CH616861A5 - Oxidation catalyst. - Google Patents

Oxidation catalyst. Download PDF

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Publication number
CH616861A5
CH616861A5 CH952175A CH952175A CH616861A5 CH 616861 A5 CH616861 A5 CH 616861A5 CH 952175 A CH952175 A CH 952175A CH 952175 A CH952175 A CH 952175A CH 616861 A5 CH616861 A5 CH 616861A5
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mixture
catalyst
catalysts
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prepared
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CH952175A
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German (de)
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Robert Karl Grasselli
Dev Dhanaraj Suresh
Harley Foch Hardman
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Standard Oil Co
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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
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876Arsenic, antimony or bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057Selenium or tellurium; Compounds thereof
    • B01J27/0576Tellurium; Compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19Molybdenum
    • B01J27/192Molybdenum with bismuth
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/24Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation 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
    • C07C45/34Preparation 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
    • C07C45/35Preparation 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
    • 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Description

The invention relates to new oxidation catalysts, the iron, bismuth, molybdenum plus nickel, cobalt, magnesium, zinc, cadmium, strontium or calcium or mixtures thereof and for activating yttrium, zirconium, silver, sulfur, cerium, thorium, praseodymium, ruthenium, gallium, Contain niobium, germanium, chromium, tin, manganese, indium, copper, tellurium, lanthanum, tantalum, tungsten or a mixture thereof and are ideal for various oxidation reactions.

Oxidation catalysts containing one or more of the above elements are already known (see, for example, U.S. Patents 3,642,930 and 3,414,631). Although these known catalysts are advantageous oxidation catalysts, the catalysts according to the invention offer considerable advantages over these known catalysts.

It was an object of the present invention to find oxidation catalysts which can be used in the conventional manner and in a wide variety of oxidation processes, but which, with improved selectivity, bring about greater conversion and a higher yield.

It was then surprisingly found that this problem could be solved with the catalysts according to the invention, the improvements mentioned in the oxidation and oxydehydrogenation of olefins being of particular interest.

The invention thus relates to new oxidation catalysts which are characterized by the general formula

XaAbDcEdFe, BigMoi2Ox where:

X yttrium, zirconium, silver, sulfur, cerium, thorium, praseodymium, ruthenium, gallium, niobium, germanium, chlorine, tin, manganese, indium, copper, tungsten, tantalum, tellurium, lanthanum or a mixture thereof,

A an alkali metal, thallium or a mixture thereof, D Nicke], cobalt, magnesium, strontium, calcium, zinc, cadmium or a mixture thereof,

E phosphorus, arsenic, boron, tungsten, antimony or a mixture thereof, where E can also be sulfur if X is tungsten,

a is a number greater than 0 and less than 5,

5

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35

40

45

50

55

60

65

3rd

616 861

b and d numbers from 0 to 4,

c is a number from 0.1 to 20,

f and g numbers from 0.1 to 10 and x the number of oxygen atoms required to saturate the valence of the other elements present.

The invention includes all catalysts which fall under the general formula given above. These catalysts are prepared as described in the specific embodiments given below and are suitable for a wide variety of known oxidation reactions. In these reactions, the novel catalyst according to the invention can be used instead of the catalysts used hitherto, and the reaction is carried out practically under the same conditions. Of particular interest is the oxidation, the oxidative dehydrogenation of olefins, but the catalysts according to the invention can also be used in other reactions, for example in the oxidation and ammoxidation of methyl-substituted aromatic compounds.

The invention is explained in more detail in the following examples on the basis of specific embodiments, but without being restricted thereto.

Examples 1 to 9 Oxidative Dehydrogenation of Butene-1 A reaction vessel was made from a stainless steel tube with a diameter of 0.8 cm and an inlet for the reactants and an outlet for the products. The reaction vessel had a reaction zone into which 2.5 cm 3 of catalyst could be filled.

As described below, various catalysts according to the invention were produced. All catalysts contained 80% active ingredients and 20% silicon dioxide.

example 1

Cro, sKoiiNÌ2J5Co4j5Fe3BiMoi20x

63.56 g of ammonium heptamolybdate (NH4) 6Mo7024 • 4H20 was dissolved in 100 ml of water, and 51.66 g of Nalco 40% silica sol were added with stirring and heating. 1.50 g of CrO 3 was added to this slurry.

