DE1920868A1 - Process for the production of higher molecular weight olefins - Google Patents

Description

Process for the production of higher molecular weight olefins.

The invention relates to a process for converting low molecular weight olefinic hydrocarbons into higher molecular weight olefinic hydrocarbons.

According to the invention, a process for the production of higher molecular weight olefinic hydrocarbons is created, that consists in that one or more lower molecular weight olefins with a disproportionation catalyst and a polymerization catalyst re-contacted under such temperature and pressure conditions causes disproportionation and polymerization to occur,

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The lower molecular weight olefin refers to an olefin that contains 2-6 carbon atoms per molecule.

The starting olefin can be ethylene, propylene, butylene, Be pents, witches and the like. The olefin can be an olefin or a mixture of an od -olefin and an inner one Be olefin. Preferably, ethylene is used as an integral part or as the sole component of the Feeding present, in which case particularly useful products are obtained. When the disproportionate- function of the catalyst in relation to the polymerization * function predominates, then in this case, under suitable conditions, a product is obtained which is im consists essentially of linear od-olefins.

When ethylene is used as a starting material, any other linear olefin can be terminated or internal, with the ethylene at any stage either as a component of the feed or in be introduced into a recirculating stream. Branch-chain olefins also take part in the reaction, however the branch remains in the product.

As polymerization catalysts are suitable those which selectively for the formation of linear polymers of ethylene and other olefins are Ot _o These include cobalt-carbon, which may be prepared as described in British Patent Specification 1 02 V 314 and the British Application 8360/67 ^and; * 3176/67 of the Anuielderin described, nickel complex - aluminum - alkyl and related catalysts, described in the

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British. Patent specification 1 101 498 and the British application 58823/67 and the German application P 18 13 II5.2 of the applicant, aluminum halides and other transition metal catalysts, as they are for example in the applications P 15 68 130.8, P 15 68 135.3 »P 15 95 372.7, P 15 68 226.5, P 15 68 224.3 and P 16 16 072.6 of the applicant are described, and catalysts, such as nickel oxide-silicon dioxide-aluminum oxide, molecular sieves, exchanged with nickel, as described in British application 5049I / 67 by the applicant, and aluminum -Siliciunidioxidi- _s exchanged with nickel, such as are obtained, for example, by treating silica gel with an aluminum compound such as aluminum sulfate, and then impregnation with a Niokelsalz, for example, nickel nitrate, and heating, British Patent specification 1 Ο69 296th

Specific ranges of reaction conditions must be determined for the selective formation of linear olefins and applied to any particular catalyst. Either or both of the catalyst components can be used be homogeneous with the olefin mixture provided that an appropriate procedure is followed. Catalysts which easily convert internal olefins branch-chain products among the required Polymerize reaction conditions are not suitable in this process.

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A disproportionation catalyst is a catalyst who has the ability to convert an olefin into a mixture of olefins with higher and lower To effect carbon numbers as the starting olefin. "The catalyst can be a heterogeneous disproportionation- catalyst, for example a mixture of molybdenum oxide and aluminum oxide, which is preferably cobalt oxides contains and optionally contains smaller amounts of alkali metal or alkaline earth metals, molybdenum, volfram or Rhenium carbonyls applied to aluminum oxide, silicon dioxide or silicon dioxide-aluminum oxide, Tungsten oxide applied to aluminum oxide and rhenium heptoxide applied to aluminum oxide.

However, a homogeneous disproportionation catalyst can also be used.

In British Patent 1,125,529 there is a homogeneous catalyst system of three components described: A) an organometallic compound of . Groups Ia, Ha, Hb or IHa of the periodic table, B) a salt of molybdenum or tungsten and C) a defined organic compound containing oxygen or contains sulfur, e.g. ethyl alcohol. In the applicant's British application 1062/68 is a homogeneous disproportionation catalyst system described which l) a salt of molybdenum or Tungsten and 2) an organometallic compound of a metal in Group IVb of the Periodic Table of Mendelejeff contains.

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The process can be carried out at a temperature in the range of% O to + 20O ⁰ C. The pressure is preferably at least sufficient, including maintaining a suitable concentration of the starting material in the liquid phase. added mini aldruok about 7 atmospheres (100 psig).

When selecting catalyst pairs, care should be taken to ensure that they are tolerated well and that catalysts are selected which have reasonably optimal working temperatures, for the case of the polymerization catalysts described in British Patent 1 101 498 and British Application 58823/67 and the application P 18 13 115 * 2 describes the preferred Arbeitsteaperatur in de · Bereioh 20 - 6O ⁰ C. For other Polyaerisationskatalysatoren is the preferred temperature range 20 -> 180 ° C. Cobalt throat and phenylene oxide are a very suitable pair. When working on this system, the preferred temperature range is 0 to 60 ° C. On the other 'hand, the Kobaltaolybdat-Aluainiuaoxidkatalysator is Niokeloxid-Silioiuadioxid-Aluainiuaoxid Onea or related catalyst can be used at about 150 ⁰ C zweokaäBigerweise old comparatively unwirksaa at Teaperaturen at 10O ⁰ C and can.

