CA1048481A - Chromium-containing catalysts useful for oxidation reactions - Google Patents
Chromium-containing catalysts useful for oxidation reactionsInfo
- Publication number
- CA1048481A CA1048481A CA74208346A CA208346A CA1048481A CA 1048481 A CA1048481 A CA 1048481A CA 74208346 A CA74208346 A CA 74208346A CA 208346 A CA208346 A CA 208346A CA 1048481 A CA1048481 A CA 1048481A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- propylene
- isobutylene
- chromium
- butene
- 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
-
- 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
- B01J23/8878—Chromium
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/8995—Catalyst and recycle considerations
- Y10S585/906—Catalyst preservation or manufacture, e.g. activation before use
Abstract
CHROMIUM-CONTAINING CATALYSTS
USEFUL FOR OXIDATION REACTIONS
ABSTRACT OF THE INVENTION
Catalysts containing at least nickel or cobalt, chromium, bismuth and molybdenum have been found to be especially useful for the ammoxidation of olefins, the oxidation of olefins and the oxidative dehydrogenation of olefins.
USEFUL FOR OXIDATION REACTIONS
ABSTRACT OF THE INVENTION
Catalysts containing at least nickel or cobalt, chromium, bismuth and molybdenum have been found to be especially useful for the ammoxidation of olefins, the oxidation of olefins and the oxidative dehydrogenation of olefins.
Description
~(K~I~OlJI~l) 0l lll~ lNVENIlON
I`he ammoxid.ltion Or olefins, oxidative dehydr-,~tenatior of olefins and oxidation oL` ole~`ins with catalysts ,imilar to those of the present invention are known. See for example, U.S. 3,642,930, U.S. 3,414,631. Canadian F-atent 905,418 and U.S. 3,576,764.
The catalysts of the present invention have a composition different from those of the art and are very selective catalysts even at high temperatures.
SUMMARY OF THE INVENTION
The present invention us a catal~st composition having the empirical formula A Db NiC Cd Cre Bif M12 x wherein A is an alkali metal, Tl, In, Ag, Cu, rare earth or mixture thereof; and D is P, As, Sb, Sn, Ge, B, W, Th, V, Ti, Si or mixture thereof;
and wherein a and b are 0-4;
c and d are O to 20 with c + d greater than or equal to 0.1;
(4738) 1C~48481 e 18 0.1 to about 10;
r 18 about 0.01 to 6; and X i8 the number of oxygens required to satlsfy the valence requlrements o~ the other elements presont.
ffl ese cataly~ts have been ~ound to be e~peclally userul ror the ammoxldatlon, oxidstlon and oxldatlve dehydrogenatlon of oleflns.
The central aspect o~ th~ present inventlon 18 the catalyst. The catalyst can be any of the catalysts dellmited by the general ~ormula above. Preferred are those catalysts that contaln an alkall met~l and those catalysts that contaln both nlckel and cobalt.
The catalyst~ Or the lnventlon are convenlently prepared by any o~ the methods assoclated wlth the slmllar oxldatlon catalysts in the art. Among the methods o~ comblnlng the elements Or the catalyst are the copreclpltatlon Or soluble salts from a solutlon snd the mixlng Or salts or oxld~s Or the variou~ compounds. After the elements Or the catalyst are comblned, the preparatlon of the catalyst i8 completed by calclnatlon Or the catalyst at an elevated temperature. Temperature~ between about 200 and about 700C.
are most ~ultabl~.
Speclflc preparatlons Or catalysts of the lm entlon are shown in the Specl~lc Embodiments. m ese preparstlons are glven pre~erred cataly~ts of the inventlon.
The cataly~ts o~ the invention may be used as pure catalytlc material or they msy be used in the ~upported form. Suit~ble support material~ lnclude sillc~, ~lumina~
tltanla, zirconia, boron pho~phate and the llke. ffl e use Or catalysts supported on ~illca 18 preferred.
(4738) The catalysts of the inventlon have utlllty for a broad range o~ oxldatlon, ammoxldation and oxldatlve dehydroeenatlon resctions. Pre~erred are the ammoxidatlon o~ propylene or lsobutylene, the oxldatlon o~ propylene or lsobutylene and the oxldatlve dehydrogenatlon o~ ole~lns contalnlng about 4 to about lO carbon atoms.
ffle reactlons ln whlch the cataly~ts Or the lnventlon are utlllzed are well known. Essentlally, the lnventlon with respect to these processes le the use o~
the new catalyst o~ the lnventlon wlthln the parameters of the known proce~s. Broadly, the processes ~ll utlllzo molecular oxygen, preferably alr, ln the resctant feed, and the reactions are normally conducted wlthln the range o~ about 200 to about 60~C. wlth temperatures of about 300C. to about 500C. belng pre~erred. The reactsnt ratlos may vary as the dlf~erent reactions are conducted but generally range withln abo~t 5 to about 15 moles of alr per mole of olefln.
ffle reactlons can bo run at atmospherlc, superatmospherlc or subatmosph~rlc pressures us$ng contact tlmes o~ a ~ractlon of a second to 20 seconds or mor~.
ffl e reactlons can be run ln a rixed-bed or fluld-bed reactor.
In a fluld-bed reactor, the catalyst 1~ normally used ln the ~orm o~ pelleta, tablets or spheres and the like. In a fluld-bed re w tor, the catalyst 18 small partlcles, such as mlcrospherolds9 that are fluldlzed ln the reactlon.
As noted above, the cstaly~ts of the lnventlon are very selectlve even at hlgh temperatures. fflu~, hlg~
temperatures ean be used in the reactlon wlthout a sub3tantlal (4738) adverse effect on the deslred yleld of the reaetlon. me eatalysts ~xhlblt hlgh per pass converslons to useful produets st hlgh reactant through-put.
