US3862256A - Method for preparing mono- and di-olefine hydrocarbons - Google Patents

Method for preparing mono- and di-olefine hydrocarbons Download PDF

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US3862256A
US3862256A US27865472A US3862256A US 3862256 A US3862256 A US 3862256A US 27865472 A US27865472 A US 27865472A US 3862256 A US3862256 A US 3862256A
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butane
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Anatoly Lvovich Isailingold
Veniamin Anatolievich Levin
Fedor Semenovich Pilipenko
Tatyana Pavlovna Vernova
Gennady Arkadievich Stepanov
Alexandr Nikitich Bushin
Boris Vasilievich Sirotkin
Valentin Vasilievich Kozin
Mark Ekhetskelevich Basner
Aida Vladimirovna Erofeeva
Nina Prokopievna Peshkova
Luiza Saidovna Tuktarova
Yakov Yakovlevich Kirnos
Ruslan Konstantinovi Mikhailov
Nikolai Zakharovich Dolinin
Jury Nikolaevich Rastvorov
Valeria Lvovna Eratova
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Anatoly Lvovich Isailingold
Veniamin Anatolievich Levin
Fedor Semenovich Pilipenko
Tatyana Pavlovna Vernova
Gennady Arkadievich Stepanov
Alexandr Nikitich Bushin
Boris Vasilievich Sirotkin
Valentin Vasilievich Kozin
Mark Ekhetskelevich Basner
Aida Vladimirovna Erofeeva
Nina Prokopievna Peshkova
Luiza Saidovna Tuktarova
Yakov Yakovlevich Kirnos
Ruslan Konstantinovi Mikhailov
Nikolai Zakharovich Dolinin
Jury Nikolaevich Rastvorov
Valeria Lvovna Eratova
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/31Chromium, molybdenum or tungsten combined with bismuth
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor

Abstract

A method for the production of mono- and diolefinic hydrocarbons by subjecting paraffinic hydrocarbons to catalytic oxidative dehydrogenation at 400* to 700* in the presence of a catalyst comprising oxygen-containing compounds of molybdenum and magnesium taken in a molybdenum/magnesium atomic ratio of 1:0.9 to 1:357, optional components of said catalyst being oxygencontaining compounds of cobalt, iron, chromium, vanadium, nickel, silicon, antimony, boron, gadolinium, dysprosium, gallium, bismuth, titanium, zirconium or niobium.

Description

United States Patent [191 Isailingold et al.

[ Jan. 21, 1975 METHOD FOR PREPARING MONO- AND DI-OLEFINE HYDROCARBONS [76] Inventors: Anatoly Lvovich lsailingold, ulitsa Chekhova, 25, kv. 31; Veniamin Anatolievich Levin, Svobody, 75/37, kv. 24; Fedor Semenovich Pilipenko, zhskaya naberezhnaya, 25/2, kv. 7; Tatyana Pavlovna Vernova, Uglichskoe shosse, 10, kv. 40; Gennady Arkadievich Stepanov, ulitsa Pervomaiskaya, 9, kv. 3', Alexandr Nikitich Bushin, ulitsa Pervomaiskaya, 9, kv. 21; Boris Vasilievich Sirotkin, ulitsa l Zhilaya, 6, kv. 23; Valentin Vasilievich Kozin, ulitsa Kolesovoi, 34, kv. 18; Mark Ekhetskelevich Basner, prospekt Lenina, 36, kv. 30; Aida Vladimirovna Erofeeva, prospekt Lenina, 11/74, kv. 30; Nina Prokopievna Peshkova, Leningradsky prospekt, 59, kv. 49; Luiza Saidovna Tuktarova, ulitsa Junosti, 5, kv l5; Yakov Yakovlevich Kirnos, ulitsa Pervomaiskaya, 9, kv. 5; Ruslan Konstantinovich Mikhailov, ulitsa Tolbukhina, 45/14, kv. 43; Nikolai Zakharovich Dolinin, prospekt Lenina, 23, kv. 26; Jury Nikolaevich Rastvorov, Tutaevskoe shosse, 51, kv. 50; Valeria Lvovna Eratova, ulitsa Bljukhera, 36, kv. 5, all of YEoslavl, USSRI [22] Filed:

Aug. 7, 1972 21 Appl. No.: 278,654

Primary Examiner-Paul M. Coughlan, Jr.

[57] ABSTRACT A method for the production of monoand diolefinic' hydrocarbons by subjecting paraffinic hydrocarbons to catalytic oxidative dehydrogenation at 400 to 700 in the presence of a catalyst comprising oxygencontaining compounds of molybdenum and magnesium taken in a molybdenum/magnesium atomic ratio of 120.9 to 1:357, optional components of said catalyst being oxygen-containing compounds of cobalt, iron, chromium, vanadium, nickel, silicon, antimony, boron, gadolinium, dysprosium, gallium, bismuth, titanium, zirconium or niobium.

19 Claims, No Drawings METHOD FOR PREPARING MONO- AND DI-OLEFINE HYDROCARBONS The invention relates to the for preparing monoand di-olefinic hydrocarbons.

