JPS60110338A - Oxidation of olefin and catalyst for ammoxydation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to oxidation and/or ammoxidation catalysts containing the elements iron, antimony, copper, tellurium, molybdenum and oxygen, optionally tungsten and vanadium, and the preparation of such catalysts. It relates to methods and uses of such catalysts in ammoxidation reactions.

It is known that olefins can be oxidized to oxygenated hydrocarbons such as unsaturated aldehydes and acids such as acrolein and methacrolein and acrylic and methacrylic acids. It is also known that olefins can be ammoxidized to unsaturated dihydrogens such as acrylonitrile and methacrylonitrile. The value of such oxygenated hydrocarbons and unsaturated nitriles is generally well recognized, and acrylonitrile is one of the most effective monomers available to the polymer industry to produce useful polymer products. be. The catalysts of the present invention are useful in such oxidation and ammoxidation reactions.

Various contact methods are known for the oxidation and/or ammoxidation of olefins. In such processes, an olefin or olefin-ammonia mixture is usually reacted with oxygen in the gas phase in the presence of a catalyst. Propylene is a commonly used olefin reactant for the production of acrolein and acrylonitrile, and imbutylene is a commonly used olefin reactant for the production of methacrolein and methacrylonitrile.

A number of catalysts have been disclosed as suitable for olefin oxidation and ammoxidation. This more advanced catalyst is disclosed in U.S. Pat. No. 3,988,359;
No. 4,208,303. This catalyst has the empirical formula % formula % (where Me is at least one element selected from the group consisting of V, Mo and W, and Q is Cu, Mg% Zn
%La, Ce%AI, Cr, Mn%Co, Ni
, B1 and Sn.
If R is a group consisting of P and B or 10, then b is from 15 to 60, C is from 1 to 10, and d
is from 0.5 to 10, e is from 0.1 to 10, f is from 0 to 5, and g represents the number of oxygen atoms corresponding to the oxide resulting from the combination of active ingredients). Ru. It is said that the Me acid component and the Te component are substantially dissolved in the iron-antimony oxide compound (Fe5b04) to form a solid solution.

Although the yield and selectivity of the catalyst are generally sufficient, nevertheless this catalyst has significant drawbacks, the essence of which is the loss of Te during long-term use. This loss of Te results in a decrease in activity and selectivity over long periods of use, thereby requiring expensive and complicated regeneration of the catalyst by Te replacement. Therefore, 2)
The economics of producing IJL (eg, acrylonitrile) from olefins (eg, propylene) are severely affected. The economics of acrylonitrile production dictate increasingly high yields and selectivities of the conversion of the reactants to acrylonitrile, in order to minimize the difficulties involved in processing the product N and large recycle streams. As is known, a catalyst that maintains its high activity and selectivity over long periods of use would be a clear advance in the state of the art.

SUMMARY OF THE INVENTION It is an object of the present invention to provide highly active oil over a long period of use.
It is an object of the present invention to provide a stabilized catalyst composition useful in the production of unsaturated nitriles by ammoxidation of olefins, which is characterized by maintaining high selectivity and high selectivity.

Another object is to provide a catalyst composition that retains its Te under long-term use conditions.

Yet another object is to provide catalysts useful for the oxidation of olefins to the corresponding unsaturated aldehydes.

A further object of the invention is to provide a method for producing such a catalyst.

It is also an object of the present invention to provide a process for the production of acrylonitrile by using a stabilized catalyst composition, which is characterized by maintaining high activity and high selectivity over a long period of use.

