JPS6242654B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an ammoxidation catalyst. Oxidation catalysts are already known, for example, in US Pat. No. 3,642,930 and US Pat. No. 3,414,631. 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 X _a A _b D _c E _d F _f B _g Mo _{12 O} It is a mixture, and X is Y, Zr, 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 to 20, and d is 0 to 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 represented} by the _{general formula :} , 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. ] The present invention relates to an olefin ammoxidation catalyst shown in the following. 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 ammoxidation 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. Specific Examples Comparative Examples A and B and Reference Examples 1 to 34 Comparison of Base Catalyst and Catalyst Comprising Cocatalyst of the Invention A 5 c.c. fixed bed reactor was constructed from stainless steel tubing with an internal diameter of 8 mm. The catalyst prepared as described below was charged to the reactor and heated to 420° C. under a flow of air. At the reaction temperatures of Comparative Example B and Reference Examples 1 to 34, propylene/ammonia/oxygen/nitrogen/
WWW where a reactant composition with water vapor of 1.8/2.2/3.6/2.4/6 was fed onto the catalyst with a contact time of 3 seconds.
(defined as the amount of olefin fed per weight of catalyst per hour) was 0.10 in this reaction. In comparative example A, propylene/
The ratio of ammonia/oxygen/nitrogen/steam is 1/
Using a reactant feed of 1.1/2.1/7.9/4,
The contact time was 6 seconds. WWH was 0.03.
This comparative example was included to demonstrate the basic catalyst working under normal operating conditions at low WWH. The catalyst was manufactured as follows. _{Comparative Examples A and B} 80 _{% K0.1Ni2.5Co4.5Fe3BiP0.5Mo12Ox + 20 %}
An aqueous solution of 127.1 g of SiO ₂ ammonium heptamolybdate (NH ₄ ) ₆ Mo ₇ O _{24.4H 2} O was prepared. To this solution, 6.9 g of H ₃ PO ₄ 42.5% solution and 102.7 g of Nalco 40% silica sol were added to form a slurry. Separately,
72.7 g of ferric nitrate, Fe(NO ₃ ) ₃ ·9H ₂ O, and 29.1
g of bismuth nitrate, Bi(NO ₃ ) _{3.5H 2} O, 78.7 g
of cobalt nitrate, Co(NO ₃ ) ₂ ·6H ₂ O, 63.6 g
of nickel nitrate, Ni(NO ₃ ) _{2.6H 2} O and 6.1 g of
An aqueous solution containing 10% potassium sulfate 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 heated at 290°C for 3 hours, 425°C for 3 hours, and 550°C.
It was heated for 16 hours. _Reference example 1 _{80%Ge 0.6 K 0.1 Ni 2.5 Co 4.5} Fe ₃ BiP _{0.5 Mo 12} Ox+20
%SiO ₂ 63.56 g of ammonium heptamolybdate was added to 60 c.c.
dissolved in warm water. Add 53.25g of this solution to
Added to 40% silica sol. The mixture was heated on low heat for about 5 minutes with constant stirring. 3.46 g of a 42.5% H ₃ PO ₄ solution was added to the resulting slurry and the mixture was heated for 2 minutes. Separately, 36.36 g of ferric nitrate was mixed with 10 c.c. of water and melted on a hot plate with constant stirring.
After waiting for the previously added metal nitrate to melt, 14.55 g of bismuth nitrate, 39.29 g of cobalt nitrate, and 21.80 g of nickel nitrate were successively added.
Combine 3.03g _KNO3 10% solution and _1.88g GeO2
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. Stir this mixture occasionally
Dry in an oven at 120°C. Dry catalyst at 550℃
Calcined for 16 hours. Reference Examples 2 to 26 Other catalysts of this reference example were produced in the same manner as the catalyst of reference 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 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 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. _{Reference example 27 80%Ga 1.0 K 0.1 Ni 2.5 Co 4.5 Fe 3 BiP 0.5 Mo 14 Ox ＋} 20
%Sio ₂ In the same manner as described in the above reference example, 24.7 g of ammonium heptamolybdate and 19.4 g of Nalco 40%
A first slurry containing silica and 1.15 g of a 42.5% H ₃ PO ₄ solution was used to prepare the catalyst. The second slurry contains 12.1 g of ferric nitrate, 4.8 g of bismuth nitrate, 13.1 g of cobalt nitrate, 7.3 g of nickel sulfate, 1.0 g of a 10% solution of potassium nitrate, and 2.5 g of ferric nitrate.
g of gallium nitrate, Ga(NO ₃ ) _{3.3H 2} O. These slurries were combined, evaporated and heat treated as above. _{Reference example 28} 80%In _{1.0 K 0.1 Ni 2.5} Co _4.5 Fe ₃ BiP _0.5 Mo _13.5 Ox _＋ 20
% SiO ₂ 71.6 g of ammonium heptamolybdate and 58.0
g of Nalco 40% silica sol and 3.4 g of phosphoric acid 42.5
% solution was prepared. 36.4g
of ferric nitrate, 14.6 g of bismuth nitrate, and 39.3
g of cobalt nitrate, 21.8 g of nickel nitrate,
A second slurry was prepared containing 3.0 g of a 10% solution of potassium nitrate and 4.5 g of indium chloride. These slurries were combined and the solid catalyst was heat treated as described above. _{Reference example} 29 80 _{% B2.4 W0.6 K0.1}
Ni _2.5 Co _4.5 Fe _{3 BiP 0.5} Mo _10.8 Ox + _{20 %} SiO ₂ 57.2 _g of ammonium heptamolybdate and 4.8
g of ammonium heptatungstate,
(NH ₄ ) ₆ W ₇ O ₂₄・6H ₂ O, 4.5 g of boric acid, and 3.5
A slurry was prepared having 52.3 g of Nalco 40% silica sol and 52.3 g of 42.5% phosphoric acid solution. to this slurry
A solution consisting of 36.4 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 1 shows the results of an experiment in which acrylonitrile was produced by ammoxidizing propylene. The words used in Table 1 have no particular meaning other than to emphasize the difference in catalyst.