Separately, 36.36 g of iron (III) nitrate Fe (N03) 3 • 9H20 were heated and dissolved in 10 cm3 of water. Then 14.55 g of Bi (N03) 3 • 5H20, 39.29 g of Co (N03) 2 • 6H20, 21.81 g of Ni (N03) 2 • 6H20 and 3.03 g of a 10% solution were in the solution solved by KN03. The nitrate solution was slowly added to the slurry containing the molybdenum. The mixture was heated and stirred until it started to become thick. The solid was dried in an oven at 120 ° C with occasional stirring. The final catalyst was calcined in air at 550 ° C for 16 hours.

Example 2

Teo, sKo, iNÌ2.5Co4isFe3BiMo120x

The catalyst was prepared in the same manner as in Example 1, except that the Cr03 was replaced by 4.04 g TeCl4.

Example 3

Geo, sKo, iNi2i5Co4i5Fe3BiMoi2Ox

The catalyst was prepared in the same manner as in Example 1, except that the Cr03 was replaced by 1.57 g Ge02.

Example 4 Wo, 5Ko, iNi2isCo4! SFe3BiMOi2Ox The catalyst was prepared as in Example 1, but this time the Cr03 was replaced by 4.04 g (NH4) 6W7024 ■ 6H20.

Example 5 Mn0.5K0. iNÌt.sCXXi ^ F e3 BìMoj2Ox The catalyst was prepared as in Example 1, but this time replacing the Cr03 5.37 g of a 50% manganese nitrate solution.

Example 6 Tho, sKo1iNi2) sCo4isFe3BiMoi2Ox The catalyst was prepared as in Example 1, but this time the Cr03 was replaced by 8.28 g Th (N03) 4 • 4H20.

Example 7 Nbo, 5Ko1iNi2! SCo4isFe3BiMoi2Ox 31.8 g of ammonium hep-tamolybdate were dissolved in 50 cm3 of warm water. To this solution were added 2.0 g of NbCls, slurried in water, 26.5 g of Nalco 40% silica sol and a mixture of 10.9 g of nickel nitrate and 19.7 g of cobalt nitrate.

Separately, a solution of 18.2 g of iron (IH) nitrate, 7.2 g of bismuth nitrate and 0.19 g of KOH was prepared in the form of a 40% solution and the solution was slowly added to the molybdenum slurry. The rest of the preparation was the same as in Example 1.

Example 8

PibjsKo, 1Ni2jsCo4i5Fe3BiMoi2Ox

The catalyst was prepared as in Example 1, but this time the Cr03 was replaced by 2.60 g of Pr02.

Example 9

Ce0, sKojiNÌ2) 5Co4! 5Fe3BiMo12Ox

The catalyst was prepared as in Example 1, but this time the Cr03 was replaced by 8.22 g (NH4) 2Ce (N03) 6.

The catalyst samples were ground and sieved to produce a 0.84 to 0.50 mm (20 to 35 mesh) fraction which was charged into the 2.5 cm3 reaction zone of the reaction vessel. At a temperature of 350 ° C, a butene-1 / air / steam feed with a molar ratio of 1/11/4 was passed over the catalyst with an apparent contact time of 1 second. The results of these experiments are defined as follows:

_ TT ,, converted olefin x 100

% Conversion =

imported olefin product x 100

% Selectivity ——...

converted olefin

% Yield in one pass

recovered product x 100 supplied olefin

The results of these experiments are given in Table I below. The isomerization of butene-1 was not calculated as an implemented olefin.

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15

20th

25th

30th

35

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55

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65

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4th

Table I

Oxidative dehyration of butene-1 to butadiene with Xo, sKo, iNÌ2, sCo4! SFe3BiMo120x

example

catalyst

Results in

%

No.

X =

Around

selectivity

Butadiene

change for

Butadiene yield in one pass

1

Cr

100

98

97.7

2 *

Te

98.8

98

97.3

3rd

Ge

98.8

98

96.8

4th

W

98.6

96

95.7

5 *

Mn

98.4

97

95.2

6 *

Th

98.4

97

95.2

7

Nb

97.6

95

92.6

8th*

Pr

92.1

97.5

94

Q *

Ce

92.1 100

92

Potassium was added and the Cr03 was replaced by 1.57 g Ge02.

Example 11

The catalyst was prepared as in Example 10, except that 5 times the normal amount of potassium was added and 61.04 g of nickel nitrate was used instead of nickel and cobalt.

Example 12

The catalyst was prepared as described in Example 11, but this time the nickel nitrate was replaced by 61.12 g of cobalt nitrate.

* No water vapor was supplied

Examples 10 to 17 Oxidative Dehydrogenation of Butene-1 with Germanium-Containing Catalysts Various germanium-containing catalysts were prepared as follows:

Example 10

The catalyst was prepared in the same manner as the catalyst of Example 1, but this time none

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Example 13

The catalyst was prepared as in Example 11, but this time 72.83 g of ammonium heptamolybdate and 3.03 g of a 45% KOH solution were used.