In order to achieve these and other objects that are apparent from the accompanying description and claims, the following elements FeaS'bbCucTedMooWfMegOx in the indicated atomic ratios [wherein Me is ■, B, P%Mg, Sn , Zn, M
a member of the group consisting of n and mixtures thereof, where a is from 5 to 10, b is from 10 to 30, and C is from 1 to 5
, d is from 0.5 to 5, e is from 0.1 to 5,
f is from 0 to 5, g is from 0 to 0.5, and X is a number taken to meet the valence requirements of other elements present). . According to the present invention, such a catalyst comprises a preformed tellurium-containing component selected from the group consisting of an iron component, an antimony component and a copper component, tellurium molybdate, tellurium tungstate and mixtures thereof, and a metal component containing molybdenum and tungsten. and a supplementary metal-containing component selected from a mixture thereof, provided that if the preformed tellurium-containing component is tellurium molybdate, the metal component of the supplementary metal-containing component is tungsten, and if the preformed tellurium-containing component is tellurium tungstate, The metal component of the supplemental metal-containing component is molybdenum. Optionally, a vanadium component may be included in an amount sufficient to meet the elemental atomic ratio requirements and a tungsten component if the supplemental metal-containing component does not contain tungsten. The mixture is formed into particles and the particles are dried and calcined.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the present invention, catalysts useful for olefin oxidation and ammoxidation are composed of the following elements in specified atomic ratios: FeaSbbCuoTedMOoWfMegOX, where Me is ■, B, P+Mg, Sn, Zn,
n and a member of a group consisting of these members (where a is 5
to 10, b from 10 to 60, C from 1 to 5, d from 0.5 to 5, e from 0.1 to 5, f
is from 0 to 5, g is from 0 to 0.5, and X is a number taken to satisfy the valence requirements of other elements present). The catalyst comprises an iron component, an antimony component and a copper component and a preformed tellurium-containing component selected from the group consisting of tellurium molybdate, tellurium tungstate and mixtures thereof, and a metal component selected from molybdenum, tungsten and mixtures thereof. (However, if the preformed tellurium-containing component is tellurium molybdate, the metal component of the supplementary metal-containing component is tungsten, and if the preformed tellurium-containing component is tellurium tungstate, the metal of the supplementary metal-containing component is The component is molybdenum). Any K may contain a tungsten component if the vanadium component and the supplementary metal-containing component do not contain tungsten in an amount sufficient to satisfy the element atomic ratio requirements. The mixture is formed into particles and the particles are dried and calcined. The catalyst is characterized in that the tellurium (T
e) is particularly useful during long periods of use. As a result, the catalyst is characterized by maintaining high activity and high selectivity over such long periods of use. In other aspects, the invention is directed to methods of using such catalysts.

As used herein, the term "tellurium molybdate" refers to a compound of tellurium, molybdenum, and oxygen. Such compounds can be formed by interaction of a tellurium compound with a salt of molybdic acid, such as ammonium molybdate, in which tellurium acts as a cation, or by solid state reaction between tellurium oxide and molybdenum oxide.

Similarly, as used herein, the term "tellurium tungstate" refers to a compound of tellurium, tungsten, and oxygen. Such compounds are similar to those described above for tellurium molybdate, except that a salt of tungstic acid, such as ammonium tungstate, is substituted for a salt of molybdate, and tungsten oxide is substituted for molybdenum oxide. It can be formed by

If the tellurium-containing component according to the invention is tellurium molybdate, this component may contain tellurium and/or molybdenum oxides in addition to the tellurium molybdate compound. Similarly, the tellurium tungstate component may contain oxides of tellurium and/or tungsten. However, it is preferred that the tellurium-containing component is substantially free of tellurium, molybdenum and/or tungsten oxides. In this manner, tellurium loss from the catalyst under long-term use conditions is substantially reduced or eliminated, thereby allowing the catalyst to be used for extended periods of time without substantial reduction in catalyst activity and selectivity.

The tellurium-containing component of the catalyst according to the invention is prepared by forming an aqueous solution of metallic tellurium in nitric acid, forming an aqueous solution of a molybdenum- or tungsten-containing salt, oxide or hydroxide, combining these two solutions, and then It can be produced by recovering the precipitated tellurium-containing component by filtration or decantation. Accordingly, suitable tellurium component-forming tellurium compounds include, but are not limited to, elemental tellurium when used in solution with nitric acid, tellurium dioxide and tellurium halides when hydrolyzed. Suitable tellurium component-forming molybdenum compounds include molybdenum trioxide, molybdic acid, molybdenum halides and ammonium molybdates, such as ammonium molybdate and ammonium paramolybdate. Similarly, suitable tellurium-forming tungsten compounds include tungsten trioxide, tungstic acid, tungsten halides, and ammonium tungstate.