SPECIFIC EMBODIMENTS
Exam~les 1 - 15 - Ammoxldatlon o~ propylene.
A r~actor was eonstrueted of a 3talnloss tube havlne an inslde dl~meter of o,8 cm., an inlet ~or reactants and an outlet rOr produets. The reaetor had a eatalytle reaetlon zone havlng a ~olum~ o~ 5 ec. and was externally heated.
Varlous eatalyst composltlons eontalnlng 80%
actlve catalytlc lngrodients and 20% S102 were prepared as rOllow~: , Examplea 1-3 K0.1N12.5C4.sCr3BlPo.sMolzOx In 30 ce. o~ wanm water 31.8 g. of ammonla heptamolybdate, (NH4)6Mo7024.4HzO, wero dlssolred and 26.8 g. Or 40% s~llea 501 were added.
With eonstant ~tlrrlng, t~e mlxtur~ was slowly heated ~or about 5 mlnutes, and 0.9 g. of 8~% phosphorle acld, 10.9 g.
o~ nickel nitrate, Nl(N03)2-6H20 and 19.7 g. o~ eobalt nltrate, Co(N~3)z.6HzO, were sequentlally added. Heatlng and stlrrlng wore con~inued ~or a few minutes.
Separately, an aquoou~ mlxture contalnlng 18.0 g.
Or chromlum nltrate, Cr(~03)3-9H20, 7.2 g. of blsmuth nltrate, Bi(N03)3.5H~ and 0.19 g. o~ a 45~ solutlon o~ potasslum hydroxlde ~as preparod. Thls second ~ixture wa6 810~1y added to the rlrst slurry on a hot plato. After the addltlon (4738) was complete, the heat was lncre~sed untll the mixture started to thlcken. The resultant thlck paste was drled ln a drying oven at 120C. wlth occaslonal stlrrlng. Tho drled catalyst was then heat trested st 550C. ~or 20 hours.
Examples 4 and 5 Ko.lN12Co4Cr3BlMolzOx In 60 cc. Or warm water 63.56 g. of ammon~ heptamolybdate was dissolved and 50.90 g. of 40% sillca 801 was ~dded to fonm a slurry.
Separately, 9.00 g. chromlum oxlde, CrO3, 14.55 g.
blsmuth nltrate, 34.93 e. of cobalt nltrate, 17.45 g. nlckel nltrate and 3.03 g. o~ a 10~ ~olutlon o~ potasslum nitrate were comblned ln an aqueous mlxture. me aqueous mlxture was slowly added to the slurry,and the resultant mlxture was heated on a hot plate untll lt began to thlcken. Thc paste was dried at 120C. and then calclned at 550C. ~or 16 hours.
Exam~les 6 and I
Ko lNi~Cr3BlPo.5MolzOx A slurry was made by dissolvlng 63.56 g. Or ~mmonlum heptsmolybdate in 60 cc. Or warm water and addlng 52.95 g. o~ 40% sillca 801 ~nd 3.46 g. of a 42.5 solutlon o~ phosphorlc acld.
Separately, ln a small amount Or water on a hot plate 9.00 g. o~ chromlum oxlde, 61.07 g. o~ nlck~l nltr~t~, 3.03 g. o~ a 10~ solutlon o~ potas~lum nitrate and 14.55 g.
Or blsmuth nltrate were dlssol~ed. me resultant solutlon wa8 slowly added to the slurry wlth he~tlng. When the mixture started to thlcken, lt was removed rrom the hot pl~te and placed ln an oven at 120C. The drled material (4738) was heated at 290C. ~or three hours, at 425C. ~or t~ree hours and at 550C. ~or 16 hours.
Exa~Dles 8 and 9 KO.lCo7Cr ~iP0.5Mol20x The catalyst ~as preparod ln exactly th~ sa~e ~ay a8 Example~ 6 and 7 exccpt that 61.12 ~. o~ cobalt nltrate was substltuted ~or the nlck~l nltrate.
Exa~sl~ 10 Ge0.5XO.lN12.5C4.5Cr3BlMl20X An aqueous slurry was prepar~d uslng 63.56 g. of smmonlum heptamolybdate, 53.28 g. o~ 40% slllca ~ol and 1.57 g. o~ german~um oxlde, GeO2.
An aqueous solutlon was ~onmed uslng 9.00 g.
chromlum oxide, 14.55 g. bl~muth nltrate, 39.29 g. cobalt nltrate, 21.80 g. o~ nlckel nitrat~ ~nd 3.03 g. Or a 10~
solutlon o~ pota~slum nitrate. The eomblnlng o~ the mixture~, drylng and calclnatlon were con~uctod ~8 shown ln Exa~plos 6 snd 7.
Exam~
SnO.~XO.lNl2.~C04.sCr3BlM0l20X me catsly~t ~as prepared a~ ~hown in Example 10 aub~tltutlng 1.75 cc. o~
stannic chlorld~, SnC14, ~or the germanlum oxlde.
Examsl~ 12 B0.5KO.lN~2.5c4.5cr3BlMol2ox me catalyst ~a~
prepared a~ shown ln Example 10 substltutlng 0.93 g. Or borlc ~cld ~or th~ gormanlum oxlde.
(4738) Exam~le 13 WO.5KO.lNl2.5C04.5Cr3BlMol20X me catalyBt ~8B
prepared as shown ln Example 10 substltutlng 4.05 g.
(NH4)6W7024.6H~o rOr the germanlum oxlde.
ExamDle 14 V0.5RO.lNl2.5c4.5cr3BiMolzo~ The catalyst was prepared as descrlbed ln Example 10 ~ubstltutlng 1.75 g. Or NH4Y~3 ~or the genmanlum oxldc and 22.24 g. chromlum acetate, Cr(c2H3o2)3-H2o for the chromlum oxlde.