Said hydrocarbons are used in the synthesis of various organic compounds, and in the manufacture of synthetic rubbers in particular.

Methods are known in the art for preparing monoand di-olefinic hydrocarbons by catalytic oxidative dchydrogenation of paraffin hydrocarbons. Thus, for example, a method is known for preparing n-butenes andbutadiene by the oxidative dehydrogenation of n-butane on the phosphomolybdate of sodium or lithium at 400 650C. The yield of butadiene in reactors with a fluidized catalyst is 17.2 percent, the conversion of n-butane being 28 percent. The selectivity with the stationary catalyst bed does not exceed 41 percent, the conversion of n-butane being 42 percent (of U.S. Pat. No. 3,1 19,1 1 1).

A method is also known for oxidative dehydrogenation of paraffin hydrocarbons on an oxidic aluminophosphate catalyst at a temperature of 420 660C. According to this method, the conversion of n-butane does not exceed 40 percent, the total selectivity with respect to butadiene and n-butenes being 39 42 percent, and the ratio C H C H in the reaction products being 0.16 0.46 (cf. U.S. Pat. No. 3,320,331).

I Also known is a method for preparing monoand diolefinic hydrocarbons by the oxidative dehydrogenation of paraffin hydrocarbons at a temperature from 400 to 700C and molar ratio of oxygen to the paraffin hydrocarbon of 0.1 3, in the presence of an inert diluent, e.g. water vapor, nitrogen, argon, helium or their mixtures, on a catalyst, which is an oxy compound of molybdenum and/or tungsten, and of at least one of the following metals: chromium, manganese, iron, nickel or cadmium. During oxidative dehydrogenation of nbutane according to this method, the conversion of nbutane is 55.5 percent, the total selectivity with respect to butadiene and n-butenes being 43.2 percent. The yield of butadiene is 19.1 percent (cf. British Pat. No. 1,197,537).

The disadvantages inherent in these methods are low conversion of the hydrocarbon stockmaterial and low selectivity with respect to the main products.

The object of this invention is to work out a method for catalytic oxidative dehydrogenation of paraffin hydrocarbons into monoand di-olefinic hydrocarbons which would ensure higher conversion of the starting material and higher yields of the main products.

In accordance with this and other objects the invention consists in oxidative dehydrogenation of paraffin hydrocarbons at a temperature from 400 to 700C and the molar ratio of oxygen to the paraffin hydrocarbon of 0.1 3, in the presence of an inert diluent, such as water vapor, nitrogen, argon, helium or mixtures thereof, on a catalyst containing oxy compounds of molybdenum. The catalyst according to the invention contains also oxy compounds of magnesium and absorbs in the infra-red region of the spectrum, the wave numbers being 780 cm, 830 cm, 890 cm, 950 cm and 970 cm.

It is recommended that use should be made of a catalyst in which the atomic ratio of Mo to Mg is from 1 0.9 to l 357, preferably from 113.6 to 1268.5.

With the purpose of increasing the yield of the main cobalt, iron, chromium, vanadium, silicon or nickel.

The content of the oxy compounds of at least one of the above metals in the catalyst can be varied from 0.01 to 20 percent by weight calculated with reference to the metal oxides.

ln order to increase the yield of the main products, it is possible also to use a catalyst which, in addition to the oxygen-containing compounds of molybdenum and magnesium, also contains oxy compounds of at least one of the following metals; antimony, boron, gadolinium, dysprosium, gallium, bismuth, titanium, zirconium or niobium. The amount of the oxy compounds of at least one of the above metals in the catalyst can vary from 0.01 to 5 percent by weight calculated with respect to the metal oxides.

In addition to the above two cases, the yield of the main products can also be increased by using a catalyst which in addition to the oxy compounds of molybdenum and magnesium, also contains oxy compounds of at least one of the following elements: cobalt, iron, chromium, vanadium, silicon or nickel, and also oxy compounds of at least one of the following metals: antimony, boron, gadolinium, dysprosium, gallium, bismuth, titanium, zirconium or niobium. The amount of the oxy compounds of the above metals in the catalyst can vary within the above specified limits (from 0.01 to 20 percent by weight and from 0.01 to 5 percent by weight respectively).

In order to increase the mechanical strength of the catalyst so that the process can be carried out with a fluidized catalyst, the latter should be applied onto carriers, such as aluminosilicates, silica gel or alumina.

In the proposed method according to the invention, the oxidative dehydrogenation of paraffin hydrocarbons was effected at temperatures within a wide range (from 400 to 700C), the molar ratio of oxygen to the paraffin hydrocarbon of 0.1 3 and the rate of the starting hydrocarbon input of 20 to 1,000 hour. The oxidative dehydrogenation of the hydrocarbons was carried out in the presence of an inert diluent, e.g. water vapor, nitrogen, argon, helium, or mixtures thereof. The preferable molar ratio of the inert diluent to the paraffin hydrocarbon should be 1 l to 40 l.

Carrying out the process in the presence of inert diluents improves the conditions for removal of heat and increases the selectivity of the process.