Typical of suitable antimony compounds for the antimony component are antimony trioxide, antimony tetroxide, antimony pentoxide and antimonic acid.

Compounds which form oxides of antimony upon chemical reaction or calcination, such as antimony metal, antimony hydroxide, and antimony halides such as antimony trichloride, antimony tribromide and antimony pentachloride, are also suitable.

Suitable iron compounds for the iron component are of many types, such as ferrous oxide, ferric oxide and ferrous oxide (Fe3O4
) can be selected from. Compounds which are ultimately stabilized as iron oxides after chemical or calcination treatments can also be used. Such compounds include, for example, inorganic iron salts such as iron nitrate, iron sulfate and iron chloride, or organic acid iron salts such as iron acetate and iron oxalate. Iron hydroxide and solutions of metallic iron in nitric acid can also be used.

Suitable copper compounds for the copper component include cupric oxide, cupric nitrate, cupric acetate, cupric oxalate and cupric hydroxide obtained by hydrolysis of cupric chloride. .

The catalyst of the present invention described above contains a tellurium-containing component selected from the group consisting of tellurium molybdate, tellurium tungstate, and mixtures thereof.

If the tellurium-containing component is tellurium molybdate, a tungsten component must be provided. This requirement is based on the selection of tungsten as its metallic component.
(or selected from the group consisting of molybdenum, tungsten, and mixtures thereof) of the catalyst. Tungsten as the metal component is preferably provided as a metal tungstate, such as copper tungstate or tellurium tungstate. However, the tungsten compounds mentioned above as suitable for the production of tellurium tungstate are also suitable.

Similarly, if the tellurium-containing compound is tellurium tungstate, a molybdenum component must be provided. This requirement is met as described above by choosing molybdenum as the metal component of the metal-containing component with tungsten. Suitable molybdenum compounds include those mentioned above as suitable for the preparation of metal molybdates, such as tellurium molybdate or copper molybdate and tellurium molybdate.

When the tellurium-containing component is a mixture of tellurium molybdate and tellurium tungstate, a mixture of molybdenum and tungsten can be used as the metal of the supplementary metal-containing component in an amount sufficient to meet the elemental atomic ratio requirements of the catalyst.

The catalyst of the invention optionally contains a vanadium component. Preferably, the vanadium component is provided as vanadium antimonate. However, vanadium pentoxide,
Other vanadium compounds are also suitable, such as ammonium metavanadate, vanadyl oxalate and panazoum helokenenide.

As used herein, the term "vanadium antimonate" is used to refer to a complex mixture of vanadium, antimony and oxygen. Compounds that can be formed by the interaction of antimony and vanadium compounds are intended to be included within the term "vanadium antimonate" as used in Unknown Ia. The "vanadium antimonate" component of these catalysts may contain free oxides of antimony and/or vanadium.

The optional vanadium antimonate component may be a compound that is i/cyfe formed under calcination conditions in air at elevated temperatures. However, as used herein, the term vanadium antimonate also encompasses (uncalcined) precursors of true vanadium antimonate compounds. Such precursors are produced, for example, by producing an aqueous slurry of vanadium and antimony compounds.

The slurry is boiled until the solids contained become a greenish-brown color, indicating a partial interaction of the vanadium antimonate compound whose nature is not well understood. The vanadium antimonate precursor can be calcined to form a true vanadium antimonate compound, if desired.

The vanadium antimonate component of these catalysts can be formed by adding a vanadium-containing compound to an aqueous slurry of a suitable antimony-containing compound and then boiling the resulting slurry. In a preferred preparation, the vanadium and antimony compounds are vanadium pentoxide (V2O3) and antimony trioxide (5b2), respectively.
03). The slurry is boiled until the solids contained turn a greenish-brown color, indicating interaction or partial reaction of the two metal oxides to form the precursor of panazoum antimonate. In a more preferred manufacturing operation, the vanazole oxalate solution gradually converts oxalic acid into carbon dioxide (C
O2) is added to an aqueous slurry of ammonium metavanadate at about 60° C. until evolution ceases. The desired amount of antimony trioxide is added to the clear blue solution of vanadyl oxalate and the resulting slurry is then dried to form the vanadium antimonate precursor. In any event, in a particularly preferred embodiment of the present invention, the greenish-brown vanadium antimonate precursor is heated from about 500°C to about 800°C, preferably from about 550°C to about 750°C.
C. for 0.5 to 24 hours to form a gray-black vanadium antimonate compound.

