JP2003205240A - Method of manufacturing complex oxide catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a catalyst having improved catalytic performance such as a raw material conversion or selectivity for a selective reaction such as a vapor phase catalytic oxidation reaction for producing acrolein or metacrolein from propylene. <P>SOLUTION: In the method of manufacturing a molybdenum-bismuth complex oxide catalyst in a water system through a process including incorporation and heating, the complex oxide catalyst that gives an desired oxide product having high activity with high yield is obtained by preparing through a pre- process for manufacturing a catalytic precursor powder by heating a dried material obtained by drying a raw material salt aqueous solution containing at least one of molybdenum, iron, nickel or cobalt, and silica as a part of compounds which are supply sources of each component in the complex oxide catalyst, and after that, through a post-process that is drying and firing for incorporating the catalytic precursor powder and a bismuth compound with a water based solvent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, and a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene. , And a method for producing a composite oxide catalyst used for a selective reaction such as a gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene.

[0002]

2. Description of the Prior Art Gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butadiene from butene. It is well known that a molybdenum-bismuth-based complex oxide catalyst is a useful catalyst in a selective reaction such as a gas-phase catalytic oxidative dehydrogenation reaction to be produced, and it is industrially widely used. .

Patent documents relating to the composition and manufacturing method of the molybdenum-bismuth-based composite oxide catalyst in these various reactions include Japanese Patent Publication Nos. 39-3670 and 48-48.
1645, 48-4763, 48-1
7253, 49-3498, 55-4
No. 1213, No. 56-14659, No. 56-
No. 23969, No. 56-52013, No. 57.
-26245, JP-A-48-503, 4
No. 8-514, No. 48-52713, No. 48
-54027, 48-57916, and 5
No. 5-20610, No. 55-47144, No. 55-84541, No. 59-76541,
Many publications such as JP-A-60-122041 are known.

Among these, some examples of the production method are given, for example, Japanese Patent Publication No. 43-22746, a method of adding an aqueous solution of bismuth citrate to an aqueous solution of molybdic acid, Japanese Patent Publication No. 53-10387. JP-A-5
JP-A-3-10388 and JP-B-55-12298 disclose a method of adding a bismuth compound in a solid state to a molybdic acid aqueous solution, and JP-B-59-51848 discloses p.
A method of simultaneously adding an aqueous solution of a bismuth salt and aqueous ammonia to an aqueous solution of molybdic acid having H in the range of 6 to 8, JP-B-5
9-51849, a method of adding an aqueous solution of a bismuth salt to a suspension of a molybdenum compound, JP-A-55-13.
No. 187, JP-A-55-47144 and JP-B-60-29536 disclose various methods for forming various molybdates in advance, and JP-B-52-22359 and JP-B-52-47435 disclose various methods. A method of forming a bismuth compound in advance, a method of using bismuth oxide or bismuth subcarbonate as a bismuth source in JP-A-62-23548, and at least one of iron, bismuth and tellurium in JP-A-2-59046. A method of adjusting a slurry containing a molybdenum compound to a range exceeding pH 7;
In JP-A-2-214543, a chelating agent is added to a slurry containing a molybdenum compound containing silica to adjust the pH to 6
A method of adjusting the above, JP-A-2-251250 discloses a method of mixing a bismuth compound after adjusting a slurry containing molybdenum to pH 6 or more.

Further, JP-A-1-168344 discloses a method of adding an iron molybdate gel, JP-A-9-
Japanese Patent No. 10588 discloses a method of mixing molybdenum and iron in advance, and Japanese Patent Application Laid-Open No. 12-37631 discloses a method of mixing a molybdenum compound and a specific metal compound under specific conditions and mixing the iron compound to produce the compound. Has been done.

[0006]

As described above, various methods such as devising a method of mixing an aqueous molybdenum solution and a bismuth compound or devising a method of mixing molybdenum and iron in order to improve the performance of the catalyst have been proposed. Proposed. However, when these methods are applied to the production of a molybdenum-bismuth-containing composite oxide catalyst containing at least one metal element selected from the group consisting of divalent metal elements and trivalent metal elements, the target oxidation The product yield was not always satisfactory.

Therefore, the present invention provides a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and An object of the present invention is to provide a catalyst used in a selective reaction such as a gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene, which has further improved catalytic performance such as raw material conversion rate and selectivity.

