~enation of ethanes to ethylene.
The effectiveness of the oxydehydrogena~ion of eth~ne Jo ethylene is usually primarily determined by two parameters conversion of eth3ne, end select$vlty efficiency to ethylene. As used herein these terms ore defined as follows:
owe] 1~2+[C2] /2+~C2H4]
nver~i~n ox thin = coequal [ 2
- 2 selectivity (efficiency) to ethylene =
[C2H4]
[Cakewalk 4]
wherein: [I = relative moles of the component an the production of scetlc acid is negligible. The terms in the art are sometimes calculated differently but the values calculated either way are substantially the some.
Under certain reaction conditions, substantial mounts ox acetic acid can be formed as co-product end the effectiveness of the reaction to ethylene end acetic Clyde is calculated by the following equations:
[Cowlick [C2H4]+~CH3COOH]
version of ethane=[co]/2+[co2]l2+lc2 I 2 6 selectivity efficiency) to ethylene end acetic acid =
[C2H4~+[C~3COOH]
[C~:)]t2+[C02~/2t[C2M~,~+[C2H6~+tCH3COOH]
' US. Potent No. 4,250,346 discloses catalytic oxydehydrogenation of ethanes to ethylene it temperatures less than 550C in which the catalyst us a cslcined composition comprising the elements My 9 X end Y in the ratio Max c wherein:
X = Or, My, Nub, To, Tip Y, nor W
Y = Bit Cue, Co, Cut Fe, K, My, Nix P, Pub, Sub, Six Sun, To, nor U
~-~423~
= 1 b = 0.05 to 1.0 c 0 Jo 2 Thy numerical values of a, b, and c represent the relative gr~m-~tom ratios of the elements Mow X, end Y, respectively, which are present in the catalyst composition. The elements Mow X; and Y ore present in the catalyst composition in combination with oxygen.
The patent discloses a wide variety of compositions; however, Roll ox the examples of the patent which include antimony, examples 27, 28, end 41, disclosed very poor results. Example 27 had a catalyst having composition V3Sbl2Cel and resulted in no selectivity for the formation of ethylene. Example 28 had catalyst having composition Sb5VlNblBi5 and had an initial ac~lvity it 525 with a selectivity of only 26%.
Example I hod a catalyst having a composition of ~o16V4Sb~ which provided conversion of I
with a selectivity of 95% it 300C, end conversion of 23% end selectivity of 75% By 400C.
US. Potent No. 4,339,355 discloses catalytic oxide of molybdenum, vanadium, niobium, end fourth metal which is Co, Or, Cut Fe, In My nor Y. The patent discloses what the catalyst is suitable for the vapor phase catalytic oxidation of unsaturated ~liphatic ~ldehyd~s Jo the corresponding strutted alpha tic c~rboxylic Acadia US. Potent No. 4,148~757 discloses catalysts for the oxide lion nor ammoxidation of olefins. The patent is particularly directed to 8 novel process for producing oxidstlon and/or ammoxidation catalysts and sets forth the following general formula for such c~t~lyst:
[Mm Nun I A- I Do, Ed. e f Y
wherein:
M = By, To, Sub, Sun, and/or Cut N = My and/or W
A = alk~lip To and/or Sum C = No, Co, My, My, Be, I Six Be, Zen, Cud and/or Hug D = Fe, Or, Cue, Andre V
E = P, As, B, Sub = rare earth, To, or, Nub, To, Rev Rut go A, Al, Gay In, Six Go, Pub, Thy andlor U
R = O to 4 b 0 to 20 c = 0.01 to 20 d = 0 to 4 e - 0 to 8 f = 8 to 16 m a O . 10 to 10 n = 0.1 to 30, and x end y ore numbers such that the valence requirements of the other elements for oxygen are stifled and the rot q/p is 0.1 to lo None of the e~talysts disclosed in US.
Patent No. 4,148,757 ore disclosed as being suitable for the oxydehydrogen~ion of ethanes to ethylene.
[C2H4]
[Cakewalk 4]
wherein: [I = relative moles of the component an the production of scetlc acid is negligible. The terms in the art are sometimes calculated differently but the values calculated either way are substantially the some.
Under certain reaction conditions, substantial mounts ox acetic acid can be formed as co-product end the effectiveness of the reaction to ethylene end acetic Clyde is calculated by the following equations:
[Cowlick [C2H4]+~CH3COOH]
version of ethane=[co]/2+[co2]l2+lc2 I 2 6 selectivity efficiency) to ethylene end acetic acid =
[C2H4~+[C~3COOH]
[C~:)]t2+[C02~/2t[C2M~,~+[C2H6~+tCH3COOH]
' US. Potent No. 4,250,346 discloses catalytic oxydehydrogenation of ethanes to ethylene it temperatures less than 550C in which the catalyst us a cslcined composition comprising the elements My 9 X end Y in the ratio Max c wherein:
X = Or, My, Nub, To, Tip Y, nor W
Y = Bit Cue, Co, Cut Fe, K, My, Nix P, Pub, Sub, Six Sun, To, nor U
~-~423~
= 1 b = 0.05 to 1.0 c 0 Jo 2 Thy numerical values of a, b, and c represent the relative gr~m-~tom ratios of the elements Mow X, end Y, respectively, which are present in the catalyst composition. The elements Mow X; and Y ore present in the catalyst composition in combination with oxygen.
The patent discloses a wide variety of compositions; however, Roll ox the examples of the patent which include antimony, examples 27, 28, end 41, disclosed very poor results. Example 27 had a catalyst having composition V3Sbl2Cel and resulted in no selectivity for the formation of ethylene. Example 28 had catalyst having composition Sb5VlNblBi5 and had an initial ac~lvity it 525 with a selectivity of only 26%.
