DE1768993A1 - Process for the production of heptenes - Google Patents

Description

(US 661 225 - prio I7.8.67

US 661 309 - prio 17.8.67 '

US 683 447 - prio I6.ll.67 5652)

Esso Research and Engineering Company

Elizabeth, N.J., V.St.A.

Hamburg, July 18, 1968

Process for the production of heptenes

The invention relates to a method for ming copolymer is of propylene and n-butylenes to predominantly straight-chain or mono--branched Cg, C ₇ - and Cg-olefins in high yields, which particularly useful as starting materials for the production of low-branched alcohols by oxonation are. Lightly branched alcohols can be used to produce high-quality plasticizers. In particular, the invention relates to a method for selectively codimerising of propylene and n-butylenes in liquid phase in the area --irt of a nickel oxide-supported catalyst to form reaction products ω ^ It hohc-v;.] Heptenes content of which oxcaricr to Isoocfcylalkohcl ;. λ can be grounded. By regulating the _{Reaktionstedingungen:} .ΐ-ι ^ ο'ϋ'Υη ^ ν 'of the ratio of the starting materials ,, the pressure and ^ -r Tempe temperature, selectivities for the formation of hop t: ;;. : ■■■■. . ■ .., viir- ' about y \% and about ^ 5 % and above got w « ■■.!' Y; · !! '; ·. ^, Σ; -! · Ei are Cg-, C _? - and Cp-olefin; ν .; age.

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It is well known to use olefins in thermal or catalytic Reaction systems with the same or different olefins to condense to polymerization products. These condensations are, for example, catalysts such as concentrated Sulfuric acid, aluminum chloride and various manganese, chromium, molybdenum, vanadium, iron, cobalt and Nickel oxides and sulphides are used.

US Pat. No. 3,255,275 describes a catalytic process for the preparation of heptenes by copolymerizing cyolefins with C 1-4 olefins in the vapor phase, with which high heptene yields are achieved. In this process, propylene and isobutylene are dimerized by reaction under elevated pressure and at temperatures of at least about IJiS ⁰ C to about 288 ° C to au a certain degree. In order to reduce the heptene yield, dilsobutylene is used instead of or added to the mixture of C, - and Cj ^ -olefins

Acid catalysts, ie PiioDpL-ßfe or phosphoric acid, on suitable supports are used for the balanced process. These catalysts are known as commercial products and consist, for example, of phosphoric acid on kieselguhr supports, in which the phosphoric acid is present ^{on the} _{support, for example, in partially dehydrated form and essentially as P 2} Oc "

1C28A9 / 1928

Heptenes are obtained with this method, however There are still various disadvantages, which one in the first place consist in the fact that the process is controlled thermodynamically, whereby the C -, - and C ^ «olefins used strongly to it tend to form both homopolymers and copolymers, and it is extremely difficult to regulate or limit the chain length of the molecules. In addition, the PoljTneren tend too much branching.

In contrast, in the process according to the invention, propylene and n-butylenes are reacted in the liquid phase in the presence of supported nickel oxide catalysts under conditions under which hepten-rich reaction products consisting _{predominantly of weakly branched Cg, C 7 and Cg olefins are obtained} expediently under increased pressure and at temperatures in the range of about. Performed 60 ⁰ C to about 149 ° C and preferably about T9 ° C to about 121 ⁰ C. The pressure is so high that the reaction system remains in the liquid state at the chosen reaction temperature. Preferably

2 becomes a pressure of about 10.5 to about 70 kg / cm and especially

2
from about 4 to 35 kg / cm above atmospheric pressure.

In the codimerization is the molar ratio of C ^ - to C-olefins an important variable in the starting material, which the

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The selectivity of the reaction system for the formation of heptenes and weakly branched Cg, 0 "- and Cg olefins is strongly influenced. Under normal process conditions, the ratio of Cu " to Cv ~ olefins is between about 1: 1 and about 5: 1 and above, and preferably between about 2: 1 and about 5.5: 1. The optimum ratio is still to a certain extent influenced by other process conditions.

