JPS59123537A - Dehydrogenation reaction catalyst containing iron oxide, chromium oxide and lanthanum oxide and production thereof - 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 The present invention provides novel catalysts for dehydrogenation, particularly for the dehydrogenation of low molecular weight (e.g. ethylbenzene or diethylbenzene) to vinyl aromatic hydrocarbons (e.g. styrene or divinylbenzene). The present invention also relates to these catalysts and methods of dehydrogenation using them.

Dehydrogenation of the above hydrocarbons, preferably with the addition of a high proportion of water vapor (1 to 30 mol H2
0/mole of hydrocarbons) on one catalyst at a volume rate of 0.05 to 5, preferably 0.01 to 1 volume (TPN) of liquid hydrocarbon per hour per volume of catalyst, about 450 to 750. ℃
It is known that it can be passed at a temperature of .

In the prior art, catalysts have been described for the dehydrogenation of olefinic hydrocarbons such as butene (to butadiene) or for the dehydrogenation of alkylaromatic hydrocarbons such as ethylbenzene (to styrene). These catalysts contain large weight proportions of iron oxides, potassium compounds (oxides or carbonates), vanadium oxides, and even chromium oxides, for example aluminum, cadmium, copper, magnesium, manganese, niratil, rare earths. A small proportion (0.01-10% by weight) of at least one additional oxide of metals such as metals such as uranium and zinc
)including. Such catalysts are particularly described in French Patent No. 238
No. 7200 describes this. This patent is substantially U.S. Pat. Corresponds to L43083 and L4152300. In these patents, rare earth metals are defined as metals with atomic numbers 58 to 71 (inclusive), ie, metals from cerium to ruthenium. The rare earth metals used in the examples are cerium, praseodymium and neodymium.

It has now been found, however, that it is advantageous to use lanthanum (atomic number 57) as rare earth metal in catalysts of this type. This results in improved catalyst properties over catalysts for dehydrogenation (especially of ethylbenzene to styrene) at lower cost.

U.S. Pat. No. 41'34858 (substantially corresponding French patent No. 2270003) also describes the use of clay materials in the production of dehydrogenation catalysts based primarily on iron oxides, chromium oxides and potassium oxides. Suitable temperature, generally 850-110
At a temperature of 0° C., the clay material combines with potassium oxide to form a silicate double salt of aluminum and potassium (more specifically, potash nepheline). This method makes it possible in particular to reduce the packing density of the catalyst.

The main object of the present invention is to address the prior art with improved catalysts that exhibit increased activity and/or selectivity compared to the described catalysts. This catalyst life is substantially equal to, and often superior to, that of known catalysts.

Another object of the invention is to describe a method for the preparation of said catalyst.

Another object of the present invention is to describe the use of these catalysts for the dehydrogenation of hydrocarbons.

These objectives are achieved by the catalyst of the invention, which is generally defined as comprising iron oxide, chromium oxide and potassium oxide present in the following weight ratios: 0.3/l; and 6203 □ 21571~ 40/1 preferably 25/1-35/
1; r03 case + c, more specifically Af203.2Si0
2. 5 to 40% by weight of aluminum and potassium silicate double salt having the composition of K2O (potash nepheline); and 1 to 15% by weight of lanthanum oxide, preferably 3 to 10% by weight
Percentage of %.

When the catalyst comprises a double silicate salt of aluminum and potassium, it contains an amount of potassium oxide in excess of the combined amount in the form of the double silicate salt.

The excess potassium, calculated in this case as oxides, is in the following weight ratios to iron oxide and chromium oxide:
5% of heavy toxicity, oxides of alkali metals other than potassium or oxides of alkaline earth metals (e.g. N1120, Ba
O1Cab).

The catalyst may also contain an oxide proportion of 0.1 to 5% of its weight,
It may also contain at least one metal such as cobalt or vanadium.

It is also advantageous for lanthanum to be present in the catalyst, at least in part, in combination with at least one metal, such as cobalt or vanadium, as a mixed oxide. It is.