Exam~le 15 CUO.lKO.lNl2~C04.~Cr3BlPo.yMolzOx The cat~lyst was prspare~ as shown ln Example 10 except that chromium w etate was added as ln E~ample 14, and 3.46 g. o~ a 42.5%
solutlon Or pho~phorlc acld was added ln place o~ the genm~nium oxide and 0.72 g. Or Cu(N~3)2-3HzO was ad~ed to the second solutlon.
In preparatlon ~or use, the catalysts w~re ground and screened to glve a 20 to 35 mesh ~ractlon. FlYe cc.
Or thi~ catalyst wa~ placed ln the catalytlc reactor, and the ammoxldatlon Or propylene was ~onducted uslng a ~eed o~
propylene/ammonla/air/~te~m o~ lh.lhO/4 and an apparent contact time Or 8iX seconds. ma result~ Or these experiments are shown ln ~able I. It will be notea that evsn though-the temperatur~ 1B lncreased, the selectlvity remains remar~ably stable. It would be expected that at these hlgh temperatures, the ~electlvlty would rapldly decllne.
(4738) me results are stated ln the follo~ing ten~ss conver~lon _ e~nount o~ olefln r~cted x 100 amolmt o~ olefln fed ,~ ~electlvlty - ~Imount of olefln reacted u~ount of ~roduct obtained x 100 % slngle pas8 yl~ld ~ ~.mo~nt of ole~in red (4738) 1~48481 D
æ ~ ~ 0~ ~ cU ~ t ~ N ~ ~ t U~ D O ~ C~ 0 ~4 U~ ~ ~ ~ ~ ~ t- ~ ~ ~D
~ ;~1 m o~ ~ ,1 U~ ,1 O~ 0 N
~ ~ 0 CD ~ ~ ~ ~ ~ CO ~ ~ t~
~D ~1 ~ $
~ ;~ N ~ ~. . . . r1 1~1 0 N 0 U~ ~ 00 rl ~ 0 0 Cl :~: ~ ~ 0 a~ 0 O~ O ~, l C~
l o OOOOOOO'C:~OO
¦ O --t ;~ ~
I . oK
~ o ~
~ X ~ ~
æ QN ON V~
b ~ ~ ~ V~
~ ~ æ æ N
m N N ~ ~ ~ _ o 0 Z ~ V,~
~ ~ ~ O ~
~31 A CU ~ O
_ 9 _ (4738) 1~ 4 8 48 ~
Exam~les 16-24 - Oxidstive dehydrogenatlon Or butene.
me eatalyst propared ~or Example~ 1-3 ~a~ hoat treatod ~or an additlonal three hours at 650C. To the reactor, a8 deserlbed abov~J was eharged 2.5 ce. o~ the eatalyst. A roed o~ butene-l/a~r/stea~ Or 1/11/4 ~as pa~ed over the eatalyst for an apparent eontact t~me o~ one ~eeond.
The results are gi~en in Table II. The eon~ersion and selectlvlty ~igures gl~en ignores the isomerlzatlon o~
butene-l to butene-2 by ealeulatlng butene-2 as unr~seted reaetsnt.
Tabl~ II
OXIDATIVE DEHYDROGENAT10~ OF BUTENE-l _ - R~sults, ~ Slngle Pa~
15 Exam~le Tem~.,C. Converslon Seloctl~lty Yield 16 350 48.4 99 48.1 17 400 70.1 99 69.3 18 420 77.3 98 76.4 19 440 83.8 94 79.0 460 89.o 93 82.7 21 480 92.6 91 84.6 22 500 95-5 87 83.1 231- 400 78.6 98 76.8 242- 440 92.4 93 85.5 1. ~eed: 1 but~ne-1/27 alr/4 st~am eontaet time 1.5 soe.
I`he ammoxid.ltion Or olefins, oxidative dehydr-,~tenatior of olefins and oxidation oL` ole~`ins with catalysts ,imilar to those of the present invention are known. See for example, U.S. 3,642,930, U.S. 3,414,631. Canadian F-atent 905,418 and U.S. 3,576,764.
The catalysts of the present invention have a composition different from those of the art and are very selective catalysts even at high temperatures.
SUMMARY OF THE INVENTION
The present invention us a catal~st composition having the empirical formula A Db NiC Cd Cre Bif M12 x wherein A is an alkali metal, Tl, In, Ag, Cu, rare earth or mixture thereof; and D is P, As, Sb, Sn, Ge, B, W, Th, V, Ti, Si or mixture thereof;
and wherein a and b are 0-4;
c and d are O to 20 with c + d greater than or equal to 0.1;
(4738) 1C~48481 e 18 0.1 to about 10;
r 18 about 0.01 to 6; and X i8 the number of oxygens required to satlsfy the valence requlrements o~ the other elements presont.
ffl ese cataly~ts have been ~ound to be e~peclally userul ror the ammoxldatlon, oxidstlon and oxldatlve dehydrogenatlon of oleflns.
The central aspect o~ th~ present inventlon 18 the catalyst. The catalyst can be any of the catalysts dellmited by the general ~ormula above. Preferred are those catalysts that contaln an alkall met~l and those catalysts that contaln both nlckel and cobalt.
The catalyst~ Or the lnventlon are convenlently prepared by any o~ the methods assoclated wlth the slmllar oxldatlon catalysts in the art. Among the methods o~ comblnlng the elements Or the catalyst are the copreclpltatlon Or soluble salts from a solutlon snd the mixlng Or salts or oxld~s Or the variou~ compounds. After the elements Or the catalyst are comblned, the preparatlon of the catalyst i8 completed by calclnatlon Or the catalyst at an elevated temperature. Temperature~ between about 200 and about 700C.
are most ~ultabl~.