[0008]

In order to solve the above-mentioned problems, the present invention integrates a composite oxide catalyst represented by the following general formula (1) in an aqueous system of a source compound of each component element. In the method of producing through a step including oxidization and heating, at least one of molybdenum, iron, nickel or cobalt as a part thereof, and a raw material salt aqueous solution containing silica are dried to obtain a catalyst by heat treatment. After undergoing the pre-process for producing the precursor powder, the catalyst precursor powder and the bismuth compound are integrated with an aqueous solvent, dried, and calcined to prepare a post-process to obtain a highly active and desired oxidation product. It was found that a composite oxide catalyst that gives a product in a high yield can be obtained. Mo _a Bi _b Co _c Ni _d Fe _e X _f Y _g Z _h Si _i O _j (1) (In the formula, X is magnesium (Mg), calcium (C
a), at least one element selected from the group consisting of zinc (Zn), cerium (Ce) and samarium (Sm), and Y is sodium (Na), potassium (K), rubidium (Rb), cesium ( Cs) and thallium (T
l) is at least one element selected from the group consisting of, and Z is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As) and tungsten (W). . Further, a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5 to 7 and c =
0-10, d = 0-10 (however, c + d = 1-10), e
= 0.05-3, f = 0-2, g = 0.04-2, h =
It is in the range of 0 to 3, i = 5 to 48, and j is a numerical value that satisfies the oxidation states of other elements. )

In the present invention, the preferable heating temperature in the previous step is 200 to 400 ° C.

In the latter step, it is preferable to add aqueous ammonia when the catalyst precursor and the bismuth compound are mixed in the aqueous solvent.

Further, the firing in the subsequent process is carried out at a temperature of 450.
It is preferably carried out in the range of up to 600 ° C.

As a supply source of bismuth, at least one of bismuth oxide and bismuth subcarbonate, bismuth subcarbonate in which at least a part of required Na is dissolved, and a complex carbonic acid of Bi and X containing at least a part of X component. Bi containing a salt compound, at least a part of each of the required Na and X components
And a complex carbonate compound of Na and X can be used.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material salt aqueous solution used in the previous step in the production method of the present invention is an aqueous solution, water slurry or cake containing at least one of molybdenum, iron, nickel or cobalt as a catalyst component, and silica.

The raw material aqueous solution is prepared by integrating the source compounds in an aqueous system. In this invention,
The integration of the source compound of each component element in the aqueous system means collectively or stepwise mixing or aging treatment, mixing and aging treatment of the aqueous solution or dispersion of the source compound of each component element. Say. That is, (a) a method of collectively mixing the above-mentioned respective source compounds, (b) a method of collectively mixing the above-mentioned respective source compounds, and a aging treatment,
(C) A method of stepwise mixing the above-mentioned respective source compounds,
(D) The method of repeating the stepwise mixing and aging treatment of each of the above-mentioned source compounds, and the method of combining (a) to (d) are both integrated in the aqueous system of the source compound of each component element. It is included in the concept of incarnation. Here, aging means that industrial raw materials or semi-finished products are treated for a certain period of time under a certain condition such as a certain temperature to obtain required physical properties, chemical properties, increase or progress of a predetermined reaction. Good operation,
The constant time in the present invention is usually in the range of 10 minutes to 24 hours, and the constant temperature is usually room temperature to the boiling point range of the aqueous solution or the aqueous dispersion. As a specific method of the above integration, for example, a solution obtained by mixing an acidic salt selected from the catalyst component, and a solution obtained by mixing a basic salt selected from the catalyst component And the like. Specific examples thereof include a method of adding a mixture of an iron compound and a nickel compound and / or a cobalt compound to an aqueous solution of a molybdenum compound, and mixing silica.

The raw salt aqueous solution (slurry) containing silica thus obtained is sufficiently stirred and then dried.
There is no particular limitation on the drying method and the state of the obtained dried product, and for example, a powdery dried product may be obtained by using an ordinary spray dryer, a slurry dryer, a drum dryer, or the like, and an ordinary box. A block-shaped or flake-shaped dried material may be obtained using a mold dryer or a tunnel-type baking furnace.

The dried granules or cakes are in air at 200 to 400 ° C., preferably 250 to 350.
Heat treatment is performed in the temperature range of ℃ for a short time. The type and method of the furnace at that time are not particularly limited, and for example, the dried product may be heated in a fixed state using an ordinary box-type heating furnace, tunnel-type heating furnace, or the like, or a rotary kiln. Alternatively, the dried product may be heated while flowing.

In the subsequent step in the manufacturing method of the present invention,
The catalyst precursor powder obtained in the previous step and the bismuth compound are mixed in an aqueous solvent. At this time, it is preferable to add aqueous ammonia. Further, the bismuth supply source compound of the present invention is bismuth that is sparingly soluble to water and insoluble. This compound is preferably used in the form of a powder. Although these compounds as a raw material for producing a catalyst may have particles larger than powder, smaller particles are preferable in view of a heating step for causing thermal diffusion thereof. Therefore, if these compounds as raw materials were not such small particles, crushing should be done before the heating step.