Example 14

The catalyst was prepared as in Example 11, this time using 53.85 g of Mg (N03) 2 • 6H20 instead of nickel and cobalt and 3.22 g of GeCL instead of Ge02.

Example 15

The catalyst was prepared as in Example 11, this time replacing the nickel nitrate with magnesium nitrate and using GeCl4 as in Example 14.

The catalysts were tested as in Examples 1-9. The results obtained are shown in Table II below.

Table II

Catalysts containing germanium for the conversion of butene-1 to butadiene

example

catalyst

Results in%

No.

conversion

selectivity

Yield in

one pass

10th

Ge0jSNi2) 5Co4isFe3BiMo12Ox

98.8

91

90.4

11

Ge0.5Ko, iNi7Fe3BiMo12Ox

99.9

94

94.3

12

Geo.sKo.iCoyFesBiMOüOx

87.4

99-

86.8

13

Geo, sKo, 8NÌ2jsCo4! SFe3BiMoi3j75Ox

100.0

99

99.2

14

Geo, sKo, iMg7Fe3BiMo12Ox

98.7

98

96.8

15

Ge0, sKo, iMg2lsCo4) 5Fe3BiMo12Ox

99.4

99

98.1

Example 16

Two promoters in a thallium-containing catalyst

As described in the examples above, a catalyst was made up to 80%

Ge0, sCri, sTl0, iNÌ2Co3Fe0i5BiMoi2Ox and 20% Si02, and it was used for the oxydehydrogenation of butene-1 at a temperature of 350 ° C and an apparent contact time of 1 second using a butene / air ratio of 1/1 used. The conversion of butene-l 'was 89.6%, the selectivity was 98% and the yield in one pass was 88.1%.

Example 17 Catalyst containing cesium

In the manner given in Example 5, but using 0.59 g of cesium nitrate CsN03 instead of the potassium compound, a catalyst was prepared which was 80%

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consisted of Mn0.5Cs0, iNÌ2) sCo4jsFe3BiMoi2Ox and 20% Si02. Using the feed and reaction conditions of Example 18, butene-1 was 100% converted to products, the selectivity for butadiene was 99% and the one-pass yield was 98.6%.

Examples 18-26 Oxydehydrogenation of butene-2 The catalysts prepared in the above examples were used for the oxydehydrogenation of butene-2 to butadiene. A mixture of 57.5% trans and 42.5% cis-butene-2 was reacted using the reaction vessel, the catalyst volumes of the above examples and using an apparent contact time of 1 second. The ratio of butene-2 / air was 1/11. The results of these tests are given in Table III below. The parentheses in the catalyst compositions indicate the identical parts in all experiments.

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Table III Oxydehydrogenation of butene-2 to butadiene

example

catalyst

Reaction

Results in

%

No.

Temp., ° C

conversion

selectivity

Yield in one go

18th

Ceo) s (Ko, iNÌ2,5Co4isFe3BiMo120x)

350

95.4

93

88.3

19th

Nbo, s (K0, iNÌ2.5Co4i5Fe3BiMo120x)

350

93.0

95

88.1

20th

Pr0.5 (Ko, iNÌ2, sCo4jSFe3BiMoi20x)

375

97.7

89

87.3

21st

Mn0, s (Ko, iNÌ2.5Co4, sFe3BiMo120x)

385

95.1

93

88.9

22

Cr0, s (Ko, iNi2.5Co4.5F c3 BiMoi2 Ox)

385

95.6

95

90.9

23

Ge0, s (Ko, iNÌ2, sCo4; 5Fe3BiMo12Ox)

385

84.4

95

80.5

24th

W0, s (KoliNÌ2! 5Co4! SFe3BiMoi20x)

385

85.0

95

80.3

25th

Th0) s (K0jlNÌ2, sCo4j5Fe3BiMox2Ox)

400

90.5

92

82.7

26 *

Ge {) isK08NÌ2! 5Co45Fe:, BiMo13j75Ox

375

95.7

90

86.5

* Contact time 4 seconds.

Examples 27 to 35 Working at high air / olefin ratios The catalysts according to the invention prepared as described above were used for the oxydehydrogenation of a mixture of butene-2 in the manner given in Examples 18 to 26, but this time the butene / air / Ratio 1/31 fraud. The reaction temperature was 350 ° C and the apparent contact time was 1 second. The results of these experiments are given in Table IV below. The lantane catalyst of Example 35 was made by replacing the Cr03 in the catalyst of Example 1 with 6.22 g of La (N03) 3 • 5H20.

