Method of producing oxide catalyst for oxidation or ammoxidation of propylene

专利摘要:
In the production of a Mo-Bi-Na composite oxide catalyst by the process comprising incorporating compounds as respective element sources into a composite and subjecting the composite to heating treatment in an aqueous system, bismuth oxide and/or bismuth subcarbonate are/is used as a Bi source compound and at least a part of the heat treatment is conducted at a temperature of 450 to 600°C. The activity of the catalyst is significantly improved by introducing Bi in the form of the specified water insoluble compound into the catalyst.
公开号:SU1598858A3
申请号:SU874202240
申请日:1987-03-23
公开日:1990-10-07
发明作者:Сарумару Кохеи；Ямамото Ецудзи
申请人:Мицубиси Петрокемикал Компани Лимитед (Фирма)；
IPC主号:

专利说明:

The invention relates to methods for preparing catalysts, in particular to methods for preparing oxide catalysts based on molybdenum and bismuth for oxidation in the production of acrolein from propylene or methacrolein, or isobuthen or tertiary butanol. paraphase ammoxidation reactions in the production of acrylonitrile from propylene or methacrylonitrile from isobutene.
The purpose of the invention is to obtain a catalyst with increased activity and selectivity due to the use of bismuth in the form of an oxide or basic carbonate in the form of a powder, as well as a certain temperature calcination.
Examples 400 ml of pure water dissolve 94.1 g of ammonium paramolybdate with heating. Then, in 60 ml of pure water, 7.18 g of iron (III) nitrate and 51.7 g of nickel nitrate are dissolved under heating. These two solutions are slowly mixed with each other with vigorous stirring. Thereafter, 0.85 g of borax is dissolved in 40 ml of pure water and the solution is added to the suspension. Next, 33.4 g of crushed silica (Karplex brand) and 51.7 g of bismuth oxide are added and the mixture is thoroughly mixed, and then evaporated to dry soil.
00 00
ate
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th residue. Thus obtained solid mass is subjected to heat treatment in an atmosphere of air at 300 ° C for 1 h to the oxide. The solid mass is formed into tablets with a diameter of 5 mm and a height of 4 mm using a small molding machine, and then calcined in a muffle furnace at 500 ° C for 4 hours to obtain a catalyst.
The catalyst composition calculated from the loaded raw materials is presented in the form of a composite oxide catalyst having the following ratios:
Mo: BI; Fe: NI: B: Na: Si: 0 12: 5: 0.4: 4: 0.2: 0.1:
: 24: 96.45.
An amount of 40 ml of this catalyst is loaded into a tubular stainless steel reactor having an inner diameter of 15 mm, and the oxidation reaction of propylene is carried out by passing a raw gas having a propylene concentration of 10%, a pair of 17% and air of 73% through a tube at atmospheric pressure and contact time 4.8 s.
At a reaction temperature of 290 ° C under real conditions, the following results of the reaction are obtained,%:
Propylene Conversion95.4
The output of acrolein80,8
Acrylic acid yield7.8
Total output 88.6
Note (comparative). The catalyst with the composition of Example 1 is prepared under the technological conditions of Example 1, but an aqueous solution is used in which 108 g of bismuth nitrate is dissolved in 98 ml of pure water, to which 12 ml of nitric acid is added.
Using this catalyst, the oxidation reaction of propylene is carried out under the same reaction conditions as in Example 1. The results are obtained at a reaction temperature of 290 ° C,%:
Propylene Conversion82,6
The output of acrolein66,2
Acrylic acid yield6.9
Total output73.1
PRI me R 3. In 400 ml of pure water, 94.1 g of ammonium paramolybdate dissolved in 400 ml of pure ammonia was dissolved. Then, in 60 ml of pure water, when n & heating, 7.18 g of iron (111) nitrate, 25.8 g of cobalt nitrate are dissolved. These two solutions are slowly mixed with each other with vigorous stirring.
To the stirred solution (suspension) is added a solution, in which 0.85 g of borax, 0.38 g of sodium nitrate and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water with heating, and the mixture is vigorously stirred. Then, 57.8 g of basic bismuth carbonate and 64 g of silicon oxide are added to the mixture and the whole is mixed. After heat drying the suspension is subjected to heat treatment at 300 ° C for 1 h in an atmosphere of air. The solid mass thus obtained is formed into tablets with a diameter of 5 mm and a height of 4 mm using a small molding machine, and 0 is then calcined in a muffle furnace at 480 ° C for 8 hours to obtain a catalyst. The compositional ratios of the metal-catalyst ingredients, calculated from the loading of the starting materials, are illustrated by a composite oxide having the following atomic ratios: Mo: Bi: Co: Ni: Fe: Na: B: K: Si: 0 12: 5: 2: 3: 0.4: 0.2: 0.2: 0.08: 24: 95.54.
Using this catalyst in real conditions, the oxidation reaction of propylene is carried out in the same reactor as in example 1 by passing a feed gas containing propylene at a concentration of 12%, water vapor at a concentration of 10% and 5 air at a concentration of 78%. through the reactor at ordinary pressure, with a contact time of 4.2 seconds.
At a reaction temperature of 290 ° C, the following results are obtained,%: Propylene conversion of 99.5