To prepare the catalyst of the invention, water, at least one iron compound, at least one chromium compound, at least one potassium compound and at least one lanthanum compound, as oxides, correspond to the following weight ratios: Form a mixture containing in proportions.

The lanthanum compound is used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, based on the total reactants calculated as oxides.

If clayey materials are used, this represents a proportion of approximately 3.5 to 30% by weight, calculated as oxides, based on the total of the components used. The potassium compound is used in excess of the amount that can be combined with the clay material. Excess potassium, calculated as oxides, is in the following weight ratios relative to iron and chromium:

The mixture is then kneaded to obtain a paste. The kneading may be carried out using a Hover (HC)RBART kneader or a Waring blender.

The paste obtained is then subjected to subsequent extrusion PA (ANDOUART, HUTTE), for example by extrusion.

ALEXANDERWERKE, 0'TOOLE i
1tWERNERPFLE I DERER extruder)
It may also be molded. Examples of extruded products are 1 to 7.
It may be cylindrical in shape with a suitable diameter and height. In general, drying may be carried out in a dryer and thermal activation may be carried out, for example, in an electric or gas oven. Dry for example 100~3
At 00°C for 1 to 24 hours, fixation may be carried out at 850 to 1100°C, preferably 870 to 105°C, for 1 to 3 hours.

The iron compounds used are generally finely ground (e.g. 2
Ferric oxide (particles with a size of 0.00 mesh or less). This iron oxide is preheated at 800°C.

For example, the Société Française d'El
ecLrom5Lallurgie-8OFRFM)
A product sold by the company under the product name fHA16o, J' is used. However, it is possible to replace a portion, for example 5 to 20% by weight of the total iron oxide, with iron hydroxide, which is itself obtained by ammonium, sodium or potassium precipitation of an aqueous solution of an iron salt. In addition, some of the salts may be replaced, such as total nitrate or ironmonbanban.

Chromium compounds may be used alone or in combination, and include, in general, chromic anhydride, chromates such as sodium, potassium or ammonium chromates or dichromates, trivalent chromium (CR+3) compounds such as nitrates, sulfuric acid. salt, oxide or hydroxide.

The compounds used to introduce potassium, possibly other alkali or alkali metals (Na, Ca, Ba) as well as cobalt and vanadium, are:
Common carbonates, oxides and hydroxides. Furthermore, other salts such as sulfates, phosphates or nitrates may be used. For vanadium, vanadate or metavanadate may also be used.

lanthanum in the form of its oxide or hydroxide or a carbonate of said element selected for its heating in the preparation of the catalyst;
Nitrates, nitrites, sulfides and salts of organic acids such as formic acid, acetic acid, oxalate, tartrate, citrate, acetylacetonate, benzoate.

Examples of clayey materials optionally used to prepare the catalysts of the present invention are disclosed in French Patent No. 22700, cited above.
No. 03. Preferably, kaolinite is used, for example in the form of Cornwall kaolin.

Finally, a small proportion of extrusion accelerator G1 may be used.

Such materials are known to those skilled in the art. Examples include graphite, vegetable gums (gum arabic), dammar (
Dambar> Rubber, locust beans (CIl, r o
ub e ) rubber) or alkyl cellulose (methyl cellulose, ethyl cellulose, or carboxymethyl cellulose).

all individual components of the catalyst are mixed with water to form a paste;
This paste may then be dried or calcined, or certain components may be introduced after undergoing a preliminary treatment to form chemical bonds between them.

Lanthanum may therefore be introduced in the form of a product resulting from a preliminary reaction of at least one lanthanum compound with at least one metal compound or vanadium compound.

In this preliminary step, the lanthanum compound and the compound of metal M are generally used in a ratio corresponding to the La7M atomic ratio of 0.5/1 to 2/1, more specifically about 1/11.

In the case of cobalt, a reaction in solution between soluble salts led to a precipitate may be carried out. This reaction is followed by separation of the product obtained (e.g. by filtering and washing the precipitate), drying, e.g. heating to a temperature of 400 to 950<0>C. In that case, a mixed oxide La at least partially of the perovsgian type
CoO3 is formed.