Example I hod a catalyst having a composition of ~o16V4Sb~ which provided conversion of I
with a selectivity of 95% it 300C, end conversion of 23% end selectivity of 75% By 400C.
US. Potent No. 4,339,355 discloses catalytic oxide of molybdenum, vanadium, niobium, end fourth metal which is Co, Or, Cut Fe, In My nor Y. The patent discloses what the catalyst is suitable for the vapor phase catalytic oxidation of unsaturated ~liphatic ~ldehyd~s Jo the corresponding strutted alpha tic c~rboxylic Acadia US. Potent No. 4,148~757 discloses catalysts for the oxide lion nor ammoxidation of olefins. The patent is particularly directed to 8 novel process for producing oxidstlon and/or ammoxidation catalysts and sets forth the following general formula for such c~t~lyst:
[Mm Nun I A- I Do, Ed. e f Y
wherein:
M = By, To, Sub, Sun, and/or Cut N = My and/or W
A = alk~lip To and/or Sum C = No, Co, My, My, Be, I Six Be, Zen, Cud and/or Hug D = Fe, Or, Cue, Andre V
E = P, As, B, Sub = rare earth, To, or, Nub, To, Rev Rut go A, Al, Gay In, Six Go, Pub, Thy andlor U
R = O to 4 b 0 to 20 c = 0.01 to 20 d = 0 to 4 e - 0 to 8 f = 8 to 16 m a O . 10 to 10 n = 0.1 to 30, and x end y ore numbers such that the valence requirements of the other elements for oxygen are stifled and the rot q/p is 0.1 to lo None of the e~talysts disclosed in US.
Patent No. 4,148,757 ore disclosed as being suitable for the oxydehydrogen~ion of ethanes to ethylene.
3.5~
Moreover, the suitability of the catalyst for oleflns teaches wow from the use of the catalysts 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 process for the low temperature ca~slytic oxydehydrogenation of ethanes to ethylene in a gas phase and features the use of a catalyst having a cfllcined composition ox Mo~VbNbcS d e x - a least one of the following: H, So, pa, Be, My, I So, Be, Tip Or, Hi, Y, Tax Or, Fe, Co, Nix Cue) La, Zen, Cud, Hug, Al, To, Pub, As) Bit To, U, and W; end 0.5 to 0.9 = 0.1 Jo 0.4 c = 0.001 to 0.2 d = 0.001 to 0.1.
e = 0.001 to 1.0 ., The values of a, b, c, d and e constitute relative gr~m-atoms of the elements Mow Vg Nub, Sub, and X respectively, in the catalyst. The elements ore present in com~lnation with oxygen in a form of various oxides.
Discussion of the Invention The coolest of the invention con be used with or without a support The choice of the compounds used us well us the specific procedures arc followed in preparing a catalyst can have s significant effect on the performance of catalyst. The elements of the catalyst composition are in combination with oxygen as oxides.
Preferably, the catalyst is prepared from a solu~lon of soluble compounds andlor complexes and/or compounds of each of the metals. The solution is preferably an aqueous system hiving pi of 1 to 12 and more preferably a pi of 5 + 3, at a temperature of from about 20C to about 100C.
Generally, a mixture of compounds containing the elements is prepared by dissolving sufficient quantities of soluble compounds and di-~persin~ the insoluble compounds so as to provide a desired gram-~om ratios of the elements in the catalyst composition. The catalyst composition us 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 temperature prom about 220C to about 550C in sir or oxygen for a period of lime from about one minute to about 24 hours to produce the desired koalas composition. Generally, the higher the temperature the shorter the period ox time required.
Suitable supports for the catalyst include Salk ~lumlnum oxide silicon c~rblde, zircon, titanic, end mixtures thereof. When used on a support the supported catalyst usually comprises from about 10 to 50% my weight of the catalyst composition, with the remainder being the support.
Preferably, the molybdenum is introduced into the solution in the form of ammonlum silts such - 7 - Jo as ammonium paramolybdste~ or organic acid salts of molybdenum such us acetates, oxalates, mandelates, end glycolates. Some other partially water soluble molybdenum compound which may be used include molybdenum oxides, molybdic acid, end chlorides of molybdenum.
Preferably, the vanadium is introduced into the solution in top form of minim salts such US
minim met~-v~nadate and ammonium decavanadate, or organic acid salts of vanadium such as acetates, oxalates, end t~rtr~tes. Partially water soluble vanadium compounds such as vanadium oxides, and sulfates of vanadium can be used.
Preferably, the niobium end tantalum when used, are in the f or of ox ales Other sources of these metals in soluble form include compounds in which the metal is coordinated, bonded or complexes to a beta-dlketon~te, carboxylic Clyde, end amine, end alcohol, or an alkanolamlne.
Preferably, the antimony is introduced into sultan in the form of Antimony oxalate. Other voluble end insoluble compounds of antimony con be used such as antimony oxide and antimony chloride.
The X component of the catalyst can be soluble or insoluble compounds preferably soluble.
Compounds which ore strongly reducing may adversely reduce the oxidation states of the metals.
The following ore some preferable compounds for the X components. One is titanium in the form of a water soluble shalt coordinated with minim 1AC~te, and others are tl~anium compounds in which the metal is coordln~ted, or complexes Jo betu-dlketon~te, 8 carboxyllc Clyde, an mine on alcohol or on alkRnolsmine. Generally, nitrites ore desirable along with water soluble chlorides end organic acid 881t~ such I septets, oxalates, artistes l~ct~tes, ~alicylates, formats, end carbonates. Preferred compounds for tungsten are in the form of ammonium 8~1ts such us ammonlum p~r~tungst~te or other water soluble compounds such as tungstle acids.
