JPS6118435A - Oxidizing catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to oxidation catalysts. Already used as oxidation catalysts, e.g. U.S. Pat. No. 3,642,930 and U.S. Pat.
, No. 414.631 is known. Although these catalysts described in that patent are desirable oxidation catalysts, the catalyst of the present invention has additional advantages over these catalysts.

The present invention is based on the general formula % (where X is 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 is an alkali metal, thallium, or a mixture thereof; D is nickel, cobalt, magnesium, strontium, calcium, zinc, cadmium, or a mixture thereof; E is phosphorus, arsenic, boron, tungsten, antimony, or a mixture thereof; a is greater than O and less than 5, b and d are O to 4, C is 0.1 to 20, f and g are 0.1 to 10, and X is any other element present. Indicates the number of oxygens required to meet the valence requirements of . ) is an oxidation catalyst.

The present invention relates to any catalyst specified by the above formula. Although these catalysts are prepared as shown in the specific examples, they are effective in a wide range of well-known oxidation reactions. In these reactions, the novel catalyst of the present invention is used in place of the conventionally used catalyst, but the reactions are carried out under substantially the same conditions. Of particular interest are the oxidation of olefins, oxidative dehydrogenation, but other reactions such as the oxidation and ammoxidation of methyl-substituted aromatics are also contemplated for the use of these catalysts.

Refer to specific examples.Oxidative dehydrogenation of -1-butene diameter 0.8
The reactor with a reactant inlet and a product outlet was made of cm stainless steel tubing. This reactor has a reaction zone capable of charging 2.5 cc of catalyst.

Various catalysts of the invention were prepared as described below. All catalysts had 80% active components and 20% silica.

Reference flameout Cro, sKo, + Niz, 5
croa, 5FeJilo+ 20X water 100ml
63.56 g of ammonium heptamolybdate, (N
Ha) Melt 6M01Oia・4■20, heat it,
While stirring, add 51.66g of Nalco 4.
0% silica sol was added. 1.50g of C in this slurry
rys was added.

Separately, 36.36 g of ferric nitrate, Fe(NOx)3
・9H20 was heated and dissolved in 1Qcc of water. Then 1
4, 55 g of Bi (NO3) 3.5H20 and 3
9.298 Co(NO3) 2 ・61) 20 and 2
1.814 Nt (NO3) t 6HJ and 3.3
0 g of 10% KNO2 solution was dissolved in the above solution.

This nitrate solution was slowly added to the slurry containing molybdenum. The mixture was heated and stirred until it began to thicken. The solid was dried in an oven at 120° C. with occasional stirring. Finally, the catalyst was calcined in air at 550° C. for 16 hours.

1) Example 2 Te. . Jo, Jiz, 5Coa
, 5ees old? The 1o1zOx catalyst was prepared in the same manner as described in Reference Example 1, except that Cr (h was replaced with 4.04 g of TeCJt).

Reference example 3 Geo, sKo, +Nii, 5CO4,s
The Fe3BiMoBOx catalyst was produced in the same manner as in Reference Example 1, except that Cry was replaced with 1.57 g of Ge0z.

Reference example 4 Wo, 5Ko-+N1z-scOa, 5F
eJiMO+zOX This catalyst was manufactured as described in Reference Example 1, except that Cr (h was 4.04 g (Nu<
)JvOzn ・Changed to 6HzO.

Reference example 5 Mno, sKo, +Niz, 5Co4. s
The FeJiMo+zOx catalyst was produced as described in Reference Example 1, except that Crys was replaced by 50% of manganese nitrate.
% solution was changed to 5.37 g.

Tho, sKa, +Niz, 5CO4
, sFe3BiMoI2OX This catalyst was manufactured as described in Reference Example 1, except that CrO3 was replaced with T of 8.288.
h (NOi) 4-41). Changed to o.

g Nbo, 5Ko-Doi Fuo4.5Fe3Bi Work□
31.8 g of ammonium heptamolybdate was dissolved in 50 cc of Kano A water. 2,0 slurried with water in this solution
26.5 g of Nalco 40% silica, and a mixture of 10.9 g of nickel nitrate and 19.7 g of cobal nitrate) were added.

Separately, 18.2 g of ferric nitrate and 7.2 g of bismuth nitrate.
A solution was prepared from 19 g of KOHO as a 45% solution and this solution was slowly added to the molybdenum slurry. The manufacturing method other than this is the same as in Reference Example 1.

