DE1940433A1 - Process for the production of C7 olefins - Google Patents

Description

19-0433

PATENT LAWYERS

DR.-ING. BY KREISLER DR.-ING. SCHÖNWALD DR-ING. TH.MEYER DR. FUES DlPL.-CHEM. ALEK VON KREISLER DIPL, -CHEM. CAROLA KELLER DR.-ING. KLÖPSCH

COLOGNE 1, DEICHMANNHAUS

Cologne, August 5th, 1969 Fu / Ax.

(Dhe British Betroleum Company Limited,

Britannic House, Moor Lane / London, - "E ', 0.2 (England).

Process for the production of Ο «-olefins

The invention "relates to a method of manufacture -From Cr ^ olefins by a two-stage process, which is a bisproportionation stage and a ...,. ■ - comprises an oodimerization step.

The method according to the invention for the preparation of C ^ olefins is characterized in that butene-1 with butene-2 in the presence of an olefin disproportionation catalyst to propylene and pentene-2 converts and the pentene-2 with ethylene in the presence of an Olefi-n-Oli- » gomerization catalyst to a G «-01efi.n implemented

G-emiaohe. of n-butenes .. "of any origin can be used as feedstock, which can optionally contain paraffinic material and / or small amounts of other olefins * The Ό, raffinate stream obtained from thermal cracking from which the most of the butadiene and isobutene has been removed " _o

The feed is used to remove and 00 980 8/176 4

_ ρ -

Ethylenes are preferably subjected to a selective hydrogenation treatment beforehand, for example by treatment with a catalyst containing sulphurized nickel on sepiolite, as described in the applicant's British patent application 40 375/65. After hydrogenation, the product should be less than 500 ppm, preferably less than 10 ppm Contain diene and / or acetylene. The bond · record material can then be an isomerization unterv / orfen in which the butene-1 is isomerized to butene-2 and a product is obtained in which no more than 8O ^c / o and not less than $ 10 of the total n- Butenes consist of butene-1.

Isomerization is used when the butene-1 / Butene-2 ratio for good conversions and good selectivity is unsatisfactory in the disproportionation reaction described below. For thermodynamic considerations is a maximum conversion of butene-1 and butene-2 to propylene and pentene-2 with a butene-1 / butene-2 ratio of 1.0 possible. .Butene-1 (but not butene-2) can, however, react with itself, whereby mainly ethylene and hexene-3 are formed. As part of According to the invention, this is an undesirable side reaction which can be suppressed to a certain extent, by making sure that butene-2 predominates over butene-1 in the feed. Are suitable Butene ~ i / butene-2 ratios in the range from 0.1 to 4, however ratios between 0.4 and 1.1 are preferred «

The isomerization stage has the purpose, if necessary, of adjusting the ratio of n-butenes in the "product" provide that a suitable feed for the disproportionation step Numerous catalysts are known which convert 1-butene into 2-butene, but it is advantageous to use the isomerization properties of the preferred for the selective hydrogenation reaction Exploit the catalyst. This catalyst can ever do

009808/1764

according to the chosen reaction conditions, different ■ ·> Isomerisierungsgrade simultaneously with the removal of dienes un <L.Aoetylenen to. In general, low temperatures and high space flow rates inhibit isomerization, while it is favored by high temperatures and low space flow rates. In practice, it is a relatively simple task to adjust these variables so that any butene feed that one is undesirable contains high levels of butene-1 can be treated to form a product which is well suited for the disproportionation reaction.

The reaction of butene-1 with butene-2 can be carried out with any known disproportionation catalysts, e.g. with molybdenum and aluminum oxide, which are preferably cobalt oxides and optionally small amounts of alkali metal or contain alkaline earth metal, colybdenum-j tungsten oxide Rhenium carbonyls on aluminum oxide, silicon dioxide or silicon dioxide-aluminum oxyä as a carrier, tungsten oxide on aluminum oxide as a carrier and rhenium heptoxide Aluminum oxide as a carrier.