Speclflc preparatlons Or catalysts of the lm entlon are shown in the Specl~lc Embodiments. m ese preparstlons are glven pre~erred cataly~ts of the inventlon.
The cataly~ts o~ the invention may be used as pure catalytlc material or they msy be used in the ~upported form. Suit~ble support material~ lnclude sillc~, ~lumina~
tltanla, zirconia, boron pho~phate and the llke. ffl e use Or catalysts supported on ~illca 18 preferred.
(4738) The catalysts of the inventlon have utlllty for a broad range o~ oxldatlon, ammoxldation and oxldatlve dehydroeenatlon resctions. Pre~erred are the ammoxidatlon o~ propylene or lsobutylene, the oxldatlon o~ propylene or lsobutylene and the oxldatlve dehydrogenatlon o~ ole~lns contalnlng about 4 to about lO carbon atoms.
ffle reactlons ln whlch the cataly~ts Or the lnventlon are utlllzed are well known. Essentlally, the lnventlon with respect to these processes le the use o~
the new catalyst o~ the lnventlon wlthln the parameters of the known proce~s. Broadly, the processes ~ll utlllzo molecular oxygen, preferably alr, ln the resctant feed, and the reactions are normally conducted wlthln the range o~ about 200 to about 60~C. wlth temperatures of about 300C. to about 500C. belng pre~erred. The reactsnt ratlos may vary as the dlf~erent reactions are conducted but generally range withln abo~t 5 to about 15 moles of alr per mole of olefln.
ffle reactlons can bo run at atmospherlc, superatmospherlc or subatmosph~rlc pressures us$ng contact tlmes o~ a ~ractlon of a second to 20 seconds or mor~.
ffl e reactlons can be run ln a rixed-bed or fluld-bed reactor.
In a fluld-bed reactor, the catalyst 1~ normally used ln the ~orm o~ pelleta, tablets or spheres and the like. In a fluld-bed re w tor, the catalyst 18 small partlcles, such as mlcrospherolds9 that are fluldlzed ln the reactlon.
As noted above, the cstaly~ts of the lnventlon are very selectlve even at hlgh temperatures. fflu~, hlg~
temperatures ean be used in the reactlon wlthout a sub3tantlal (4738) adverse effect on the deslred yleld of the reaetlon. me eatalysts ~xhlblt hlgh per pass converslons to useful produets st hlgh reactant through-put.
SPECIFIC EMBODIMENTS
Exam~les 1 - 15 - Ammoxldatlon o~ propylene.
A r~actor was eonstrueted of a 3talnloss tube havlne an inslde dl~meter of o,8 cm., an inlet ~or reactants and an outlet rOr produets. The reaetor had a eatalytle reaetlon zone havlng a ~olum~ o~ 5 ec. and was externally heated.
Varlous eatalyst composltlons eontalnlng 80%
actlve catalytlc lngrodients and 20% S102 were prepared as rOllow~: , Examplea 1-3 K0.1N12.5C4.sCr3BlPo.sMolzOx In 30 ce. o~ wanm water 31.8 g. of ammonla heptamolybdate, (NH4)6Mo7024.4HzO, wero dlssolred and 26.8 g. Or 40% s~llea 501 were added.
With eonstant ~tlrrlng, t~e mlxtur~ was slowly heated ~or about 5 mlnutes, and 0.9 g. of 8~% phosphorle acld, 10.9 g.
o~ nickel nitrate, Nl(N03)2-6H20 and 19.7 g. o~ eobalt nltrate, Co(N~3)z.6HzO, were sequentlally added. Heatlng and stlrrlng wore con~inued ~or a few minutes.
Separately, an aquoou~ mlxture contalnlng 18.0 g.
Or chromlum nltrate, Cr(~03)3-9H20, 7.2 g. of blsmuth nltrate, Bi(N03)3.5H~ and 0.19 g. o~ a 45~ solutlon o~ potasslum hydroxlde ~as preparod. Thls second ~ixture wa6 810~1y added to the rlrst slurry on a hot plato. After the addltlon (4738) was complete, the heat was lncre~sed untll the mixture started to thlcken. The resultant thlck paste was drled ln a drying oven at 120C. wlth occaslonal stlrrlng. Tho drled catalyst was then heat trested st 550C. ~or 20 hours.
Examples 4 and 5 Ko.lN12Co4Cr3BlMolzOx In 60 cc. Or warm water 63.56 g. of ammon~ heptamolybdate was dissolved and 50.90 g. of 40% sillca 801 was ~dded to fonm a slurry.
Separately, 9.00 g. chromlum oxlde, CrO3, 14.55 g.
blsmuth nltrate, 34.93 e. of cobalt nltrate, 17.45 g. nlckel nltrate and 3.03 g. o~ a 10~ ~olutlon o~ potasslum nitrate were comblned ln an aqueous mlxture. me aqueous mlxture was slowly added to the slurry,and the resultant mlxture was heated on a hot plate untll lt began to thlcken. Thc paste was dried at 120C. and then calclned at 550C. ~or 16 hours.
Exam~les 6 and I
Ko lNi~Cr3BlPo.5MolzOx A slurry was made by dissolvlng 63.56 g. Or ~mmonlum heptsmolybdate in 60 cc. Or warm water and addlng 52.95 g. o~ 40% sillca 801 ~nd 3.46 g. of a 42.5 solutlon o~ phosphorlc acld.
Separately, ln a small amount Or water on a hot plate 9.00 g. o~ chromlum oxlde, 61.07 g. o~ nlck~l nltr~t~, 3.03 g. o~ a 10~ solutlon o~ potas~lum nitrate and 14.55 g.