Koko N8 Pro-5Ko-+Ni4. sCO*, s
FeJiMO+zOx This catalyst was manufactured as described in Reference Example 1, except that CrO3 was mixed with 2.60 g of Pry
, changed to .

m CEO, sKo, +'Niz, 5Coa, sFe
JiMolJx This catalyst was prepared as described in Reference Example 1, except that 8.22 g of CrO3 (Nl14)
Changed to ice (NOx) h.

This catalyst sample was crushed and sieved to obtain a 20-35 mesh fraction, which was charged to the 5 cc reaction zone of the reactor. - Butene/air/steam feed in a molar ratio of 1/1)/ 4 was fed onto the catalyst at a temperature of 350° C. and an apparent contact time of 1 second.

The results of these experiments are shown below.

The results of these experiments are shown in Table 1. Isomerization of 1-butene is not counted as a reactive olefin.

Acid, Trivial Dehydrogenation of Butene Using Germanium-Containing Catalysts Various germanium-containing catalysts were prepared as follows.

The present catalyst was prepared in the same manner as the catalyst of Reference Example 1, except that potassium was not added and Crys was replaced with 1.57 g of GeO2.

A soil-based catalyst was prepared as described in Reference Example 1O, except that the usual amount of potassium was added and 61.04 g of nickel nitrate was used in place of the nickel and cobalt.

[12] This catalyst was produced as described in Reference Example 1), except that nickel nitrate was replaced with 61.12 g of cobalt nitrate.

Reference Example 3" [L running catalyst was produced as described in Reference Example 1), except that 72.83 g of ammonium heptamolybdate and 3.
03 g of 45% KOH solution was used.

The present catalyst was produced as described in Reference Example 1), except that 53 and 85 g of M were used instead of nickel and cobalt.
g(NOi)i 61)zO was added, and 3.22 g of GeCIt was used instead of Gem.

1 Koyu Doko This catalyst was produced as described in Reference Example 1), except that nickel nitrate was replaced with magnesium nitrate, and Reference Example 14 was prepared.
GeC124 was used as described in .

Toyoka Irregular Earthwork This catalyst was produced as described in Reference Example 1), except that the cobalt was replaced with manganese nitrate in the form of a 50% solution.

1 On the spinning wheel 1 This catalyst was manufactured as described in Reference Example 1), except that 2.72 g of GeCβ4 was used as germanium, and 48 g of nickel t-21, 5-note solution of manganese nitrate was used. .

The catalysts may be tested as described in Reference Examples 1-9. sa
80% Geo-5Crt. sT j! o. tNizcO
zFeo. sBtMO+ @Ox and 20% Sin
Prepare a catalyst of the formula g, with a 1-butene/air ratio of 1/1),
It was used for oxidative dehydrogenation of 1-butene at a temperature of 350°C and an apparent contact time of 1 second. The conversion rate of 1-butene was 89.6%,
The selectivity was 98% and the yield per pass was 88.1%.

Food "■ Limited J" - Cesium-containing catalyst as described in Reference Example 5, except that the potassium compound was 0.
．． 5 9 g of cesium nitrate, 8 instead of CsNO3
0% Mno. 5Cso- +Nfz- 5cOi. '
sPeJLMoIzox and 20% Sin. A catalyst having the formula was prepared. Using the feed and conditions of Reference Example 18, 1-butene was converted to the product at 100%, with a selectivity to butadiene of 99% and a yield per Mipass of 98.6%.

Moxibustion Consideration 1 Oxidative Dehydrogenation of 2-Butene The catalyst prepared in the above reference example was used for oxidative dehydrogenation of 2-butene to butadiene. Using the reactor and catalyst volume of the above-mentioned reference example, a 57.5% trans O,..., 195% cis mixture of 2-butene was reacted with an apparent catalyst time of 1 second. 2-
The butene/air ratio was 1/1). The results of these experiments are shown in Table 2. The parentheses surrounding the elements in the catalyst formula indicate the elements used in subsequent experiments.

Operation at a high air-to-olefin ratio The catalyst of the present invention produced as described above was used in Reference Examples 20-
It was used for oxidative dehydrogenation of a mixture of 2-butene in the same manner as described in 28, except that the 2-butene/air ratio was 1/31.The reaction temperature was 350'C and the apparent catalyst time was 1 second. The results of these experiments are shown in Table ■.Example 37
The lanthanum catalyst is the Cry of the catalyst of Reference Example 1, which is 6.22
g (7) La(NOal+ ・51) Produced by changing to 20.