Products with a high oC olefin content can be obtained, but a high ratio of disproportionation catalyst to polyaerization

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catalyst used with a large excess of ethylene. However, these conditions generally result in relatively low molecular weight products. If it is necessary to use lower ratios of disproportionation catalyst to polymerization catalyst, to use sator and lower ethylene concentration, usi to promote the formation of lower molecular products, The difficulty can be overcome if the product from the main reactor is fed into an auxiliary reactor, which is a disproportionation catalyst contains alone. B * can contain excess ethylene in the Auxiliary reactor are pumped. It can if necessary low molecular weight olefins from the end effluent river separated off by distillation and fed back into the main reactor, with the higher ao-ocular Ot -Olefine as a «product stream.

The process »can be in swti separate catalytic converter. beds are carried out with loading first a polymerization catalyst sweoks conversion into an Oenlseji venoi "and internal olefins and then a" Dlsproportionierungskatalysator if necessary with the addition of ethylene to convert the internal olefins is fed in φέ-olefins. The product or part The same is then returned to the polyaeration catalyst, if necessary, to repeat the process as often as necessary. This method is involved, but it is on one

BATH ORIGINAL

continuous basis is feasible and is necessary when the two catalysts operate under different conditions of temperature and pressure etc. have to work. However, it is preferred to select catalysts that operate under the same conditions, in which case an appropriately proportioned mixture of the Catalyst components can be used in a single reactor.

The invention is illustrated, but not limited, by the following examples. example 1

Coconut shell charcoal of the Ultrasorb SC II class of 8-12 mesh (British Carbo Norit Union Ltd.) was used. Washed in 10% v / v nitric acid for 1 hour, then washed thoroughly with water and at 300 ° C for 1 hour dried in nitrogen. The coal was in 0.880 Ammonia (91 ccm / 100 g coal) was stirred in and stood for an hour. The bulk of the excess Ammonia was removed by heating on a hot plate. The ammonia treated charcoal then became one Solution of 492 g of cobalt nitrate hexahydrate in 80 ecm of water added. After standing for an hour, the mixture was transferred to a filter funnel and air was drawn through the solid until it was dry to the touch. Next was another 50 οcm 0.880 ammonia added to the solid with stirring;

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the mixture was sucked dry again with air. A portion of the solid (50 g) was passed through a condenser tube under nitrogen into 250 ecm boiling pure n-undecane for 5 hours. Decomposition gases were evolved and were removed in a purge stream of nitrogen. Excess water that evolved was collected in a Dean & Stark trap. After cooling, the n-undeoane was filtered off and the solid was transferred to a Soxhlet extraction apparatus. Excess n-undecane was then extracted from the solid with boiling n-pentane for 18 hours under nitrogen. Finally, the solid was transferred to a muffle furnace and ^{heated in a slow stream of nitrogen at 400 °} C. for 1 hour. The activated catalyst was then allowed to cool and was stored under nitrogen prior to use. The catalyst contained 15% by weight cobalt.

Some aluminum oxide (Peter Spenoe Class A) was immersed in a 10% strength by weight aqueous solution of ammonium perrhenate, which was heated on a boiling water bath. The mixture was stirred until the solvent was evaporated substantially "The solid was dissolved in a" oven at 11O ⁰ G overnight ge "* trooknet and was then activated, it indent 24 hours at 58Ö ^east C heated in tattt was; it was finally flushed nitrogen through the catalyst, int dlie

to displace, and the solid was allowed to cool and was stored in nitrogen until needed '. The catalyst contained 8% by weight of rhenium.

The cobalt-carbon catalyst (5.0 g), the rhenium heptoxide-alumina catalyst (10.0 g) and 50 oon n-Pentane was placed under Stioketoff in a 1 liter stainless steel autoclave.

The pentane was used to maintain a liquid phase in the early stages of the polymerization reaction. Ethylene was pressed into the autoclave at up to 105 atii (1500 pe ig) at 10 ° C. The autoclave was shaken for 17 1/2 hours. Initially the temperature rose to 21 ° C, but soon fell to a constant temperature of 12 ° C, which was maintained without the addition of heat. The pressure steadily dropped to 49.9 atU (710 psig) during the experiment. The contents of the bomb were slowly drained into cold traps (solid carbon dioxide / acetone), unreacted ethylene and some propylene being let into the atmosphere. The liquid product was analyzed and found to contain n-pentane and 200 g olefins which consisted of 1 g propylene, 114 g butenes, 28 g pentenes, 28 g hexenes, 5 g heptenes, 10 g octenes and 14 g higher molecular weight material . The butenes contained 86% butene-1 and were 100% linear; the pentenes contained 40% pentene-1 and were 97% limemr; ile Hexene would contain * 51% lexem-l imi ware «su 95% limear; i le »te» e would contain »84% ■ eytem-l« M was «s« $$ % lime ar. Wr sesame t content Im

BATH

Linear CC olefin product was therefore greater than 62%. It will be appreciated that the linear internal olefins could be reacted with more ethylene in a bed of the disproportionation catalyst to further increase the yield of linear α-olefins. Example 2

Cobalt / carbon catalyst (lüg) and molybdenum oxide / aluminum oxide catalyst (20g) were mixed and taken Nitrogen in a 1 liter autoclave

* Sealed stainless steel. The cobalt / charcoal catalyst was produced according to the method of British patent specification 1,024 and consisted of 18% by weight of cobalt, as it was dispersed in an unknown form on coconut coal with parts of 12-18 mesh. Catalyst was prepared by impregnating Spence "A" alumina, dried under vacuum at 120 ° C, with an aqueous solution of ammonium molybdate

k and the mixture evaporated on a steam bath; the Catalyst was dried at 110 ° C and activated by heating in dry nitrogen at 58O ° C for one hour; the catalyst contained 8% by weight of molybdenum. The autoclave was heated to 40 ⁰ C. Ee ethylene was pumped in up to 23 * 2 atmospheres (330 psig). These conditions were maintained for 17½ hours. The contents of the autoclave were then drained into the cooled storage container (solid ·· throats * lexit / aft · th); ·· me 4 en

BAO ORIGINAL

480 g of liquid condensed. Analysis of this product showed the presence of 60 g propylene, 72 g linear butenes, 10 g pentenes of which 95-100 % were linear pentenes, 172 g hexenes, of which 86.0% were linear hexenes, 72 g heptenes, 32 g octenes and 62 g. Nonenes, decenes and other olefins of higher molecular weight.
Example 3

There was prepared a Nickeloxld / rhenium / Alurainiumoxid catalyst by some Spence ^{Η Α Μ} Alirniniumoxyd under vacuum at 120 ⁰ C dried and then dipped in a saturated aqueous solution of nickel nitrate for 3 hours at room temperature; the solid was filtered off and dried at 110 ° C. in air. A portion of this material was then added to an aqueous solution of ammonium perrhenate; the mixture was heated on a steam bath until essentially dry and was finally activated by heating in dry nitrogen at 550 ° C. for one hour. The rhenium content of the catalyst was 5% by weight.

A portion AEE & catalyst (10 * 2 g) was itat he nitrogen eat a 1 liter autoclave made of nichtrosteficte »steel verschlössen atif and heated to 120 ° C. Es feines Ät ftylew Felsen jsö 1Ö5 & iü (± 500 peig) eiage- wtä € f ÄutuMfiv ± 7 hours lattg under a € t TempGf & tti * fe # i m &^& U geicfeüttelt »Then

the Ißhalt this ΑοΙοΚΪSv # ö iä cooled receptacle

■ .-. Ät- - ' drained (solid carbon dioxide / acetone); it was 93 g

Condensed liquid consisting of 58 g of propylene and n-butenes, 4 g of pentenes, of which 89 % were linear pentenes, 13 g of hexenes, of which 77 % were linear hexenes, 5 g of heptenes and 12 g of octenes and higher molecular weight products. Example 4

There was prepared a nickel / alumina catalyst from the restliohen impregnated with nickel nitrate alumina of Example 3 after drying at IiO ⁰ C. The material was activated by passing it was heated for 1 hour at 55O ⁰ C in dry nitrogen. A portion of the catalyst (20.1 g) was sealed in a 1 liter stainless steel autoclave under nitrogen and was heated to 120 ° C. It was pumped pure ethylene up to 105 atm (15OO psig) and the autoclave shaken for 19 hours maintaining the temperature at 120 ⁰ C. The contents of the autoclave were drained into cooled receiving containers (solid carbon dioxide / aoetone); only 31 g of liquid were condensed, of which 22 g were linear butenes, 4.5 g were hexenes, of which only 21 were linear, and 4.5 g were octenes, oeoenes and other ethylene oligomers with a higher molecular weight «

Example 2 is similar to Example 1 with the difference that the rhenium catalyst was replaced by a molybdenum catalyst and the cobalt / carbon catalyst naoh a “process was established that was somewhat raging

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that of example 1 differs. Example 3 shows the use of a supported Niokel catalyst used at a higher temperature. The catalyst is remarkable in that both disproportionation and oligomerization functions are present in a single catalyst. Example k is for comparison purposes only and shows the lower activity and inferior quality of the product which is obtained when the disproportionation function (rhenium) is omitted from the catalyst of Example 3.

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Claims (6)

Claims 1. A process for the production of higher molecular weight olefinic hydrocarbons, characterized in that one or more lower molecular weight olefins with a disproportionation catalyst and a polymerization catalyst under such temperature and pressure conditions brings in contact that disproportionation and polymerization occur. 2. The method naoh claim 1, characterized in that the charge contains ethylene. 3. The method according to any one of the preceding claims, characterized in that the polymerization catalyst Contains cobalt on coal. k. Process according to one of the preceding claims, characterized in that the disproportionation catalyst contains rhenium heptoxide on aluminum oxide. 5. The method naoh one of the preceding claims, characterized in that the method is performed at a temperature in the range ⁰ to 4200 HTO C. 6. The method according Anspruoh 3 and k, characterized in that the process is carried out at a temperature in the range 0 to 60 ⁰ C. '9,098 4 47 17 07