This operation can also be carried out by reaction between oxides of lanthanum and cobalt or vanadium or between compounds of the type that can be decomposed into oxides by the application of heat.

In the case of vanadium used in the form of pentavalent vanadium (y+5) compounds, it can be heated under a (hydrogen) reducing atmosphere at high temperatures e.g.
The operation is carried out at 00-900°C. In either case, baking is then carried out at a temperature of 900 to 1250°C. The resulting product is at least partially in the form of a Perovsky-type mixed oxide.

The product obtained in this preliminary step is then mixed with other ingredients and water, and the catalyst is then prepared by drying and heating at a high temperature (e.g. 850-1100°C).
Continue as shown above.

The catalyst of the invention as described above can be used with hydrocarbons, especially saturated aliphatic hydrocarbons or monoethylene series hydrocarbons and alkyl aromatic hydrocarbons (ethylbenzene, diethylbenzene).
(used under operating conditions known per se and repeated above).

In particular, the dehydrogenation of ethylbenzene to styrene
Catalysts of the invention (thereby making it possible to obtain good conversion of ethylbenzene and/or good styrene selectivity).

The following examples illustrate the invention. This example should not be considered limiting in any way.

Examples 3-8, 11, 12 and 15 are listed as comparative.

Example 1 (Catalyst A) In a Waring blender, ferric oxide rH
A160J300j7, potassium dichromate 145g,
Anhydrous potassium carbonate 100!7 and oxidation rank: /La
Knead 203279.

The amounts of reactants used were calculated in the following proportions (wt%) as oxides:
).

Fc203 = 73.23% CrO3 = 2.41% 20 = 17.77% La2O3 = 6.59% The weight ratios between iron, chromium and potassium, calculated as oxides, are as follows.

Next, 677 nl of a 2% by weight aqueous solution of MbLhocel (manufactured by Dow Chemical Company) and 70 ml of water were processed to obtain a paste with high consistency. Knead this for 20 minutes.

Transfer to an extruder with a stone and extrude into a cylindrical bar with a diameter of 4 x length of 2 to 6 m.

The extrudate was heated at 250°C for 15 hours and then at 960°C for 2 hours.
Activate time. Catalyst A is thus obtained.

Analysis of the final catalyst confirms the presence of iron oxide, chromium oxide, potassium oxide, and lanthanum oxide.

In all the examples below, the kneading, extrusion and drying of the components of the catalyst are carried out under the same conditions as in Example 1. Activation of the catalyst is carried out by heating for 2 hours at temperatures ranging from 940 to 970°C.

Example 2 (Catalyst B) In a Waring blender, ferric oxide “HA160J”
300j7, potassium dichromate 14.5! i', anhydrous potassium carbonate l OO! 7. cornwall kaolin 2
8,5g and oxidation rank 7 La 203279 -
Practice R. The amounts of reactants used correspond to the following weight proportions as oxides.

Fe2O3 = 68.47% CrO3 = 2.25% to 2(J2 16.62% La2O3 = 6.16% Kaolin = 6.50% The weight ratios between iron, chromium and potassium calculated as oxides are as follows: The one shown in Example 1 (has a similar value).

The amount of potassium that can be combined with kaolin corresponds to a weight proportion of 2.76% as oxides, based on the total oxides. The proportion of "excess" potassium oxide is therefore 13.8
6<.

The ratios between iron oxide and chromium oxide and excess 20, respectively, are as follows: : (weight ratio): Methocel (M
67 ml of a 2% by weight aqueous solution of 5thocel (manufactured by Dow Chemical Company) and 70 rnl of water were added to obtain a paste with high consistency.

Then, the operation is carried out as shown in Example 1.

Analysis of the final catalyst confirms its iron oxide, chromium oxide, potassium oxide and lanthanum oxide content. Analysis by X-ray diffraction revealed the presence of a silicate double salt of aluminum and potassium (potash nepheline). Its weight content is 9.3%.

