JPS6036812B2 - oxidation catalyst - Google Patents

Description

[Detailed description of the invention] The present invention relates to oxidation catalysts.

Already used as an oxidation catalyst, for example, US Pat. No. 3,642,9
No. 3 and US Pat. No. 3,414,631 are known. These soots described in the patent are desired L. death,
Although it is an oxidation catalyst, the catalyst of the present invention has more advantages than these catalysts. The present invention relates to the general formula XaAbDcEdFefBjgMo, 20× (however, X
are 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 0 and less than 5, b and d are 0 to 4, C is 0.1 to 20, f and g are 0.1 to 10, and x is the valence requirement of other elements present. Indicates the number of oxygen required for flooding.

) 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 and oxidative dehydrogenation of olefins, but other reactions such as the oxidation and ammoxidation of methyl-substituted aromatics are also contemplated for the use of these catalysts. Specific Specific Examples Reference Examples 1 to 9 Oxidative dehydrogenation of 1-butene.

The reactor was constructed from 0.8 diameter stainless steel tubing with a reactant inlet and a product outlet.

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 example 1 Cr.

．． 5K. ．． ,Ni2.5Co4.5Fe3BiMo,2
Dissolve 63.56 molar ammonium heptamolybdate, (NH4)6Mo 70 m2/4 ratio in 0x100 m of water, heat and stir while stirring.
ico) 40% silica sol was added. This Sura River 1.
Added 3 of C of 50 evenings. Separately, 36.36 ferric nitrate, Fe (N03) 3. Group 20 was heated and melted in 10 cc of water.

Next, Bi (No3) 3 on 14.55 evening. Beat 20 and
39.29 evening Co (N03) 2. Thin 20 and 21.8
1 evening Nj (N03) 2. Group 20 and 10% of 3.30 evening
KN03 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 120q0 with occasional stirring.
Finally, the catalyst was heated in air at 550° C. for 1 hour.
Reference example 2 Teo. 5KO. ,Ni2.5Co4.5Fe3BiM
o, 2○ Borumoto's catalyst was produced in the same manner as described in Reference Example 1, except that 3 of C was replaced with TeC14 of 4.04 m.

Reference example 3Ce■&. ,Ni2.5Co4.5Fe3B
iMo, 20x This catalyst was produced in the same manner as in Reference Example 1, except that C^]3 was increased by 1.57.

Reference example 4 W.

．． 5K. ．． ,Ni2.5Co4.5Fe3BiMo,2
0x This catalyst was manufactured as described in Reference Example 1, but
However, Cr03 is 4.04 evening (N ratio) 6W7024.8
Changed to day 20. Reference example 5 Mn.

．． 5K. , Ni2.5Co4.5Fe3BiMo. 20
The catalyst was prepared as described in Reference Example 1, except that CrO3 was replaced with a 50% solution of manganese nitrate. Reference example 6 Tho. 5 &. ,Ni2.5Co4.5Fe3BiMo
, 20× This catalyst was produced as described in Reference Example 1, except that 3 in C was changed to 20 in Th (N03) 4.4 days at 8.28 pm.

Reference example 7 Nchi. 5K.

．． , Ni2.5Co4.5Fe3BiMo, 31.8 g of ammonium heptamolybdate was dissolved in 50 cc of 20× warm water. This solution was slurried with water and NO.
C15, 26.5 hours of Nalco 40% silica sol, and a mixture of 10.9 hours of nickel nitrate and 19.7 hours of cobalt nitrate were added. Separately, 18.22% of ferric nitrate, 7.2% of bismuth nitrate and KOHO. 19
A solution was prepared in the evening and slowly added to the molybdenum slurry.

The manufacturing method other than this is the same as in Reference Example 1. Reference example 8 Pr.

．． 5K. ．． ,Ni2.5Co4.5Fe3BiMo,2
0 Hiromoto catalyst was produced as described in Reference Example 1,
However, I changed the C 3 to the Pro 2 at 2.60 pm. Reference example
9Ce■Unit. INi2,5C.

4,5Fe3BiM.

120× This catalyst was produced as described in Reference Example 1, except that 3 of C was replaced with (NH4)2Ce(N0
3) Changed to 6.

The catalyst sample was crushed and sieved to obtain a 20-35 mesh section, which was charged to the 2.5 cc reaction zone of the reactor.

1-butene/air/steam feed in molar ratio 1/11/
4 was fed onto the catalyst at a temperature of 35° C. and an apparent contact time of 1 second.

The results of these experiments are shown below.

Reactive olefin x 100 % conversion = Feed olefin % selection rate = Ura collection Ashi Hayabusa now.