Most preferable are the following conditions for the process: temperature form 500 to 650C, the molar ratio of oxygen to the paraffin hydrocarbon of 0.5 2, and input rate of the starting hydrocarbons, 20- 200 hour".

The catalyst to be used according to the invention oxidative dehydrogenation of paraffin hydrocarbons into monoand di-olefinic hydrocarbns is carried out with a high conversion of the starting hydrocarbon raw material (to 70 percent) and high yields of the main products (to 45 mol percent).

For a better understanding of the present invention, it will be illustrated by examples of its practical embodiment. (The quantities of oxy compounds of cobalt, iron, chromium, vanadium, silicon, nickel, antimony, boron, gadolinium, dysprosium, gallium, bismuth, titanium, zirconium and niobium are given with reference to the oxides of the respective elements).

EXAMPLE 1 Oxidative dehydration of n-butane was carried out in a reactor with a stationary bed and a catalyst consisting of oxy compounds of magnesium, molybdenum and vanadium. The catalyst was prepared by the following procedure. 45 g of magensia were mixed with a solution of 6.15 g of ammonium paramolybdate in distilled water. The moist paste was shaped into granules, dried at 110 120C for 10 hours and calcined at 700C for 10 hours. The calcined granules were then impregnated with a solution of 0.44 g of ammonium metavanadate in 12.5 ml of distilled water and dried at 110 120C for 10 hours. The finished catalyst contained molybdenum, magnesium (Mo to Mg atomic ratio being 1 31.4) and 3 percent by weight of vanadium pentoxide V The catalyst absorbed in the infra-red region of the spectrum, the wave numbers being 780 cm, 830 cm, 890 cm, 950 cm and 970 cm.

The infra-red absorption spectrum of the catalyst was obtained by suspending its sample in vaseline oil. The record was made on model UR-lO spectrophotometer (K. Zeiss, Jena).

The process of oxidative dehydrogenation of nbutane with the said catalyst was carried out at a temperature of 570C, the molar ratio of n-butane to oxygen and to water vapor was 1 1.5 20, and the input rate of the n-butane was 50 hour. The charge of the catalyst was cu.cm.

The yield of butadiene with respect to the n-butane passed through was 36.6 mol percent and of n-butenes, 6.4 mol percent, the selectivity being 54.7 and 9.6 mol percent respectively. The conversion of n-butane was 67.0 percent.

EXAMPLE 2 The oxidative dehydrogenation of n-butane was carried out in a reactor with a suspended bed of a catalyst consisting of oxy compounds of magnesium, molybdenum and vanadium. The catalyst was prepared by the method as described in Example 1 and contained molybdenum & magnesium atoms in the ratio of 1 32.1, and also 1 percent by weight of V 0 The catalyst had an absorption spectrum similar to that specified in Example l.

The oxidative dehydrogenation of n-butane was carried out at a temperature of 620C, the molar ratio of n-butane to oxygen and to water vapor was 1 1.5 and the volumetric input rate for n-butane was 50 hour". The charge of the catalyst was 100 cu.cm.

The yield of butadiene with respect to the n-butane passed through was 34.2 mol percent, and of butenes, 3.8 mol percent, the selectivity being 48.8 and 5.6 mol percent respectively. The conversion of n-butane was 70.5 percent.

EXAMPLE 3 The oxidative dehydrogenation of n-butane was carried out in a reactor with a stationary bed of the catalyst as described in Example 1. The process temperature was 450C, the molar ratio of n-butane to oxygen and to water vapor was 1 1.5 l0 and the volumetric input rate ofn-butane was 20 hour". The charge of the catalyst was 10 cu.cm.

The yield of butadiene with respect to the n-butane passed through was 1 1.6 mol percent, and of n-butenes, 3.3 mol percent. the selectivity being 38.7 and 11.0 mol percent respectively. The conversion of n-butane was 30.0 percent.

EXAMPLE 4 The oxidative dehydrogenation of n-butane was carried out in a reactor with a stationary bed of a catalyst containing oxy compounds of magnesium, molybdenum and chromium. The catalyst was prepared by the method described in example 1, and contained molybdenum and magnesium atoms in the ratio of 1.32.3 and also 0.5 percent by weight of Cr O The catalyst had an absorption spectrum in the infra-red region similar to that specified in Example I.

The oxidative dehydrogenation of n-butane was carried out at a temperature of 630C, the molar ratio of n-butane to oxygen and to water vapor l 1.5 20, and the volumetric input rate of n-butane was 5 0 hour. The charge of the catalyst was 10 cu.cm.

The yield of butadiene with respect to the n-hutane passed through was 26.6 mol percent, and of n-butenes, 4.0 mol percent, the selectivity being 45.7 and 6.8 mol percent respectively. The conversion of n-butane was 58.2 percent.

EXAMPLE 5 The oxidative dehydrogenation of n-butane was carried out in a reactor with a stationary bed of a catalyst consisting of oxy compounds of magnesium, molybdenum and cobalt. The catalyst was prepared by the method described in Example 1, and contained molybdenum and magnesium atoms in a ratio of l 32.4, and also 0.1 percent by weight of C0 0 The catalyst had an IR spectrum similar to that described in Example 1.

