DE1901648A1 - Catalyst and process for the disproportionation of olefins - Google Patents

Description

Patent attorneys

Dr. D. ^r ; _: T!

π :: i.zätke W ₄ V ** ■ ^Jan W69

Γ. ., iing description

...,; -v _cS 94 to the patent application of 1901648

Imperial Chemical Industries Limited, London, S.V.1.,

concerning}

Catalyst and process for disproportion · » ation of olefins

The priority of filings in Great Britain on 19.1.1968 u. 02.27.1968 is used

The invention relates to the disproportionation of olefins.

It is known that olefins, such as propylene and butenes, in the presence of buckets of disproportionation catalyst in a mixture of olefins with higher and lower molecular weights than that or the starting olefins are converted can, the olefins obtained from the exchange of Fragments between the originally existing olefin molecules develop. Propylene can be converted into a mixture of ethylene and butene, whereas normal butenes into a mixture of olefins with 5 to 6 carbon atoms in the molecule can be implemented. Propylene is also a product of the disproportionation of a mixture of ethylene and butene-2. But there is the formation of broth at the double bond takes place of olefins, symmetrical olefins alone cannot give new molecular weight products. Acquaintance Dispropertiomierum gas catalysts are molybdamtrioside, Volframtrioaqrd and Iheniumheptoxyd, which are usually on one Carriers made from alumina and / or silica are used.

I · it has now been found that the scope of Catalysts for the disproportionation of olefins are made worse by the fact that the Dieproportionierungskatalysttor • is added to the catalyst, which is used for the double bond system ve * olefins is effective. As is well known, Idelmetalle is the toramy · till of the periodic system of Ilcmemt · for Al · Iseaerisatiem of olefins effective. she beverswc * · * IscsMrisatiemskatalysatorcm are platinum and

909846/1237

The degree of formation thus becomes “a catalyst for disproportionation Clay olefins are created on products in an extended molecular weight range that binds a catalyst component, which is effective for the disproportionation of τοη olefins, and at least one catalyst component which is effective for the double bond isomerization τοη olefins, consists. The invention also proposes a method of disproportionate τοη olefins before, in which such a catalyst Tarwendet, and after the solohe products are produced.

The disproportionation component can consist of Holybdantrioxyd, VoIfraatrloxyd or Bheniumheptoxyd or Torsugweise Cobalt oxide and hollybdane trioxide exist.

Torsugaweiet © in noble metal of group viii of the periodic system of elements, e.g. platinum, ruthenium and Torsugsweiee FaIlKdIum _{1, is} used as the isomerization component.

The Isomerisationskomponsnte can isomerization τοη the Ausgangsiolefi & Mt that sS symmetrisch® »olefins may be, and / OTDR isomerization τοη Bispropo ^ ^ tioiiieruiig - products cause, di # daan another disproportionation may be subjected.. In this way, # 3i products are produced in an expanded Ifolekulargewiohtebereleli. Ais Auegangeole fine keasea. in general terms or Tarss ¥ ®igt @, \ in the interior or on the Sa & in, unsaturated olefins with 3 to 2 carbon atoms are used for the inventive process. A starting olefin mixture can also contain ethylene. The process ", according to which Izflndumg kasn is carried out in a series of open gate stages, where" in the holiermolecular fraction the product of an earlier stage than the supply current at the later epatere "stage or as a part of this supply current is continued and at the same time as the low molecular weight practical from the earlier stage worked up as a preduct or desired "if mladestems partially throws a" Tentuell Torhtrgthtntn stage lurttckführung.

909846/1237

It has also been found that by using τοη Alkali metal or alkaline earth metal ions as bases the oli gome ri eat ion τοη branched olefins, such as isobutene, inhibited and thus the participation of the branched olefins in the Codieproportionierung with straight-chain olefins ge can be requested. Another essential feature of the invention is therefore that the catalyst alkali » contains metal or alkaline earth metal ions. These ions can expediently be provided that the Catalyst an alkali metal »or alkaline earth metal oxide, such as sodium or potassium oxide is added.