Nickel oxide on a silica gel or other suitable carrier is preferred as the catalyst. The microfluidic oxide can be present as nickel oxide, nickel dioxide, nickel sesquioxide, nickel peroxide or mixtures of these and other oxides. Such mixtures mostly contain nickel oxide. The silica gel can be used alone or together with a catalysis accelerator and can be prepared by any known method. The support is expediently impregnated with about 0.1 to about 55 % and preferably about 15 to about 30% nickel oxide or oxide mixture , based on the total weight of the finished catalyst. Amorphous silica-alumina Ge? Has proven to be a very suitable carrier. which, based on the total weight of the carrier, contains about 15 to about 25 % aluminum oxide.

109849/1928 BAD original

It has been found that the urea ratio is a puncture of the catalyst concentration. Based on the total weight of the reactants ¹ , about 1 to about 100 % and preferably about 2 to about 50 % catalyst are used in the reaction mixture.

The following examples were run as batch trials in one Carried out stirred autoclave under autogenous pressure. The nickel oxide catalyst was initially applied to the autoclave a support made of silica-alumina gel and then given the respective η-butene. Then the propylene added and then brought the autoclave to reaction temperature.

Example 1 to 3

In all three examples, the reactor was charged with 5 g of catalyst and sufficient propylene and η-butene that a molar ratio of C _k to Cy olefins of 1.8 was present in the reaction mixture. The reaction was carried out at a temperature of SO ^{0 C for 60 minutes.} In each experiment, the reaction product was removed from the reactor after the end of the experiment and analyzed. The analysis results were as follows:

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example

butene used

Qlefin distribution in the product, Qew.jS Cf-

cH

^C 8

Total Cg ~, C ₇ - and Cg oxefins

'12

Butene-1 cis-butene-2 trans-butene-2 18.8
33.2
19.9 24.8
32.0
20.7 33.0
31.1
13.5 (71.9) (77.5) (77.6) 5.5
15.7
6.8 2.8
13.6
6.1 6.6
12.4
3.4

From the above values it is evident that were obtained regardless of the as ^rt usgangsraaterial used n-butene isomers relatively high yields of heptene and Cg to Cg olefin-ynes.

In contrast, in the same experiments in which the n-butylene was replaced by isobutylene, only a codimerization of isobutylene with propylene of about 1 to 2 % and a broad distribution of reaction products were obtained, with both the propylene and the isobutylene monomer homopolymerizing.

To understand the importance of setting the molar ratio of C ^, - to Showing C-2 lines in the starting material has been a number of Tests carried out in which this ratio varied, but the other reaction conditions were kept constant. the Results are shown in the following example.

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Example 4 .

A series of tests was carried out under the same conditions as in Examples 1-3, but the reaction time was reduced to 30 minutes and butene-1 used as Cj, -Ol of in. The molar ratio of C ^ to C ^ olefins in the starting mixture vmrde varied in the individual experiments. The reaction products of the experiments were analyzed and the following results were obtained:

Molar ratio Witches Weight % Olefins in the product Butene: propylene
in the starting mixture 56 Heptene Octene Cg »to Cg olefins 0.5: 1 38 all in all 1: 1 18th 20th 7th 83 2: 1 14th 30th .12 80 3: 1 12th 40 22nd 80 4: 1 8th 45 28 87 5: 1 43 34 89 42 38 88

From this it can be seen that optimum conditions for the selectivity can be selected which, under the experimental conditions, were at molar ratios of about 3: 1 or slightly above, in which the highest yield of heptenes of about 45 % was achieved. It was found here that the temperature and the mol ratio in the starting material are essential influencing variables, but that the product distribution no longer changes significantly after a conversion of about 50% propylene. The ratio of the starting materials is therefore the most important process variable.

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The table above also shows that the yields of Cg · and Cg olefins can be varied substantially while maintaining good heptene yields. Furthermore, it can be seen from the above values and from other observations that the product distribution is not regulated by equilibrium but rather kinetically. Under the reaction conditions, the Cg and Cg olefins are practically "inert", ie they neither convert back into the starting material nor dimerize further. Further experiments have shown that other n ~ butene isomers behave in a similar manner.