Or blsmuth nltrate were dlssol~ed. me resultant solutlon wa8 slowly added to the slurry wlth he~tlng. When the mixture started to thlcken, lt was removed rrom the hot pl~te and placed ln an oven at 120C. The drled material (4738) was heated at 290C. ~or three hours, at 425C. ~or t~ree hours and at 550C. ~or 16 hours.
Exa~Dles 8 and 9 KO.lCo7Cr ~iP0.5Mol20x The catalyst ~as preparod ln exactly th~ sa~e ~ay a8 Example~ 6 and 7 exccpt that 61.12 ~. o~ cobalt nltrate was substltuted ~or the nlck~l nltrate.
Exa~sl~ 10 Ge0.5XO.lN12.5C4.5Cr3BlMl20X An aqueous slurry was prepar~d uslng 63.56 g. of smmonlum heptamolybdate, 53.28 g. o~ 40% slllca ~ol and 1.57 g. o~ german~um oxlde, GeO2.
An aqueous solutlon was ~onmed uslng 9.00 g.
chromlum oxide, 14.55 g. bl~muth nltrate, 39.29 g. cobalt nltrate, 21.80 g. o~ nlckel nitrat~ ~nd 3.03 g. Or a 10~
solutlon o~ pota~slum nitrate. The eomblnlng o~ the mixture~, drylng and calclnatlon were con~uctod ~8 shown ln Exa~plos 6 snd 7.
Exam~
SnO.~XO.lNl2.~C04.sCr3BlM0l20X me catsly~t ~as prepared a~ ~hown in Example 10 aub~tltutlng 1.75 cc. o~
stannic chlorld~, SnC14, ~or the germanlum oxlde.
Examsl~ 12 B0.5KO.lN~2.5c4.5cr3BlMol2ox me catalyst ~a~
prepared a~ shown ln Example 10 substltutlng 0.93 g. Or borlc ~cld ~or th~ gormanlum oxlde.
(4738) Exam~le 13 WO.5KO.lNl2.5C04.5Cr3BlMol20X me catalyBt ~8B
prepared as shown ln Example 10 substltutlng 4.05 g.
(NH4)6W7024.6H~o rOr the germanlum oxlde.
ExamDle 14 V0.5RO.lNl2.5c4.5cr3BiMolzo~ The catalyst was prepared as descrlbed ln Example 10 ~ubstltutlng 1.75 g. Or NH4Y~3 ~or the genmanlum oxldc and 22.24 g. chromlum acetate, Cr(c2H3o2)3-H2o for the chromlum oxlde.
Exam~le 15 CUO.lKO.lNl2~C04.~Cr3BlPo.yMolzOx The cat~lyst was prspare~ as shown ln Example 10 except that chromium w etate was added as ln E~ample 14, and 3.46 g. o~ a 42.5%
solutlon Or pho~phorlc acld was added ln place o~ the genm~nium oxide and 0.72 g. Or Cu(N~3)2-3HzO was ad~ed to the second solutlon.
In preparatlon ~or use, the catalysts w~re ground and screened to glve a 20 to 35 mesh ~ractlon. FlYe cc.
Or thi~ catalyst wa~ placed ln the catalytlc reactor, and the ammoxldatlon Or propylene was ~onducted uslng a ~eed o~
propylene/ammonla/air/~te~m o~ lh.lhO/4 and an apparent contact time Or 8iX seconds. ma result~ Or these experiments are shown ln ~able I. It will be notea that evsn though-the temperatur~ 1B lncreased, the selectlvity remains remar~ably stable. It would be expected that at these hlgh temperatures, the ~electlvlty would rapldly decllne.
(4738) me results are stated ln the follo~ing ten~ss conver~lon _ e~nount o~ olefln r~cted x 100 amolmt o~ olefln fed ,~ ~electlvlty - ~Imount of olefln reacted u~ount of ~roduct obtained x 100 % slngle pas8 yl~ld ~ ~.mo~nt of ole~in red (4738) 1~48481 D
æ ~ ~ 0~ ~ cU ~ t ~ N ~ ~ t U~ D O ~ C~ 0 ~4 U~ ~ ~ ~ ~ ~ t- ~ ~ ~D
~ ;~1 m o~ ~ ,1 U~ ,1 O~ 0 N
~ ~ 0 CD ~ ~ ~ ~ ~ CO ~ ~ t~
~D ~1 ~ $
~ ;~ N ~ ~. . . . r1 1~1 0 N 0 U~ ~ 00 rl ~ 0 0 Cl :~: ~ ~ 0 a~ 0 O~ O ~, l C~
l o OOOOOOO'C:~OO
¦ O --t ;~ ~
I . oK
~ o ~
~ X ~ ~
æ QN ON V~
b ~ ~ ~ V~
~ ~ æ æ N
m N N ~ ~ ~ _ o 0 Z ~ V,~
~ ~ ~ O ~
~31 A CU ~ O
_ 9 _ (4738) 1~ 4 8 48 ~
Exam~les 16-24 - Oxidstive dehydrogenatlon Or butene.
me eatalyst propared ~or Example~ 1-3 ~a~ hoat treatod ~or an additlonal three hours at 650C. To the reactor, a8 deserlbed abov~J was eharged 2.5 ce. o~ the eatalyst. A roed o~ butene-l/a~r/stea~ Or 1/11/4 ~as pa~ed over the eatalyst for an apparent eontact t~me o~ one ~eeond.
The results are gi~en in Table II. The eon~ersion and selectlvlty ~igures gl~en ignores the isomerlzatlon o~
butene-l to butene-2 by ealeulatlng butene-2 as unr~seted reaetsnt.