The catalyst is preferably alumina and / or silica carried. However, titanium dioxide, magnesium oxide, Volframtrioxyd or boron oxide or combinations are also used as carrier materials suitable for these oxides.

Is the component responsible for double bond isomerieation of olefins is a noble metal of Group VIII of the periodic tables of the Hemente, so it is borne in the Catalyst is present in bulk in an amount of from 0.01 to 2% by weight, preferably from 0.1 to 0.5% by weight. Also amounts the content of alkali metal or alkaline earth metal ions is expediently 0.01 to 2% by weight, preferably 0.1 to 0.5% by weight in the supported catalyst. In the case of alkali metals with higher atomic weights, an alkali metal content of over 2 wt #, e.g., up to 5% by weight, may be acceptable. Simple attempts will be show the optimal salary in each case.

Q The catalyst can be prepared in various ways, ^ For example, a support can be impregnated with an aqueous solution of a salt of a group VIII metal, dried and ^ calcined to reduce the salt to the metal. Then ^ can that product with a solution containing a Balz the Dis ^"ω proportionierungekoaponente, impregnated calclniert and optionally sohliesslich with a solution of a suitable salt, for example impregnated of carbonates, bicarbonates or acetates of alkali metals or erdalkaliechen metals and ealoiniert again .

But you can also proceed in such a way that a disproportionation catalyst, e.g. with cobalt oxide and molybdenum trioxide carried on alumina, initially with an aqueous solution of a Salt of a metal of Group VIII impregnated, dried and calcined and then, if desired, with an aqueous Solution of a suitable salt of an alkali metal or alkaline earth Metal is impregnated and dried again.

Suitable catalysts can also be formed by simultaneous precipitation of the components of the catalyst and by simultaneous Cases can be combined with impregnation.

According to the invention, a process for disproportionation with isomerization of olefins to products in one proposed extended molecular weight range in the presence of a catalyst, the catalyst being off one or more components effective in disproportionation of olefins and one or more Components necessary for the double bond isomerization of Olefins are effective. Preferably, the catalyst components are carried on a carrier, however it is not essential that each catalyst bead contain the two components. £ s lies in the path of the invention, also to use mixtures or layers of catalysts that contain either the disproportionation component or contain the isomerization component. The procedure is particularly beneficial for the disproportionation of internally unsaturated olefins, e.g. butene-2, or of Olefin mixtures containing unsaturated olefins inside.

_o Does the Auegangsmaterial for Dlsproportionierungs- ^ process a branched olefin, such as isobutene, so tends · *>, the branched olefin for strong oligomerization to form ^ a product that substantial quantities of undesirable oligomers containing ^. ^Ω mixtures in the disproportionation of olefin containing a branched olefin, according to the inventive method, it is therefore preferred that the catalyst alkali metal or base metal erdalkalieche ions that inhibit the oligomerization of branched olefins. Such ions can be provided in a catalyst

which is effective both for the disproportionation of olefins and for the double bond omerization of olefins contains active component. In the case of a physical mixture of particles from two catalysts which (each have a disproportionation component or isomerization components, the ions can in the disproportionation catalyst and preferably also in Isomerization catalyst can be provided.

Mixtures of normal butenes and isobutene. are in trade and the process of the invention provides a method of disproportionating such mixtures per se or in the presence of other olefins, e.g. ethylene, without the same large numbers of diisobutene or others Oligomers of isobutene are generated which are disadvantageous appear when the higher boiling fraction of the final Disproportionation product is further reacted by the Qxo process to produce plasticizer alcohols.

In the disproportionation process according to the invention the olefin can be gaseous or liquid and the catalyst can be in the form of a stationary bed, a fluidized bed or a slurry. The temperatures and pressures known for the disproportionation of / an * sica can be used and the product can be recycled in whole or in part as desired.

It was further found that when olefins are disproportionated with the improved catalyst, hydrogen is also found may be present. Experience has shown that the service life the catalyst is prolonged by the presence of hydrogen, especially when the Auagangolefins are a mixture n-butenes and isobutene derived from a CL stream. Presumably the hydrogen, which is useful with the olefinic starting material can be mixed before this is brought into contact with the catalyst, for Reduction of the more unsaturated types of olefins, which are only available in small quantities in technical olefins and dasu tend to get stuck on the surface of the catalyst * u adhere and thus block active sites of the catalyst.