The output of acrolein 89,7
The output of acrylic acid5,1
Total output 94,8
PRI me R 4 (comparative). A catalyst 5 having the same composition as in example 3 was prepared according to the method of example 3, but instead of bismuth oxide used in (as raw material in example 1, an aqueous solution is used in which 0 108 g of bismuth nitrate is dissolved 98 ml of pure water, to which 12 ml of nitric acid is added.
Using this catalyst
the propylene oxidation reaction is carried out
5 under the same reaction conditions as in
example 3. The results obtained with
reaction temperature 290 ° С,%:
Propylene Conversion97.2
The output of acrolein88,0
0 Exit Acrylic Acid4,1
Total output: 92.1
Example 5. In 400 ml of pure water, 94.1 g of ammonium paramolybdate are dissolved with heating. Then, 5.8 g of ammonium para-tungstate are added and the mixture is stirred.
After that, 17.9 g of iron (III) nitrate, 51.7 g of cobalt nitrate, 0.38 g of sodium nitrate, 0.85 g of borax and 0.27 g of potassium nitrate are dissolved in 100 ml of pure water. These two
the solution is slowly mixed with each other with vigorous stirring. Then, 62.0 g of bismuth oxide and 64.0 g of silicon oxide are added to the stirred solution and the mixture is stirred. 8 real conditions of the catalyst are then obtained according to the method of example 1.
The catalyst composition calculated from the loaded raw materials is represented by the following atomic ratios for the metals-ingredients of the composite oxide:
Mo: Bi: Fe: CO: W: B: Na: K: Si: 0 12: 6: 1: 4: 0.5: 0.2: 0.2: 0.06: 24: 100.43.
Using this catalyst, the oxidation reaction of propylene is carried out as in Example 3. The following results are obtained at a reaction temperature of 290 ° C,%: Propylene propylene 98.0
Acrolein yield 88.9
Acrylic acid4.8
Total output93,7
Note 94.1 g of ammonium paramolybdate are dissolved in 400 ml of pure water with heating. 7.18 g of iron (III) nitrate, 25.8 g of cobalt nitrate and 38.7 g of nickel nitrate are then dissolved in 60 ml of pure water with stirring. These solutions are slowly mixed with each other with vigorous stirring.
To the stirred solution (suspension) is added a solution in which 0.85 g of borax, 0.38 g of sodium nitrate and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water with stirring. Thereafter, 51.7 g of bismuth oxide and 64 g of silicon oxide are added to the mixture and the whole is mixed. After heat drying the suspension is subjected to heat treatment at 300 ° C for 1 h in an atmosphere of air. The solid mass thus obtained is formed into tablets with a diameter of 5 mm and a height of 4 mm using a small molding machine, and then calcined in a muffle furnace at 500 ° C for 4 hours to obtain a catalyst. The compositional ratios of metals to catalyst ingredients, calculated from the loading of raw materials, are illustrated by a composite oxide having the following atomic ratios:
Mo: Bi: Co: Ni: Fe: Na: B: K: Si: 0 12: 5: 2: 3: 0.4: 0.2: 0.2: 0.08: 24: 97.54.
Using this catalyst under real conditions, the propane ammoxidation reaction is carried out in the same reactor as in example 1, passing a feed gas containing 4.3% propylene, 10.1% ammonia, 34.2% water vapor
and 51.9% of the cart, through the reactor at atmospheric pressure with a contact time of 2.9 s.
The following reaction results are obtained when the reaction temperature is.%:
Propylene Conversion58.3
The output of acrylonitrile 48,7
/ Acrylonmtril Selectivity83,5
PRI me R 7 (comparative). A catalyst having the same composition as Example 6 was prepared according to Example 6, but instead of bismuth oxide used as bismuth raw material, an aqueous solution is used in which 108 g of bismuth nitrate is dissolved in 98 ml of pure water, to which 12 ml of nitric acid are added. Using this catalyst, the propylene ammoxidation reaction is carried out in 8 reaction conditions according to Example 6. The following results are obtained,% Propylene conversion 47.7
The output of acrylonitrile 40,8
Acrylonitrile selectivity 85,7
As follows from the presented data, the proposed method of preparation allows to obtain a catalyst with increased activity and selectivity, conversion of propylene in the process of oxidation of propylene increases to 95.4-98.5% when the output of acrolein is 80.8-89.7%, in the process of ammoxidation propylene conversion increases to 58.3% versus 47.7% with an acrylonitrile selectivity of 83.5%.

权利要求:
Claims (1)
[1]
Invention Formula
A method of preparing an oxide catalyst for the oxidation or ammoxidation of propylene based on molybdenum and bismuth, corresponding to the empirical formula
Mai2Bi5-6Co2-jr llo-dFeo.-i.oNao.i-o, 2 Ko.06-o.oe lo.oa-o.7Si2jO
where I is boron, tungsten or their mixture;
X is the number of oxygen atoms required to saturate the valence of the input elements by mixing the compounds of these active components in an aqueous medium, drying, shaping and calcining, characterized in that, in order to obtain a catalyst with increased activity and selectivity, bismuth bismuth oxide or basic carbonate is used in the form of a powder and calcination is carried out at 480-500 ° C.

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP61065279A|JPH0587299B2|1986-03-24|1986-03-24|

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