【table】

[Table] From the reference example above, it can be seen that by using the reference catalyst, a high conversion rate per pass can be obtained with a high WWH value. Reference Examples 30 to 33 Reference catalysts for ammoxidation of propylene were produced as follows. _Reference example 30 _{80%Mn 0.5 K 0.1 Ni 2.5} Co _4.5 Fe ₃ BiMO _{12 Ox} and
20% SiO ₂ The same method as in Comparative Examples A and B was used, but
However, instead of phosphorus, 10.74 g of Mn (NO ₃ ) ₂ 50% by weight
A solution was used. _{Reference example 31 80% Th 0.5 K 0.1 Ni 2.5 Co 4.5 Fe 3 BiMO 12 Ox and 20}
% _SiO2A similar method was used as above, but instead of phosphorus
16.56g _of Th( _NO3 ) _4.4H2O was used. _Reference example 32 _{80% Zr 0.5 K 0.1 Ni 2.5 Co 4.5} Fe ₃ BiMO ₁₂ Ox and 20
% _SiO2A similar method was used, but instead of phosphorus 9.68
g of ZrOCl ₂ .8H ₂ O was used. _{Reference example 33 80% Y 0.5 K 0.1 Ni 2.5 Co 4.5 Fe 3 BiMO 12 Ox and 20}
% _SiO2A similar method was used, but instead of phosphorus, 10.96
g of Y(NO ₃ ) ₃ ·5H ₂ O was used. The catalyst was crushed and sieved into 20-35 mesh sections and charged into a 5 c.c. reaction zone of a stainless steel tubular reactor. Propylene/Ammonia/
Ammoxidation was carried out using a 1.8/2.2/3.6/2.4/6 feed of oxygen/nitrogen/steam. The temperature of the bath surrounding the reactor was maintained at 420°C, with an apparent contact time of 3
Seconds. The results of these experiments are shown in Table 1.