Tabl~ II
OXIDATIVE DEHYDROGENAT10~ OF BUTENE-l _ - R~sults, ~ Slngle Pa~
15 Exam~le Tem~.,C. Converslon Seloctl~lty Yield 16 350 48.4 99 48.1 17 400 70.1 99 69.3 18 420 77.3 98 76.4 19 440 83.8 94 79.0 460 89.o 93 82.7 21 480 92.6 91 84.6 22 500 95-5 87 83.1 231- 400 78.6 98 76.8 242- 440 92.4 93 85.5 1. ~eed: 1 but~ne-1/27 alr/4 st~am eontaet time 1.5 soe.
2. no ste~m added (4738) 1G~48481 Examples 2~-39 - Oxldatlve dehydrogenstlon o~ butene-l ~ lth v~rlous catalysts.
me cataly~t~ prep~red a8 descrlbed ln Example8 1-15 were used to oxidatlve dehydrogenate butene-l u~lng ~
~eed o~ butene-l/alr/~t0sm o~ 1 h 1/4 and sn appsrent conts,ct tlme Or one ~econd. me result~ are shown ~n Table III.
(4738) ~48481 ~ I
~1 ~ o ~1 o cr~ u~ ~ ~ ~ qO ~ 0 ~ ~ u~
I cu o~ o ~ .
t- C- ~ 0 ~o ~ ~ aD ~ ~ C- ~ ~ GO
~a ~ I t~) N ~ r~ C) ~ ,~
~ ~ a~ ~ ~ ~ 0 a~
~1 ~ ~ O 0. C~ 0. ~ O .
~ ID t-- 1~ N ~ ~ 0~ 0 ~ ~1 o Irl ~ O N
~ I ~ OD 0 a~ D 0 0 c~
N ~ ~ ON
~ I E~
oK N
K ~C h I o o O ~"0e.~
~ æ æ ~ cu 2 b s~ e m ~ ~ ~ sz;
N t~ CU~ '~
0 ~1 ~1 ~1 ~1 ~ Ir~ 1~
~0 ~ ~ X C~
O
me cataly~t~ prep~red a8 descrlbed ln Example8 1-15 were used to oxidatlve dehydrogenate butene-l u~lng ~
~eed o~ butene-l/alr/~t0sm o~ 1 h 1/4 and sn appsrent conts,ct tlme Or one ~econd. me result~ are shown ~n Table III.
(4738) ~48481 ~ I
~1 ~ o ~1 o cr~ u~ ~ ~ ~ qO ~ 0 ~ ~ u~
I cu o~ o ~ .
t- C- ~ 0 ~o ~ ~ aD ~ ~ C- ~ ~ GO
~a ~ I t~) N ~ r~ C) ~ ,~
~ ~ a~ ~ ~ ~ 0 a~
~1 ~ ~ O 0. C~ 0. ~ O .
~ ID t-- 1~ N ~ ~ 0~ 0 ~ ~1 o Irl ~ O N
~ I ~ OD 0 a~ D 0 0 c~
N ~ ~ ON
~ I E~
oK N
K ~C h I o o O ~"0e.~
~ æ æ ~ cu 2 b s~ e m ~ ~ ~ sz;
N t~ CU~ '~
0 ~1 ~1 ~1 ~1 ~ Ir~ 1~
~0 ~ ~ X C~
O
3~ ~ 0 ~ O ~ N ~ O t-- CD O~ ~
(4738) 11)48481 Example 40 - Catalyst wlthout alkall metal.
A catalyst was preparod accordlng to the method for the catalyst Or Examples 1-3 except that potasslum wae omitted from the preparatlon. me catalyst hsd the formula 80~ N12.5C4.5Cr3BlPo.sMO120x 1 20~ S102.
In the same manner ss descrlbed abo~e, butene-l was oxldatlvely dehydrogenated uslng a feed of 1 butene-lh 1 alr/
(4738) 11)48481 Example 40 - Catalyst wlthout alkall metal.
A catalyst was preparod accordlng to the method for the catalyst Or Examples 1-3 except that potasslum wae omitted from the preparatlon. me catalyst hsd the formula 80~ N12.5C4.5Cr3BlPo.sMO120x 1 20~ S102.
In the same manner ss descrlbed abo~e, butene-l was oxldatlvely dehydrogenated uslng a feed of 1 butene-lh 1 alr/
4 steam at 420C. ~nd an apparent contact tlme o~ one second.
me converslon o~ the butene-l was 84.1%, the selectlvlty to butadlene was 87~ and the single pass yleld was 73.2~.
ExamPle 41 - Tln contalnlng catalyst.
A catalyet o~ the formul8 80~ Sn~.sKo.lN12.5~4.5Cr2.5 BlP0.5Mol20x and 20~ S102 was prepared ln a msnner substantlally the same as the catalyst tor Example 11 except that the amount of chromlum was reduced and phosphoric acld was add~d to the solution.
In an oxldatlve dehydrogenatlon o~ butene-l uelng 11 moles of air per mole Or butene-l and no steam at 440C.
and a contact time of one second, the conYerslon was 90.8%, the selectiv~ty was 91~ and the per pB88 converBlon ~a8 82.7~.
Example 4? - Preparatlon of acroleln ~nd acryllc scld.
A catalyst prepared accordlng to Exsmple 15 was used for the oxldatlon o~ propylene uslng a feod of propylene/
air/steam Or 1/11/4. At a temperature of 400C. ~nd a contact tlme Or 6 second~, the converslon was 82.8~, the selectlvlty to ~croleln and acryllc acld was 85%~ the slngle pass yleld to acroleln was 66.7% and the slngle pass yleld to scryllc acld was 3.5~.
(4738) Exam~le 43 - Preparatlon of methacrylonltrlle.