A major advantage of the invention is that only slightly branched products, i.e. straight-chain or simply branched Products, and no highly branched products can be obtained. To illustrate this are the following table the analytical values of the reaction product obtained according to Example 1 the analytical values of one with a commercially available phosphoric acid catalyst compared to the manufactured product;

Isomer Nickel oxide Phosphoric acid- catalyst catalyst 2,2, ^ -trimethyl soldering 0.0 1.0 2,2-dimethylpentene 0.4 1.7 3,3-dimethylpentene 0.0 0.6 2,4-diraethylpentene 0.2 14.3 2,3-dimethylpentene 19.5 31.0

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BATH ORIGINAL

17SSIiI

Isomeric nickel oxide phosphoric acid

Catalyst catalyst

2-ethylpentene 0.0 2, β

2 ~ methylhexenes 20.6 17.2

3-methylhexenes 30.2 26.8

n-heptenes 29.1 4.8

The table above shows that 80 % of the heptenes obtained by the process according to the invention are either straight-chain or have only one branch. In contrast, in the product obtained by the known process, only * μ 51 $ of the heptenes are weakly branched.

Another series of experiments was carried out in a continuous reactor carried out. The selectivity for the formation of heptenes was there not slightly different from the batch tests. The catalyst remained sufficiently active for a long time and could then be easily regenerated by burning in an oxygen-poor atmosphere at 593 ° C will. The results of these experiments are shown in the following examples.

; .; ■■■■■:; ■: i

Example ^ to 7

Sin for the continuous work orphan suitable reactor of 10 ml of fit was heated in a moving sand bed and charged with dry catalyst. Bas starting material which from a previously prepared mixture of propylene and butene-1 consisted of a refinery and had been dried over a molecular sieve, was from the top of the reactor

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- ίο -

introduced, and the effluent from the lower part of the reactor was throttled by a regulating valve so that the desired reaction pressure was obtained. The withdrawn product, i.e. both the liquid and the vaporous fractions were analyzed to determine the product distribution. the Results were as follows:

Example 5 6 7

Age of the catalyst, S ^ d n. Wt. Cg + / Qew. catalyst

R eaction terms

Reactor ^{temperature, 0} C pressure, kg / cm above atmospheric pressure

Speed of hydration, volume / ifol / hour. 2.4 2.4 4.0

3> 4 composition of the starting material

170 218 0 1067 163.0 186 5 814 85 78 123.5 35 35 35

4.3 0.00

24.5 0.09 0.02

71.22 0.14 Col Ratio 2.02 2.02 2.18

Cu Conversion, % 60.9 50.1 76.0

C / j conversion * % 41.2 28.3 36.5

Mol UB ^ converted C ^ / C,, .. 1.36 1.14 1.48

Oesa tea liquid product, 0ew. £ 46.5 34.2 41.8

4.74 4.74 0.00 0.00 25.73 25.73 0.12 0.12 0.02 0.02 69.11 69, H. 0.14 0.14 2.02 2.02

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Product distribution. Gew.Si

13.4 16.7 11.1 45 ^ 6 49, ^ 40.4 32.0 32.8 0.2 o> 1.1 5.9 8.9 2.9 1.4 is O

^U 12+

The catalyst regenerated from the experiments was at Reuse satisfactory in every situation. Thus, the product distribution when using the regenerated catalyst did not differ significantly or not at all from that Product distribution when using the fresh catalyst.

It has been found that both the batchwise and the continuous Working same products was obtained. So they had continuously heptenes produced have the same content of linear compounds as the heptenes produced in batches.

According to another embodiment of the invention, mixtures of Hersialbutfl'enen and isobutylenes can also be used as the starting material be used for copolymerizing with propylene.

Here, propylene and n-butylenes are used in a first zone liquid phase in the presence of a nickel oxide Tr agar catalyst with high yield to weakly branched, i.e. straight-chain and single-branched Cg- *, CU- and Cg-olefins. In In the same zone, isobutylene is converted to diisobutylene. the

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Cg olefins and higher olefins from this zone are then introduced into a second zone in which the Cg olefins and in particular the diisobutylenes are dedimerized and in the vapor phase in the presence of a phosphoric acid carrier catalyst be reacted with propylene. Here are the Cg olefins and the propylene is converted into a hepten-rich product mixture and the Cq- to C- ^ -olefiae can be separated off.