Moxibustion theory development main use of another potassium catalyst with high air ratio As described in Reference Example 9, but with the addition of 5 times the amount of potassium, 80% We, 5Ko-5Niz, 5cOa, sFeJi
A catalyst with Mo+ zOx and 2o% SiO□ was prepared.

using the above mixture of 2-butenes at an air to butene ratio of 31;
This catalyst was tested for the production of butadiene at an apparent catalyst time of 1 second and a temperature of 385 DEG C. The conversion of 62-butene was 96.4%, the selectivity was 91% and the yield per pass was 88.
It was 1%.

Oxidative dehydrogenation of m-isoamylene Using the catalyst of Reference Example 13, a mixture of equal volumes of 2-methyl-1-butene and 2-methyl-2-butene was oxidized and dehydrogenated to produce isoprene in a reactor having a reaction zone of 5 cc. And so.

At 400'C and an apparent catalyst time of 2 seconds, the isoamylene conversion was 85.9%, the isoprene selectivity was 82%, and the isoprene yield per pass was 70.2%.

1) Manufacture of isoprene using cr catalyst In the same manner as described in Reference Example 39, the catalyst of Reference Example 1 was used for the production of isoprene. Conversion rate is 86.2%, selectivity 70%
, the yield per pass was 60.5%.

A 5 cc fixed bed reactor was made of 1 to 3 (inner diameter 81) m stainless steel tubes prepared as described below. The catalyst was charged to the reactor and heated to 420''C under a flow of air. At the reaction temperatures of Comparative Example B and Examples 1-34, propylene/ammonia/
[-/m element/water vapor is 1.8 / 2.2 / 3.6
/2.4/6 was fed onto the catalyst with a contact time of 3 seconds. The WWI (defined as the amount of olefin fed per weight of catalyst per hour) was 0.10 in this reaction.

In comparative example A, the ratio of propylene/ammonia/oxygen/nitrogen/steam is 1/1.1/2 at a temperature of 420°C.
, 1/7.9/4 reactant feed was used. The contact time was 6 seconds. WWW was 0.03.

This example is included to demonstrate a basic catalyst that works under normal operating conditions at low WWH.

The catalyst was manufactured as follows.

20% Sin.

127, 1 g of ammonium heptamolybdate (NH4
) An aqueous solution of 6M070□4・4H20 was prepared. Add 6.9 g of H3PO442, 5% solution to this solution and 102
．． 7'g of NAL340% silica sol was added to form a slurry.

Separately, 72.7 g of ferric nitrate, Fe(N(1+)3
・9HzO and 29.1 g of bismuth nitrate, Bi (
NOz) a ・5LO, 78.7 g of cobalt nitrate, co(Noz)z H6HzO, and 43.6 g of nickel nitrate, N1(NO+)z ・6HzO, 6.
An aqueous solution containing 1 g of 10% potassium nitrate solution was prepared. The metal nitrate solution was slowly added to the slurry. The resulting slurry was evaporated to dryness and the resulting solid was 29
It was heated at 0°C for 3 hours, at 425°C for 3 hours, and at 550°C for 16 hours.

Example 1 80%Geo, 6KO, 1Ni1.5COa-5Fe
3BiPo, sMo+ 20x +20%SiO□ 63, 56 g of ammonium heptamolybdate in 60c
Dissolved in warm water of c. This solution was added to 53.25 g of NAL 340% silica sol. The mixture was heated on low heat for about 5 minutes with constant stirring.

3.46g of u, pot 42.5% to the generated slurry
The solution was added and the mixture was heated for 2 minutes.

Separately, 36.36 g of ferric nitrate was mixed with 10 cc of water and melted on a hot plate with constant stirring. Wait for the metal nitrate added before to melt, then add 14
．． 55g bismuth nitrate1. 19.29 g of cobalt nitrate and 21.80 g of nickel nitrate were added. 3.03
g of KNO3 10% solution, 1.88 g of G
Add eO2 to melt.

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

The other catalysts of this example were produced in the same manner as the catalyst of Example 1. Germanium, tin, chromium and titanium were added as oxides to the catalyst.