In the ssme manner as described for the ammoxldatlon Or propylene, lsobutylene was res~ted to fonm methacrylonltrlle.
Uslng a reactant ~eed of lsobutylene/ammonla/alr/stesm o~
1/1.5/10/4 at a temperature of 400C. and an apparent contact tlme of 81x seconds, the slngle pass yl~ld o~ meths,crylonltrlle was 56.9~
In the same manner as descrlbed by the examples above butene-2 or lsoamylene 1~ oxldatlvely dehydrogenated wlth slmllar results. Also, in the same manner, lsobutylene 18 oxldlzed to methscroleln uslng the cat~lysts o~ the lnvention.
_ 14 -
me converslon o~ the butene-l was 84.1%, the selectlvlty to butadlene was 87~ and the single pass yleld was 73.2~.
ExamPle 41 - Tln contalnlng catalyst.
A catalyet o~ the formul8 80~ Sn~.sKo.lN12.5~4.5Cr2.5 BlP0.5Mol20x and 20~ S102 was prepared ln a msnner substantlally the same as the catalyst tor Example 11 except that the amount of chromlum was reduced and phosphoric acld was add~d to the solution.
In an oxldatlve dehydrogenatlon o~ butene-l uelng 11 moles of air per mole Or butene-l and no steam at 440C.
and a contact time of one second, the conYerslon was 90.8%, the selectiv~ty was 91~ and the per pB88 converBlon ~a8 82.7~.
Example 4? - Preparatlon of acroleln ~nd acryllc scld.
A catalyst prepared accordlng to Exsmple 15 was used for the oxldatlon o~ propylene uslng a feod of propylene/
air/steam Or 1/11/4. At a temperature of 400C. ~nd a contact tlme Or 6 second~, the converslon was 82.8~, the selectlvlty to ~croleln and acryllc acld was 85%~ the slngle pass yleld to acroleln was 66.7% and the slngle pass yleld to scryllc acld was 3.5~.
(4738) Exam~le 43 - Preparatlon of methacrylonltrlle.
In the ssme manner as described for the ammoxldatlon Or propylene, lsobutylene was res~ted to fonm methacrylonltrlle.
Uslng a reactant ~eed of lsobutylene/ammonla/alr/stesm o~
1/1.5/10/4 at a temperature of 400C. and an apparent contact tlme of 81x seconds, the slngle pass yl~ld o~ meths,crylonltrlle was 56.9~
In the same manner as descrlbed by the examples above butene-2 or lsoamylene 1~ oxldatlvely dehydrogenated wlth slmllar results. Also, in the same manner, lsobutylene 18 oxldlzed to methscroleln uslng the cat~lysts o~ the lnvention.
_ 14 -
Claims (9)
1. A catalyst composition having the empirical formula Aa Db Nic Cod Cre Bif Mo12 Ox wherein A is an alkali metal, Ti, In, Ag, Cu, rare earth or mixture thereof;
and D is P, As, Sb, Sn, Ge, B, W, Th, V, Ti, Si or mixture thereof;
and wherein a and b are 0-4;
c and d are 0 to 20 with c + d greater than or equal to 0.1;
e is 0.1 to about 10;
f is about 0.01 to 6; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.
and D is P, As, Sb, Sn, Ge, B, W, Th, V, Ti, Si or mixture thereof;
and wherein a and b are 0-4;
c and d are 0 to 20 with c + d greater than or equal to 0.1;
e is 0.1 to about 10;
f is about 0.01 to 6; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.
2. The catalyst of Claim 1 which contains an alkali metal.
3. The catalyst of Claim 1 which contains potassium.
4. The catalyst of Claim 1 which contains nickel and cobalt.
5. The catalyst of Claim 1 wherein the catalyst is K0.1Ni2.5C04.5Cr3BiP0.5Mo12Ox.
6. The catalyst of Claim 4 promoted with copper.
7. In the process for the ammoxidation of propylene or isobutylene comprising contacting the propylene or isobutylene with ammonia and molecular oxygen in the presence of a catalyst at a temperature of about 200° to about 600°C., the improvement comprising using as the catalyst the catalyst of Claim 1.
8. In the process of oxidizing propylene or isobutylene to the corresponding unsaturated aldehyde or acid by contacting the propylene or isobutylene and molecular oxygen with a catalyst at a temperature of about 200° to about 600°C. the improvement comprising using as the oxidation catalyst the catalyst of Claim 1.