Examples 3-5 (Catalysts C, -, E) The preparation described in Example 1 is repeated, except that lanthanum oxide La2O3 is replaced by the same heavy poisons of the other rare earth oxides listed below.

Example 3 Cerium dioxide Ce02 (catalyst C)0 Example 4
Praseodymium dioxide Pr8011 (Catalyst D).

Example 5: Neodymium oxide Nd03 (catalyst E).

Examples 6 to 8 (Catalyst F-H) Instead of lanthanum oxide La2O3, other rare example 6 below
Cerium dioxide Ce02 (catalyst F).

Example 7 Praseodymium dioxide prsou (Catalyst G).

Example 8: Neodymium oxide Nd03 (catalyst H).

Example 9 (catalyst engineering) In a Waring blender, ferric oxide [HA1
60J 3oog, potassium bicarbonate 14.5z17, anhydrous potassium carbonate 100g, Cornwall kaolin 28
5 g of lanthanum oxide La, 20317.9 g of lanthanum oxide La, and 2039.1 g of cobalt oxide Co are kneaded. Equal amounts of lanthanum and cobalt atoms were selected.

The amounts of reactants used correspond to the following proportions (weight M%) as oxides:

Fe2O3 = 68.47% CrO3 = 2.25% 20 = 16.62% La2O3 = 4.08% C,203 = 2.08% Kaolin = 6.50% 50 yd of Methocel 2X% aqueous solution and 100 ml of water Add so as to obtain a paste, which is kneaded for 15 minutes.

Extrusion, drying and deposition of the catalyst are carried out as indicated above.

The content of aluminum and potassium silicate double salt (potash nepheline) in the final catalyst is around 9.3% by weight.

Example 10 (Catalyst J) The preparation described in Example 9 is repeated, except that the cobalt oxide Co2O3 is replaced with the same weight of vanadate anhydride V2Q5.

The amounts of reactants used, as oxides, are in the following proportions (
(% by weight).

Fe2O3 = 68.47% CrO3 = 2.25% 20 = 16.62% La2O3 = 4.08% V2O5 = 2.08% Kaolin -6,60% The weight ratio between iron, chromium and potassium is acidic.

Analysis of the final catalyst confirms the oxide content of iron, chromium, potassium, lanthanum and vanadium.

Example 11 (Catalyst K) The preparation described in Example 9 is repeated, except that the same weight of cerium oxide CeO2 is used instead of lanthanum oxide.

Example 12 (Catalyst L) Instead of rankan oxide La2Q3 (cerium oxide Ce
The preparation described in Example IQ (Catalyst J) is repeated except using the same weight of O2.

Example 13 (Catalyst M) 145.5 g of cobalt nitrate and 190 mA of a 2.63 mol/l aqueous solution of lanthanum nitrate are poured into 2.5 l of water at 80° C. containing 212 g of Na2CO3. The amounts of reactants used correspond to an atomic ratio of cobalt to lanthanum of 171.

A precipitate is obtained which is washed with 121 ml of distilled water. Aged at 80'C for 6 hours, filtered, and aged at 50°C for 24 hours.
Dry at 00°C for 72 hours and 1' at 20°C for 24 hours.

Finally, heat at 600°C for 2 hours.

The structure of the resulting product was not clearly identified. At least partially perovskite-type mixed oxide LaCoO
3 seems to be involved.

27 g of the product thus prepared was added to ferric oxide r
HA 160j 30Qg, potassium bicarbonate 14.51
, mixed with 10 (l) of potassium anhydride and 28.5 g of Cornwall kaolin.

The amounts of reactants used, as oxides, correspond to the following proportions: (% by weight) Fe203 = 68.47% CrO3"" 2.25% to 20 = i6.62% LaCo03 = 6.16% Kaolin -6,50% then the previous (operated under the same conditions as shown) Do the following.