Preferred as the disproportionation catalyst is Rheniumheptoxyd on alumina because of its exceptionally high activity at low temperatures _(e h. <Below 150 ⁰ C). * The Re ₂ Oo / algo ^ catalyst is preferably at temperatures in the range of. -20 to 200 ⁰ O, preferably 15 to 100 G is used.

The reaction can be carried out at normal pressure, reduced pressure or elevated pressure. It is preferred to operate at least at the pressure which is necessary to supply the reactants and products to the liquid phase at the reaction temperature Ια. keep. When the process is carried out continuously, the reaction times can be between 0.01 seconds and 10 hours, a time between G _f 1 seconds and 10 minutes being preferred.

. ■ - "" · Ο "9 S C 3rd / 1 T 6 · 4- - · ■ ■

If the process is carried out batchwise , weight ratios of olefin are too. Catalyst in the range from 1ΌΟΟί1 to 1: 1 suitable. The Verfahreηlann gegebe ene • optionally an inert diluent, Z will be ₀ as a paraffinic hydrocarbon or cycloparaffinisohen carried out in the presence of &.

The pentene-2 can by conventional methods, e.g. by Fractionation, from unreacted feedstock and optionally from isomeric pentenes and higher molecular weight, Separated products and passed over a cooligomerization catalyst for further reaction with ethylene " will. Any catalysts that favor the addition of ethylene to pentene can be used, however, the procedure is preferably used

the subject of the German patent, (patent

. registration P 19 24 865.8) is the applicant.

Suitable catalysts for codimerization are the pentenes and ethylene, for example, the alkali metals and / or their hydrides and / or their organometallic derivatives, the alkaline earth metals and / or their hydrides.

These compounds can be finely dispersed, e.g. by slurrying in oil *, or they are preferably on suitable carriers, e.g. alkali or alkaline earth salts, Coal, silicon dioxide and aluminum oxide, applied,

Preference is given to the one made from sodium or sodium hydride Potassium carbonate existing catalyst, which is described in British patents 933 253 and »1 066 113, respectively is.

For the codimerization reaction, the conditions lie in the following areas! . .

Temperature 0-25O ⁰ C, preferably 50-140 ⁰ C, Pressure 0-280 atm, preferably 56-140 atm

Space velocity

(calculated as liquid) 0.1-20 V / V / hour,

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- pentene / ethylene molar ratio: 6: 1 to 1: 6,

. . .- 'preferably 3s1 to 1: 3

The heptenes formed in this process are suitable as chemical intermediates for the manufacture of a wide variety of Products, e.g. from lubricants, adhesives, elastomers, plastics, pharmaceutical preparations, insecticides, insect repellants etc. They are particularly well suited for making Cg oxo alcohols over the hydroformylation reaction.

example

A typical, butene-1-rich, thermal cracking C 1-4 refinery stream, from which most of the butadiene and some of the isobutene had been removed, was passed over a sulfurized nickel catalyst under the conditions given in the table. The product contained essentially no dienes and the butene-1 remained in the product in such an amount that the butene-1 / butene-2 ratio was close to 1.0. This product was freed from excess hydrogen and passed over a rhenium heptoxide / aluminum oxide catalyst, which is mentioned in the table below. The total product only a small amount of heavy material which has been formed in the reaction which contained 36.7 wt -.% Of the major disproportionation products, namely, propylene and pentene-2. These products were 17.2 wt -.% (Based on the total product) of pentene-2.

Experimental data for the production of pentene-2 for the Conversion into heptene

1) hydrogenation / isomerization reactions .

a) catalyst: sulphurized nickel on sepiolite,

manufactured according to the German patent

(Patent application P 17 93 ^ 55V3) by the applicant S / Ni atomic ratio 0.07.

009808/1764

b) reaction conditions . - ~ ~

Pressure "5.6 atm

H ₂ / C. Molar ratio 5.0.

Space flow velocity
(based on the liquid state) 3.0 V / V / hour.

