DE1283203B - Process for the production of metal oxides of the ó¶. to ó ÷. Subgroup of the periodic system, optionally together with aluminum oxide, and halogen-containing catalysts - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

German class:

BOIj

C08f

12 g -11/64

39 b4-1 / 36

Number: 1283 203

File number: P 12 83 203.0-41 (B 76817)

Filing date: May 16, 1964

Opening day: November 21, 1968

The invention relates to a method of manufacture of metal oxides of the IV. to VI. Subgroup of the periodic system, possibly together with aluminum oxide, and halogen-containing catalysts, in which the metal oxides with a halogenated compound of methane which contains more than 1 halogen atom at temperatures up to 593 ° C under such conditions that the halogen is from the oxide is included in an amount of 1 to 15 percent by weight.

It has already been suggested in processes of this type for the preparation of very effective catalysts in particular for the oligomerization of -olefins the product obtained then with a finely ground, reducing metal to mix.

According to the invention it has now been found that there is still a considerable increase in effectiveness of the catalyst can be achieved by the product obtained then at least 50 hours, in particular at least 100 hours, preferably in a ball mill with a reducing acting metal milled. Metals with a reducing effect come within the scope of the invention Aluminum and metals of groups IVa, Va, VIa, VII a and VIII in question.

As metal oxides of IV. To VI. Subgroups that may be used with aluminum oxide can, oxides of Ti, Zr, Hf, Th, V, Nb, Ta, Cr, Mo, W and U come into question, with titanium dioxide is preferred.

The oxide mixtures can be produced mechanically by mixing. If necessary, a Oxide can be applied to another oxide, or two or more oxides can be mixed precipitated.

The oxides of the metals of subgroups IV, V or VI are preferably mixed with aluminum oxide mixed liked. If titanium dioxide is used as the oxide, the precipitation is expedient from mixtures made of alkyl titanate and aluminum alkoxide. The mixtures can be in the form of solutions can be used in diluents, especially hydrocarbons such as benzene. as Aqueous media, especially deionized water, are used as precipitants. Appropriately are the oxides of aluminum and the metals of subgroups IV, V or VI in molar ratios used in the range from 100: 1 to 1: 100 or mixed liked.

When the metal oxides are mixed precipitated with water, the products are usually hydrated.

Process for the production of metal oxides
the IV. to VI. Subgroup of the periodic
Systems, if necessary together
with aluminum oxide, and halogen
containing catalysts

Applicant:

British Petroleum Company Ltd., London

Representative:

Dipl.-Chem. Dr. Werner Koch,

Dr.-Ing. Dipl.-Ing. Richard Glawe

and Dipl.-Ing. Klaus Delfs, patent attorneys,

»5 2000 Hamburg and 8000 Munich

Named as inventor:
Peter Desmond Holmes,

_ao Derek William Ray, Sunbury-on-Thames,
Middlesex (UK)

Claimed priority:

Great Britain May 22, 1963 (20 376)

In general, it is then necessary to calcine them at such temperatures that the obtained Oxides still contain a small amount of hydrogen, usually less than 1 percent by weight. Suitable conditions for the calcination are, for example, a duration of one hour and one Temperature of 500 ° C. It is generally assumed that this residual hydrogen in Form of superficial hydroxyl groups is present and that the halogen compounds with the superficial Hydroxyl groups reacts to form active catalyst sites. It is actually considered a Formed reaction product water. Therefore, not all of the hydrogen should be removed, but it the procedure is such that the treated catalyst still contains a measurable amount of hydrogen.

Suitable halogenated compounds for the treatment of metal oxides are methylene dichloride, Chloroform, carbon tetrachloride, methylene difluoride, fluoroform and carbon tetrafluoride. The ones from The amount of halogen taken up by oxide is in the range from 1 to 15 percent by weight. That amount depends on the size of the surface, measured for example by nitrogen adsorption at low temperature will. All other things being equal are

809 638/1676

the amount of halogen absorbed and thus the activity of the catalyst, the greater the greater the Surface is. Oxides with a large surface area are therefore preferably used.

