Method of preparing catalyst for oxidizing propylene to acroleine

专利摘要:

公开号:SU1253422A3
申请号:SU3358558
申请日:1981-11-25
公开日:1986-08-23
发明作者:Деррьян Жан-Ив；Белон Поль
申请人:Рон-Пуленк Эндюстри (Фирма)；
IPC主号:

专利说明:

The invention relates to methods for preparing catalysts for the oxidation of propylene, in particular to a method for preparing a catalyst based on oxide compounds of molybdenum or tungsten, bismuth, iron and cobalt.
The purpose of the invention is to provide safe working conditions, which is achieved by a certain sequence of preparation stages.
Example 1. Obtaining a catalyst of the formula Co Co. - Fe, Bi, 0,. o / i 1
Prepare the first aqueous solution.
ammonium heptamolybdate by dissolving 167.6 g (NH) gMOjOj -ЧН О in 760 cm of water at room temperature. To this solution, with stirring, a mixture of 72.5 cm of a density of 1.33 and 72.5 cm of water of the resulting solution of 0.8,
Filtered. A white crystalline solid is obtained which is molybdic acid (containing 93.8 g of MoOg).
The percentage of molybdenum precipitation is 97%.
HNO PH
Ammonium heptamolybdate NH ions are contained in the filtrate in the form of ammonium nitrate. Analysis of the filtrate shows that the NH ions are completely removed.
Prepare a suspension of this precipitate in 600 ml of water. The pH of the resulting suspension is 1.9.
A second aqueous solution is prepared by mixing 38.4 g of BKNOj) in 28.5 cm of НО, acidified with 4.5 cm of nitric acid and 32.1 g of FeCNOj) .9HjO in 25 cm of HjO.
This second aqueous solution is added with stirring to the suspension obtained above. The pH is 0.6. Then 94 g of CoGO in powder form are added with stirring. The release of CO is observed. At the end of the addition, the pH is 3.4. Stirring is continued for another 30 minutes.
Water is heated by heating to 80 ° C, and this temperature is maintained for 3 hours.
The paste thus obtained is dried at 20 hours. The dried product is calcined at 400 ° C for 6 hours. A solid product of the formula Co Mo ,, FejBijO j, which is the active phase, is emitted.
The solid product obtained after calcination is crushed to obtain a particle size below 400 microns. A glucose solution is then prepared.
a solution of 10 g of glucose in 100 cm of water at room temperature. 95 g of solid ground product is then added to this solution, then
heated to with good stirring for about 30 minutes. A drazer containing 433 g of enamelled rough alumina balls 4.8 mm in diameter heated
up to 70 ° C, pour the prepared pa-i suspension into it. The rotation of the drazer and the temperature are maintained until all the water is evaporated. Dried with balls that received
5 shell in this way. Then they are placed in a furnace for calcination with a thickness of 2-3 cm, then calcined at 480 ° C for 6 hours in a closed atmosphere. This first calcination results in
0 removal of glucose. After this calcination, the mixture is cooled slowly, then calcined at 480 ° C a second time. Thus, a finished catalyst is obtained, which contains approximately 18% of the active phase.
Example 2. Catalyst obtained.
In the first aqueous solution prepared according to Example 1, add
0
five
a mixture of 73 cm HNOj (density 1.33) and 146 cm BUT. The final pH is 1.3. Fil-: trumpet, a white crystalline solid is obtained, which is molybdic acid, containing 95.2 g of MoOj. The molybdenum precipitation percentage is 98.5%.
All NH ions. Contained in the filtrate as ammonium nitrate. Prepare a suspension of this sediment in
Q 750 ml of water. The pH is 1.8.
A second water solution is obtained by mixing 19.2 g of BKNOj), 5H O in 28.5 cm of water, acidified with 4.5 cm of nitric acid, and 16 g of Fe (NO,),
5 9Н20 to 25 cm.
This second aqueous solution is added to the suspension obtained above with stirring. The pH is now 1.3.
Then 75.1 g of cobalt carbonate is added, in the form of a powder, with stirring. The release of CO is observed. At the end of the addition stage, the pH is 2.8. Stirring is continued for another 30 minutes.
The mixture is evaporated at 3 h. The paste thus obtained is dried for 10 hours at PO C, and the dried product is calcined at 6 hours.
55
shine tverd-1
the product of the formula, which is COjMo, Fe., is an active phase.
The catalyst based on the active phase receive according to example 2.
The catalysts prepared in Examples 1 and 2 are tested during the oxidation of propylene to acrolein.
The oxidation process is carried out in a reactor with a height of 50 cm and 2.1 cm in diameter, containing tOO cm of catalyst.
number of moles of missing propylene number of moles of propylene on inlet
S., Is the selectivity of product X, i.e. an attitude
the number of moles of the formed product X ion. number of moles of converted propylene
fjf is the yield of product X. It is the product of Hu S.
The results of the tests of catalysts in the process of oxidation of propylene to acrolein in examples 1 and 2 are given in the table with the following abbreviated and mi C — propylene; A — acrolein; AA - acrylic acid; - acetaldehyde; - acetic acid. Example J. Getting
Co, o W «Fe, Bi, (.
Prepare an aqueous solution of ammonium para-tungstate by dissolving 248 g of (NH) W, j 0, 5HjO in 10 l of water; pH value 6.0. With stirring, 100 cm HKOj density of 1.33 is added to this solution.
The pH of the resulting solution is 1.22. Filter and obtain a white solid, crystalline substance, which is tungstic acid, containing 215 g of WOj. The deposition rate of tungsten is 97%.
12
57 57
36 36
in the form of DiepoxoBaTbK, glazed beads of aluminum hydroxide, coated to 18 wt.% with an active phase relative to the aggregate, the active carrier phase.
The reactor outlet gases are a mixture of nitrogen, oxygen, water, propylene, acrolein, acrylic acid, acetic acid, acetaldehyde, and carbon monoxide (CO, CO).
X is the conversion factor.
those. an attitude
100;
The ammonium NH ions of ammonium paratungstate are in the filtrate as ammonium nitrate. Analysis of the filtrate shows that all NH ions are removed. .
This precipitate is suspended in 600 ml of water; the pH value of the resulting suspension 2.
Prepare a second aqueous solution with the previous suspension with the addition of 38.4 g of Bi (NOj, 5Н „0 in 28.5 cm - -
HNO 23 cm
. -
acidified 4.5 cm
 W, and 32.1 g FeCNOj)
bf u n
Hjo.
This aqueous solution is added to the previous slurry. The resulting pH value is 0.7.
The following operations are carried out analogously to example 1. A net mass is obtained, which, processed according to a known technology, is converted into a catalyst of the formula Co W Her Bi 0.