Preferably, the catalyst is prepared by the following general procedure. The vanadium compound is mixed with water to form R first solution or suspension, the niobium, end antimony, ore mixed with water to form 8 second solution or suspension, and molybdenum compound it mixed with water to form third solution or suspension. Any X compounds which ore smmonium salts are mixed with the first 501utlon. Otherwise, X compounds ore mixed into the second solu~lon. the first and second solutions are hosted separately end mixed for bout Fifteen minutes; end then combined end mixed with hefting for about fifteen minutes. The third solution it heated end mixed, end then added to the combined fir end second solutions to form a combined solution. after mixing end he~tlng ox the combined ~olutlons for about fifteen minutes, the combined 801ution is eVapOrflted to dryness r~pldly in sir usually, buy the drying could be curried out in an inert atmosphere.
When the cstaly~t it to be used with support, it 18 believed desirable to filter the combined solution to remove the insoluble portion before impregnating the support. The filtering can _ g 3 be curried out using sistered glass, or a paper filter with or without suction.
It has been found that catalyst surface urea and activity depend on the digestion lye i.e., the time then to evaporate the combined solution to dryness. Compositions allowed to digest for relatively long periods of time, thirty minutes or more, before drying at 12DC generally undergo particle growth with loss in surface urea.
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 calcinlng is carried out with the flow of elf or some other oxygen con~alning gas over the dry solids prepared prom the solutions to control the reducing Cannes of reducing agents such as NH3 or organic reducing agents which fire introduced into the solution system from which the catalysts ore prepared. The rate of flow of the gas con 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 free valances of metals in the catalyst are occupied by one or more of oxide hydroxyl, and COY.
In general the coolest, supported or unsupported con be used in a fixed or fluidized bed.
The raw material used as the source of the ennui can be a was stream which contains it least three volume percent of ethanes The gas stream con also contain minor amounts of hydrogen carbon D-14~38 monoxide, and the C3-C4 slickness end alikeness, less than five volume percent ox each. The gas stream can Also contain major amounts, more than five volume percent, of nitrogen, methane, carbon dioxide, end water in the form of steam.
The catalyst of the invention is subs~ntially limited to the oxydehydrogen~tion of ethan2 to ethylene because the catalyst does not e~ficicntly oxydehydrogen~te propane, n-but~ne, end buttonhole, but medaminantly burns these gases to carbon dioxide and other oxidized carbonaceous products.
The reaction mixture in crawling out the process it general one mow of ethanes 0.01 to I
mow ox molecular oxygen either us pure oxygen or in the form of sir, sod zero to 4.0 mow of water in the form of steam. The water or steam is used us reaction dlluent and us heat moderator for the rewaken. Other gases my be used as resection Dylan or host moderators such us nitrogen, helium, carbon dioxide, Rod methane.
During the course of the reaction, one mow of water is formed for each mow ox ennui that is oxydehydro~en~ted. The water from the reaction results in the pheromone of some swish acid. Under several atmospheres of pressure, about 0.05 to 0.25 mow of acetic acid per mow of ethylene us formed.
The water that I added Jo the feed stream will also cause the formation ox additional mounts of acetic acid, up to. bout 0.25 to 1.0 mow of acetic Clyde per mow of ethylene ho is formed.
The gaseous oomponen~s of the reaction mixture include eth~ne end oxygen, and possibly a 35~
delineate, and these components ore 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 2008C Jo about 450CC.
The reaction zone generally has a pressure of from about l to 30 misfires and preferably 1 Jo 20 atmospheres; temperature of from about 150C
bout to 450C, end preferably from bout 200C to bout 400C; contact time between the reaction mixture end the catalyst of from about 0.1 to bout 100, sod preferably from bout 1 to 10 seconds; and a spice velocity ox from bout 50 Jo 5000h l, 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 the gaseous re~ctiQn mixture feed to the catalyst bed under the given rewaken conditions in unit of time.
The spice velocity is calculated by determining total rector utile gas equivalent in liters of the total effluent evolved over period of one hour divined by the liters of catalyst in the rector. This root temperature volume is converted Jo the volume it OKAY at 760mm Hug:
liters of outlet gas spice velocity = ~uiv~lents per hour -h-liters of cRt~lyst in reactor The reaction pressure is initially provided by the feed of the gaseous reactant and delineate sod after the reaction has commenced, the pressure is maintained, preferably, by the use of suitable back-pressure controllers placed on the rector outlet stream.
The reaction temperature is preferably provided by placing the catalyst bed within tubular converter having walls immersed in a suitable heft transfer medium such as tetralln, molten salt mixtures, or other suitable heat transfer agents hosted to the desired reaction temperature.
Generally, the process can be curried out in a single stage with ~11 of the oxygen for the reaction being supplied long with on inert delineate. It is deslrsble to operate without a delineate to facilitate the isolation of the ethylene produced. When a delineate is not used this presents several problems because large amount ox oxygen can create a hazardous condition and the uncontrolled presence of w ton end acetic acid can adversely effect the production of ethylene.
Accordingly, it is believed that the use of multiple toes improves the process. Multiple stages allows the oxygen needed for the total reaction of the ethene to be introduced at various stages and thereby volleyed potentially hazardous cond{~lon.
Surprisingly, the supply of oxygen in various stages rather than A supply of the total mount of the oxygen on the ln~lal sage has no detrimental effect on the production of ethylene.
In addition the use of stages nobles the control of the amount of water present in stages subsequent V-14~3~
to the first sty. If desired, water can be withdrawn end 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 convene or economically justified.