[Table] Reference Examples 34 to 37 Ammoxidation of isobutylene Various catalysts were produced in the same manner as above and tested for ammoxidation of isobutylene to methacrylonitrile. The reaction was carried out at 400° C. using a 1/1.5/11/4 feed of isobutylene/ammonia/air/steam. The apparent contact time was 3 seconds. All catalysts contained 20% _SiO2 . The results for methacrylonitrile are shown in Table 1.

[Table] Reference Example 38 Ammoxidation of propylene A catalyst containing CrW _0.5 K _{0.1 Ni 2.5} Co _{4.5 Fe 2} BiMo ₁₂ Ox was produced and heat treated at 550°C for 18 hours and at 600°C for ₂ hours _. did. Ammoxidation of propylene was carried out in a 5 c.c. reactor at a temperature of 440°C, a contact time of 3 seconds, and a WWH of 0.10.
The experiments were carried out using propylene/ammonia/oxygen/nitrogen/steam feeds of 1.8/2.2/3.6/2.4/6. The conversion rate of propylene was 96.8%, the selectivity to acrylonitrile was 86%, and the yield of acrylonitrile per pass was 83.2%. Reference Example 39 Ammoxidation of propylene Same as described in Reference Example 38, 80%
MnCr _{0.5 K 0.1 Ni 2.5 Co 4.5 Fe 2} BiMo ₁₂ Ox and 20%
Prepare a catalyst with SiO ₂ at 550 °C for 16 hours and
Heat treatment was performed at 600°C for 2 hours. When this catalyst was used to produce acrylonitrile, the conversion rate of propylene was 99.0%, and the selectivity to acrylonitrile was 85.6%.
%, yield per pass was 84.7%. Reference Example 40 Ammoxidation of propylene 80% as described in Reference Example 38
_{GeW 0.5} ^- _{K 0.1} Ni _{2.5 Co 4.5 Fe 2 BiMo 12} Ox and 20%
A catalyst containing SiO ₂ was prepared and heat treated at 550°C for 16 hours. Propylene conversion rate 97.8%, selectivity 85.1
%, yield per pass was 83.1%. Reference Example 41 Ammoxidation of propylene Same as described in Reference Example 39, 80%
PrW _0.5 ^- K _0.3 Ni ₂ . ₅ Co ₄ . ₅ Fe ₂ BiMo ₁₂ Ox and 20
% _SiO2 was prepared and used for ammoxidation of propylene. 99.2% of propylene was converted, yield per pass was 82.7%, and selectivity was 83%. Reference example 42 Ammoxidation of propylene 80% in the same manner as described in reference example 40
_{MnSb 0.5} ^- K _0.1 Ni _{2.5 Co 4.5 Fe 2} BiMo _{12 Ox} and 20
% SiO ₂ was prepared and tested, but the reaction temperature was 420°C. The conversion rate of propylene is
At 100%, yield and selectivity per pass is 80.4%
It was hot. Reference Examples 43-50 Fluidized Bed Ammoxidation Ammoxidation of propylene was carried out using reference catalysts containing 20% silica in a 1-1/2" internal diameter fluidized bed reactor with perforated plates. These catalysts is 550
C. for 16 hours, and then further heat treated for 2 hours at the temperatures shown in Table 1. The reactor was charged with 395 c.c. of catalyst. Propylene/Ammonia/
Air feed is 1/1.2/10.5 and WWH is
The contact time was 5.5 seconds at a pressure of 0.12 psig. The catalysts used and the results are shown in the table.