909846/1237

Han, a hydrogen concentration (based on the olefinic Ausgengematerial) of 10 ", using a hydrogen concentration of up to 10 vol% of the starting gas mixture, for example" * to 1, for example 10 ^-2 to 10 "" ¹ moles of hydrogen per mole of olefin.

The catalyst is preferably activated before use by calcination, for example at 550 ° C. for M hours. The spent catalyst can be regenerated by carefully burning off carbon and other organic batches and, if necessary, calcining the catalyst again.

The invention is explained in more detail below on the basis of exemplary embodiments.

example 1

The catalyst a) was an extruded catalyst with 3.6% cobalt-II oxide and 11 # molybdenum trioxide applied Clay.

The catalyst b) was prepared by stirring 12 g of catalyst a) with 120 ml of water and adding 120 ml of a 0.16N aqueous sodium bicarbonate solution to this mixture over a period of 2 hours, whereupon the mixture was left to stand overnight and then filtered and the beads were then dried for 4 hours at 100 ° C. It contained 0.236 sodium.

The catalyst c) was prepared by suspending 15 g of catalyst a) in 21 ml of water and adding a solution of 0.15 g of palladium chloride in 15 ml of O ₁ In aqueous hydrochloric acid solution to the suspension, whereupon the geese were added for 30 minutes stirred wJ / rd * .and the beads were then filtered off, dried for 2 hours at 100 ° C. and then calcined for> 4 hours in a stream of air at 480 ° C. ~ ° The product thus obtained was 12 g as in the case of the catalyst

b) treated. The final catalyst contained 0.2% sodium and 0.25S6 palladium. ·

Ban were three attempts in the given below Manner carried out, the catalysts a), b) and c) were used.

10 g of catalyst were poured into a quartz tube and then activated by a flow of air through the catalyst layer heated to 54O * C in an hourly Quantity of 15 liters was passed through for 3.5 hours. The air was then displaced by nitrogen and the catalyst was cooled to 150 * G, whereupon cis-butene-2 for 1 hour passed through the catalyst at an hourly rate of 15 liters. The composition of the product obtained Gas did not experience any change during the respective experiment. The products were determined by gas-liquid chromatography analyzed, with the following results:

Component Mo 1 # of the component at

Catalyst abc

Propylene 11.5 0.9 * 8.6 Butene-1 2.5 0.7 0.9 6.0 tranB-butene-2 28 26th 26th cis-butene-2 47 71 51 Pentene-1 0.1 0.2 Eis- and trans-Fenten-2 10.8 8.4

♦ not detectable

Thus, the rate of disproportionation with the _o catalysts a) and c) is about the same, while the catalyst b) ^ results in a lower rate. Thereby recognizes ** ■ that Hatrium the speed of the disproportionation co .. ..

·> - * slows down, while palladium increases it.

^ω Example 2

The experiments according to Example 1 were repeated with the Deviation that instead of cis-butene-2 alone a mixture of 75 ^ cis-butene-2 and 25% isobutene was used. the Analysis of the products had the following set of results

component Mole% of the component in C. catalyst 9.1 a b 5.2 Propylene 7.3 2.7 19.7 Butene-1 1.5 0.5 14.0 Isobutene 16.2 21.0 42.3 trans-butene-2 7.4 8.7 0.1 cis-butene-2 55.5 62.3 4.2 Pentene-1 • * 4.8 cis- and trans-pentene-2 5.6 0.9 0.5 Isopentes 3.7 1.9 Isobutene oligomers 4 7 2.1 (expressed as isobutene)

•not detectable

From this it can be seen that aatrium “was the speed of the Disproportionation decreased, jβdooh strongly hampers oligomerization of isobutene (catalyst b)). Veiter gives a catalyst containing both Hatriua and palladium a higher die * proportional to the rate of oligomerization Clay inhibits isobutene instead in the disproportionation reaction goes into how dl · · duroh the high content of isopentene is inclined in the product (catalyst c)).