A reasonably good basis for comparing catalyst performance con be achieved by comparing selectivity to ethylene for the same conversion of ethanes This con be accomplished essay by taking advantage of the discovered substantially linear relationship between selectivity to ethylene find 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 do EXAMPLES
Several examples were carried out to demonstrate the invention end compare it to the prior art.
The process or the various c~t~lys~s were carried out on tubular rector under the following conditions:
Gas feed composition was I by volume ethanes 6.5% by volume oxygen, end 85.5% by volume helium. The space velocity was bout 720 h l it a one atmosphere tool pressure. The reactor consisted of 9 millimeter diameter stainless steel ~2~33~l straight tube hefted on an oven with blower and at a temperature of from 330C to 425C. The reactor contflined 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 end truces of acetic Swede were condensed in trap end the gaseous products were analyzed for oxygen and carbon ~onoxlde at 65~C
on a em x 3mm column of 5 A molecular sieve (60/80 mesh). An analysis at 65C was carried out fox carbon dioxide, ethylene, and eth~ne on a 1.8 m x 3mm column of material told under the trademark POROPAK Q (50/80 mesh). In all cases, the conversion and selectivity calculations were based on the Stoichiometry:
C2H6 1/2 2 Do 2 4 ~2 C2H~ 5/2 2 ~~~
C2H6 7/2 2--~~2C02 3 H20 Example l catalyst was prepared to have the following composition:
My 6lV 26Nb Buick minim metavanadatc in the mount of 9.90 grams (0.0~5 grim Tom of V) was added to 100ml of water end heated to 70~C with stirring for fifteen minutes. Niobium oxala~e amounting to 31.1 grams of solution continuing lo by weight calculated us Nb205 ~0.0234 gram atom of Nub), antimony oxalate amounting to 3.12 rums (0.0123 gram-atom of Sub) hod calcium nitrite tetrahydrate amounting to 1.46 grams (0.0062 gram-atom of Cay were added to a second 100 ml of water end heated to 70C with stirring for fifteen minutes. The second mixture was combined with the f lust mixture and the combination was hefted it 70DC with stirring for phony minutes. To a third 100 ml of water was added 35.3 grams (0.200 gram-atom of Mow of minim paramolybdate. This mixture was heated to icky with stirring for fifteen minutes and then added to the combined mixtures. The final mixture was heated at 70C 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 find sieved to on 8 x 30 mesh end dried additionally in an oven it 120C for sixteen hours. The dried materiel was transferred to three swooper lucks beakers and calcined in an oven equipped with blower at a temperature of 350C.
The temperature was raised from room temporizer to 350C over period of twenty minutes and thereafter held it 350C for five hours.
The catalyst was tested according to the above described jest end the results are shown in Table II.
Example 2 Using the procedure of Example 1, catalyst having the following composition was prepared:
My 60~ 25N~ 07Sb kiwi 04 I
The same amounts of compounds were used except that 2.92 grams of calcium nitrate tetrahydr~te (0.0124 gr~m-~tom of Cay was used Jo that the catalyst produced hod a higher calcium content Han he catalyst of Example 1. The result of the tests with this catalyst ore riven in Table IT
Ho Using the procedure ox Example 2, a catalyst having the following composition was prepared:
My YO-YO 26Nb 07Sb,04C~.01 The same mounts of compounds were used except that 0.73 gram of calcium nitrate (owe gram Tom of Cay was used so that the c2tRlyst produced hod lower calcium Canaan thfln the catalyst of Example 1. Thy results of the tests with this outclass are given in Table II.
Examples 4 to 28 Examples 4 to 28 were carried out using the same procedure en used in Example 1 with the some quints of the compounds used for Mow V, Nub, and Sub. The X component was varied end in some cases several metals. Table I shows the X component, X
sly, welsh of the X silt, gram-atom of the X
met no the composition of the catalysts for Examples 4 Jo 28v The results of the tests with these calcites ore given lo Table II.
14~38 33~i~
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~2~3 Example 29 Using the procedure of Example 1, a catalyst hiving the following composi~lon was prepared:
My 62V 26Nb ~7Sb 04Mn.olCd.02W.01U.01Ce.0004 ~1 The same amounts of the compounds for Mow V, by and Sub were used as in Example 1. Ammonium tungstate in the amount of 0.92 gram (0.0035 gram-s~om W) and ammonium diursnate in the amount of 0.68 grim (0.0021 gram-atom of U) were mixed with the ammonlum metavanadate solution. Curium (III) nitrite in the mount of 0.05 gram (0.0001 gr~m-~tom Cue), cadmium nitrate in the amount of 1.63 grams (0.0053 gr~m-atom of Cud), lead IT nitrate in the amount of 0.76 gram (0.0023 grum-atom of Pub) and manganese IT nitrate in the amount of 1.04 grams of 50% aqueous solution (0.0029 ram atom of My) were mixed with the niobium oxalate and Antimony oxala~e solution. The results of the tests with this catalyst ore given in Table II.
.1 I
- Jo -Table II
Temp. Conversl~n Selectivity En. X Metal C ox Ethanes to Ethylene Cay 330 ` 34 66 35~ 55 76
Moreover, the suitability of the catalyst for oleflns teaches wow from the use of the catalysts 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 process for the low temperature ca~slytic oxydehydrogenation of ethanes to ethylene in a gas phase and features the use of a catalyst having a cfllcined composition ox Mo~VbNbcS d e x - a least one of the following: H, So, pa, Be, My, I So, Be, Tip Or, Hi, Y, Tax Or, Fe, Co, Nix Cue) La, Zen, Cud, Hug, Al, To, Pub, As) Bit To, U, and W; end 0.5 to 0.9 = 0.1 Jo 0.4 c = 0.001 to 0.2 d = 0.001 to 0.1.
e = 0.001 to 1.0 ., The values of a, b, c, d and e constitute relative gr~m-atoms of the elements Mow Vg Nub, Sub, and X respectively, in the catalyst. The elements ore present in com~lnation with oxygen in a form of various oxides.