As mentioned above, if the amount of tungsten in the supplementary metal-containing component is less than desired, the tungsten component may be added within the above atomic ratio range or the total amount may be added within the above atomic ratio range. good. In such cases, the tungsten component may be any non-interfering tungsten compound.

After preparation of the tellurium-containing components of the catalyst, these components are combined in the desired proportions with appropriate metal-containing components and optionally vanadium and tungsten components in an aqueous slurry and then thoroughly mixed. At this point, if desired, a suitable catalyst support may be added as described below.

The homogeneously mixed slurry is then heated to remove most of the aqueous phase. Desirably, the concentrated slurry contains some amount of water, which water is then removed by some form of drying process to form a dry catalyst precursor. This may take the form of a simple open drying process in which the water-containing solid phase is exposed to temperatures high enough to evaporate the water and yet completely dry the solid phase.

Another drying method that may be used involves spraying the water-containing solid phase particles in contact with a hot gas (usually air) to evaporate the water.
This is a so-called spray drying method. This drying is controlled by the temperature of the gas and the distance traveled by the particles in contact with the gas. Generally, it is desirable to adjust these parameters to avoid drying too quickly. This is because, as a result of this rapid drying, there is a tendency to form a dry skin on the partially dried particles in the solid phase, which subsequently breaks down when the water occluded within the particles evaporates and attempts to escape. be done. At the same time, it is desirable to provide the catalyst with as little occluded water as possible.

Therefore, when a fluidized bed reactor is used and microspheroidal particles are desired, it is preferred to choose spray drying conditions to obtain substantially complete drying without particle breakage.

After the drying operation, the catalyst precursor is calcined to form the catalyst. Calcination methods typically operate essentially at atmospheric pressures and temperatures of about 60°C.
From about 500℃ to about 8℃, such as from 0℃ to about 80.0℃
It is carried out in air at up to 50°C. The time to complete calcination can be anywhere up to 10 hours - but for many purposes calcination needs to take from about 1 hour to about 3 hours.

In some applications, it may be advantageous to include a support material that provides the catalyst with a large surface area, yet works by producing a harder and more durable catalyst for use in the highly abrasive environment of a fluidized bed reactor. Dew.

The support material can be any of those commonly proposed for such applications, such as silica, zirconia, alumina, titania, antimony pentoxide, or other oxide substrates. From the standpoints of availability, cost and performance, silica is usually a satisfactory support material, and the form of silica silica is preferred for easy dispersion.

Although the proportions present of the components of the supported catalyst can vary widely, the support comprises from about 10% to about 90% by weight, more preferably from about 35% to about 65% by weight of the total combined weight of catalyst and support. It is usually preferred to give In order to incorporate the support into the catalyst, the support material is preferably added to the slurry containing the active ingredients discussed above.

As mentioned above, the catalyst according to the present invention has the following elemental atomic ratio: 5
to 10, b from 1o to 3o, C from 1 to 5, d from o, 55 to 5, θ from 0.1 to 5,
f is from 0 to 5, g is from 0 to 0°5, and x is taken to meet the valence requirements of other elements present). In a more preferred embodiment of such a catalyst, a is from 5 to 8 and b is 10
to 20, C from 2 to 4, d from 0.5 to 3, e from 0.5 to 2, f from C1,5 to 2,
and g is from 0.01 to 0.2.

Catalyst preparation of the present invention results in catalysts useful in the production of nitriles from olefins. Olefins suitable for use in the trap of the present invention are those characterized by having at least one methyl group attached to a triangular carbon atom. A non-limiting representative of such olefins are:
Examples include propylene, isobutylene, 2-methy/I/-1-pentene, and 1°4-hexadiene. Although the production of acrylonitrile from propylene is of particular interest, it will be appreciated in the discussion below that the catalysts described are also useful for the ammoxidation of other suitable olefins and the oxidation of such olefins to aldehydes and acids. This method is specially mentioned.