Inlet temperature 25 ° C

2) disproportionation reaction

a) Catalyst: 2.5 * Gew _e -? £ Re ,, O ~ on aluminum oxide,

manufactured by impregnation and activated "iO" according to British patent 1 105 564 of the applicant.

b) reaction conditions

Bridge 14 atü

Space flow velocity

(based on liquid level) 5.0 V / V / hour.

Inlet temperature ^{25 0 C}

3) Composition of feed and product from hydrogenation and disproportionation _.

Composition in wt .- ^

Use Uach selek- After Dispro-

tive Hp Isomers portioning - ization tion *

Ethylene - - 0.3

Propylene lane lane 19.5

Butanes 12.4 13.3 14.0

Butene-1 49.2 37.7 15.6

Isobutene 13.8 13.3 6.4

Butene-2 23.8 35.8 24.2

Butadiene-1.3 0.8 10 ppm 0.0

Pentene-2 - - ■ 17.2

Isopentenes - - 0.5

Witches ■ - - 2.3

Total 100.0 100.1 x 100.0

* After a running time of 7 days, excluding about 60 wt .- '/ product that is heavier than Og.

0 0 980871764

The product from the disproportionation was collected at about -70 ^Q C and distilled in a Hormaldru.ckkolonne with high efficiency, wherein a top fraction

■ ■> ■ "was obtained, which consisted of 98.4% by weight of pentene-2, 1.3% by weight of 2-methyH3utene-2 and 0.3% by weight of other material. 2 was passed with ethylene (2 mol G ^ "/ mol O ₂ ") over hydrogenated IJatriim on potassium carbonate, as described in the German patent ....... V. (patent application P 19 24 865.8) of the applicant, the middle The temperature of the catalyst bed was 78 ⁰ O (hot spot 80 ^ 0), the pressure was 105 atmospheres and the total amount fed in was 1 V / V / hour. Unconverted ethylene and unconverted pentenes were stripped from the product and recycled a hepten-containing fraction with the following composition:

Product wt .- ^

3-ethylpentene-1 81VT cis / trans -4-methylhexene-2 .V: - 6.6 trans-heptene-3 \ 5.7 ois-heptene-3 5.7 Other connections track

■ 100.0

The average yield of heptene fraction over 5 days of continuous operation was 128 g / hour / mol of sodium. '■' - ', ■ -. ;

009 8 0 8/1 7 6Λ

Claims (8)

Pat e nt a nap back e A process for the preparation of C ^ olefins, characterized in that 1-butene is reacted with 2-butene in the presence of an olefin disproportionation catalyst to give propylene and 2-pentene and 2-pentene with ethylene in the presence of an olefin oligomerization catalyst to give a C. ₇ -01efin implements. 2) Method according to claim 1, characterized in that rhenium heptoxide on aluminum oxide as a disproportionation catalyst is used. 1 or 3) Method according to claim / 2, characterized in that that the disproportionation is carried out at a temperature in the range from -20 ° to +200 ⁰ C, preferably in the range from 15 ° to 100 ⁰ C » 4) Method according to claim 1 to 3, 'marked thereby- net that an oligomerization catalyst is used which is an alkali metal, an alkali hydride organometallic alkali derivative, an alkaline earth metal or an alkaline earth hydride. 5) Method according to claim 4, characterized in that that one made of sodium or sodium hydride on potassium carbonate existing catalyst is used as an oligomerization catalyst. ' 6) A method according to claim 4 ^ or 5, characterized labeled in 25 'is characterized in that the codimerization is carried out at a temperature ranging from 0 ° to 25O ⁰ C, preferably in the range of 50 ° to 140 ⁰ C. 7) Method according to claim 4 to 6, characterized in that that the codimerization at a pressure in the range from 0 to 280 atmospheres, preferably in the range of 56 to 140 atm. · 0098087176Λ 8) Method according to claim 1 Ms 7, characterized in that that with a pentene / ethylene molar ratio in Range of 6; 1 Ms 1s6, preferably in the range of 3s 1 Ms 1: 3 is worked. · 00 98 08/176