Discussion of the Invention The coolest of the invention con be used with or without a support The choice of the compounds used us well us the specific procedures arc followed in preparing a catalyst can have s significant effect on the performance of catalyst. The elements of the catalyst composition are in combination with oxygen as oxides.
Preferably, the catalyst is prepared from a solu~lon of soluble compounds andlor complexes and/or compounds of each of the metals. The solution is preferably an aqueous system hiving pi of 1 to 12 and more preferably a pi of 5 + 3, at a temperature of from about 20C to about 100C.
Generally, a mixture of compounds containing the elements is prepared by dissolving sufficient quantities of soluble compounds and di-~persin~ the insoluble compounds so as to provide a desired gram-~om ratios of the elements in the catalyst composition. The catalyst composition us 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 temperature prom about 220C to about 550C in sir or oxygen for a period of lime from about one minute to about 24 hours to produce the desired koalas composition. Generally, the higher the temperature the shorter the period ox time required.
Suitable supports for the catalyst include Salk ~lumlnum oxide silicon c~rblde, zircon, titanic, end mixtures thereof. When used on a support the supported catalyst usually comprises from about 10 to 50% my weight of the catalyst composition, with the remainder being the support.
Preferably, the molybdenum is introduced into the solution in the form of ammonlum silts such - 7 - Jo as ammonium paramolybdste~ or organic acid salts of molybdenum such us acetates, oxalates, mandelates, end glycolates. Some other partially water soluble molybdenum compound which may be used include molybdenum oxides, molybdic acid, end chlorides of molybdenum.
Preferably, the vanadium is introduced into the solution in top form of minim salts such US
minim met~-v~nadate and ammonium decavanadate, or organic acid salts of vanadium such as acetates, oxalates, end t~rtr~tes. Partially water soluble vanadium compounds such as vanadium oxides, and sulfates of vanadium can be used.
Preferably, the niobium end tantalum when used, are in the f or of ox ales Other sources of these metals in soluble form include compounds in which the metal is coordinated, bonded or complexes to a beta-dlketon~te, carboxylic Clyde, end amine, end alcohol, or an alkanolamlne.
Preferably, the antimony is introduced into sultan in the form of Antimony oxalate. Other voluble end insoluble compounds of antimony con be used such as antimony oxide and antimony chloride.
The X component of the catalyst can be soluble or insoluble compounds preferably soluble.
Compounds which ore strongly reducing may adversely reduce the oxidation states of the metals.
The following ore some preferable compounds for the X components. One is titanium in the form of a water soluble shalt coordinated with minim 1AC~te, and others are tl~anium compounds in which the metal is coordln~ted, or complexes Jo betu-dlketon~te, 8 carboxyllc Clyde, an mine on alcohol or on alkRnolsmine. Generally, nitrites ore desirable along with water soluble chlorides end organic acid 881t~ such I septets, oxalates, artistes l~ct~tes, ~alicylates, formats, end carbonates. Preferred compounds for tungsten are in the form of ammonium 8~1ts such us ammonlum p~r~tungst~te or other water soluble compounds such as tungstle acids.
Preferably, the catalyst is prepared by the following general procedure. The vanadium compound is mixed with water to form R first solution or suspension, the niobium, end antimony, ore mixed with water to form 8 second solution or suspension, and molybdenum compound it mixed with water to form third solution or suspension. Any X compounds which ore smmonium salts are mixed with the first 501utlon. Otherwise, X compounds ore mixed into the second solu~lon. the first and second solutions are hosted separately end mixed for bout Fifteen minutes; end then combined end mixed with hefting for about fifteen minutes. The third solution it heated end mixed, end then added to the combined fir end second solutions to form a combined solution. after mixing end he~tlng ox the combined ~olutlons for about fifteen minutes, the combined 801ution is eVapOrflted to dryness r~pldly in sir usually, buy the drying could be curried out in an inert atmosphere.
When the cstaly~t it to be used with support, it 18 believed desirable to filter the combined solution to remove the insoluble portion before impregnating the support. The filtering can _ g 3 be curried out using sistered glass, or a paper filter with or without suction.
It has been found that catalyst surface urea and activity depend on the digestion lye i.e., the time then to evaporate the combined solution to dryness. Compositions allowed to digest for relatively long periods of time, thirty minutes or more, before drying at 12DC generally undergo particle growth with loss in surface urea.
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 calcinlng is carried out with the flow of elf or some other oxygen con~alning gas over the dry solids prepared prom the solutions to control the reducing Cannes of reducing agents such as NH3 or organic reducing agents which fire introduced into the solution system from which the catalysts ore prepared. The rate of flow of the gas con 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 free valances of metals in the catalyst are occupied by one or more of oxide hydroxyl, and COY.
In general the coolest, supported or unsupported con be used in a fixed or fluidized bed.
The raw material used as the source of the ennui can be a was stream which contains it least three volume percent of ethanes The gas stream con also contain minor amounts of hydrogen carbon D-14~38 monoxide, and the C3-C4 slickness end alikeness, less than five volume percent ox each. The gas stream can Also contain major amounts, more than five volume percent, of nitrogen, methane, carbon dioxide, end water in the form of steam.
The catalyst of the invention is subs~ntially limited to the oxydehydrogen~tion of ethan2 to ethylene because the catalyst does not e~ficicntly oxydehydrogen~te propane, n-but~ne, end buttonhole, but medaminantly burns these gases to carbon dioxide and other oxidized carbonaceous products.