Copper and silver were added to the catalyst as nitrates. Ruthenium and helium were added to the catalyst as chlorides. Tungsten was added to the catalyst as ammonium tungstate along with ammonium heptamolybdate. Although different anion species were used, the particular anion of the catalyst component does not appear to be the determining factor.

In the phosphorus-free catalyst, the cocatalyst elements of the present invention were added to the catalyst from a molybdenum-containing slurry.

80%Ga+, oKo, +Niz, 5CO4,J
e3BiPo, SMO+40X+20%Sio.

As described in the example above, 24.7 g of ammonium heptamolybdate and 19.4 g of Na340%
A first slurry containing silica and 1.15 g of H3PO442, 5% solution was used to prepare the catalyst. The second slurry contained 12.1 g of ferric nitrate, 4.8 g of bismuth nitrate, and 13.1. g of cobalt nitrate, 7.3 g of nickel nitrate, i, oga potassium nitrate 10% solution, 2.5 g of gallium nitrate, Ga(NOx)s・31)
□Contains 0. These slurries were combined, evaporated and heat treated as above.

71.6 g of ammonium heptamolybdate and 58.0
g of Naru 340% silica sol and 3.4 g of phosphoric acid 42
．． A first slurry containing a 5% solution was prepared. 36.4
g of ferric nitrate, 14.6 g of bismuth nitrate,
39.3 g cobalt nitrate, 21.8 g nickel nitrate, 3.0 g potassium nitrate 10% solution, 4.5
A second slurry was prepared containing g of indium chloride.

These slurries were combined and the solid catalyst was heat treated as described above.

57, 2 g of ammonium heptamolybdate, and 4.8
g of ammonium heptungstate, (NHJ) J?
A slurry was prepared having O□4.6LO, 4.5 g of boric acid, 3.5 g of 42.5% phosphoric acid solution, and 52.3 g of Na340% silica sol. 36 in this slurry
．． A solution consisting of 4 g of ferric nitrate, 14.6 g of bismuth nitrate, 39.3 g of cobalt nitrate, 21.8 g of nickel nitrate, and 3.0 g of a 10% solution of potassium nitrate was added. The resulting slurry was evaporated and the solid was heat treated as described above.

Table 7 shows the results of an experiment in which acrylonitrile was produced by ammoxidizing propylene. The parentheses used in Table V have no particular meaning other than to emphasize the difference in catalyst.

From the above examples, it is clear that by using the catalyst of the present invention, W
It can be seen that a high conversion rate per bath can be obtained based on the WH value.

30-33 Ammoxidation of Propylene Various catalysts of the present invention were prepared as follows.

The same method as in Comparative Examples A and B was used, except that instead of lino, D 10.748 (D Mn(NO+)z 50
A weight percent solution was used.

The same method as above was used except that instead of phosphorus, 16,5
6 g of Th (NOs) a ·-4HtO was used.

and 20%5in2 A similar method was used, but instead of phosphorus, 9.68
Zr0C1)z·8 HzO of g was used.

A similar method was used except that 10.96 g of Y(NOs)+.51)□0 was used instead of phosphorus.

The catalyst was ground and sieved to obtain 20-35 mesh fractions and charged to a 5 cc reaction zone of a stainless steel tubular reactor. Propylene/ammonia/oxygen/nitrogen/steam 1.8/2.2/3.6/2, 4/
Ammoxidation was performed using feed No. 6.

The temperature of the bath surrounding the reactor was maintained at 420°C and the apparent contact time was 3 seconds.

The results of these experiments are shown in Table 2.

37- In the same manner as the ammoxidation vapor of isobutylene, various catalysts were prepared and tested for the ammoxidation of imbutylene to methacrylonitrile.The reaction was 1/1.5 of isobutylene/ammonia/air/steam. /1)
The test was carried out at 400°C using a feed of /4. The apparent contact time was 3 seconds. All contacts contained 20% SiO□. The results for methacrylonitrile are shown in Table 2.

m Propylene ammoxidation CrWo, SKO, +Niz, 5CO4, sFe2B
A catalyst with iMo+ 20X was prepared and 18
Heat treatment was performed at 600° C. for 2 hours. Ammoxidation of propylene was carried out in 9 reactors of 5 cc at a temperature of 440 °C, a contact time of 3 seconds, a WWW of 0.10, and a ratio of 1.8/2.2/of propylene/ammonia/oxygen/nitrogen/steam.
A feed of 3.6/2.4/6 was used.