In the most commonly used ammoxidation process, a mixture of olefin, ammonia and oxygen (or air) is fed to a reactor and then passed through a bed of hot catalyst particles. Such temperatures typically range from about 400°C to about 500°at and pressures from about 1 atm to about 6 atm (
100 kPa to about 6 Q Q kPa). Ammonia and olefin are required in stoichiometrically equimolar amounts, but it is usually necessary to operate at a molar ratio of ammonia to olefin greater than 1 to reduce the occurrence of side reactions. Similarly, the stoichiometric oxygen requirement is 1.5 times the molar amount of olefin. The feed mixture is typically applied to the catalyst bed at a W/F (defined as the weight of the catalyst, I, divided by the flow rate of the reactant stream, ml/sec, at standard temperature and pressure) from about 2 to about 15, preferably from about 4 to about 10
It will be introduced within the range.

Although the ammoxidation reaction is exothermic, it is desirable for the catalyst bed to be fluidized to facilitate heat distribution and removal. However, fixed catalyst beds can also be used with other heat removal means such as cooling coils within the bed.

Catalysts produced by the process of the present invention demonstrate that the tellurium losses exhibited by similar prior art catalysts are substantially reduced during long-term use due to the unique and novel manufacturing operations used in the present invention. It is particularly well suited for use in such methods in that it is removed at all.

The following examples are set forth to facilitate a clear understanding of the invention, illustrating current and well-known methods of carrying out the invention. However, the description in the application specification of the invention, while indicating preferred embodiments, is given by way of example only and is not to be construed as limiting the invention, since various modifications will be apparent to those skilled in the art from this description. I want to be understood.

EXAMPLES In the examples given below, the general preparation of catalyst compositions is illustrated. These compositions must have properties that make them advantageous for use in the ammoxidation of propylene to produce acrylonitrile.

As used herein, the following terms are defined as follows: 1. [W/FJ is defined as the weight of the catalyst, y, divided by the flow rate of the reactant stream, ynl/sea, measured at the STP.

2. [Propylene CC3He) conversion rate' is defined as.

6. [Acrylonitrile (AN) selectivity] is defined as.

4. "Acrylonitrile (AN) yield" is defined as.

In the following sections, the example catalyst (approximately 60 g) has an inner diameter of approximately 13
It should show high acrylonitrile selectivity and yield and propylene conversion as evaluated in a fluidized bed reactor with mm. 0217 capacity chi to 17.8
Propylene (03H6) up to a volume of 7.6 volumes to 8.6 volumes, NH38 volumes up to 9% by volume and the remainder of helium sufficient to give the desired ψθ value. The catalyst layer passes through the catalyst layer at a certain speed. maintaining the temperature between about 425°C and about 500°C (preferred temperature);
Moreover, the pressure is maintained at approximately 205 kPa.

It is therefore clear that the present invention provides a catalyst and method of using the catalyst that fully satisfies the objects and advantages set forth above. Although the invention is described with respect to various specific examples and embodiments thereof, it is not limited thereto, and many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. I understand. Accordingly, it is intended to cover all alternatives, modifications, and variations falling within the spirit and broad scope of the invention.

Example 1 (Comparison) 5b2o3223.4 g Fe(NO3)39H20310.3g (NH4)6M of the following components in the indicated amounts
O70244H209,2, ji'H2Te0421(
2024,01 cu(No3)23H2059,311NH,VO31
, 376 g (NH4)6W702415H201, 62 g Silica sol (Nalco 2327) 600.0 g was used to prepare the catalyst.

The manufacturing method is as follows: 1. Dissolve Fe(NHs)39H20 in 1901 dK of water in a 2,000 d beaker.

2, (NH4)6 MO70244H20 and H2T
Dissolve eO4 in 17g of water.

3. Dissolve O,u(NO3)23H20 in 600 g of water.

4, NH4VO3 and (NH4)6W70246H2
0 in 50 d of water. The solution is heated to complete dissolution.

5. Add (2), (6) and (4) to (1) in sequence.

6. Add Eib203 and silica sol.

Z mixture p+4 in water i: I NH4OH33
Adjust to 2 with Qml.