Yield % per pass = Ura Shisho Ashita 3≧o The results of these experiments are shown in Table 1.

Isomerization of 1-butene is not counted as a reactive olefin.

Table 1 *Do not add water vapor to the feed.

Reference Examples 10-17 Oxidative dehydrogenation of 1-butene using a germanium-containing catalyst.

Various germanium-containing catalysts were prepared as follows.

Reference Example 10 This catalyst was produced in the same manner as the catalyst of Reference Example 1, except that potassium was not added and 3 of C was replaced with 1.57% of C2.

Reference Example 11 This catalyst was prepared as described in Reference Example 10, except that a normal amount of potassium was added and 61.04% of nickel nitrate was used in place of nickel and cobalt.

Reference Example 12 This catalyst was prepared as described in Reference Example 11, except that the nickel nitrate was replaced with cobalt nitrate.

Reference Example 13 This catalyst was produced as described in Reference Example 11, except that 72.832 ammonium heptamolybdate and 3.0
Three days of 45% KOH solution was used.

Reference Example 14 This catalyst was prepared as described in Reference Example 11, except that nickel and cobalt were replaced with 53.
Mg(N03)2 Mother LO of 85 days was added, and QC14 of 3.22 days was used instead of 02.

Reference Example 15 This catalyst was produced as described in Reference Example 11, except that nickel nitrate was replaced with magnesium nitrate, and the catalyst was produced as described in Reference Example 14.
WC14 was used as described in .

Reference Example 16 This catalyst was prepared as described in Reference Example 11, except that the cobalt was replaced with a 50% solution of manganese nitrate.

Reference Example 17 This catalyst was produced as described in Reference Example 11, except that QC14 of 2.72 days was used as germanium.
The nickel was replaced with a 50% manganese nitrate solution at 21.48 pm, and a 45% KOH solution at 3.03 pm was used.

The catalysts were tested as described in Reference Examples 1-9. The results are shown in Table 0. Day Table Reference Example 18 Two types of promoters in thallium-containing catalysts.

In the same manner as described in the above example, 80% C was also reduced to 5Cr, . 5TIMNj2Co3Fesmall5BiM
o, 20 戊 and 20% Si02 formula catalysts were prepared;
It was used for oxidative dehydrogenation of 1-butene at a 1-butene/air ratio of 1/11, a temperature of 350 oo, 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%.

Reference example 19 Cesium-containing catalyst.

As described in Reference Example 5, except that the potassium compound was 0.
．． 59 cesium nitrate, 80% M instead of CsN03
~． 5Cs,. ,Ni2.5Co4.5Fe3BiMo
, 20× and 20% Si02 were prepared.

Using the feed and conditions of Reference Example 18, 1-butene is 1
00% conversion to product but selectivity to butadiene 99
%, yield per pass was 98.6%. Reference example 20
~28 Oxidative dehydrogenation of 2-butene.

The catalyst produced in the above reference example was used for oxidative dehydrogenation of 2-butene to butadiene.

Using the reactor and catalyst volume of the reference example above and an apparent contact time of 1 second, 57.5% of the trans and 4
A 2.5% cis mixture was reacted. The 2-butene/air ratio was 1/11.

The results of these experiments are shown in Table m. The parentheses surrounding the elements in the catalyst formula indicate the elements used in subsequent experiments. mth
Table * Simulation interval, 4 seconds Reference example 29-37 Operation at high air to olefin ratio.

The catalysts of the present invention produced as described above were used in Reference Examples 20-
It was used for the oxidative dehydrogenation of a mixture of 2-butenes in the same manner as described in 28.

However, the 2-butene/air ratio was 1/31. The reaction temperature was 350° C. and the apparent contact time was 1 second. The results of these experiments are shown in Table W. In the lanthanum catalyst of Example 37, C3 of the catalyst of Reference Example 1 was replaced with La(N03)3 of 6.22 days.
．． It was manufactured by changing to SLO. Table N 1. Reaction temperature: 340°C.

2. Reaction temperature: 385°C.

Reference example 38 Use of different potassium catalysts at high air ratios.

As described in Reference Example 9, but with 5 times the amount of potassium.
80% W ship K o. 5Ni2
．． 5Co4.5Fe3BiMo, 2 melon and 20%Sj
A catalyst with 02 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 a temperature of 38,500 with an apparent contact time of 1 second.

The conversion rate of 2-butene was 96.4%, the selectivity was 91%, and the yield per pass was 88.1%.

Reference example 39 Oxidative dehydrogenation of 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 obtain isoprene in a reactor having 5 cc of reaction zone.