With this combination process it is possible to achieve high yields to obtain heptenes from the normally available Butylengemlsohen. In the first zone, the Normal butylene is converted into heptene and isobutylene is dimerized to diisobutylene. Die.Cg- and higher olefins are then converted into a Second reaction zone introduced, where the diisobutylene is converted to isobutylene and codirasrisiert with propylene in high yields to give heptene will. With this process, almost twice the yields of heptenes can be achieved than with the known processes from the customary butylene mixtures can be obtained. So it is not necessary the C ^ olefin mixtures in normal butylene and isobutylene fractions to separate, but the mixed butylenes can be used as starting material.

_{The C 7} -01efins obtained in good yield in the first zone are of exceptionally good quality. These C ^ olefins can

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either used alone or mixed with the C10 olefins from the second zone to form a first-class product. In this combination method also Cg ~ olefins high quality are obtained which are superior to the "with phosphoric acid catalysts alone or with Nickeloxydkatalysatoren mis Butylengemischen received Cg olefins.

The combination process is extremely flexible. Bs can ' μ for the production of all olefins suitable as intermediates for chemical processes ^ ie. from Cg ~ to C ^^ O ^ i'A * ¹⁶ ^ ¹ ^ d in particular of C ,, », Cq = and Cjg ^ olefins. The relative amounts of these olefins can be varied within a considerable range by changing the distribution of the propylene and butylene streams between the two zones of the process.

The invention is best understood from the accompanying flow sheet and is shown below in a preferred execution form. ™

The scheme shows a series of reaction vessels A and a series of reaction vessels-B. Row A contains a first reactor 10 ^ in which anodized oxide supported catalysts are used, and series B contains a reactor 20 _Å in which phosphate supported catalysts are used .

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L'W'jQ

A butylene blend from a refining plant, i.e. a blend of n-butylenes and isobutylenes, together with propylene introduced into the reactor 10 and in the liquid phase in the presence of a nickel oxide »supported catalyst among those described above Conditions for the formation of hepten-rich, predominantly from weak branched Cg, CL and Cg olefins implemented. Under normal operating conditions, a molar ratio of n-butylene to propylene will be from about 1.5s -1 to about 5: 1 or above and preferably from about 2: 1 to 3.5: 1 ang @ ~ turns.

The reaction mixture from the reactor 10 can optionally be introduced into an expansion drum 11, from which the residue fraction is then fed to a distillation column 12 and the top fraction to a second distillation column 13. The residue from the distillation column 12, which _{consists essentially of Gg +} olefins and isobutylene dimers, is then fed through a line 16 to the reactor 20 as feedstock.

C, "and Ch-paraffins and unreacted olefins are im essentially as the top fraction from the distillation column 13 withdrawn, Cg olefins as the top fraction from a column 14 and Heptenes of extremely good quality as the top fraction from a column 15. The residue fraction from the distillation «

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- ¹⁵ τ

column 15 is fed to column 14 and the residue fraction from column 14 is fed to column 15. The residue fraction from column 15, which _{consists essentially of xsobutylene dimers and Co +} -01efinen, is fed through line 16 to reactor 20 as feed material.

The residue fractions from columns 12 and 15, which _{contain isobutylene dimers and Cg +} olefins, are introduced together with propylene and C « ₊ polymers from a column 22 (row B) into the reactor 20 and there in the vapor phase in the presence of a PhosphorsMure supported catalyst under conditions to achieve a hepten-rich, essentially C- to C ₁₂ -olefin-containing reaction product reacted. In this reaction, the molar ratio of isobutylene to propylene (including diisobutylene, calculated as isobutylene) is between about 0.15 s! and 3z 1 and preferably about 0.3si and about> sl. The reaction is carried out in * the vapor phase at temperatures of about 1? 8 ° to about 288 ⁰ C and preferably about 177 ° C to about 232 ° C. The pressure is expediently between about 17.5 and about 211 kg / cm and preferably between about 35 and about 105 kg / cm above atmospheric pressure,

A partially dehydrated catalyst is used in the reactor 20 as a catalyst liquid phosphoric acid or equivalent compound on a suitable carrier such as kieselguhr, diatomaceous earth,

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Silica and the like are used; such catalysts are described in U.S. Patent 3,255,273. Appropriate liquid phosphoric acid is used; a concentration of about precalcined to about 110 ° C at about 204 ° C to about 260 ° C.