The process temperature was 630C, the molar ratio of n-butane to oxygen and to water vapor was 1 1 1.5 20, and the volumetric input rate of n-butane was 50 hour. The charge of the catalyst was 10 cu.cm.

The yield of butadiene with respect to the n-butane passed through was 22.6 mol percent, and of n-butenes, 3.6 mol percent, the selectivity being 45.8 and 7.3 mol percent respectively. The conversion of n-butane was 39.4 percent.

EXAMPLE 6 The oxidative dehydrogenation of n-butane was carried out in a reactor with a stationary bed of a catalyst consisting of oxy compounds of magnesium, molybdenum and iron. The catalyst was prepared by the method described in Example 1, and contained molybdenum and magnesium atoms in the ratio of l 32.4, and also 0.1 percent by weight of i e- 0 The IR absorption spectrum of the catalyst was the same as in Example 1.

The process temperature was 630C, the molar ratio of n-butane to oxygen and to water vapor was 1 1.5

: l and the rate of delivery of n-butane was 50 hour. The input charge of the catalyst was 10 cu.cm.

The yield of butadiene with respect to the n-butane passed through was 33.5 mol percent and of n-butenes, 8.9 mol percent, the selectivity being 41.3 and 10.9 mol percent respectively. The conversion of n-butane was 81.1 percent.

EXAMPLE 7 The oxidation dehydrogenation of n-butane was carried out in a reactor with a stationary bedof a catalyst consisting of oxy compounds of magnesium, molybdenum and silicon. The catalyst was prepared by the method described in Example 1, and contained molybdenum and magnesium atoms in the ratio of l' 31.7, and also 2 percent by weight of SiO The IR absorption spectrum of the catalyst was similar to that in Example The process was carried out at a temperature of 630C, the molar ratio of n-butane to oxygen and to water vapor was 1 l.5 20, the input of n-butane was 25 hour". The charge of the catalyst was 10 cu.cm.

The yield of butadiene with respect to the n-butane passed through was 30.3 mol percent, and of n-butenes, 6.1 mol percent, the selectivity being 47.3 and 9.4 mol percent respectively. The conversion of n-butane was 64.2 percent.

EXAMPLE 8 The oxidative dehydrogenation of n-butane was carried out in a reactor with a stationary bed of a catalyst consisting of oxy compounds of magnesium, molybdenum, silicon and vanadium. The catalyst was prepared by the method described in Example 1, and contained molybdenum and magnesium atoms in the ratio of l 30.2, and also 1 percent by weight of V 0 and 5 percent by weight of SiO The catalyst had an absorption spectrum in the IR region similar to that in Example 1.

The process was carried out at a temperature of 605C, the molar ratio of n-butane tooxygen and to water vapor was 1 1.5 20, and the rate of n-butane was 100 hour". The charge of the catalyst was 12.5

cu.cm.

The yield of butadiene with respect to the n-butane passed through was 33 mol percent, and of .n-butenes, 5.5 mol percent, the selectivity being 51.8 and 8.7 mol percent respectively. The conversion of n-butane was 63.6 percent.

EXAMPLE 9 The oxidative dehydrogenation of n-butanewas carried out in a reactor with a stationary bed of a catalyst consisting of oxy compounds-0f magnesium, molybdenum, iron and vanadium. The catalyst was prepared by the method described in Example I, and contained molybdenum and magnesium atoms in the ratio of l 31.7, and also 1 percent by weight of Fe O and 1 percent by weight of V 0 The IR absorption spectrum of the catalyst was as in Example 1.

The process temperature was 615C, the molar ratio of n-butane to oxygen and to water vapor was 1 l.5 20, and the volumetric input rate of n-butane was 50 hour. The charge of the catalyst was cu.cm.-

The yield of butadiene with respect to the n-butane passed through was 38.3 mol percent, and of n-butenes,

' 3.7 mol percent, the selectivity being 54.6 and 5.4 mol EXAMPLE 10 The oxidative dehydrogenation of isopentane was carried out in a reactor with a stationary bed of a catalyst similar to that used in Example 2.

The process was carried out at a temperature "of 605C, the molar ratio of isopentane to oxygen and to water vapor was I z 2.5 20, and the input rate of isopentane was l hour". The charge of the catalyst was 10 cu.cm.

The yield of isoprene with respect to the passed isopentane was 15.4 mol percent. and of isoamylenes. 2.6 mol percent, the selectivity being 40 and 7- mol percent respectively. The conversion of isopentane was 38.5 percent.

EXAMPLE 11 v The oxidative dehydrogenation of isopentane was carried out in a reactor with a stationary bed of a catalyst similar to that used in Example 9.

The process was carried out at a temperature of 6l7C, the molar ratio of isopentane to oxygen and to water vapor was 1 1.5 20, and the input rate of isopentane was 50 hour". The charge of the catalyst was 10 cu.cm.