At 400 qo and an apparent contact time of 2 seconds, the conversion of isoamylene was 85.9%, the selectivity of isoprene was 82%, and the yield of isobrene per pass was 70.2%. Reference Example 40 Production of isobrene using Cr catalyst.

The catalyst of Reference Example 1 was used in the production of isoprene in the same manner as described in Reference Example 39.

Conversion rate is 86.2%, selectivity 70%, yield per pass 6
It was 0.5%. Comparative Examples A and B and Examples 1-34 Comparison of base catalyst and catalyst containing cocatalyst of the invention.
A 5 cc fixed bed reactor was constructed using Naipong 8-Yanagi stainless steel pipes. A catalyst prepared as described below was charged to the reactor and heated to 42,000°C under a flow of air. At the reaction temperatures of Comparative Example B and Examples 1 to 34, propylene/ammonia/oxygen/nitrogen/steam was 1.8/2.2/
A reaction composition having a ratio of 3.6/2.4 to 6 was fed over the catalyst with a contact time of 3 seconds. The WWH (defined as the amount of olefin fed per weight of catalyst per hour) was 0.10 in this reaction. Comparative Example A has a propylene/ammonia/oxygen/nitrogen/steam ratio of 1 at a temperature of 42,000.
A reactant feed of /1.1/2.1/7.9/4 was used. The contact time was 6 seconds. WWH was 0.03. This example is included to demonstrate a basic catalyst that works under normal operating conditions at low WWH. The catalyst was prepared as follows. Comparative Examples A and B 80% KMNi2.5Co body Fe3BiP small 5Mo12
An aqueous solution of ammonium heptamolybdate (NH)6Mo7024 and bait 20 was prepared.

Add 2.5% solution of HJ044 and 102
．． Nalco 40% silica sol prepared on July 7th was added to make a slurry. Separately, ferric nitrate, Fe(N03)3・
Group 20 and bismuth nitrate, Bi(NQ)3 on 29.1 evening
・Group 20 and cobalt nitrate, Co (N03
) 2. Thin 20 and 43.6 nickel nitrate, Ni(N
03) An aqueous solution containing 2.mother LO and a 10% potassium nitrate solution from 6.1 was prepared. The metal nitrate solution was slowly added to the slurry. The resulting slurry was evaporated to dryness, and the resulting solid was evaporated at 290°C for 3 hours and at 425°C for 3 hours.
The glue was heated for 1 hour at 550 ooohs. Example 1 80%G is also 〇. 6KO. , Ni2・5C.

4.5Fe3BiP.

・5M〇, 2〇X + 20% Si0263.56 ammonium heptamolybdate was dissolved in 60 cc of hot water.

This solution was added to Nalco 40% silica sol at 53.25 pm. The mixture was heated on low heat for about 5 minutes with constant stirring. 3.46 Sunset 3P04 to the generated slurry
The 42.5% solution was added and the mixture was heated for 2 minutes.
Separately, 36.36 evening ferric nitrate was mixed with 10 cc of water and melted on a heating ramp with constant stirring.

After waiting for the previously added metal nitrate to melt, bismuth nitrate was added at 14.55 pm, cobalt nitrate at 39.29 pm, and nickel nitrate at 21.80 pm. 3.0
Combine the 10% solution of KN03 for 3 days, and make 0 for 1.88 days.
2 was added and melted.

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 12°C with occasional stirring. The dried catalyst was calcined at 550 oo for one morning.
Examples 2-26 The other catalysts of this example were prepared in the same manner as the catalyst of Example 1.

Catalysts included germanium, tin, chromium and titanium as oxides. Copper and silver were added to the catalyst as nitrates. Ruthenium and beryllium 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 specific 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. Example 27 80% Gal. 〇KO, INj2.5C04,5Fe3
BjP or 5MO140k + 20% Si02 Ammonium heptamolybdate of 24.7 days, Nalco 40% silica of 19.4 days and 1.15 minutes as described in the above example
A catalyst was prepared using a first slurry containing a 2.5% solution of Yuhi 3P04.

The second slurry contains ferric nitrate of 12.1 minutes, bismuth nitrate of 4.8 hours, cobalt nitrate of 13.1 hours, and 7.1 hours of ferric nitrate.
Nickel nitrate for 3 days and potassium nitrate 10% for 1.0 days
solution and 2.5 mL of gallium nitrate, Ga(N03)3
・Contains navy blue 20. These slurries were combined and exothermally heat treated as described above. Example 28 80%ln,. .

debt. , Ni2.5Co4.5Fe3BiP. ．． 5Mo,
A first slurry was prepared containing 3.50x + 20% Si0271.6 ammonium heptamolybdate, 58.0x Nalco 40% silica sol and 3.4x phosphoric acid 42.5% solution.