360 400 355 390
1.2 74
1.2 69
188 84 7.7 3.1 3.5 0.8 92 81
284 82 11.5 2.61 3.2 0.7 93.5 78
Table continuation

权利要求:
Claims (1)
[1]
METHOD FOR PREPARING KATA-. LYSATOR FOR OXIDATION OF PROPYLENE TO ACROLEIN based on oxide compounds of molybdenum or tungsten, bismuth, cobalt glands, the composition of which corresponds to the empirical formula ^ ° 8-10 ^ ° t2 ^ ^е о.5 - *, 0
OR
C ° ₁₀ Fe _I BijO _x , ί where x is the number of oxygen atoms needed to saturate the valencies of the incoming elements, including mixing an aqueous solution of ammonium heptamolybdate or ammonium paratungstate with a solution of iron and bismuth nitrates, adding cobalt salt, drying and calcining, characterized in that , in order to ensure safe working conditions, an aqueous solution of ammonium heptamolybdate or ammonium paratungstate is acidified with nitric acid to a pH of 0.8-1.3, the resulting precipitate is suspended in water to a pH of 1.8-2.0, a solution is added to the resulting suspension p of iron and bismuth nitrates, then cobalt carbonate powder is added and the resulting mixture is evaporated.
1253422 AZ

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引用文献:

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US3232887A|1962-05-07|1966-02-01|Nalco Chemical Co|Stabilized aqueous solutions for use in impregnating catalyst carriers and method of making same|

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FR1604942A|1968-12-30|1971-05-15|Acrolein from propylene - by catalytic oxidation by oxygen and steam|

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FR1600128A|1968-12-30|1970-07-20|

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US3907712A|1970-05-26|1975-09-23|Nippon Catalytic Chem Ind|Catalyst composition for the preparation of unsaturated carbonyl compounds|

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US3875220A|1973-10-11|1975-04-01|Standard Oil Co Ohio|Process for the preparation of methacrylic acid from methacrolein|

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JPS575787B2|1975-09-05|1982-02-01|

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DE2735414A1|1976-08-06|1978-02-09|Nippon Zeon Co|OXYDATION OF OLEFINS|

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FR2364061B1|1976-09-14|1981-07-31|Rhone Poulenc Ind|

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US4224187A|1978-11-13|1980-09-23|Celanese Corporation|Olefin oxidation catalyst and process for its preparation|JPH07224439A|1994-02-14|1995-08-22|Oume Concrete Kogyo Kk|Side lump of manhole|

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SE502931C2|1994-06-10|1996-02-26|Sandvik Ab|Method for producing powder for WC hard material|

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DE19855913A1|1998-12-03|2000-06-08|Basf Ag|Multimetal oxide mass for the gas-phase catalytic oxidation of organic compounds|

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KR100497175B1|2003-03-26|2005-06-23|주식회사 엘지화학|Method for preparing catalysts for partial oxidation of propylene and iso-butylene|

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JP5869169B1|2015-06-01|2016-02-24|公立大学法人大阪府立大学|Perovskite oxide catalyst for oxygen evolution reaction|

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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FR8025261A|FR2495015B1|1980-11-28|1980-11-28|PROCESS FOR THE PREPARATION OF CATALYSTS BASED ON MOLYBDENE OXIDES AND / OR TUNGSTENE AND OXIDES OF OTHER METALS|

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