The yield of isoprene with respect to the isopentane passed through was 15.5 mol percent, and of isoamylenes, 5.5 mol percent, the-selectivity being 35.3 and 12.5 mol percent respectively. The conversion of isopentane was 44 percent. A

EXAMPLE 12 The oxidation dehydrogenation of n-butane was carried out in a reaction kettle with a stationary bed of a catalyst consisting-of oxy compounds of magnesium, molybdenum and vanadium. The catalyst was prepared by the following procedure. An aqueous solution of 23.8 g. of magnesium nitrate was mixed with aqueous solutions of 0.525 g of ammonium paramolybdate and 0.165 g of ammonium paravanadate, and the'thus obtained solution was used to impregnate an aluminosilicate carrier. The impregnation was carried out at room temperature for 2 hours. The sample was then dried at a temperature of 120C for 12 hours and calcined at a temperature of 700C for l0 hours. The finished catalyst contained molybdenum and magnesium atoms in the ratio of l 31.4, and also 3 percent by weight of V 0 The active principle of the catalyst was 10 percent by weight. The IR absorption spectrum of the catalyst was the same that specified in Example 1.

The oxidative dehydrogenation of n-butane with the said catalyst was carried out at a temperature of 600C, the molar ratio of n-butane to oxygen and to water vapor was l l.5 20 and the input rate of n-butane was 50 hour". The charge of'the catalyst was l0 cu.cm.

The yield of butadiene with respect to the n-butane passed through was 4.7 mol percent, and of n-butenes, 8.8 mol percent. The selectivity of the process was 14.3 and 26.9 mol percent respectively. The conversion of n-butane was 32.8 percent.

EXAMPLE 13 65 The process was carried out at a temperature of EXAMPLE 141037.

The oxidative dehydrogenation of n-hutane was carried out in a reactor with a stationary bed o1 a catalyst. The charge 01' the catalyst was 10 cu.cm. The catalyst was prepared by the procedure described in Example 1. The IR absorption spectrum of the finished catalyst was similar to that specified in Example 1. The conditions and the results of the test are summarized in the cent.

11) Table.

Table Catalyst Test conditions Test results Nos. Type MozMg tempen-Butane Molar ratio Butadin-Bu- Selecti- Selee Converf rature, input ene tenes vity tivity sion Examratio "C hour C H ,:O,:H O yield. yield, with with of ples mol.% mol.% respect respect n-hutato butato hu ne.

diene, tenes, mol.% mol.% 1 2 3 4 5 4 6 7 8 9 10 l l 14 Mg-Mo 110.9 630 50 111.5120 1.9 5.4 10.5 29.8 18.1 15 Mg-Mo 1:2 601 100 111.510 2.53 7.03 9.28 25.72 27.3 16 Mg-Mo 1:140 630 50 111.5120 1.8 4.3 9.4 22.5 19.1 17 Mg-Mo-Ni 1110 568 25 110.3120 13.4 4.4 52.1 17.1 25.8

wt.% N10 18 Mg-Mo-Ni 1128.8 590 1 1.0120 17.5 6.2 44.0 15.5 39.8

10 wt.% N10 1 19 Mg-Mo 121.4 640 50 1 1.5120 28.2 3.2 46.5 5.3 (10.7 20 Mg-Mo-Sb 1:32.3 630 50 1 1.5120 31.5 4.3 57.3 8.0 5 .0

0.5 wt.%Sb- O;1 1- 21 Mg-Mo-B 1:28.8 620 25 111.5120 31.8 3.7 51.3 (1.2 61.7

wt.% B Q,

32 -Mo-sb-cr 1128.8 630 50 1 1.5120 31.1 4.3 55.0 7.3 511.5

0.5 wt.% Sb Oy, 0.5 wt.%Cr- -O=1 23 MgMo-Gd 1128.8 615 25 111.5120 22.1 5.7 43.0 11.0 1.5

0.5 wt.% Gdgog 24 Mg-Mo-Dy 1128.8 620 50 121.5120 26.4 5.0 56.5 10.8 46.8

0.5 wt.% Dy Ofl 25 Mg-Mo-Ga 1:288 630 100 1:1120 32.3 3.1 46.0 4.5 700 0.5 wt.% (121 0. 26 Mg-Mo-Bi 1.28.8 630 25 111.5120 22.9 8.8 37.3 14.2 61.5

0.5 wt.% B1201, 27 Mg-Mb-Nb 1132.1 630 50 111.5120 26.1) 4.1) 41.3 (1.4 (13.0

2 wt.% 811510.. 28 Mg-Mo-Zr 1:28.8 630 50 111.5120 14.0 3.2 40. 35.0

5 wt.% Zr 02 29 Mg-M0 Ti 1.32.1 630 50 111.5:20 28.8 2.9 42.7 -3

1 wt.% T10; 30 Mg-Mo-V 1:1 610 30 111.0120 3.1 4.7 15.1 22.) 20.5

2 wt.% V205 31 Mg-MO-Ga 1:357 670 100 1:1.5120 1.3 2.1 7.4 12.0 17.5

0.25 wt.% 6320;] 32 M' 1:2 605 100 111.5:20 4.5 8.4 14.1

1 wt.% Fe- O 2.5 wt.% S10: 0.5 wt.% 81.0,, A 34 Mg-MoC0-Dy-Gd 1132.1 621) 50 111.5120 27.3 5.2 57.7 10,9 476 0.1 wt.% C0110. 0.05 wt.% DygOa 0.5 wt.% Gd o 35 MgM0-Cr-Ga 1132.1 625 100 121:15 33.0 4.0 58.0 7.3 57.0