8. Heating the slurry and concentrating it to a volume of 1400ml;
Then spray dry.

Calcinate at 9700° C. for 4 hours.

The power was on.

Example 2 using the ingredients below Teo 86-15,! 9 M0O38,859 Tellurium molybdate was produced.

The production of the compound is as follows 1. Mix the oxide with 50 g of ethanol.

2. Ball mill the mixture in a small jar overnight.

6. Evaporate the mixture to dryness on low heat and then dry in the open at 110° C. for 4 hours.

4. Calcinate for 1 hour at 500°C with air passing through the furnace.

5. Cool the solid and then grind it into a slight powder.

6. Calcinate again at 500°C for an additional 6 hours.

The tellurium molybdate prepared above can be combined with other compounds 5b2o3223.4 shown below! 9 ye (No3) 39H, 20310, 31Cu (NO3
)23H2059,39 Silica sol (Nalco 2327) 600.0
&NH,VO31,376# (NH4)6W70246H201,62,! 9Te2
A catalyst was prepared with Mo07 24.29.

The catalyst is produced by the following procedure 1.
Add to 4 ml of mixture. Heat at 95°C for 4 hours. The mixture was then diluted with 1500 g of water and then decanted twice.

2. F+1 dissolved in 290 ml of water! (NO3)3
Add 9H20.

6. Cu(NO3)23H20 dissolved in water 150-
Add.

4. Add silica sol. PH to NH40H (1:
1) Adjust to 2 with 360 go.

5, NH4VO3 and (NH4)6W70246H2
Dissolve 0 in 50ml of water. Heat to complete dissolution. (
Add 5) to (4).

6. Add Te2M0O7.

l - Night (16 hours) ball milling, PH 1,5
゜Adjust to 4 with 100ml of NH4OH.

8. Concentrate to 1600-, pH 3, 85°9 Spray dry.

10. Calcinate for 4 hours at 750°C.

According to

The catalysts of Example 1 and Example 2 were similarly tested in a 13 mm diameter reactor. A description of the reaction conditions and feed and product streams is shown in the table below.

Table 1 Temperature, '0 425 430 425 430 Pressure, k
Pa 191 219 191 219 Feed, Chi.
C! 3H66,788,0+5.78 8.0NH37
,148,47,148,4 0218,0617,518,0617,5H1ll
68.0266.168.0266,IW/F,,li
lsecml' 5 6 5 6"3H6, conversion rate %
94.2 96.3 94.0 96.7AN, selectivity% 76.9 75.7 80.5 77.5Alj,
Yield, CH 72.5 72.8 75.7 74.9 Carbon balance, % 98.6 97.9 97.4 98
．． 2 These results show that the use of preformed tellurium molybdate produces a catalyst with significantly enhanced acrylonitrile selectivity.

The activity of the catalyst, as measured by propylene conversion, is approximately the same as the prior art catalyst, but the A1 selectivity and therefore the A1
M yield increases significantly. When operating at relatively low pressure, the AN yield increased from 72.5% to 75.7%.

Although the laboratory test lasted only 23 hours, it is believed that the tellurium molybdate catalyst remains active for an extended period of time.

This is because tellurium molybdate is a stable component and does not lose tellurium to the same extent as prior art catalysts. These data show that this catalyst is substantially more selective for acrylonitrile than the prior art catalyst.

Agent Asamura Hako

Claims (1)