Example 14 (Catalyst N) Lanthanum oxide La203163g and vanadic anhydride V2
591 fl of O was homogeneously mixed and then heated at 850° C. for 6 hours under hydrogen flow in a tube furnace, and finally heated at 1200° C. for 18 hours.
■ Bake at ℃. The amount of reactants used is L a, /
This corresponds to a V atomic ratio of approximately 1/1. The resulting leta product is an at least partially Perovsky-type mixed oxide LaVO3.

Boat maneuvers are then performed as described in Example 13.

Example 15 (Catalyst O) Between lanthanum and vanadium (instead of the pre-formed mixed oxide). Example 14 (this described preparation) except that the
Repeat catalyst N).

Tactile pharynx A~0 was subjected to long-term catalytic testing.

Catalyst testing is carried out using a cuff test in which industrial ethylbenzene and water are supplied under normal pressure.
r.

) I did it with the utmost care. The volume of catalyst tested was 10
0ml (60-120g catalyst). Catalysts A to O are in the form of extrudates with a diameter of 4 m and a length of 4 to 5 m.

First, the catalyst is preheated to about 500°C. Steam is then introduced followed by ethylbenzene at about 550°C. The temperature is then adjusted to obtain a temperature of 614±2° C. in the catalyst bed.

The hourly flow rates chosen are as follows:

[1 shows the conversion of ethylbenzene (EB), styrene selectivity (SST) and styrene yield (R8T).

These various numbers are expressed in mole % and correspond to the following definitions.

These magnitudes are related to the following relational expression.

R3T -CEB From the comparison numbers of catalyst 0 and catalyst 0, it can be seen that the use of lanthanum improves the styrene yield compared to the use of other rare earths cerium, praseodymium, and neodymium. Alternatively, the rare earth metals may be used in the form of two separate metal compounds or in the form of a combination of oxides prepared in a preliminary step (in the case of the combination of cobalt and vanadium). , it turns out that it is good to combine it with another additional metal.

Continuation of page 1 Priority claim @ December 14, 1982 ■ France (P
R) [Owned] 8221086 0 Inventor: Philippe Vaillan, Rue de Saucelot, Massy (91300), Essonne, France 0 Inventor: Jean-François Le Perche, Hauts-de-Seine, France Sueil-Malmaison (92500) No. 13 Rue des Brimves (inventor: Serche Leporc) No. 6 Rue-Villanderie, Mantes-u-Vuilles, Yvelines, France (78200) Amendment of Procedures 1982 February 1st Commissioner of the Japan Patent Office Kazuo Wakasugi 5 Date of amendment order Showa month month 6
Number of inventions increased by amendment 7 Subject of amendment Claim 8 of the specification, content of amendment Claim (1) A catalyst containing iron, chromium and potassium in the form of oxides, comprising iron, chromium and potassium. and potassium, calculated as oxide, are present in a weight ratio of: lanthanum in the form of oxide, in a proportion of 1 to 15 wt%, calculated as oxide, relative to the weight of the catalyst. A dehydrogenation reaction catalyst characterized by:

(2) Formula AJ203.2SiO2, K20+7) contains an excess of potassium compared to the potassium present in the potassium nepheline, and the proportion of potassium nepheline is 5-4% of the catalyst.
The catalyst according to claim 1, characterized in that the excess potassium is in the weight ratio of iron and chromium: (3) The weight ratio between iron, chromium and potassium is calculated as an oxide, and the proportion of lanthanum is calculated as an oxide, and is 3~
The catalyst according to claim 1 or 2, characterized in that the content is 10% by weight.

(4) At least one metal that has passed away from cobalt and vanadium is also calculated as an oxide of 01 to 5 N
% of the catalyst according to any one of claims 1 to 3.

+5) a) forming a mixture comprising water, at least one iron compound, at least one chromium compound, at least one potassium compound and at least one lanthanum compound, which is kneaded to form a paste, and b) said Dry the paste as it is or after shaping, and heat activate it at a temperature of 850 to 1100°C. Weight ratio of iron, chromium and potassium compounds or as oxides: Lanthanum compounds are calculated as oxides and used. A method for producing a catalyst for dehydrogenation reaction, characterized in that the catalyst is introduced at a rate of 1 to 15 weight % based on the total amount of the compound.