Next, the resulting slurry is thoroughly stirred and then dried. The dried product thus obtained is shaped into an arbitrary shape by a method such as extrusion molding, tablet molding, or carrier molding. Then, this one, preferably 4
It is subjected to a final heat treatment for about 1 to 16 hours under a temperature condition of 50 to 600 ° C.

As described above, a composite oxide catalyst having high activity and giving a desired oxidation product in a high yield can be obtained.

Specific examples of the method for producing the composite oxide catalyst according to the present invention will be described below. First, an aqueous solution of a suitable molybdenum compound, preferably ammonium molybdate,
An aqueous solution of iron, cobalt and nickel compounds, preferably their respective nitrates, is added. Furthermore, sodium, potassium, rubidium, thallium, boron, phosphorus, arsenic,
And / or compounds of tungsten, preferably the respective water-soluble salts, are added as their aqueous solution. Add more silica. Next, the obtained slurry is sufficiently stirred and then dried. The dried granules or cakes are in air at 200 to 400 ° C, preferably 250 to 3
Heat treatment is performed in a temperature range of 50 ° C. for a short time.

Next, this is dispersed in water, preferably ammonia water is added, and then bismuth powder is added. The bismuth powder is composed of (1) at least one of bismuth oxide and bismuth subcarbonate, (2) bismuth subcarbonate in which at least a part of required Na is dissolved, and (3) Bi and X containing at least a part of components. Complex carbonate compound or (4) A complex carbonate compound of Bi, Na and X containing at least part of each of the required Na and X components.

Next, the obtained slurry is thoroughly stirred and then dried. The dried product thus obtained is shaped into an arbitrary shape by a method such as extrusion molding, tablet molding, or carrier molding.

Next, this is preferably 450 to 6
A final heat treatment is performed for about 1 to 16 hours under the temperature condition of 00 ° C.

The thus-prepared complex oxide catalyst is a gas phase catalytic reaction for producing acrolein from propylene and methacrolein from isobutene or tertiary butanol, acrylonitrile from propylene and methacrylonitrile from isobutene. It can be used for a gas-phase catalytic ammoxidation reaction and a gas-phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene.

For example, the gas phase catalytic oxidation reaction for producing acrolein from propylene is as follows: 1 to 10% by volume of propylene, 5 to 18% by volume of molecular oxygen, 0 to 60% by volume of steam and 20-70% by volume
Of an inert gas such as nitrogen or carbon dioxide on the composite oxide catalyst prepared as described above.
It is carried out by introducing under a temperature range of 50 to 450 ° C. and a pressure of atmospheric pressure to 10 atmospheres with a contact time of 0.5 to 10 seconds.

[0026]

EXAMPLES A more specific method for producing a composite oxide catalyst according to the present invention and the results of carrying out an oxidation reaction of propylene using the obtained composite oxide catalyst are shown below.

Example 1 (Preparation of complex oxide catalyst) Ammonium paramolybdate 9
4.1 g is heated and dissolved in 400 ml of pure water. Next, 7.18 g of ferric nitrate, 25.8 g of cobalt nitrate and 37.8 g of nickel nitrate are heated and dissolved in 60 ml of pure water. These solutions are gradually mixed with thorough stirring. Next, 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water under heating and added to the above slurry. Next, 64 g of silica is added and sufficiently stirred. After drying this slurry by heating,
It is subjected to heat treatment at 00 ° C./1 hour. The obtained granular solid is crushed, and 10 ml of aqueous ammonia is added to 150 ml of pure water to disperse. Next, 58.1 g of bismuth subcarbonate containing 0.45% Na as a solid solution is added and mixed with stirring. After drying this slurry by heating, the obtained granular solid is tablet-molded by a small molding machine into a tablet having a diameter of 5 mm and a height of 4 mm, and then 500 ° C.
It was calcined for / 4 hours to obtain a catalyst. The catalyst calculated from the charged raw materials is a complex oxide having the following atomic ratio. Mo: Bi: Co: Ni: Fe: Na: B: K: Si =
12: 5: 2: 3: 0.4: 0.35: 0.2: 0.0
8:24

(Propylene Oxidation Reaction) Using the composite oxide catalyst prepared as described above, propylene oxidation reaction was carried out, and the propylene conversion rate, acrolein yield, and acrylic acid yield were calculated. Complex oxide catalyst 20m
1 was filled in a reaction tube with an inner diameter of 15 mm and made of a stainless steel niter jacket, and a raw material gas having a propylene concentration of 10%, a steam concentration of 17%, and an air concentration of 73% was passed under normal pressure with a contact time of 1.8 seconds. Then, when an oxidation reaction of propylene was carried out, the results shown in Table 1 were obtained at a reaction bath temperature of 310 ° C.