[Claims] (1)'FeaSbbCucTodMo8WfMθg
Ox (in the formula, Me+'lV, B, P, Mg, Sn, Zn
, Mn and mixtures thereof [where the subscripts are atomic ratios, a is from 5 to 10, b
is from 10 to 30, C is from 1 to 5, d is from 0.5 to 5, θ is from 0.1 to 5, f is from 0 to 5,
g is a number from 0 to 0.5 and xGt is a number taken to satisfy the valence requirements of other elements present). The catalyst comprises a preformed tellurium-containing component selected from the group consisting of an iron component, an antimony component and a copper component, tellurium molybdate, tellurium tungstate and mixtures thereof, and a metal component selected from the group consisting of molybdenum, tungsten, and mixtures thereof. (provided that if the preformed tellurium-containing component is tellurium molybdate, the metal component of the supplementary metal-containing component is tungsten, and if the preformed tellurium-containing component is tellurium tungstate, then the supplementary metal-containing component is selected from the metal component of the metal-containing component being molybdenum) and optionally a vanadium component and a tungsten component in an amount sufficient to meet the elemental atomic ratio requirements; forming the mixture into particles; A mixed oxide catalyst for the oxidation and ammoxidation of olefins, characterized in that it is produced by subsequently drying and calcining the particles. (2) The tellurium-containing component is tellurium molybdate,
The catalyst of claim 1, and wherein the supplementary metal-containing component is tungsten trioxide. (3) The catalyst according to claim 1, wherein the vanadium component is vanadium antimonate. (4) a is from 5 to 8, b is from 10 to 20, C is from 2 to 4, d is from 0.5 to 3, e is from 0.5 to 2, f is from 0.05 to 2 , and g is from 0.01 to 0.2. (5) The catalyst according to claim 1, wherein the antimony component is antimony trioxide. (6) Claim 1, in which the iron component is ferric nitrate
term catalyst. (7) The catalyst according to claim 1, wherein the copper component is cupric nitrate. (8) The catalyst of claim 1, wherein the mixture is in the form of an aqueous slurry. (9) Adding to the slurry a support material comprising from about 10% to about 90% of the total weight of the catalyst.
term catalyst. a(]) The support material is about 65% to about 65% of the total weight of the catalyst.
The catalyst according to claim 9, characterized in that: θD The support material is silica, claim 10
term catalyst. The catalyst of claim 1, wherein the dry particles are formed by spray drying an aqueous slurry. The catalyst of claim 1. (14) The catalyst of claim 16, wherein the calcination temperature is from about 600°C to about 800°C.
WfMe gOx (where Me is V, B, P%Mg
, a member of the group consisting of Sn, Zn+Mn and mixtures thereof [where the subscript is the atomic ratio and a is 5
to 10, b from 10 to 60, C from 1 to 5, d from 0,5 to 5, e from 0.1 to 5, f
0 to 5, g is 0 to 0.5, and X is a number taken to meet the valence requirements of other elements present) for the oxidation and ammoxidation of olefins. In the method for producing a mixed oxide catalyst, (1) a preformed ten-saving component selected from the group consisting of an iron component, an antimony component, a copper component, tellurium molybdate, tellurium tungstate, and a mixture thereof and a metal component are molybdenum; , tungsten, and mixtures thereof (provided that if the preformed tellurium-containing component is tellurium molybdate, then the metal component of the supplemental metal-containing component is tungsten and the preformed tellurium component is forming a mixture containing a vanadium component and a tungsten component in amounts sufficient to meet the elemental atomic ratio requirements; A method for producing a mixed oxide catalyst for the oxidation and ammoxidation of olefins, comprising: (2) forming the mixture into dry particles; (6) drying the particles; and (4) calcining the particles. (le the tellurium-containing component is tellurium molybdate,
16. The method of claim 15, wherein the metal-containing component is tungsten trioxide. 16. The method of claim 15, wherein the aη vanadium component is vanadium antimonate. (+81 a is from 5 to 8, b is from 10 to 20,
C is from 2 to 4, d is from 0.5 to 3, θ is 0.5
to 2, f is 0.05 to 2, and g is 0.0
16. The method of claim 15, wherein the value is between 1 and 0.2. a9 The method of claim 15, wherein the antimony component is antimony trioxide. (b) Claim 1 in which the iron component is ferric nitrate
Method in Section 5. (The method of claim 15, wherein the 211 copper component is cupric nitrate. (The method of claim 15, wherein the 22 mixture is in the form of an aqueous slurry. (c) Total weight of catalyst 23. The method of claim 22, wherein a support material comprising from about 10% to about 90 inches of the total weight of the catalyst is added to the slurry.