(6) At least one compound of at least one metal selected from cobalt and vanadium is added to the step (
It is added to the mixture of the metal compound and the clay material of a), characterized in that the total content of the added metal, expressed as an oxide, is 0.1 to 5% by weight of the total compound used. The method according to claim 5.

(7) In step (a), the clay material is
The potassium compound is used in excess of the amount that can be combined with the clay material, and the excess potassium compound is calculated as an oxide with respect to iron and chromium, in a weight ratio of 30% by weight: 7. A method according to claim 5 or 6, characterized in that the proportions are corresponding.

(8) The method according to claim 7, wherein the clay material is at least partially kaolinite.

(9) Activation temperature in step (b) - 870-105
The method according to any one of claims 5 to 8, characterized in that the temperature is 0°C.

(10) The catalyst according to any one of claims 1 to 4, for use in the dehydrogenation reaction of saturated aliphatic or monoethylene series hydrocarbons or alkyl aromatic hydrocarbons.

(1j) The catalyst according to claim 10, wherein the alkyl aromatic hydrocarbon to be dehydrogenated is ethylbenzene.

Claims (1)

[Scope of Claims]
In catalysts containing rc, in which iron, chromium and potassium are present in a weight ratio of 2, calculated as oxides, a proportion of 1 to 15% by weight, calculated as oxides, based on the weight of the catalyst. A catalyst for dehydrogenation reactions, characterized in that it also contains lanthanum in the form of an oxide. (2) Formula A, g2o3,2sio2. Is the potassium nepheline of 2 O compared to the potassium nepheline present in the potassium nepheline?
Contains 1% potassium and 5-40% of potassium nepheline or catalyst
Catalyst according to claim 1, characterized in that the excess potassium is % by weight. (3) The weight ratio between iron, chromium and potassium, calculated as oxides, is , and the proportion of lanthanum, calculated as oxides, is 3~
Claim 1 characterized in that the amount is 10% by weight.
Or the catalyst according to item 2. (4) Any one of claims 1 to 3, characterized in that it also contains 0.1 to 5% by weight of at least one metal selected from cobalt and vanadium, calculated as an oxide. Catalyst according to item 1. (5) a) forming a mixture comprising water, at least one iron compound, at least one chromium compound, at least one potassium compound and at least one lanthanum compound and kneading the same to form a paste, and (1) ) Drying the paste as it is or after molding, and thermally activating it at a temperature of 850 to 1100°C, introducing iron, chromium and potassium compounds or oxides in weight ratio: and lanthanum compounds being oxidized. A method for producing a catalyst for a dehydrogenation reaction, characterized in that the catalyst is introduced in an amount of 1 to 15% by weight based on the total amount of compounds used. (6) At least one compound of at least one metal selected from cobalt and vanadium is added to the step (
A patent characterized in that the total content of the added metals, expressed as oxides, is from 01 to 5% by weight of the total of the compounds used, expressed as oxides. The method according to claim 5. (7) Step (a) + Place clay material in 3.
The potassium compound is used in an amount of 5 to 30%, and the excess potassium compound is calculated as an oxide with respect to iron and chromium. Weight ratio: No. 1: [The method according to claim 5 or 6, characterized in that the ratio corresponds to this. (8) The method according to claim 7, wherein the clayey material is at least partially kaolinite. (9) Activation temperature in step (1)) is 870-105
The method according to any one of claims 5 to 8, characterized in that the temperature is 0°C. (10) Dehydrogenation reaction of saturated aliphatic or monoethylenic hydrocarbons or alkyl aromatic hydrocarbons [The catalyst according to any one of claims 1 to 4 for this use. (11) Claim 10, wherein the alkyl aromatic hydrocarbon to be dehydrogenated is ethylbenzene.