The reaction mixture in crawling out the process it general one mow of ethanes 0.01 to I
mow ox molecular oxygen either us pure oxygen or in the form of sir, sod zero to 4.0 mow of water in the form of steam. The water or steam is used us reaction dlluent and us heat moderator for the rewaken. Other gases my be used as resection Dylan or host moderators such us nitrogen, helium, carbon dioxide, Rod methane.
During the course of the reaction, one mow of water is formed for each mow ox ennui that is oxydehydro~en~ted. The water from the reaction results in the pheromone of some swish acid. Under several atmospheres of pressure, about 0.05 to 0.25 mow of acetic acid per mow of ethylene us formed.
The water that I added Jo the feed stream will also cause the formation ox additional mounts of acetic acid, up to. bout 0.25 to 1.0 mow of acetic Clyde per mow of ethylene ho is formed.
The gaseous oomponen~s of the reaction mixture include eth~ne end oxygen, and possibly a 35~
delineate, and these components ore 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 2008C Jo about 450CC.
The reaction zone generally has a pressure of from about l to 30 misfires and preferably 1 Jo 20 atmospheres; temperature of from about 150C
bout to 450C, end preferably from bout 200C to bout 400C; contact time between the reaction mixture end the catalyst of from about 0.1 to bout 100, sod preferably from bout 1 to 10 seconds; and a spice velocity ox from bout 50 Jo 5000h l, 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 the gaseous re~ctiQn mixture feed to the catalyst bed under the given rewaken conditions in unit of time.
The spice velocity is calculated by determining total rector utile gas equivalent in liters of the total effluent evolved over period of one hour divined by the liters of catalyst in the rector. This root temperature volume is converted Jo the volume it OKAY at 760mm Hug:
liters of outlet gas spice velocity = ~uiv~lents per hour -h-liters of cRt~lyst in reactor The reaction pressure is initially provided by the feed of the gaseous reactant and delineate sod after the reaction has commenced, the pressure is maintained, preferably, by the use of suitable back-pressure controllers placed on the rector outlet stream.
The reaction temperature is preferably provided by placing the catalyst bed within tubular converter having walls immersed in a suitable heft transfer medium such as tetralln, molten salt mixtures, or other suitable heat transfer agents hosted to the desired reaction temperature.
Generally, the process can be curried out in a single stage with ~11 of the oxygen for the reaction being supplied long with on inert delineate. It is deslrsble to operate without a delineate to facilitate the isolation of the ethylene produced. When a delineate is not used this presents several problems because large amount ox oxygen can create a hazardous condition and the uncontrolled presence of w ton end acetic acid can adversely effect the production of ethylene.
Accordingly, it is believed that the use of multiple toes improves the process. Multiple stages allows the oxygen needed for the total reaction of the ethene to be introduced at various stages and thereby volleyed potentially hazardous cond{~lon.
Surprisingly, the supply of oxygen in various stages rather than A supply of the total mount of the oxygen on the ln~lal sage has no detrimental effect on the production of ethylene.
In addition the use of stages nobles the control of the amount of water present in stages subsequent V-14~3~
to the first sty. If desired, water can be withdrawn end 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 convene or economically justified.
A reasonably good basis for comparing catalyst performance con be achieved by comparing selectivity to ethylene for the same conversion of ethanes This con be accomplished essay by taking advantage of the discovered substantially linear relationship between selectivity to ethylene find 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 do EXAMPLES
Several examples were carried out to demonstrate the invention end compare it to the prior art.
The process or the various c~t~lys~s were carried out on tubular rector under the following conditions:
Gas feed composition was I by volume ethanes 6.5% by volume oxygen, end 85.5% by volume helium. The space velocity was bout 720 h l it a one atmosphere tool pressure. The reactor consisted of 9 millimeter diameter stainless steel ~2~33~l straight tube hefted on an oven with blower and at a temperature of from 330C to 425C. The reactor contflined 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 end truces of acetic Swede were condensed in trap end the gaseous products were analyzed for oxygen and carbon ~onoxlde at 65~C
on a em x 3mm column of 5 A molecular sieve (60/80 mesh). An analysis at 65C was carried out fox carbon dioxide, ethylene, and eth~ne on a 1.8 m x 3mm column of material told under the trademark POROPAK Q (50/80 mesh). In all cases, the conversion and selectivity calculations were based on the Stoichiometry:
C2H6 1/2 2 Do 2 4 ~2 C2H~ 5/2 2 ~~~
C2H6 7/2 2--~~2C02 3 H20 Example l catalyst was prepared to have the following composition:
My 6lV 26Nb Buick minim metavanadatc in the mount of 9.90 grams (0.0~5 grim Tom of V) was added to 100ml of water end heated to 70~C with stirring for fifteen minutes. Niobium oxala~e amounting to 31.1 grams of solution continuing lo by weight calculated us Nb205 ~0.0234 gram atom of Nub), antimony oxalate amounting to 3.12 rums (0.0123 gram-atom of Sub) hod calcium nitrite tetrahydrate amounting to 1.46 grams (0.0062 gram-atom of Cay were added to a second 100 ml of water end heated to 70C with stirring for fifteen minutes. The second mixture was combined with the f lust mixture and the combination was hefted it 70DC with stirring for phony minutes. To a third 100 ml of water was added 35.3 grams (0.200 gram-atom of Mow of minim paramolybdate. This mixture was heated to icky with stirring for fifteen minutes and then added to the combined mixtures. The final mixture was heated at 70C 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 find sieved to on 8 x 30 mesh end dried additionally in an oven it 120C for sixteen hours. The dried materiel was transferred to three swooper lucks beakers and calcined in an oven equipped with blower at a temperature of 350C.
The temperature was raised from room temporizer to 350C over period of twenty minutes and thereafter held it 350C for five hours.
The catalyst was tested according to the above described jest end the results are shown in Table II.
Example 2 Using the procedure of Example 1, catalyst having the following composition was prepared:
My 60~ 25N~ 07Sb kiwi 04 I
The same amounts of compounds were used except that 2.92 grams of calcium nitrate tetrahydr~te (0.0124 gr~m-~tom of Cay was used Jo that the catalyst produced hod a higher calcium content Han he catalyst of Example 1. The result of the tests with this catalyst ore riven in Table IT
Ho Using the procedure ox Example 2, a catalyst having the following composition was prepared:
My YO-YO 26Nb 07Sb,04C~.01 The same mounts of compounds were used except that 0.73 gram of calcium nitrate (owe gram Tom of Cay was used so that the c2tRlyst produced hod lower calcium Canaan thfln the catalyst of Example 1. Thy results of the tests with this outclass are given in Table II.
Examples 4 to 28 Examples 4 to 28 were carried out using the same procedure en used in Example 1 with the some quints of the compounds used for Mow V, Nub, and Sub. The X component was varied end in some cases several metals. Table I shows the X component, X
sly, welsh of the X silt, gram-atom of the X
met no the composition of the catalysts for Examples 4 Jo 28v The results of the tests with these calcites ore given lo Table II.
14~38 33~i~
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8 g o o 8 $ o g o o o o ox o I o I
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~2~3 Example 29 Using the procedure of Example 1, a catalyst hiving the following composi~lon was prepared:
My 62V 26Nb ~7Sb 04Mn.olCd.02W.01U.01Ce.0004 ~1 The same amounts of the compounds for Mow V, by and Sub were used as in Example 1. Ammonium tungstate in the amount of 0.92 gram (0.0035 gram-s~om W) and ammonium diursnate in the amount of 0.68 grim (0.0021 gram-atom of U) were mixed with the ammonlum metavanadate solution. Curium (III) nitrite in the mount of 0.05 gram (0.0001 gr~m-~tom Cue), cadmium nitrate in the amount of 1.63 grams (0.0053 gr~m-atom of Cud), lead IT nitrate in the amount of 0.76 gram (0.0023 grum-atom of Pub) and manganese IT nitrate in the amount of 1.04 grams of 50% aqueous solution (0.0029 ram atom of My) were mixed with the niobium oxalate and Antimony oxala~e solution. The results of the tests with this catalyst ore given in Table II.
.1 I
- Jo -Table II
Temp. Conversl~n Selectivity En. X Metal C ox Ethanes to Ethylene Cay 330 ` 34 66 35~ 55 76
4~0 73 71 4 So 340 32 I
S My 340 30 87 6 By eye, 33 86 7 I No 35û 32 I
8 Be 350 31 86 Pub 335 31 By 3~5 I 73 I
Table IT (coned) Temp. ConversionSelectivi~y Ex.X Metal I of Eth~ne_to Ethylene No 340 38 By 37~ I 72 400 7û 69 11 Lo 350 I 85 12 Co 330 31 By 35~ 46 79 13 Zen 330 30 86 375 5g I
14 Cue 350 27 86 Cud 344 30 84 16 Or 350 33 83 17 By 350 34 82 4~0 65 70 18 No 357 30 86 ~00 61 75 19 Cud 343 32 85 I
Table II keynote) Tempo Conversion Selecetvity En. X Metal I of Eth~ne to Ethylene 2Q Foe 353 35 83 4~0 I 69 21 Lo 355 30 85 3~5 56 76 22 Hug 340 32 84 23 Al 353 30 84 24 Sb(II) 360 29 79 375 36 . 74 Fe ( I I )350 25 74 27 Rub 350 19 78 boo 41 76 28 Mn,Cd, 345 30 By WgU,Ce, 375 So 76 Pi 400 70 72
S My 340 30 87 6 By eye, 33 86 7 I No 35û 32 I
8 Be 350 31 86 Pub 335 31 By 3~5 I 73 I
Table IT (coned) Temp. ConversionSelectivi~y Ex.X Metal I of Eth~ne_to Ethylene No 340 38 By 37~ I 72 400 7û 69 11 Lo 350 I 85 12 Co 330 31 By 35~ 46 79 13 Zen 330 30 86 375 5g I
14 Cue 350 27 86 Cud 344 30 84 16 Or 350 33 83 17 By 350 34 82 4~0 65 70 18 No 357 30 86 ~00 61 75 19 Cud 343 32 85 I
Table II keynote) Tempo Conversion Selecetvity En. X Metal I of Eth~ne to Ethylene 2Q Foe 353 35 83 4~0 I 69 21 Lo 355 30 85 3~5 56 76 22 Hug 340 32 84 23 Al 353 30 84 24 Sb(II) 360 29 79 375 36 . 74 Fe ( I I )350 25 74 27 Rub 350 19 78 boo 41 76 28 Mn,Cd, 345 30 By WgU,Ce, 375 So 76 Pi 400 70 72
Claims (4)
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 MOaVbNbcSbdXe in the form of oxides wherein:
X = at least one of the following: Li, Sc, Na, Be, Mg, CR, Sr, Ba, Ti, Zr, Hf, Y, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, Tl, Pb, As, Bi, Te, U, and W; and a = 0.5 to 0.9 b = 0.1 to 0.4 c = 0.001 to 0.2 d = 0.001 to 0.1 e = 0.001 to 1.0
X = at least one of the following: Li, Sc, Na, Be, Mg, CR, Sr, Ba, Ti, Zr, Hf, Y, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, Tl, Pb, As, Bi, Te, U, and W; and a = 0.5 to 0.9 b = 0.1 to 0.4 c = 0.001 to 0.2 d = 0.001 to 0.1 e = 0.001 to 1.0
2. The process of claim 1, wherein the selectivity to ethylene is greater than 65% 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.