9. In the process for the oxidative dehydrogenation of an olefin containing 4 to 10 carbon atoms by contacting the olefin with molecular oxygen at a temperature of about 200° to about 600°C. in the presence of a catalyst, the improvement comprising using as the catalyst the catalyst of Claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/393,732 US3956181A (en) | 1973-09-04 | 1973-09-04 | Oxidation catalyst |
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| Publication Number | Publication Date |
|---|---|
| CA1048481A true CA1048481A (en) | 1979-02-13 |
Family
ID=23556013
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA74208346A Expired CA1048481A (en) | 1973-09-04 | 1974-09-03 | Chromium-containing catalysts useful for oxidation reactions |
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|---|---|
| US (1) | US3956181A (en) |
| JP (1) | JPS5064191A (en) |
| AR (1) | AR205351A1 (en) |
| BE (1) | BE819533A (en) |
| BG (1) | BG36494A3 (en) |
| BR (1) | BR7407285D0 (en) |
| CA (1) | CA1048481A (en) |
| CH (3) | CH605477A5 (en) |
| CS (1) | CS220305B2 (en) |
| DD (1) | DD112906A5 (en) |
| DE (1) | DE2440329C2 (en) |
| DK (1) | DK146583C (en) |
| EG (1) | EG11372A (en) |
| ES (1) | ES429744A1 (en) |
| FI (1) | FI62959C (en) |
| FR (1) | FR2242146B1 (en) |
| GB (1) | GB1473530A (en) |
| HU (2) | HU181951B (en) |
| IE (1) | IE39886B1 (en) |
| IL (1) | IL45503A (en) |
| IN (1) | IN143036B (en) |
| IT (1) | IT1020135B (en) |
| MY (1) | MY7800190A (en) |
| NL (1) | NL186138C (en) |
| NO (1) | NO141830C (en) |
| PH (1) | PH12128A (en) |
| PL (1) | PL108045B1 (en) |
| RO (1) | RO66352A (en) |
| SE (1) | SE403104B (en) |
| SU (1) | SU588906A3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA708973A (en) * | 1960-01-02 | 1965-05-04 | Knapsack-Griesheim Aktiengesellschaft | Process for the manufacture of unsaturated nitriles |
| NL298115A (en) * | 1962-09-20 | |||
| CH442272A (en) * | 1963-08-07 | 1967-08-31 | Knapsack Ag | Process for the production of nitriles |
| US3625867A (en) * | 1967-06-02 | 1971-12-07 | Takachika Yoshino | Process for production of metal oxide-antimony oxide catalysts |
| US3761424A (en) * | 1968-08-31 | 1973-09-25 | Degussa | Catalysts for the oxidation of alkenes |
| US3678124A (en) * | 1968-10-24 | 1972-07-18 | Gennady Arkadievich Stepanov | Process for the production of mono- and diolefin hydrocarbons |
| US3642930A (en) * | 1968-12-30 | 1972-02-15 | Standard Oil Co Ohio | Process for the manufacture of isoprene from isoamylenes and methyl butanols and catalyst therefor |
| BE749305A (en) * | 1969-05-02 | 1970-10-01 | Nippon Kayaku Kk | OXIDIZATION CATALYST AND ITS USE ( |
| BE757476A (en) * | 1969-10-17 | 1971-03-16 | Nippon Kayaku Kk | OXIDESHYDROGENATION PROCESS |
| JPS4843096B1 (en) * | 1970-01-31 | 1973-12-17 | ||
| JPS5112603B1 (en) * | 1971-05-26 | 1976-04-21 | ||
| JPS516649B2 (en) * | 1971-11-11 | 1976-03-01 | ||
| US3786000A (en) * | 1972-01-06 | 1974-01-15 | Rohm & Haas | Catalyst for the production of acrolein and acrylic acid |
| GB1434581A (en) * | 1972-05-26 | 1976-05-05 | Ube Industries | Catalyst and process for catalytic ammoxidation of propylene or isobutylene |
| GB1426303A (en) * | 1972-08-25 | 1976-02-25 | Ube Industries | Catalyst and process for oxidation of ammoxidation of olefin mixtures |
-
1973
- 1973-09-03 PH PH16238A patent/PH12128A/en unknown
- 1973-09-04 US US05/393,732 patent/US3956181A/en not_active Expired - Lifetime
-
1974
- 1974-01-01 AR AR255456A patent/AR205351A1/en active
- 1974-08-12 SE SE7410289A patent/SE403104B/en not_active IP Right Cessation
- 1974-08-20 IL IL45503A patent/IL45503A/en unknown
- 1974-08-22 DE DE2440329A patent/DE2440329C2/en not_active Expired
- 1974-08-22 IT IT26534/74A patent/IT1020135B/en active
- 1974-08-26 JP JP49097802A patent/JPS5064191A/ja active Pending
- 1974-08-26 DD DD180711A patent/DD112906A5/xx unknown
- 1974-08-27 ZA ZA00745492A patent/ZA745492B/en unknown
- 1974-08-28 CS CS745928A patent/CS220305B2/en unknown
- 1974-08-30 NL NLAANVRAGE7411580,A patent/NL186138C/en not_active IP Right Cessation
- 1974-08-31 EG EG365/74A patent/EG11372A/en active
- 1974-09-02 BR BR7285/74A patent/BR7407285D0/en unknown
- 1974-09-03 CA CA74208346A patent/CA1048481A/en not_active Expired
- 1974-09-03 ES ES429744A patent/ES429744A1/en not_active Expired
- 1974-09-03 HU HU74SA2687A patent/HU181951B/en unknown
- 1974-09-03 FR FR7429941A patent/FR2242146B1/fr not_active Expired
- 1974-09-03 SU SU742057097A patent/SU588906A3/en active
- 1974-09-03 DK DK465074A patent/DK146583C/en active
- 1974-09-03 CH CH700177A patent/CH605477A5/xx not_active IP Right Cessation
- 1974-09-03 IN IN1972/CAL/74A patent/IN143036B/en unknown
- 1974-09-03 RO RO7479900A patent/RO66352A/en unknown
- 1974-09-03 CH CH1196074A patent/CH600946A5/xx not_active IP Right Cessation
- 1974-09-03 FI FI2570/74A patent/FI62959C/en active
- 1974-09-03 TR TR18345A patent/TR18345A/en unknown
- 1974-09-03 CH CH700077A patent/CH603514A5/xx not_active IP Right Cessation
- 1974-09-03 HU HU802231A patent/HU181732B/en unknown
- 1974-09-03 NO NO743150A patent/NO141830C/en unknown
- 1974-09-04 GB GB3864674A patent/GB1473530A/en not_active Expired
- 1974-09-04 IE IE1832/74A patent/IE39886B1/en unknown
- 1974-09-04 BE BE148198A patent/BE819533A/en not_active IP Right Cessation
- 1974-09-04 BG BG7427622A patent/BG36494A3/en unknown
- 1974-09-04 PL PL1974173855A patent/PL108045B1/en unknown
-
1978
- 1978-12-30 MY MY190/78A patent/MY7800190A/en unknown
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