The halogenated compounds are used to treat the metal oxide or metal oxides, particularly in the vapor phase, expediently in an inert carrier gas. If necessary, the metal oxides can be preheated before treatment with the halogen-containing compound. In general, the treatment is carried out at elevated temperatures of 93 to 593 ° C. The treatment is usually stopped before the metal halide is released. These conditions naturally depend on the particular oxide system and the halogen compound used. When using titanium dioxide or Titandioxyd- aluminum oxide and carbon tetrachloride as the chlorinating agent, in particular, treatment temperatures are from 100 to 25Q ⁰ C. In general, the desired degree of treatment may be determined by a preliminary test, in which, for example, the treatment time or the halogen recording up to the point at the metal halide is just being released, is measured.

It is believed that under treatment conditions where the treatment prior to Release of metal halide is terminated, the halogen is bonded to metal atoms that form a part form a solid catalyst surface.

The catalysts are generally under an inert gas, ζ. Β. Hydrogen or nitrogen, and kept under this inert gas after their formation. Water must be excluded from the system, at least to the extent that there are no more than a few parts of H ₂ O per million in the inert gas.

The catalysts prepared according to the invention are particularly suitable as polymerization catalysts for mono-, di- and polyolefins, acetylenes and organic compounds which contain a functional group and an olefinic and / or acetylenic bond, including copolymerization, interpolymerization, graft polymerization and block polymerization. They are particularly suitable for the oligomerization of "-olefins of the general formula R - CH = CH ₂ , in which R is an alkyl, cycloalkyl or aryl radical, and especially of ethylene, propylene, butene-1, 4-methylpentene- l, butadiene, isoprene and styrene.

The polymerization, which is not the subject of the invention, can be batchwise or continuous be carried out, the catalyst for example as a fixed bed, moving bed or fluidized bed can be used. The reaction is carried out especially in the presence of a diluent. It is expedient to use diluents and the solvents for at least some of them

is of the product.

example

4.9 g of titanium dioxide (produced by hydrolysis of tetra-n-butyl titanate) were chlorinated by tetra-

chlorocarbon vapors were passed over the support in a stream of nitrogen at a temperature of 191 to 202 ° C. until the escape of _{TiCl 4} vapors from the reactor was visible, at which point the treatment was stopped immediately. The chlorine

content of this catalyst was about 5 percent by weight. Well, he was cooling off along with Coarse aluminum metal in a ball mill and ground under dry nitrogen. 1.5 to 2 g of the mixture obtained were then

transferred to a glass reaction vessel and used to polymerize 100 cm ^{3 of} 4-methylpentene-1. The polymerization was carried out for 2Q to 24 hours at room temperature in the presence of hydrogen and 100 cm ^{3 of} n-heptane with stirring.

After this time, the polymer was extracted with hot n-heptane at 80 to 98 ° C and the extract evaporated on a hot plate, the conditions used and the yields of polymer are given in the following table, in which the results

of three experiments of this type and for comparison the results of an experiment (experiment no. 1) are given in which the aluminum metal added to the chlorinated titanium dioxide for 1 hour 400 ° C was heated, but not ground.

attempt
No. TiO ₂ : Al
Weighted ratio Grinding time
hours Deployment
em ³ K ^ catalyzer
weight
G Pplymerisaiionsr
duration
hours Polymer yield
g / g catalyst 1
2
3
4th about 10: 1
12.1: 1
3.3: 1
1.1: 1 0
66
169
120 10
100
100
100 0.6
1.5
2.0
1.5 2
24
20th
29 0.75
1.81
10.3
6.2

In Runs 3 and 4, air and water were used carefully during all phases of the reaction locked out. The polymers formed were very viscous liquids with boiling points above 500 ° C (corrected to normal pressure).

The comparative tests were carried out until the final maximum yield was effectively reached became. This means that in comparative experiment 1, even after 2 hours, there was no higher yield could be achieved, but in the other examples the mentioned considerably higher Yield is approached long before this final result is achieved. The extraordinary high yields with long milling times cannot even come close to being achieved without milling will.

Claims (1)

Claim: Process for the production of metal oxides of the IV. To VI. Subgroup of the periodic System, optionally together with aluminum oxide, and halogen-containing catalysts, in which the metal oxides with a halogenated compound of methane, which contains more than 1 halogen atom, at temperatures up to 593 ° C under such conditions 5 6 be halogenated so that the halogen is different from that in a ball mill with a reducing Oxide ground in an amount of 1 to 15 parts by weight of metal. percent is absorbed, thereby indicates that the product obtained is considered: then at least 50 hours, French patent no. 1163 071; especially at least 100 hours, preferably British Patent No. 858185. 809 638/1676 11.68 © Bundesdruckerei Berlin