[Table] Examples 1 to 4 and Reference Examples 51 and 52 Example ₁ Cs _{0.05 K 0.1 Ni 7} Fe ₂ Mn ₂ BiCr _0.5 Mo ₁₂ O ₄₈ +20%
SiO ₂ Fe (NO ₃ ) ₂・9H ₂ O (24.24 g) was dissolved in a small amount of water while heating, and 50% Mn was added to the resulting aqueous solution.
(NO ₃ ) ₂ aqueous solution (10.74g), Bi(NO ₃ ) ₂・5H ₂ O
(14.55g), Ni(NO ₃ ) ₂・6H ₂ O (61.07g), 10%
Slurry A was obtained by sequentially adding a KNO ₃ aqueous solution (3.03 g) and a 10% CsNO ₃ aqueous solution. Separately (NH ₄ ) ₆ Mo ₇ O ₂₄・
4H ₂ O (63.56 g) was dissolved in 200 ml of water, and silica sol (NALCO 2327, 40%,
Solution B was obtained by sequentially adding NH ₄ ⁺ ) (51.52 g) and CrO ₃ (1.50 g). Slurry A was added to solution B, and the resulting slurry was heated and evaporated at 290°C for 3 hours.
Then, it was dried by heating at 425°C for 3 hours. The dried catalyst was calcined at 550°C for 16 hours. Example 2 _{Cs 0.05} K _0.1 Co _{7 Fe 2 Mn 2 BiCr 0.5 Mo 12 O 48 + 20} %
SiO ₂ Ni(NO ₃ ) ₂・6H ₂ O (61.07g) was converted to Co(NO ₃ ) ₂・
A catalyst of the present invention was obtained in the same manner as in Example 1 except that 6H ₂ O (61.12 g) was used. Reference example _{51 Cs 0.05} K _0.1 Ni _2.5 Co _4.5 Fe ₂ MnBiCr _{0.5 Mo 12 O 48 +20}
%SiO ₂ Ni (NO ₃ ) Ni instead of ₂・6H ₂ O (61.07g)
(NO ₃ ) ₂・6H ₂ O (21.81g) and Co(NO ₃ ) ₂・
The title catalyst was obtained in the same manner as in Example 1, except that 6H ₂ O (39.29 g) was used. Example 3 Cs _0.05 KNi ₇ Fe ₂ Mn ₂ BiCr _{0.5 Mo 12} O ₄₈ +20% _{SiO 2} KNO ₃ instead of 10% KNO ₃ aqueous solution (3.03 g)
A catalyst of the present invention was obtained in the same manner as in Example 1 except that (3.03 g) was used. Example 4 Cs _0.05 KCo ₇ Fe ₂ Mn ₂ BiCr _0.5 Mo ₁₂ O ₄₈ +20%SiO ₂ Ni(NO _{3 ) 2.6H 2} O (61.07g) replaced with Co
Example 3 except that (NO ₃ ) ₂ ·6H ₂ O (61.12 g) was used.
A catalyst of the present invention was obtained in the same manner as described above. Reference example 52 Co _{0. 05} KNi _{2. 5} Co _{4. 5} Fe ₂ MnBiCr _{0. 5} Mo ₁₂ O ₄₈ +20%
SiO ₂ Ni (NO ₃ ) Ni instead of ₂・6H ₂ O (61.07g)
(No ₃ ) ₂・6H ₂ O (21.81g) and Co (NO ₃ ) ₂・
The title catalyst was obtained in the same manner as in Example 3 except that 6H ₂ O (39.29 g) was used. Each catalyst was ground and sieved to obtain 20-35 mesh particles. The catalyst particles were charged into a 5 c.c. reaction zone of a stainless steel tubular reactor. Propylene/Ammonia/Oxygen/Nitrogen/Water vapor 1.8/
Ammoxidation was performed using feeds of 2.2/3.6/2.4/6. The temperature of the bath surrounding the reactor was maintained at 420°C, giving an apparent contact time of 3.1 seconds. The results of these experiments are shown in Table 1.

【table】

Claims (1)

[Claims] 1 General formula: X _a A _b D _c E _d Fe _f B i _g Mo ₁₂ O _x [However, A is a mixture of alkali metals, and D
is Ni or Co, E is B, Sb or a mixture thereof, X is Y, Zr, 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 to 20, and d is 0 to 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 olefin shown by: 2 General formula: X _a A _b D _c E _{d Fe f} B i g P _h Mo _{12 O} It is a mixture, 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 olefin shown by: