DE1618084A1 - Process for the dimerization of olefins - Google Patents

Description

DIPUCHEM. DR. WERNER KOCH · D R.-l N G, HI CHA RP GLAWE DIPL-ING. KLAUS DELFS HAMlUtG MÖNCHEN '1618084

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UNSCR ZBCHCN HAMIUKG, DCN

^HAMBÜtG P 4357/67
O / T

THE BRITISH PßTROLEÜM COMPANY LIMITED, London / England

Process for the dimerization of olefins,

The present invention relates to a process for the dimerization of an olefin to form predominantly linear diners in the presence of a cobalt or nickel-containing catalyst deposited on activated carbon. The term ■ dimerization "as it is used in the present specification, the union usfaßt of two molecules of the same olefin" and dl · union of a molecule • Ine .olefin · · with a "molecule a · different olefins.

* 1 m-

109813/1821

Such catalysts and processes are described in DRP 599 and U.S. Patents 2,380,358, 2,407,813, 2,407,814 and 2,692,295. From this prior art it is known that catalysts that by initial Impregnation of activated carbon with a cobalt or nickel salt of an oxygen-containing mineral acid, such as nitric acid, generally have the most favorable activities.

It was previously assumed that dienes are strong catalyst poisons, so that they are purified accordingly Starting materials for such processes found use. It has now surprisingly been found that not only the presence of limited "amounts of service is portable is, but that even their presence is expedient and the proportion and the apparent amount linear dimer increased.

According to the invention, therefore, a process for the dimerization of one or more olefins is proposed, which is characterized in that the olefin or olefins with a catalyst obtained by decomposing a salt of cobalt or nickel deposited on activated carbon, in the presence of an effective amount of a These are brought into contact under temperature and pressure conditions suitable for the dimerization.

Suitable dienes are cyclopentadiene, isoprene and especially butadiene.

1Q9813 / 1828

The dienes may be incorporated together with ■ DENR Aüsgan-gsmaterial _s or the catalyst may be pretreated with the diene before seIuesa contact with the starting material * If necessary cases, a combination of both procedures are followed.

Suitable starting materials for the process are (a) alpha «= oil, which is a double bond isomerization with internal olefins / such as butene-i, pentene-ij hexene« = ·! _s 4-Methylpehten-i, and (Ib) alplia "= oleefins _s which, while they are incapable of entering into a double bond isomerization with internal olefins, dimerize to products which contain alpha-olefins, which such isomerization can enter, e.g. ethylene and propylene.

For example, ethylene will form more butene-1 and less butene-2 when first dimerized by the process of the invention than it would form when dimerized by a similar process in the absence of a diene. The Simerisierung _s is preferably carried out at a temperature between -40 ° and + 200 ° G in particular la range of 0 ° to 100 ⁰ C in order to keep the Response ionsteilnehmer at least partially in the liquid state under sufficient pressure. "

The most suitable pressure depends on the starting material used. For example, the diaerization or coding of ethylene is preferably carried out at a pressure in the range of 500-1000 psi, while pressures lower than 300 psi are very suitable for butene and

109813/1828

are higher olefins. VS ίu

- 3 - ORIGINAL BATHROOM

It is believed that the main effect of butadiene consists in the suppression of a double) indion isomerization with insignificant dimerization. In the presence of a cobalt or nickel on activated carbon containing catalyst homodi— Alpha-olefins rapidly convert to linear products. Internal olefins slowly code with alpha olefins homodiinerize to branched chain products and internal olefins not.

If the starting product contains an alpha-olefin, that usually to a certain extent rait an inner one Olefin undergoes isomerization, and if this isomerization is suppressed, the product then becomes a higher one Content of linear olefins, and the apparent rate of polymerization is increased provided the formation of internal olefins, the branched chain dimers at a low reaction rate condition is reduced.

Likewise, if the initial reaction product is an alpha-olefin which normally undergoes some isomerization with an internal olefin, and if this isomerization is suppressed , a higher alpha-olefin-containing product is recovered.

Venn this product then dimerizes or codimerized are the added benefits of the in the previous paragraph, apparently.

10 ^ * 13/1828

BATH ORIGINAL

In the manufacture of catalysts, preference is given to an aqueous solution of a cobalt salt is used, as the catalysts so produced at lower Temperatures are more active than those containing nickel.

The activated charcoal, which is expediently an active, charcoal is like z, 3. Coconut shell charcoal, becomes expedient pretreated with nitric acid before impregnation ». The nitric acid can be used as an aqueous solution in one concentration of 8 - 40 wt. ^ are used, and the coal will Treated with the acid until the evolution of gas ceases. Purpose- ' Yes, the pretreated charcoal is then filtered and used Removal of acid traces and washed on it in, one Dried nitrogen stream. This pre-treatment-removed Traces of impurities which are present in the coal and which are detrimental to catalyst activity.

The acid pretreated coal is then preferably impregnated with an aqueous solution of cobalt or nickel nitrate or of an ammoniacal cobalt compound or of nickel formate, expediently with cobalt nitrate hexahydrate. It is advantageous to add such a large amount of a cobalt salt that a finished catalyst containing 5 to 30 % by weight of cobalt is obtained. The amount of salt solution used and its concentration can be varied to obtain suitable catalysts.

Zweokattßlg is di · aqueous ventilation of cobalt nitrate the pretreated carbon at Rauntemperatur or slightly elevated temperature added and the mixture is then allowed door βία * stand for half an hour or longer. The mixture is then filtered and the impregnated charcoal is dried, for example

ORIGINAL

Outside air, the salt is then decomposed by heating four dried and impregnated charcoal at higher temperatures. The resulting material can then be treated with hydrogen if necessary, but in many cases this is not necessary.

The exact composition of the finished catalyst is not known; it can contain cobalt or nickel in elemental form on the carbon, possibly in connection with oxygen or in connection with the carbon.

The invention is illustrated in the following examples: Example 1

A cobalt charcoal catalyst was made in the following manner:

Steam Activated Kokosnusschalenholzkohle from fineness grade "Ultrasorb * SCH 8-12 mesh in iO% (v / v) nitric acid was immersed for an hour with occasional stirring. The excess liquid was drained off and a further 10 % nitric acid was added. After a further period of 1 hour the solid was filtered off, washed vigorously with distilled water and dried under nitrogen at 300 ° C for 1 hour. This treatment reduced the ash content from 3% by weight to less than 1% by weight.

300 g of the acid-washed charcoal was stirred into a cold or slightly warmed solution of 600 g cobalt nitrate hexahydrate in 200 oca water . The mixture was then left to stand for 1 hour. The solid was filtered off and left to dry in the air for 24 hours or more »

109813/1828 bad original

The solid was placed in a vertical tube

8 cm through «=»

diameter) were placed _s-through, the a! nitrogen stream at a

2 speed.-Of 10 0 1 per hour per cm- · cross-section of the pipe (measured in the flow with cold nitrogen) was passed "-The nitrogen was heated by passing it through a coiled pipe = which was in a u S and bail he Warming with liquid - == keitsähnlich homemade bed IIAR immersed ₀ Uia eiue at the same constant temperature, the catalyst "maintain ,, -was through a tortuous at ä & s activator tube Electroseparators Hela coil additional heat sügeftöirt" Ber catalyst wwri © to approximately 20Q®C in O ₉ 5 stimden, heated and cooled in nitrogen

the lower- ¹ SqH- of the Bohr® © drain, Ss was heated again are the Φβορ / eratsar of the catalyst «during O ₀ 75 hours ojr & iiitg Ms © r was completely in the range of 280 - 3.00 * 0 *, Bar Ksfsslyaat®« · . was cooled in nitrogen - unü in . © in © ® trookscaia? Ös * rat »container, stored under nitrogen hl® for reference day-, ... '· _. ■ - .v. . . .. "

2 g of catalyst were placed in a 600 oss " SeMutteiasitQiElaven, and the autoki" old "oBrelnwB * butene-i at 600 pe ig and% 0 C 03 » 5 -Stsssigea put under pressure ^. The impure butene-i contained. 700 ppe butadiene, - -

80.7 g of a "polymer" base were obtained which contained 95 μt of octenes, of which 78.6 μt were linear octenes

The percentage of butene-i that remained in the unpolymerized butene was 61.5 %;

BATH

Example 2

Another sample of the in example i as starting material The butene used was mixed with a 6% strength by weight dispersion of Natriuni-aui-Potassium carbouate for 20 hours at Jang at 30 ° C treated. The resulting pure butene-i contained less than OK ppm butadiene. Less than $ 1 of butene — 1 was in this Treatment isomerized.

2O ₉ 2 g of another sample of the catalyst according to Example I was introduced into a 600 enr comprehensive rocking autoclave and the autoclave with pure butene-1 at 600 psig and 40 ⁰ C 23 set i / 2 hours under pressure.

24.0 grams of polymer was recovered. The polymer contained 90 % octenes of which 50.2 were linear octenes. The percentage of butene-1 ₉ you remained in the unpolynerisierten butene, amounted verifiable au * 3.5%

Eb evidently did that what was written in Example 1! Process yields a * significantly higher yield and a marked improvement in both selectivity for Oktenpolymerisation al "" ueb in the selectivity for the formation of linear octenes within the octenes and a marked decrease in the butene-1 isomerization as compared with the results of Example 2 described procedure.

The method of Example 2 does not include an example of the present invention. It has been listed for comparison purposes only.

109813/1828 bath

Example 3

Another sample of the cobalt charcoal catalyst, 20.9 grams, was placed in a 1 liter rubble. The autoclave was pressurized with 110 g of ethylene and 435 pounds of "impure" butene at 40 ° G. The pressure was initially 1030 psig but dropped to 390 psig in 24 hours.

The autoclave then contained 490 g butenes, of which 96.1 # butene-i were 42.1 g hexenes, of which not less than 93.5 f <> linear hexenes, octenes 7.1 g and 5.7 g Decenes and higher polymers.

- 9 -109813/1823

BATH

Claims (7)

to i.) Process for the dimerization of one or more olefins, characterized in that the olefin or olefins wit a catalyst, obtained by decomposing a salt of cobalt or nickel deposited on activated carbon in the presence of an effective amount of a diene to cause dimerization brought into contact with suitable temperature and pressure conditions will. 2.) The method according to claim 1, characterized gekennzeicluiet that the diene is cyclopentadiene, isoprene or butadiene. 3.) Method according to claim 1 or 2, characterized in that the diene is introduced with the starting material . 4.) The method according to claim 1 or 2, characterized in that the Auagangssaterlal or the catalyst old the diene is pretreated before the catalyst old is brought into contact with the starting material. 5.) Process according to one of the preceding claims, characterized in that butene-1 _t pentene-1, hexene-t or 4-methylpentene-1 is used as the starting material. 6.) Method according to one of the preceding claims, characterized in that the starting material contains ethylene or propylene. 7.) Method according to one of the preceding claims, characterized in that the dimerization at a temperature . voE -% Q ° C to + 2QÖ ° G is carried out under sufficient pressure to keep the reaction participants at least partially in a liquid state! hold sa ₀ . ■■ '-.10 - BATH 10SS13 / 1828 S ₈ ) ¥ © rfaliren according to claim 7> by means of the fact that the difflerization is carried out at a temperature of 0, - = 100 ° C. 9o) method according to one of the preceding claims, characterized in that -. that the catalyst by. decomposition is obtained from cobalt nitrate. 109813/1828, '""...' j _tl _ ^: '■ BAD ORIGINAL