Table IV

Oxydehydrogenation of butene-2 with the catalyst

Xo, sKo, iNi2) sCo4j5Fe3BiMoi20x

Reaction temperature 340 ° C. Reaction temperature 385 ° G.

Example 36

High air / olefin ratios with another potassium catalyst In the manner described in Example 9, but this time with the addition of five times the amount of potassium, a catalyst was prepared which was 80% W0, sK0i5NÌ2, sCo4i5Fe3BiMoi2Ox and 20% Si02 duration. Using the above-mentioned mixture of butene-2 in an air / butene-2 ratio of 31/1 with an apparent contact time of 1 second and a temperature of 385 ° C, this catalyst was tested for the formation of butadiene. The Conversion of Butene-2

25th

30th

35

example

catalyst

Results in%

No.

X =

Around

selectivity

yield

40

change

in one pass

27th

Mn

100.0

97

96.8

28

Cr

96.6

96

92.5

291

Nb

100.0

93

92.8

45

30th

Ce

100.0

89

88.9

311

Ce

100.0

91

90.9

32

Ge

81.5

98

80.0

332

W

92.9

91

84.2

342

Th

96.7

90

86.7

50

35

La

100.0

95

95.4

was 96.4%, the selectivity was 91% and the yield in one pass was 88.1%.

Example 37 Oxydehydrogenation of Isoamylene With the catalyst of Example 13, a mixture of equal parts by volume of 2-methylbutene-1 and 2-methylbutene-2 was oxydehydrogenated in a reaction vessel with a reaction zone of 5 cm 3 to form isoprene. At 400 ° C and an apparent contact time of 2 seconds, the conversion of the isoamylene was 85.9%, the selectivity for isoprene was 82% and the yield of isoprene in one pass was 70.2%.

Example 38

Preparation of isoprene with a Cr catalyst In the manner given in Example 37, the catalyst of Example 1 was used to produce isoprene. The conversion was 86.2%, the selectivity 70% and the yield in one pass was 60.5%.

Comparative Examples 39 and 40 and Examples 41 to 74 Comparison of the activator-containing catalyst according to the invention with the basic catalyst

A 5 cm3 fixed bed reaction vessel was made from a stainless steel tube with an inner diameter of 8 mm. Catalysts prepared as above were charged into the reaction vessel and heated to 420 ° C under an air stream. At the reaction temperature for Comparative Example B and Examples 41 to 74, a reactant composition of propylene / ammonia / oxygen / nitrogen / water vapor was 1.8 / 2.2 / 3.6 / 2.4 / 6 at one 55 contact time of 3 seconds passed over the catalyst. The WWH (defined as the weight of olefin fed per weight of catalyst per hour) for the reaction was 0.10.

In comparative example 39, a reactant mixture of propylene / ammonia / oxygen / nitrogen / water vapor was used in a ratio of 1 / 1.1 / 2.1 / 7.9 / 4 at a temperature of 420 ° C. A contact time of 6 seconds was used. The WWH was 0.03. This example should show that a basic catalytic converter works under normal operating conditions at a low WWH.

The catalysts used were produced as follows:

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6

Comparative Examples 39 and 40 80% Ko, iNi2.5Co4, sFeBiPo, sMo12Ox + 20% Si02 A solution of 127.1 g of ammonium hepta-molybdate (NH4) 6Mo7024 • 4H20 and water was prepared. To this solution, 6.9 g of a 42.5% solution of H3P04 and 102.7 g of Nalco 40% silica sol were added to form a slurry. An aqueous solution was prepared separately, containing 72.7 g of iron (III) nitrate Fe (N03) 3 • 9H20, 29.1 g of bismuth nitrate Bi (N03) 3 • 5H20, 78.6 g of cobalt nitrate Co (N03) 2 • 6H20.43.6 g nickel nitrate Ni (N03) 2 • 6H20 and 6.1 g of a 10% potassium nitrate solution. The solution of the metal nitrates was slowly added to the slurry. The resulting slurry was evaporated to dryness and the solid obtained was heat treated at 290 ° C for 3 hours, at 425 ° C for 3 hours and at 550 ° C for 16 hours.

Example 41

80% Ge0.6K0iiNi2j5Co4i5Fe3BiP0, sMo12Ox -I- 20% Si02

63.56 g of ammonium heptamolybdate were dissolved in 60 cm 3 of warm water. This solution was added to 53.25 g of Nalco 40% silica sol. The mixture was heated at low heat with constant stirring for about 5 minutes. To the slurry formed was added 3.46 g of H3P04 in the form of a 42.5% solution and the mixture was heated for 2 minutes.