Ferric nitrate at 36.4 pm, bismuth nitrate at 14.6 pm, cobalt nitrate at 39.3 pm, nickel nitrate at 21.8 pm, 10% potassium nitrate solution at 3.0 pm, 4 ．．
A second slurry was prepared containing 5 ml of indium chloride.

These slurries were combined and the solid catalyst was heat treated as described above. Example 29 80% B2,4 W Ship K MNi2
．． 5C.

4.5Fe3BiP〇. 5Mo, 0.8○ Boju 20%S
i○257.2 ammonium heptamolybdate and 4
．． 82 Tanabata ammonium gustate, (N ratio) 6W
7024. A slurry was prepared having 4.5 hours of boric acid, 3.5 hours of phosphoric acid 42.5% solution and 52.3 hours of Nalco 40% silica sol.

To this slurry, 36.4 days of ferric nitrate, 14.6 days of bismuth nitrate, 39.3 days of cobalt nitrate, 21.
A solution consisting of 8 hours of nickel nitrate and 3.0 hours of a 10% solution of potassium nitrate was added. The resulting slurry was evaporated and the solid was heat treated as described above. Acrylate by ammoxidizing propylene.

The results of experiments to produce nitriles are shown in Table V. The parentheses used in Table V have no particular meaning other than to emphasize the difference in catalyst. Table V *WWH is ○-0 30 From the above examples, the catalyst of the present invention has a high WWH.
It can be seen that a high conversion rate per pass can be obtained based on the WH value.

Examples 30-36 Ammoxidation of propylene Various catalysts of the present invention were manufactured as follows.

Example 30 80%Mn Cape K. ,Ni2.5Co4.5Fe3BiM
o, 20x and 20% Si02 Comparative Examples A and B
A similar method was used, except that a 10.74% wt solution of Mn(N03)25 was used instead of phosphorus.

Example 31 80% Th ship K. ,Ni2.5Co4.5Fe3BiM
o, 20x and 20% Si02 using the same method as above, except that instead of phosphorus, 16.56 pm Th(N03)
4.440 was used.

Example 3280% Zr〇. 5KMINi2.5Co4
．． 5Fe3BiMo, 20x and 20%Si02 method was used, except that 9.68 pm Zr was used instead of phosphorus.
OC12.8 day 20 was used.

Example 33 80% Y.

．． 5K. ．． ,Ni25Co4.5Fe3BjMo,20
× and 20% Si02 A similar method was used except that 10.96% of Y(N03) was used instead of phosphorus. Arc 20 was used.

The catalyst was ground and sieved to obtain 20-35 mesh sections and charged to a 5 cc reaction zone of a stainless steel tubular reactor.

1.8 of propylene/ammonia/oxygen/nitrogen/steam
Ammoxidation was performed using feeds of /2.2/3.6/2.4/6. The temperature of the enclosure 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 1.

Table W Examples 34-37 Ammoxidation of Isobutylene Various catalysts were prepared and tested for the ammoxidation of isobutylene to methachlorinitrile in a manner similar to that described above.

The reaction is isoptylene/ammonia/air/steam 1/
It was run at 400°C using a 1.5/11/4 feed. The apparent contact time was 3 seconds. All catalysts are 20% S
Contains i02. The results for methacrylonitrile are shown in Table W. *The catalyst was further heated at 650.0 for 2 hours.

** In addition to doing the same as *, I also reacted with 410.0. Example 38 Ammoxidation of propylene CrWo. 5KMM2.5Co4.5Fe2BiMo,
A catalyst with 20× was prepared and heat treated at 550 qC for 1 hour and at 600 qC for 2 hours.

Ammoxidation of propylene is carried out at a temperature of 44℃ in a 5cc reactor.
0°C, contact time 3 seconds, WWH 0.10, propylene ammonia/oxygen/nitrogen/water vapor 1.8/2.2/
A 3.6/2.4/6 feed was used. The propylene conversion rate was 96.8%, the selectivity to acrylonitrile was 86%, and the yield of acrylonitrile per pass was 83.2%.
%Met. Example 39 Ammoxidation of propylene The same machine as described in Example 38 was used, and 80% MnCr vessel KMNi2.5Co4.5Fe2BiMo,
Catalysts with 20× and 20% Si02 were prepared and 55
Heat treatment was performed at 0°C for 1 hour and at 600°C for 2 hours.

When this catalyst is used in the production of acrylonitrile, the The conversion rate of pyrene was 99.0%, the selectivity to acrylonitrile was 85.6%, and the yield per pass was 84.7%.
Example 40 Ammoxidation of propylene 80% CeW as described in Example 38.