0.5 wt.% Cr O 0.5 wt.% 621 0,; 36 Mg-Mo-Ni-Ti-Zr-Nb 1141.4 630 121.5220 29.0 5.4 55.0 10.2 52.8

10 wt.% N10 1 wt.%TiO. 1 wt.% ZrO: 1 wt.% M320. 37 Mg-Mo-Cr-B 1:357 640 111.5120 1.9 2. 10.5 13.8 18.1

We claim:

l. A method for the production of monoand diolefinic hydrocarbons which comprises passing a feed consisting essentially of a paraffin hydrocarbon, oxygen and an inert diluent selected from the group consisting of steam, nitrogen, argon, helium and mixtures thereof at an oxygen to paraffin hydrocarbon molar ratio of 0.1 to 3.0 over a catalyst at a temperature of from 400 to 700 C., said catalyst consisting essentially of oxygencontaining compounds of molybdenum and magnesium taken in a molybdenum/magnesium atomic ratio of from 120.9 to 1:357 and having absorption bands in the infra-red spectrum thereof at the wave numbers of 780 cm, 830 cm", 890 cm", 950 cm and 970 cm.

2. A method according to claim I, wherein the catalyst contains molybdenum and magnesium atoms in the ratio from 1 3.6 to l 68.5.

3. A method according to claim 1, wherein the catalyst contains oxy compounds of at least one of the elements selected from the group consisting of cobalt, iron, chromium, vanadium, silicon and nickel in an amount of 0.01 to 20 percent by weight calculated as the metal oxide.

4. A method according to claim 1, wherein the catalyst contains oxy compounds of at least one metal selected from the group consisting of antimony, boron, gadolinium, dysprosium, gallium, bismuth. titanium, zirconium and niobium.

5. A method according to claim 4, wherein the catalyst contains oxy compounds of at least one said metal in an amount offrom 0.01 to 5 percent by weight calculated as the metal oxide.

6. A method according to claim 3, wherein the catalyst contains oxy compounds of at least one metal selected from the group consisting of antimony, boron, gadolinium, gallium, bismuth, titanium, zirconium and niobium.

7. A method according to claim 6, wherein the catalyst contains oxy compounds of at least one said metal in an amount from 0.01 to 5 percent by weight calculated as the metal oxide.

8. A'method according to claim 1, wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilicates, silica gel and aluminum oxide.

9. A method according to claim 3, wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilicates, silica gel and aluminum oxide.

10. A method according to claim 4 wherein the catalyst is supported on a carrier selected from'the group consisting of aluminosilicates, silica gel and aluminum oxide.

11. A method according to claim 6, wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilieates, silica-gel, and aluminum oxide.

12. A method according to claim' I, wherein inert dil- 1 uent is used in an amount from I to 40 mols per mol of the paraffin hydrocarbon.

13. A method according to claim I, wherein the oxidative dehydrogenation of the paraffin hydrocarbon is carried out 'at atemperature from 500 to 650C.

14. A method according to claim I, wherein the molar ratio ofoxygen to the paraffin hydrocarbon is 0.5

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,862,256 January 21, 1975 Patent No. Dated I v Anatoly Lvovich et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading, the name of the first inventor,

"Isailingold" should read Tsailingold Signed and sealed this 1st day of April 1%75.

n". 1 (sins C. I'QTRSIIALL Did-II! RUTH C. T195025 Commissioner of Patents Attesting Officer and Trademarks F ORM P0-105O (IO-69) USCOMM-DC 60376-P09 U.S GOVERNMENT IRINIING OFFICE: 869. 93 o E

Claims (19)