Separately, 36.36 g of iron (Ill) nitrate were mixed with 10 cm3 of water and melted on a hot plate with constant stirring. Then 14.55 g bismuth nitrate, 39.29 g cobalt nitrate, 21.80 g nickel nitrate were added in succession, always waiting until the previous metal nitrate had melted. 3.03 g of KN03 in the form of a 10% solution and 1.88 g of Ge02 were added and melted.

The solution containing the metal nitrates was slowly added to the slurry and heating was increased until the mixture began to thick. The mixture was dried in an oven at 120 ° C with occasional stirring. The dried catalyst was calcined at 550 ° C for 16 hours

Examples 42 to 66

The other catalysts of the examples were made in the same manner as the catalysts of example 41. Germanium, tin and chromium were added to the catalysts in the form of the oxides. Copper and silver were added to the catalysts in the form of the nitrates. Ruthenium was added to the catalysts in the form of the chloride. Tungsten was incorporated into the catalyst in the form of ammonium tungstate together with ammonium heptamolybdate. Although different anions were used, the particular anion of the catalytic component did not appear to be critical.

The activator elements according to the invention were added to the catalysts which did not contain phosphorus through the slurry containing molybdenum. To this slurry was added a solution of 36.4 g iron (III) nitrate, 14.6 g bismuth nitrate, 39.3 g cobalt nitrate, 21.8 g nickel nitrate and 3.0 g of a 10% potassium nitrate solution. The resulting slurry was evaporated and the solid was heat treated as above.

The results of the experiments on the ammoxidation of propylene to form acrylonitrile are given in Table V below. The brackets given in Table V show the identical parts of the catalyst compositions or the differences between the catalysts.

Table V Production of acrylonitrile Comparison between catalysts according to the invention and the basic catalyst

Active components of the catalyst% yield play in one

No passage

See Ex.

39 (K0jiNi2! SCo4) sFe3BiP0) sMoi2Ox) 80.1 * Cf.

ex.

40 (Ko, iNi2j5Co4isFe3BiP0j5MG12Ox) 73.1

41 Ge0j6 (K0jlNi2! 5Co4) sFe3BiP0) 5Mo12Ox) 80.7

42 Geli0 (K0jlNi2t5Co4i5Fe3BiP0, sMo12Ox) 76.4

43 Sn0j5 (K0! INi2i5Co4j5Fe3BiP0) 5Mo12Ox) 75.7

44 Sniio (KoliNÌ2.5Co4i5Fe3BiPo, sMo12Ox) 75.0

45 Cuo) i (K0> 1Ni2jsCo4! 5Fe3BiP O, SMoi2Ox) 77.9

46 Agoji (KolxNi2) sCo4) sFe3BiPo, sMo12Ox) 74.2

47 Cro, s (KoJiNi2isCo4) 5Fe3BiPo1sMoi2Ox) 78.3

48 Ruo, i (K0iiNi2! SCo4j5Fe3BiP o.sMo ^ Ox) 7 6.4

49 Cuo! IGeo, 6 (Ko, iNÌ215Co4) sFe3BiP0isMoj2Ox) 76.2

50 Ago, iGeoJ6 (Ko] iNi2j5Co4] 5Fe3BiP0) 5Moi20x) 75.4

51 Ruo, iGeo, 6 (Ko, iNÌ2jsCo4; sFe3BiP0) 5Mo12Ox) 79.3

52 Geljo (Ko, iNÌ2, sCo4; 5Fe2BiPo15Mo12Ox) 79.1

53 Croj5Ge0, i (Ko, iNi2jsCo4) sFe3BiPo, sMo12Ox) 79.2

54 Sn, Ni2.5 Co45 Fe2B i F ,,, 5 Mo 12 Ox) 76.6

55 WQ5Gci! O (K (| i INÌ2.5Co4, sFe2BiMo12Ox) 78.4

56 Cr0, s (Ko) 1NÌ2, sCo4jsFe3BiMoi2Ox) 79.5

57 weeks, s (Ko, iNi2> 5Co4isFe3BiMo120x) 81.6

58 Sn0) s (Ko) iNÌ2! 5Co4i5Fe3BiMo120x) 80.6

59 Ge0.5 (K0jlNÌ2j5Co4! SFe3BiMo12Gx) 79.1

* WWH = 0.03

As can be seen from the above examples, high conversions per pass at high WWH values were achieved when using the catalysts according to the invention.