24. The method of claim 23, characterized in that: (2ω The second claim in which the carrier material is silica)
Method in Section 4. ee. The method of claim 15, wherein the dry particles are formed by spray drying an aqueous slurry. (27) The method of claim 15, wherein the dry particles are calcined at a temperature of about 500°C to about 850°C. 28. The method of claim 27, wherein the calcination temperature is from about 600°C to about 800°C. (b) FeaS-bbCucTedM08WfMegO
,X (where Me is a member of the group consisting of ■, B+P+Mg+Sn, Zn. , C is from 1 to 5, d is from 0.5 to 5, θ is from 0.1 to 5, f is from 0 to 5, g
is from 0 to 0.5, and X is a number taken to satisfy the valence requirements of other elements present). A supplementary metal-containing component whose containing compound and metal component are selected from the group consisting of molybdenum, tungsten, and mixtures thereof (provided that if the preformed tellurium-containing component is tellurium molybdate, the metal component of the supplementary metal-containing component is tungsten); , and if the preformed tellurium-containing component is tellurium tungstate, the metal component of the supplementary metal-containing component is molybdenum) and optionally a vanadium component and a tungsten component in amounts sufficient to meet the elemental atomic ratio requirements. forming a mixture; (C) forming the mixture into particles; drying and calcining the fdl particles to form a calcined catalyst;
(el) An improved process for the production of acrylonitrile, characterized in that propylene, ammonia and molecular oxygen are reacted at high temperature in the gas phase in the presence of a calcined catalyst. (g) The tellurium-containing component is tellurium molybdate ,
30. The method of claim 29, wherein the supplemental metal-containing component is tungsten trioxide. 30. The method of claim 29, wherein the Gυ vanadium component is vanadium antimonate. L3 thirst a from 5 to 8, b from 10 to 20, C from 2 to 4, d from 0.5 to 3, e from 0.5 to 2, f from 0.05 to 2, 30. The method of claim 29, wherein g is from 0.01 to 0.2. c3 (to) The method of claim 29, wherein the antimony component is antimony trioxide. C34) The method of claim 29, wherein the iron component is ferric nitrate. 09 Claim 2, in which the copper component is cupric nitrate
Method of Section 9. 29. The method of claim 29, wherein the mixture is in the form of an aqueous slurry. 37. The method of claim 36, wherein a support material comprising from about 10% to about 90% of the total weight of the t3η catalyst is added to the slurry. 38. The method of claim 37, wherein the support material comprises about 65% to about 65% of the catalyst. 0ω The carrier material is silica, claim 3
Method of Section 8. (40) The method of claim 29, wherein the dry particles are formed by spray drying an aqueous slurry. (41) The dry particles are calcined at a temperature of about 500°C to about 850°C. The method of claim 29. (4Z The method of claim 41, wherein the calcination temperature is from about 600°C to about 800°C.
30. The method of claim 29, carried out at up to kPa and at temperatures from about 400<0>C to about 550<0>C. (44) The method of claim 29, wherein the temperature is from about 425°C to about 500°C. (4 pieces, flow rate W/F is approximately 2, li' -Sea/ml
From about 15g-8ea/ml. 29. The method of claim 29, within the scope of. (b) producing a tellurium-containing compound selected from the group consisting of tellurium molybdate, tellurium tungstate and mixtures thereof;
(where Me is V, B+P, Mg, Sn%Zn, a member of the group consisting of Mn and mixtures thereof, [where the subscripts are atomic ratios, a is from 5 to 10, b is from 10 to up to 60, C from 1 to 5, d from 0.5 to 5, e from 0.1 to 5, f from 0 to 5, g
is from 0 to 085, and X is a number taken to satisfy the valence requirements of other elements present). A supplementary metal-containing component in which the containing compound and the golden component are selected from the group consisting of molybdenum, tungsten, and mixtures thereof (provided that if the preformed tellurium-containing component is tellurium molybdate, the metal component of the supplementary metal-containing component is tungsten); , and if the preformed tellurium-containing component is tellurium tungstate, the metal component of the supplementary metal-containing component is molybdenum) and optionally a vanadium component and a tungsten component in amounts sufficient to meet the elemental atomic ratio requirements. (c) forming the mixture into particles; (dl) drying and calcining the particles to form calcined particles; An improved method for the production of acrylonitrile, characterized by reacting molecular oxygen and molecular oxygen in the gas phase at high temperatures.