1. A METHOD FOR THE PRODUCTION OF MONO-AND DIOLEFINIC HYDROCARBONS WHICH COMPRISES PASSING A FEED CONSISTING ESSENTIALLY OF A PARAFFIN HYDROCARBON, OXYGEN AND AN INERT DILUENT SELECTED FROM THE GROUP CONSISTING OF STEAM, NITROGEN, ARGON, HELIUM AND MIXTURES THEREOF AT AN OXYGEN TO PARAFFIN HYDROCARBON MOLAR RATIO OF 0.1 TO 390 OVER A CATALYST AT A TEMPERATURE OF FROM 400* TO 700*C., SAID CATALYST CONSISTING ESSENTIALLY OXYGEN-CONTAINING COMPOUNDS OF MOLYBDENUM AND MAGNESIUM TAKEN IN A MOLYBDENUM/MAGNMESIUM ATOMIC RATIO OF FROM 1:0.9 TO 1:357 AND HAVING ABSORPTION BANDS IN THE INFRA-RED SPECTRUM THEREOF AT THE WAVE NUMBERS OF 780 CM-1,830 CM-1,950 CM-1 AND 970 CM-1.
2. A method according to claim 1, wherein the catalyst contains molybdenum and magnesium atoms in the ratio from 1 : 3.6 to 1 : 68.5.
3. A method according to claim 1, wherein the catalyst contains oxy compounds of at least one of the elements selected from the group consisting of cobalt, iron, chromium, vanadium, silicon and nickel in an amount of 0.01 to 20 percent by weight calculated as the metal oxide.
4. A method according to claim 1, wherein the catalyst contains oxy compounds of at least one metal selected from the group consisting of antimony, boron, gadolinium, dysprosium, gallium, bismuth, titanium, zirconium and niobium.
5. A method according to claim 4, wherein the catalyst contains oxy compounds of at least one said metal in an amount of from 0.01 to 5 percent by weight calculated as the metal oxide.
6. A method according to claim 3, wherein the catalyst contains oxy compounds of at least one metal selected from the group consisting of antimony, boron, gadolinium, gallium, bismuth, titanium, zirconium and niobium.
7. A method according to claim 6, wherein catalyst contains oxy compounds of at least one said metal in an amount from 0.01 to 5 percent by weight calculated as the metal oxide.
8. A method according to claim 1, wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilicates, silica gel and aluminum oxide.
9. A method according to claim 3, wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilicates, silica gel and aluminum oxide.
10. A method according to claim 4 wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilicates, silica gel and aluminum oxide.
11. A method according to claim 6, wherein the catalyst is supported on a carrier selected from the group consisting of aluminosilicates, silica gel, and aluminum oxide.
12. A method according to claim 1, wherein inert diluent is used in an amount from 1 to 40 mols per mol of the paraffin hydrocarbon.
13. A method according to claim 1, wherein the oxidative dehydrogenation of the paraffin hydrocarbon is carried out at a temperature from 500* to 650*C.
14. A method according to claim 1, wherein the molar ratio of oxygen to the paraffin hydrocarbon is 0.5 to 2.
15. A method according to claim 1, wherein the paraffin hydrocarbon is charged at a rate of 20 to 1000 hour 1.
16. A method according to claim 1, wherein the paraffin hydrocarbon is n-butane.
17. A method according to claim 16, wherein the n-butane is used in a mixture with n-butenes.
18. A method according to claim 1, wherein the paraffin hydrocarbon is isopentane.
19. A method according to claim 18, wherein the isopentane is used in a mixture with isoamylenes.
US27865472 1972-08-07 1972-08-07 Method for preparing mono- and di-olefine hydrocarbons Expired - Lifetime US3862256A (en)

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Cited By (21)

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US3969428A (en) * 1973-11-05 1976-07-13 Agency Of Industrial Science & Technology Process for the production of conjugated diolefins
US3972806A (en) * 1975-07-03 1976-08-03 Universal Oil Products Company Hydrocarbon conversion with an acidic multimetallic catalyst composite
US4056576A (en) * 1975-07-17 1977-11-01 The British Petroleum Company Limited Chemical process over gallium catalyst converting saturated hydrocarbons to olefins
US4080394A (en) * 1976-07-19 1978-03-21 Uop Inc. Using a nonacidic catalyst containing a platinum group metal, cobalt and gallium
US4108918A (en) * 1975-09-18 1978-08-22 The Goodyear Tire & Rubber Company Oxidative dehydrogenation of olefins to diolefins
EP0010788A1 (en) * 1978-09-28 1980-05-14 Standard Oil Company Catalyst, method for its preparation and hydrodesulfurization process using this catalyst
US4229604A (en) * 1979-02-05 1980-10-21 Tmenov Dzantemir N Process for producing unsaturated hydrocarbons
US4250346A (en) * 1980-04-14 1981-02-10 Union Carbide Corporation Low temperature oxydehydrogenation of ethane to ethylene
US4511754A (en) * 1984-04-16 1985-04-16 Atlantic Richfield Company Hydrocarbon dehydrogenation
US4973791A (en) * 1989-07-20 1990-11-27 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing an alkali-promoted molybdate catalyst
US5258347A (en) * 1989-07-20 1993-11-02 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing a molybdate catalyst composition
US5302773A (en) * 1989-07-20 1994-04-12 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing a molybdate catalyst encapsulated in a hard, glassy silica matrix
US6355854B1 (en) * 1999-02-22 2002-03-12 Symyx Technologies, Inc. Processes for oxidative dehydrogenation
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US6436871B1 (en) 1999-02-22 2002-08-20 Symyx Technologies, Inc. Catalysts for oxidative dehydrogenation
US20030187299A1 (en) * 2000-06-14 2003-10-02 Otto Machhammer Method for producing acrolein and/or acrylic acid
US6677497B2 (en) * 2001-03-22 2004-01-13 Symyx Technologies, Inc. Ni catalysts and methods for alkane dehydrogenation
CN100404481C (en) * 2002-06-13 2008-07-23 维罗西股份有限公司 Catalytic oxidative dehydrogenation, and microchannel reactors for catalytic oxidative dehydrogenation
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Cited By (33)