Examples 60 to 66 Ammoxidation of Propylene Various catalysts according to the invention were produced as follows:

Example 60

80% Mno, 5K0ilNÌ2.5Co4i5Fe3BiMoi20x -! - 20% Si02 The same procedure was used as in Comparative Examples 39 and 40, but this time 10.74 g of a 50% by weight solution of Mn (N03) 2 was used instead of phosphorus.

Example 61

80% Tho, sK0) 1NÌ2) 5Co4! SFe3BiMox2Ox + 20% Si02 The same procedure was used as in the example above, except that 16.56 g of Th (N03) 4 • 4H20 was used instead of phosphorus.

Example 62

80% Zr0, sK0iINÌ2, sCo4! SFe3BiMoi2Ox + 20% Si02 The same procedure was used, but this time 9.68 g ZrOCl2 • 8H20 was used instead of the phosphor.

Example 63

80% Yo! SKoliNÌ2,5Co4isFe3BiMo12Ox + 20% SÌO2 The same procedure was used, but this time 10.96 g of Y (N03) 3 • 5H20 was used instead of the phosphor.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

7

616 861

The catalysts were ground and sieved to form a 0.84 to 0.50 mm (20 to 35 mesh) fraction which was charged into a 5 cm3 reaction zone of a tubular stainless steel reaction vessel. The ammoxidation was carried out using a propylene / ammonia / oxygen / nitrogen / water vapor feed in a ratio of 1.8 / 2.2 / 3.6 / 2.4 / 6. The temperature of the bath surrounding the reaction vessel was kept at 420 ° C and the apparent contact time was 3 seconds. The results of these experiments are given in Table VI below.

Table VI

Ammoxidation of Propylene Using

^ 0.5 ^ 0, lNÌ2! SC04) sFe3BÌM0i20x

Example catalyst results in% No. X = Um selectivity yield

Change in one

Continuity

60

Mn

99.6

82

81.8

61

Th

94.2

83

78.2

62

Zr

98.8

77

76.3

63

Y

99.6

74

73.9

Examples 64-67 Ammoxidation of Isobutylene

In the same manner as above, various catalysts were made and tested in the ammoxidation of isobutylene to methacrylonitrile. The reactions were carried out at 400 ° C using a feed of isobutylene / ammonia / air / water vapor in a ratio of 1 / 1.5 / 11/4. The apparent contact time was 3 seconds. All catalysts contained 20% SiO 2. The results are given in Table VII below, based on methacrylonitrile.

Table VII

Ammoxidation of isobutylene to methacrylonitrile with XaAbNÌ2, sCo4! 5Fe3BiMoi20x

With catalyst, results in%

game XaAb = selectivity selectivity

No change in one

Continuity

64

Mn0, scS0, i

99.8

75

74.9

65

Cr0l5Cso, i

100.0

79

79.0

66

Ge0.5Cs0, i *

97.0

77

74.7

67

W0) 5Cs0, i **

96.0

74

71.4

* Additional heat treatment of the catalyst at 650 ° C for 2 hours

** as with * plus implementation at 410 ° C

Example 68 Ammoxidation of Propylene A catalyst of the composition CrW0, sK0ilNÌ2) sCo4i5Fe2BiMoi2Ox was prepared and heat-treated at 550 ° C. for 18 hours and at 600 ° C. for 2 hours. The ammoxidation of propylene was carried out in a 5 cm3 reaction vessel at a temperature of 440 ° C. and a contact time of 3 seconds and a WWH of 0.10 using a feed of propylene / ammonia / oxygen / nitrogen / water vapor in one Ratio of 1.8 / 2.2 / 3.6 / 2.4 / 6 performed. The conversion of propylene was 96.8%, the selectivity for acrylonitrile was 86% and the yield in one pass of acrylonitrile was 83.2%.

Example 69 Ammoxidation of Propylene In the manner given in Example 68, a catalyst was prepared which consisted of 80%

MnCro, 5Kó, iNÌ2.5Co4.5Fe2BiMo12Ox and 20% Si02, and this was heat-treated at 550 ° C for 16 hours and at 600 ° C for 2 hours. When the catalyst was used to produce acrylonitrile, the conversion of propylene was 99.0%, the selectivity for acrylonitrile was 85.6% and the yield in one pass was 84.7%.

Example 70 Ammoxidation of Propylene In the manner given in Example 68, a catalyst consisting of 80% was formed

GeWo, sK0; 1Ni2] 5Co4; 5Fe2BiMoi20x and made of 20% Si02 and heat-treated at 550 ° C for 16 hours. The conversion of propylene was 97.8%, the selectivity was 85.1% and the yield in one pass was 83.1%.