The reaction mixture from the reactor 20 is introduced into an expansion drum 21 in order to relieve the feed to the distillation column; the residue fraction from drum 21 is then distilled in distillation column 22. The residue from column 22 is returned through a line 26 to the reactor. This recycling is particularly appropriate to achieve at reactor temperatures above 232 ° C to higher yields of heptene by cleavage of the higher olefins, and to form a liquid phase for washing of tarry deposits on the catalyst in the reactor. Optionally, however, be treated and the whole residue or a part thereof may be in separate columns (not shown) to separate it into co- and C _q -01efine and C ₁ Q and C ₁ olefins. The top fractions from the expansion drum 21 and the distillation column 22 are combined and introduced into a distillation column 23 from which the C 1 = olefins are drawn off as the top fraction. The residue from the distillation column 23 becomes a distillation column 24 and the residue from the column 24 becomes a column

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fed. A mixture of Cg and CU olefins is withdrawn from column 24 as the top fraction; the C _? ~ 01efins can then optionally be isomerized to further suitable CU-olefins. The C "olefins are withdrawn as the top fraction from the column 25 and can then optionally be _{mixed with the higher-value C 7} -olefins from the column 15 (row A).

_{For further refining, a residue of C 7} - and Cg ₊ - and higher olefins can be drawn off from the distillation column 25 and further isomerized and distilled to obtain further C "-olefins.

An essential feature of the invention is the discovery of a very flexible combination process in which two different reactions are combined to produce starting materials use relatively low quality and at the same time use the

to increase valuable olefins. The combination process offers these and other advantages over the two individual processes when using them alone. Of course, there are still numerous modifications to the above based on the attached flow diagram described method possible without deviating from the essence of the invention.

booty and the quality of the valuable C ₇ »01efine and others

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For example, in cases in which the C ₇ product from both processes is to be combined, fewer distillation columns can be used. The outflowing mixture from the reactor of row A is then combined with the outflowing mixture from the reactor of row B and the residue from the first column, ie a CU / Cg splitter, is fed to a parallel column where Cg ₊ and polymers are separated .

In another modification, the outflowing mixture can from the reactor of series A can be separated into two fractions, i.e. into a C ^ / C ^ fraction, which is fed to the reactor of series B will »and a second Cj ^ Fraktlon, which with a suitable RUckstandsfraktlon of the same Siedeberelches is combined.

According to a further embodiment of the invention can also Starting materials are used which are contaminated with acetylenes and / or diolefins in such amounts that they Would normally poison the catalyst.

In this embodiment of the process according to the invention, a contaminated with acetylenes and / or diolefins is added Monoolefin starting material with hydrogen and polymerizes, i.e. dimerizes or codimerizes it in the presence of the above Niekeloxide supported catalyst described. In particular, be

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Starting olefins (innenstJindigen old or terminal double bonds) "it up to 6 carbon atoms int MoIeIcUl _1, above all propylene, n-butenes or mixtures thereof, admixed with hydrogen and the above-described conditions for the production of heptenreiehen, mainly of slightly branched ^C 6 ~ * ° 7 ~ ^ ⁰ * ¹ Cg olefins subject to existing product mixtures.

It was surprisingly found that the addition of hydrogen to reaction mixtures or starting materials suppresses the normally occurring poisoning effect of acetylene or diolefin impurities on the catalyst. This even affects the rate of change and the selectivity of the catalyst to form the desired dimers. The mode of action of this reaction has not yet been clarified, however it was found that the impurities in the presence of Hydrogen cannot be adsorbed on the catalyst surface. To avoid catalyst poisoning, an addition of about 1 mol to about 10 NoI and preferably about 2 mol to about 5 NoI hydrogen per NoI acetylene or diolefin in the reaction mixture proved to be suitable. It has proven to be practical as well Proven to saturate or almost saturate the reaction mixture under the process conditions.

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The following examples were run as a continuous process. It became one for continuous work suitable reactor of 10 ml capacity is used and heated in a moving sand bed. Before the start of the reaction, the reactor was filled with a dry nickel catalyst. oxide on silicic acid toner stick ~ (le.l loaded.