The conversion rate of propylene was 96.8%, the selectivity to acrylonitrile was 86%, and the yield of acrylonitrile per bath was 83.2%.

m ammoxidation of propylene In the same manner as described in Example 38, 80% NnCra,
sKo, ski z, 5Coa, sFezBiM
A catalyst with ot zOx and 20% SiO Selectivity to 85.6%, yield per bath 84.7%
Met.

Example 40 Ammoxidation of propylene 80% Ge-0, -Ke, +Ni2.
5(:oa, sFezBiMotgox and 20%S
A catalyst having in was prepared and heat-treated at 550° C. for 16 hours. Propylene conversion rate 97.8%, selectivity 85.
The yield per bath was 83.1%.

1iLLj E Ammoxidation of propylene In the same manner as described in Example 39, 80% PrWo, 6.3Ni in s-
A catalyst with 1.5 cOa, sFe4BiMo+ tax and 20% SiO2 was prepared and used for ammoxidation of propylene. 99.2% of propylene is converted,
The yield per bath was 82.7% and the selectivity was 83%.

Taisenen↓Main Ammoxidation of propylene 80% Mn5bo, s in the same manner as described in Example 40
-Xo, +Niz, 5Co4. sPeJiMo+tOx
and 20% SiO, were prepared and tested, with the reaction temperature being 420°C. Conversion of propylene is 100%, yield and selectivity per bath is 80.4
%Met.

Ammoxidation of propylene using various catalysts of the invention containing 20% silica in a 1-1/2" internal diameter fluidized bed reactor with perforated fluidized bed ammoxidation plates. These catalysts were heat-treated at 550°C for 16 hours and then further heat-treated for 2 hours at the temperature shown in Table 1.The reactor was charged with 395cC of catalyst.
Propylene/ammonia/air feed is 1/1
．． 2/10.5, WWW is 0.12, pressure is l'l
p, s, i, g.

The contact time was 5.5 seconds. The catalyst used and the results are shown in Table 1.

1) Oxidation of isobutylene at atmospheric pressure Various catalysts of the present invention were produced by the method described above.

5 cc of each of the above-produced catalysts was placed in a fixed bed reactor made of stainless steel tubes with an inner diameter of 0.8 mm. These catalysts were tested at a reaction temperature of 371° C. using a 1/10/4 isobutylene/air/steam feed with an apparent contact time of 4 seconds.

The results of these experiments are shown in Table 3.

, tlL ``225'' - Oxidation of Isobutylene at High Pressure In the same manner as described above in Reference Examples 41 to 51, the various catalysts prepared above were used for the reaction at high pressure.

Unless otherwise specified, the pressure was 12ρ, s, i, g.

Reaction temperatures and results are shown in Table
was 0.098 to 0.159.

1) Ammoxidation of propylene Tao, sKa, INLz-5-Coa in the same manner as described in Example 1
, sFesBiMo+ tox was prepared and tested for ammoxidation of propylene. The yield per bath was 78.8%, the selectivity was 81%, and the propylene conversion was 97.4%.

Claims (2)

[Claims] (1) General formula: X_aA_bD_cE_dFe_fBi_gMo_1_
2O_x [where A is a mixture of alkali metals,
D is Ni or Co, E is B, Sb or a mixture thereof, and X is Y, Z
r, Th, Pr, Ge, Cr, Sn, Mn, Ti, Cu
, W or a mixture thereof, a is greater than 0 and less than 5, b is greater than 0 and less than 4, c is 0.1-20, d is 0-4, f and g are from 0.1 to 10, and x is the number of oxygens required to meet the valence requirements of other elements present. ] A catalyst for ammoxidation of olefins. (2) General formula: X_aA_bD_cE_dFe_fBi_gP_hMo
_1_2O_x [where A is a mixture of alkali metals, D is Ni or Co, E is B, Sb or a mixture thereof, and X is Ag,
Ru, Ga, Ge, Cr, Sn, Mn, In, Cu, W
, Ti, or a mixture thereof, a is greater than 0 and less than 5, b is greater than 0 and less than 4, c is 0.1 to 20, and d is 0 to 4. f and g are from 0.1 to 10, h is greater than 0 and less than or equal to 4, and x is the number of oxygens required to meet the valence requirements of other elements present. ] A catalyst for ammoxidation of olefins.