Example 71 Ammoxidation of Propylene In the manner given in Example 69, a catalyst consisting of 80% was formed

PrW0lsK0! 3NÌ2> 5Co4isFe2BiMo12Ox and made of 20% Si02 and used in the ammoxidation of propylene. The propylene was converted to 99.2%, the one-pass yield was 82.7% and the selectivity was 83%.

Example 72 Ammoxidation of Propylene In the manner given in Example 70, a catalyst consisting of 80% was formed

MnSbo, 5Ko, iNÌ2,5Co4jsFe2BiMo12Ox and 20% Si02, manufactured and tested, but this time the reaction temperature was 420 ° C. The conversion of propylene was 100%, the selectivity was 80.4% and the one-pass yield was also 80.4%.

Examples 73 to 76 Fluid Bed Ammoxidation In a fluid bed reaction vessel with sieve plates with an inner diameter of 3.81 cm (1.5 inches), the ammoxidation of propylene was carried out using various catalysts according to the invention, which contained 20% silicon dioxide. The catalysts were heat treated at 550 ° C for 16 hours and then subjected to an additional 2 hour heat treatment at the temperature shown in Table VIII below. The reaction vessel was filled with 395 cm 3 of catalyst. The feed consisted of propylene / ammonia / air in a ratio of 1 / 1.2 / 10.5, the WWH was 0.12, the pressure was 1.84 kg / cm 2 (12 psig) and the contact time was 5.5 Seconds. The catalysts used and the results obtained are shown in Table VIII below.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

616 861

8th

Vili table

Ammoxidation of propylene in a fluidized bed reaction vessel using a catalyst of the composition XaK0jiNÌ2J5Co4jsFe2BiMo12Ox

Example _ Catalyst heat reaction results in%

No. Xa = treatment, temp., ° G um selectivity yield

° C change in one pass

73

74

75

76

MnCr0, s MnCr0, s CrW0, s CrW0, s

600 600 600 600

435 445 435 445

95.9 97.7 96.2 97.9

83

83

84 83

79.6 81.1 80.5 81.3

Examples 77 to 85 Oxidation of Isobutylene at Atmospheric Pressure Various catalysts according to the invention were produced by the processes described above.

In a fixed bed reaction vessel consisting of a stainless steel tube with an inner diameter of 0.8 cm, 5 cm 3 of each of the above was prepared

Catalysts introduced. These catalysts were tested at a reaction temperature of 371 ° C using a 1/10/4 ratio of isobutylene / air / water feed and an apparent contact time of 4 seconds. The results of these experiments are given in Table IX below.

20th

Table IX

Oxidation of isobutylene to methacrolein and methacrylic acid at atmospheric pressure using a catalyst of the composition XaAbNi2) 5Co4i5Fe3BiMoa2Ox

Example No.

catalyst

Results in%

Yield in one pass MA. MAA ■

a total of

conversion

selectivity

77

Pro, sKo, i

61.6

2.2

63.8

91.3

69.9

78

Mn0, sK0) i

68.5

2.9

71.4

100.0

71.4

79

Ge0jsK0ii

67.0

4.5

71.5

100.0

71.5

80

Nbo, sK0, i

52.2

2.5

54.7

82.9

66.1

81

Tho, sK0li

74.3

2.6

76.9

100.0

76.9

82

Cr0) 5Cso, 5

58.9

2.9

61.8

81.7

75.6

83

Mn0.5Cs0.5K0i5

68.3

3.4

71.7

100.0

71.7

84

Ge0) sCs0jSK0iS

77.1

1.0

78.1

94.3

82.9

85

Nb0, sCso, sKo, s

75.3

1.2

76.5

94.7

80.8

MA = methacrolein MAA = methacrylic acid * 1.84 kg / cm2 (12 psig)

Examples 86 to 89 Oxidation of Isobutylene at Atmospheric Pressure In the manner described in Examples 77 to 85 above, various catalysts as prepared above were used in reactions under pressure. The pressure was 1.84 kg / cm2 (12th

psig). The reaction temperature and the results are given in Table X below. The feed had the same composition as above and the apparent contact time was 3.5 to 4 seconds and the WWH was 0.098 to 0.159.

Table X

Oxidation of isobuytlene to methacrolein and methacrylic acid at atmospheric pressure in the presence of a catalyst of the composition XaAbNi2jsCo4isFe3BiMo120x

example

Catalyst,

Temp.