．． 5K. ．． ,Ni2.5Co4.5Fe2BiMo,2
Catalysts with 0k and 20% Si02 were prepared and 550
00 for 1 hour. Propylene conversion rate 97
．． 8%, selectivity 85.1%, yield per pass 83.1%
Met. Example 41 Ammoxidation of propylene As described in Example 39, 80% PrWo. 5~. 3Ni2.5Co4. Zue2BjMo
, 20× and 20% Si02,
Used for ammoxidation of propylene.

99.2% conversion of propylene, yield per pass of 82
．． 7% and the selectivity was 83%. EXAMPLE 42 Ammoxidation of bropyrene Example 401 80% MnSb as described above.

．． 5KO. ,Ni2.5Co4.5Fe2BiMo,2
Catalysts with 0x and 20% SiQ were prepared and tested, but the reaction temperature was 42,000. Conversion of propylene is 100%, yield and selectivity per pass is 80%.
．． It was 4%. Examples 43-50 In a fluidized bed reactor with an internal diameter of 1-1'2'' having a perforated fluidized bed ammoxidation plate,
Ammoxidation of propylene was carried out using various catalysts of the invention containing 20% silica.

These catalysts were heat treated at 55,000 ℃ for 1 hour and then further heat treated for 2 hours at the temperature shown in the Table.
The reactor was charged with 395 cc of catalyst. Propylene/ammonia/air feed is 1/1.2/10.5;
WWH is 0.12, pressure is 1 s. s. i. g. The contact time was 5.5 seconds. The catalyst used and the results are shown in the table below. Dish Table Reference Examples 41-51 Oxidation of Isobutylene at Atmospheric Pressure Various catalysts of the present invention were prepared by the above method.

In a fixed bed reactor made of stainless steel pipe with an inner diameter of 0.8 cm,
5 cc of each catalyst produced above was added.

These catalysts were tested at a reaction temperature of 371 DEG C. using a 1/10/4 isoptylene/air/steam feed with an apparent contact time of 4 seconds. The results of these experiments are shown in Table X. Table MA Methacrolein MAA Methacrylic Acid Reference Examples 52-56 Oxidation of Isobutylene at High Pressure The various catalysts prepared above were used in the reaction at high pressure in the same manner as described above in Reference Examples 41-51.

Unless otherwise noted, pressure is 12p. s. i. g. And so.
The reaction temperatures and results are shown in Table X. The feed had the same composition as above, the apparent running time was 3.5 to 4 seconds, and the WWH was 0.098 to 0.159. Table X Reference Example 57 Ammoxidation of propylene Tao. 5Ko,. Ni2.5Co4.5Fe3BjM
Catalysts with o, 20x were prepared and tested for ammoxidation of propylene.

The yield per pass was 78.8%, the selectivity was 81%, and the propylene conversion was 97.4%. Embodiments of the invention are as follows.

'1' The catalyst according to claim 1, wherein the catalyst contains Mn+Sb.

(2) The catalyst according to claim 1, wherein the catalyst contains Mn+Cr.

{3' The catalyst according to claim 1, wherein the catalyst contains Pr+W.

'4} The catalyst according to claim 1, wherein the catalyst contains Mn+O.

3. The catalyst according to claim 2, wherein the catalyst contains Mn+Sb.

'61 The catalyst according to claim 2, wherein the catalyst contains Mn+Gr.

'7} The catalyst according to claim 2, wherein the catalyst contains Mn+W.

Claims (1)

[Claims] 1 General formula: X_aA_bD_cE_dFe_fBi_gMo_1_
2O_x [where A is an alkali metal, D is a mixture of Ni and Co, E is B, Sb or a mixture thereof, and X is Y, Zr, Th, Pr, Ge, Cr, S
n, 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 or equal to 0, d is 0 to 4, and c is 0. 1 to 20, and indicates the sum of the number of atoms of Ni and Co, f and g are 0.1 to 10, and x is required to satisfy the valence requirements of other elements present. is the number of oxygen. ] A medium for ammoxidation of olefin. 2 General formula: X_aA_bD_cE_dFe_fBi_gP_hMo
_1_2O_x [However, A is an alkali metal, D is Ni
and 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, d is 0 to 4, and c is 0.1 to 20, and indicates the sum of the number of atoms of Ni and Co, f and g are 0.1 to 10, h is greater than 0 and less than or equal to 4, and x is present. It is the number of oxygens required to meet the valence requirements of other elements. ] Catalyst for ammoxidation of olefin.