Comparative Example 1 Oxidation of propylene in the same manner as in Example 1 using a composite oxide catalyst produced in the same manner as in Example 1 except that the Bi raw material was simultaneously added to the catalyst having the same composition as in Example 1. The results of carrying out the reaction are shown in Table 1.

[0030]

[Table 1]

The definitions of propylene conversion, acrolein yield and acrylic acid yield are as follows. Propylene conversion rate (mol%) = (mol number of reacted propylene / mol number of propylene fed) × 100 Acrolein yield (mol number) = (mol number of acrolein produced / mol number of propylene fed) × 100 Acrylic acid yield (moles) = (moles of acrylic acid produced / moles of propylene fed) × 100

[0032]

As described above, according to the present invention, a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, and a gas for producing acrylonitrile or methacrylonitrile from propylene or isobutene. As a catalyst used in a phase reaction ammoxidation reaction and a selective reaction such as a gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene, to obtain a catalyst having improved catalytic performance such as raw material conversion and selectivity. You can

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 51/25 C07C 51/25 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 ( 72) Inventor Togatsu Iwakura 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. F-term in company (reference) 4G069 AA03 AA08 BA02A BA02B BB01C BB04C BB06A BB06B BB16C BC02A BC02C BC25A BC09A BC10A BC09A BC09A BC09A BC09A BC09A BC09A BC09A BC09A BC09A BC09A BC09A BC09A BC27A BC35A BC35C BC43A BC43C BC44A BC44C BC59A BC59B BC60A BC66A BC66B BC67A BC67B BC68A BC68B BD01C BD03A BD06C BD07A CB10 CB20 CB54 FA01 FB06 FB09 FB29 FB30 FC02 FC03 FC07 FC08 4H006 AA02 AC45 AC46 BA02 BA06 BA07 BA09 BA13 BA14 BA19 BA20 BA21 BA30 BA33 BA35 BA81 BC10 BC11 BC13 BC18 BC30 BC32 BE30 BS10 4H039 CA62 CA65 CC30

Claims (9)

[Claims] 1. A method for producing a composite oxide catalyst represented by the following general formula (1) through a step including integration of a source compound of each component element in an aqueous system and heating, As a molybdenum, iron, at least one of nickel or cobalt, and a raw material salt aqueous solution containing silica is dried to obtain a catalyst precursor powder by a heat treatment of a dried product to obtain a catalyst precursor powder. And a bismuth compound are integrated with an aqueous solvent, and the mixture is prepared by a post-process of drying and firing. Mo _a Bi _b Co _c Ni _d Fe _e X _f Y _g Z _h Si _i O _j (1) (In the formula, X is magnesium (Mg), calcium (C
a), at least one element selected from the group consisting of zinc (Zn), cerium (Ce) and samarium (Sm), and Y is sodium (Na), potassium (K), rubidium (Rb), cesium ( Cs) and thallium (T
l) is at least one element selected from the group consisting of, and Z is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As) and tungsten (W). . Further, a to j represent atomic ratios of the respective elements, and when a = 12, b = 0.5 to 7 and c =
0-10, d = 0-10 (however, c + d = 1-10), e
= 0.05-3, f = 0-2, g = 0.04-2, h =
It is in the range of 0 to 3, i = 5 to 48, and j is a numerical value that satisfies the oxidation states of other elements. ) 2. The heating temperature in the previous step is 200 to 40.
It is 0 degreeC, The manufacturing method of the composite oxide catalyst of Claim 1 characterized by the above-mentioned. 3. The method for producing a composite oxide catalyst according to claim 1, wherein aqueous ammonia is added in the subsequent step when the catalyst precursor and the bismuth compound are mixed in an aqueous solvent. 4. The firing in the subsequent step is performed at a temperature of 450 to 60.
The method for producing a composite oxide catalyst according to any one of claims 1 to 3, wherein the method is performed in a range of 0 ° C. 5. The use of at least one of bismuth oxide and bismuth subcarbonate as a source of bismuth.
5. The method for producing the composite oxide catalyst according to any one of 4 to 4. 6. The method for producing a complex oxide catalyst according to claim 1, wherein bismuth subcarbonate in which at least a part of required Na is solid-dissolved is used as a bismuth supply source. . 7. The complex oxide catalyst according to claim 1, wherein a complex carbonate compound of Bi and X containing at least a part of the X component is used as a supply source of bismuth. Manufacturing method. 8. A complex carbonate compound of Bi, Na and X containing at least a part of each of required Na and X components is used as a source of bismuth. A method for producing the composite oxide catalyst according to 1. 9. A method for producing acrolein and / or acrylic acid using propylene as a raw material, which comprises using the composite oxide catalyst produced by the method according to any one of claims 1 to 8.