Example 5

Xs were 15 g of a Teohnisehen CoO / IloO. / AlgCy-Katalyeatore in the form τοη Kügelohen, the 3.2% OoO and 14.6% HoO. contained, la entered to 21 al distilled water. Then 0.15 S PdOl ,, in solution in 0.1N sodium acid was added, and the mixture was stirred for 30 minutes at intervals. The spheres were then filtered off, dried for 2 hours at 100.degree. C. and sealed for 4 hours in a stream of air under 1 atmosphere at 550.degree. 120 ml of a 0.28N potassium bicarbonate solution were slowly added over the course of 2 hours with stirring to a mixture of £ J aua-12 g of these spheres and 120 ml of distilled water -J. The mixture was allowed to stand overnight, after which the filtered Kugelohen and 2 ßtunden at 100 ⁰ O were dried. The catalyst thus treated contained

1.2% potassium im and 0.25% palladium. A 10 g sample was in placed in a vertical flow-through reactor made of quartz and there for 15 hours in an air stream at 550 * 0 calcined. and then to the reaction temperature ▼ on 200 * 0 cooled in nitrogen.

Starting material consisting of 71t * cis-butene-2 and 29% Isobutene was in the catalyst layer for 5 hours an hourly volume of 4.2 liters passed through it. NaBh The conversion of the butenes was 36% in the first JO minutes, but only 8% after the 5 hours.

The experiment was repeated, under the same conditions and with the same starting material, but with the addition of 10 volts hydrogen. After the first 30 minutes the conversion of the butenes was 20% and the conversion became no less during the next 5 hours of operation.

The main products were each propylene and pentenes, with approximately equal amounts of isobutene and n-butenes in each case contain these disproportionation products.

These results show that hydrogen extends the life of the catalyst.

9Ü9846 / 123 7

- 10 -

Claims (7)

MOO MÖNCHEN S TAL S3 TELEFON Mil / 2ZNM TELEQRAMMAORESSE: THOPATENT 23 July I9B9 MÖNCHEN patent application P 19 oil 648.9 Imperial Chemical Industries Limited case H.2o 777 / 2o 863 T 297o claims 1) Catalyst for disproportionation with isomerization of an olefin or an olefin mixture to give products in an extended molecular weight range through the following components: 1) molybdenum trioxide, tungsten trioxide or rhenium heptoxide, preferably cobalt oxide and molybdenum trioxide, 2) Noble metal of group VIII of the periodic table, especially platinum, palladium or ruthenium and 3) a carrier made of alumina, silica, alumina / silica, titanium dioxide, magnesium oxide, tungsten trioxide or boron oxide. 2) Catalyst according to claim 1, characterized in that it has a smaller proportion of alkali or alkaline earth metal oxide contains. 909846/1237 ORIGINAL INSPECTED dmkT · Account «CM ·· 3) Use of the catalyst according to the Ansprtt- _; , Chen 1 and 2 for disproportionation with isomerization of an olefin or an olefin mixture to products in an extended molecular weight range. 4) Use according to claim 3 with an olefin charge of butene-2 or an olefin mixture of normal butenes and isobutene. 5) Use according to claim 3 or 4 using 4es catalyst with an additional proportion of alkali or Alkaline metal oxide especially with an olefin feed with branched olefins, such as isobutene, to inhibit the oligomerization of the branched olefins. 6) Use according to one of claims 3 to 5 in the case of a quinine charge with added hydrogen, preferably in a proportion of not more than 10% by volume of the starting gas mixture and optionally
hydrogen per mole of olefin. gas mixture and optionally in the range from Io to 1 mol water 7) Use according to one of claims 3 to 6 in a number of reaction stages, each with olefin disproportionation using a higher molecular weight fraction of the products from an earlier stage as feed stream for a later stage and with the return of a lower 909846/1237 molecular fraction from the earlier stage at least partly to an optionally preceding stage. 9098 46/1237