4. The process of claim 1, wherein X
further comprises Mn in the amount of 0.001 to 1Ø
further comprises Mn in the amount of 0.001 to 1Ø
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US625,777 | 1984-06-28 | ||
| US06/625,777 US4524236A (en) | 1984-06-28 | 1984-06-28 | Process for oxydehydrogenation of ethane to ethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229351A true CA1229351A (en) | 1987-11-17 |
Family
ID=24507547
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000479614A Expired CA1229351A (en) | 1984-06-28 | 1985-04-19 | Process for oxydehydrogenation of ethane to ethylene |
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| Country | Link |
|---|---|
| US (1) | US4524236A (en) |
| EP (1) | EP0167109B1 (en) |
| JP (1) | JPS6115849A (en) |
| KR (1) | KR860000233A (en) |
| AU (1) | AU587981B2 (en) |
| BR (1) | BR8503080A (en) |
| CA (1) | CA1229351A (en) |
| DE (1) | DE3562225D1 (en) |
| MX (1) | MX167427B (en) |
| NO (1) | NO160435C (en) |
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Families Citing this family (88)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568790A (en) * | 1984-06-28 | 1986-02-04 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
| US4524236A (en) * | 1984-06-28 | 1985-06-18 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
| US4746641A (en) * | 1984-08-22 | 1988-05-24 | Standard Oil Company | Ammoxidation of paraffins and catalysts therefor |
| US4899003A (en) * | 1985-07-11 | 1990-02-06 | Union Carbide Chemicals And Plastics Company Inc. | Process for oxydehydrogenation of ethane to ethylene |
| US4657886A (en) * | 1985-07-25 | 1987-04-14 | Phillips Petroleum Company | Catalyst for conversion of C3 and C4 hydrocarbons |
| DE3681034D1 (en) * | 1986-09-24 | 1991-09-26 | Union Carbide Corp | METHOD FOR THE OXYDEHYDRATION OF ETHAN. |
| US5591315A (en) * | 1987-03-13 | 1997-01-07 | The Standard Oil Company | Solid-component membranes electrochemical reactor components electrochemical reactors use of membranes reactor components and reactor for oxidation reactions |
| US6488739B1 (en) | 1987-03-13 | 2002-12-03 | Bp Corporation North America Inc. | Oxygen production process |
| US5723035A (en) * | 1987-03-13 | 1998-03-03 | The Standard Oil Company | Coated membranes |
| 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 |
| EP0438902B2 (en) | 1989-12-27 | 2003-06-18 | The Standard Oil Company | Electrochemical reactors and multicomponent membranes useful for oxidation reactions |
| GB9027826D0 (en) * | 1990-12-21 | 1991-02-13 | Bp Chem Int Ltd | Chemical process |
| IT1252093B (en) * | 1991-11-26 | 1995-06-01 | Eniricerche Spa | CATALYST AND PROCESS FOR THE OXIDATIVE DEHYDROGENATION OF ETHANE AND ETHYLENE |
| WO2004074223A1 (en) * | 1992-10-06 | 2004-09-02 | Keiichi Sato | Process for dimerizing lower olefin and process for producing alsohol from dinerized olefin |
| DE4395195T1 (en) * | 1992-10-16 | 1994-11-10 | Mitsubishi Chem Ind | Process for the dimerization of butenes, dimeric composition of butenes and process for the preparation of alcohols by means of this |
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-
1984
- 1984-06-28 US US06/625,777 patent/US4524236A/en not_active Expired - Lifetime
-
1985
- 1985-04-19 CA CA000479614A patent/CA1229351A/en not_active Expired
- 1985-06-26 BR BR8503080A patent/BR8503080A/en unknown
- 1985-06-27 DE DE8585107948T patent/DE3562225D1/en not_active Expired
- 1985-06-27 NO NO852592A patent/NO160435C/en unknown
- 1985-06-27 MX MX205801A patent/MX167427B/en unknown
- 1985-06-27 JP JP60139258A patent/JPS6115849A/en active Granted
- 1985-06-27 KR KR1019850004581A patent/KR860000233A/en not_active Application Discontinuation
- 1985-06-27 ZA ZA854882A patent/ZA854882B/en unknown
- 1985-06-27 EP EP85107948A patent/EP0167109B1/en not_active Expired
- 1985-06-27 YU YU01081/85A patent/YU108185A/en unknown
- 1985-06-28 AU AU44288/85A patent/AU587981B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| BR8503080A (en) | 1986-03-11 |
| ZA854882B (en) | 1986-02-26 |
| DE3562225D1 (en) | 1988-05-26 |
| NO852592L (en) | 1985-12-30 |
| NO160435B (en) | 1989-01-09 |
| EP0167109A3 (en) | 1986-04-23 |
| EP0167109B1 (en) | 1988-04-20 |
| KR860000233A (en) | 1986-01-27 |
| US4524236A (en) | 1985-06-18 |
| JPH0354927B2 (en) | 1991-08-21 |
| YU108185A (en) | 1987-10-31 |
| MX167427B (en) | 1993-03-22 |
| NO160435C (en) | 1989-04-19 |
| AU4428885A (en) | 1986-01-02 |
| AU587981B2 (en) | 1989-09-07 |
| EP0167109A2 (en) | 1986-01-08 |
| JPS6115849A (en) | 1986-01-23 |
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