Results in

%

No.

XaAb =

° C

Yield per run

MA

MAA

a total of

conversion

selectivity

86

Gep) SCso, 5

371

68.4

5.6

74.0

96.5

76.7

87

Mn0lsCso, i

343

64.5

4.8

69.3

99.6

69.5

88

Tho, sCso, s

343

61.5

3.5

65.0

89.0

73.0

89

Ce0, sCs0.2

363

70.3

6.4

76.7

98.9

77.6

* 1.68 kg / cm2 (9.7 psig)

Example 90 prepared and tested in the ammoxidation of propylene.

Ammoxidation of propylene 65 The yield in one pass was 78.8%, the selectiv

In the manner indicated in Example 41, the catalyst was 81% and the conversion of propylene was the analyzer of the composition Ta0.5K0, ^ 2.5004 ^ 63 BiMoi2Ox 97.4%.

s

Claims (5)

616 861
1. Oxidation catalyst, characterized by the general formula
XaAbDcEdFefBigMo12Ox where:
X yttrium, zirconium, silver, sulfur, cerium, thorium, praseodymium, ruthenium, gallium, niobium, germanium, chromium, tin, manganese, indium, copper, tungsten, tantalum, tellurium, lanthanum or a mixture thereof,
A an alkali metal, thallium or a mixture thereof, D nickel, cobalt, magnesium, strontium, calcium, zinc, cadmium or a mixture thereof,
E phosphorus, arsenic, boron, tungsten, antimony or a mixture thereof, where E can also be sulfur if X is tungsten,
a is a number greater than 0 and less than 5,
b and d numbers from 0 to 4,
c is a number from 0.1 to 20,
f and g numbers from 0.1 to 10 and x the number of oxygen atoms required to saturate the valence of the other elements present.
2. Oxidation catalyst according to claim 1, with the general formula
XaAbDcEdFefBigMo12Ox where:
X Y, Zr, Ag, S, Ce, Th, Pr, Ru, Ga, Ta, La or a mixture thereof,
A an alkali metal, thallium or a mixture thereof, D nickel, cobalt, magnesium, calcium, strontium, zinc, cadmium or a mixture thereof,
E phosphorus, arsenic, boron, tungsten, antimony or a mixture thereof,
a is a number greater than 0 and less than 5,
b and d each represent a number from 0 to 4,
c is a number from 0.1 to 20,
f and g each represent a number from 0.1 to 10 and x the number of oxygen atoms required to saturate the valence of the other elements present.
2nd
PATENT CLAIMS
3. Oxidation catalyst according to claim 1, characterized by the general formula
XaAbDcEdFetBigMoi2Ox where:
X Nb, Ge, Cr, Sn, Mn, In, Cu, Te or a mixture thereof,
A an alkali metal, Ti or a mixture thereof, D nickel, cobalt, magnesium, calcium, strontium, zinc, cadmium or a mixture thereof,
E phosphorus, arsenic, boron, tungsten, antimony or a mixture thereof,
a is a number greater than 0 and less than 5,
b is a number greater than 0 but less than 4,
c is a number from 0.1 to 20,
d is a number from 0 to 4,
f and g each represent a number from 0.1 to 10 and x the number of oxygen atoms required to saturate the valence of the other elements present.
4. Oxidation catalyst according to claim 1, characterized by the general formula
WaAbDcEdFefBigMo12Ox where:
A is an alkali metal, Tl, or a mixture thereof,
D a metal from the group nickel, magnesium, strontium, calcium, zinc, cadmium,
E phosphorus, arsenic, boron, sulfur, antimony or a mixture thereof,
a is a number greater than 0 but less than 5,
b and d each represent a number from 0 to 4,
c is a number from 0.1 to 20,
f and g each represent a number from 0.1 to 10 and x the number of oxygen atoms required to saturate the valence of the other elements present.
5. Oxidation catalyst according to claim 1, characterized by the general formula
WaAbDcEdFefBigMoi2Ox where:
A an alkali metal, Tl, or a mixture thereof, D at least one metal from the group nickel, magnesium, strontium, calcium, zinc, cadmium plus cobalt,
E phosphorus, arsenic, boron, sulfur, antimony or a mixture thereof,
a is a number greater than 0 but less than 5,
b and d each represent a number from 0 to 4,
c is a number from 0.1 to 20,
f and g each represent a number from 0.1 to 10 and x the number of oxygen atoms required to saturate the valence of the other elements present.
CH952175A 1974-07-22 1975-07-21 Oxidation catalyst. CH616861A5 (en)

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