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Publication number Priority date Publication date Assignee Title
US3969428A (en) * 1973-11-05 1976-07-13 Agency Of Industrial Science & Technology Process for the production of conjugated diolefins
US3972806A (en) * 1975-07-03 1976-08-03 Universal Oil Products Company Hydrocarbon conversion with an acidic multimetallic catalyst composite
US4056576A (en) * 1975-07-17 1977-11-01 The British Petroleum Company Limited Chemical process over gallium catalyst converting saturated hydrocarbons to olefins
US4108918A (en) * 1975-09-18 1978-08-22 The Goodyear Tire & Rubber Company Oxidative dehydrogenation of olefins to diolefins
US4108919A (en) * 1975-09-18 1978-08-22 The Goodyear Tire & Rubber Company Oxidative dehydrogenation of olefins to diolefins
US4080394A (en) * 1976-07-19 1978-03-21 Uop Inc. Using a nonacidic catalyst containing a platinum group metal, cobalt and gallium
EP0010788A1 (en) * 1978-09-28 1980-05-14 Standard Oil Company Catalyst, method for its preparation and hydrodesulfurization process using this catalyst
US4229604A (en) * 1979-02-05 1980-10-21 Tmenov Dzantemir N Process for producing unsaturated hydrocarbons
US4250346A (en) * 1980-04-14 1981-02-10 Union Carbide Corporation Low temperature oxydehydrogenation of ethane to ethylene
US4511754A (en) * 1984-04-16 1985-04-16 Atlantic Richfield Company Hydrocarbon dehydrogenation
US4973791A (en) * 1989-07-20 1990-11-27 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing an alkali-promoted molybdate catalyst
US5146031A (en) * 1989-07-20 1992-09-08 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing a molybdate catalyst composition
US5258347A (en) * 1989-07-20 1993-11-02 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing a molybdate catalyst composition
US5302773A (en) * 1989-07-20 1994-04-12 The Dow Chemical Company Process of oxidizing aliphatic hydrocarbons employing a molybdate catalyst encapsulated in a hard, glassy silica matrix
US7498289B2 (en) 1999-02-22 2009-03-03 Celanese International Corporation Ni catalysts and methods for alkane dehydrogenation
US6417422B1 (en) 1999-02-22 2002-07-09 Symyx Technologies, Inc. Ni catalysts and methods for alkane dehydrogenation
US6355854B1 (en) * 1999-02-22 2002-03-12 Symyx Technologies, Inc. Processes for oxidative dehydrogenation
US7674944B2 (en) 1999-02-22 2010-03-09 Celanese International Corporation Ni catalysts and methods for alkane dehydrogenation
US7626068B2 (en) 1999-02-22 2009-12-01 Celanese International Corporation Ni catalysts and methods for alkane dehydrogenation
US6777371B2 (en) 1999-02-22 2004-08-17 Yumin Liu Ni catalysts and methods for alkane dehydrogenation
US7227049B2 (en) 1999-02-22 2007-06-05 Celanese International Corporation Ni catalysts and methods for alkane dehydrogenation
US20070191665A1 (en) * 1999-02-22 2007-08-16 Yumin Liu Ni catalysts and methods for alkane dehydrogenation
US20070197847A1 (en) * 1999-02-22 2007-08-23 Yumin Liu Ni catalysts and methods for alkane dehydrogenation
US20070197378A1 (en) * 1999-02-22 2007-08-23 Yumin Liu Ni catalysts and methods for alkane dehydrogenation
US6436871B1 (en) 1999-02-22 2002-08-20 Symyx Technologies, Inc. Catalysts for oxidative dehydrogenation
US7321058B2 (en) 2000-06-14 2008-01-22 Basf Aktiengesellschaft Method for producing acrolein and/or acrylic acid
US20030187299A1 (en) * 2000-06-14 2003-10-02 Otto Machhammer Method for producing acrolein and/or acrylic acid
US6677497B2 (en) * 2001-03-22 2004-01-13 Symyx Technologies, Inc. Ni catalysts and methods for alkane dehydrogenation
CN100404481C (en) * 2002-06-13 2008-07-23 维罗西股份有限公司 Catalytic oxidative dehydrogenation, and microchannel reactors for catalytic oxidative dehydrogenation
US20090312591A1 (en) * 2006-03-29 2009-12-17 Basf Se Method for producing propene from propane
DE102007006647A1 (en) 2007-02-06 2008-08-07 Basf Se Process for the regeneration of a catalyst bed deactivated in the context of a heterogeneously catalyzed partial dehydrogenation of a hydrocarbon
US20110118526A1 (en) * 2008-07-21 2011-05-19 Markus Schubert Process for industrial isolation of propene
US8530717B2 (en) 2008-07-21 2013-09-10 Basf Se Process for the industrial isolation of propene

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