The material to be fed to the reactor was connected in a Manufactured storage container, which consists of a container with supply and discharge lines and a circulation loop for return the contents of the container existed. For the sake of simplicity, a very pure monoolefin was used as the starting material, to which precisely measured amounts of the impurities were added. The contents of the storage container have been removed of moisture continuously through a ^ A molecular sieve dryer guided. Sufficient hydrogen was introduced into the storage tank to saturate the circulating feedstock which was at about room temperature and that prevailing in the reactor elevated pressure was maintained.

The starting material was from above into the reactor with fixed Bed introduced, and the drain from the lower part of the The reactor was throttled by a regulating valve in order to maintain the desired pressure in the reactor. The feed

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to the reactor of starting material per volume of catalyst per hour, the temperature in the reactor to 100 ⁰ C and the pressure in the reactor to J55 and 56 kg / cm was maintained above atmospheric pressure to 2.4 parts by volume. The withdrawn product, ie both the liquid and the vapor portion, was analyzed to determine the product distribution.

Ex i el 8

In a first series of tests (Table 1), the influence of the addition of hydrogen on the catalyst was investigated. A positive effect was found, ie the catalytic quality of the catalyst was considerably improved. Butene-1, which contained a certain amount of 1,> butadiene as an impurity, was saturated with hydrogen and dimerized in the presence of a supported nickel oxide catalyst. The withdrawn product was examined after 2 days and then at intervals of 24 hours. The results are shown in Table 1 as tests 1 to 4 in a comparison test ;;; sjuiberges, which, like experiment 1, but without the addition of hydrogen to the starting material duroli ^ eftu; · ¹ ; vrurdt:

bath

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Table 1

Catalyst: NiO on silica-alumina oil 35 kg / cm ² , 2.4 VoIAoIA, 100 ° C ,

Comparative attempt 1 2 Y? 4th

Hydrogen addition no yes yes yes yes 1,3-butadiene in the

gangue material, weight 0.05 0.05 0.05 0.05 0.05 Conversion of butene-1,

^. 41.8 46.5 47.1 52.5 51.7

Product distribution

Dimer 76.8 84.4 6.2 83.9 85.8

Trimers 20.3 15.6 13.8 16.1 14.2

Tetrareans 2.9 0 0 0 0

From the above values it is evident that the hydrogen prevents not only the poisoning of the catalyst, but even that Catalyst activity increased and the product distribution improved. A comparison of the values of the comparative experiment with those of experiment 1 shows which values after a duration of the experiment of 2 days it was determined that the butene conversion when used of hydrogen is much larger. In addition, the Uimvandlimgsveruältnis increases with prolonged exposure Hydrogen on the catalyst still to what from the experiments 2 to 4 can be seen. Product distribution will also be final significantly improved by the addition of hydrogen.

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The advantageous effect of hydrogen becomes particularly clear when one considers that the rate of catalyst poisoning in the present case is directly dependent on the diolefin concentration. It has been shown, for example, that if 1 % of 1,3-butadiene is present in the starting material under the test conditions, the catalyst activity ceases completely within 24 hours.

The catalyst is in this case without the presence of hydrogen so poisoned. This is further clear from the following Table 2, which is carried out in the same manner as above Contains test series in which the butene-1, however, contained a larger amount of impurities. The analyzes were taken at one-day intervals after the analysis of Experiment 5 was performed.

'Table 2

Catalyst: NiO on silica-alumina gel "

35 kg / cm ² . 2.4 VolAol / h, IQQ ⁰ C

Experiment 5 6 7

Hydrogen addition no 1,3-butadiene Ια starting material, % by weight 0.34 Conversion of butene-1 37.5

no no 0.34 0.34 28.4 26.4

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From a comparison of those found in tests 5 to 7 Values show that the catalyst is poisoned relatively quickly during use.

Example 9

After the analysis of Experiment 7 it became: In the same reaction mixture Hydrogen introduced and further analyzes carried out at intervals of one day, in which the following surprising results were obtained:

Table 3

Catalyst: NiO on silica-alumina gel 35 kg / cm ² , 2.4 vol / vol / h, 100 ^° C.

Try L 8 JL AiL JLi

Hydrogen addition no yes yes yes yes

Butadiene in the starting

material, weight £ 0.34 0.34 0.34 0.34 0.34 Conversion of butene-1,

0ew. # 26.4 42.3 45.3 48.7 51.4

After the introduction of hydrogen, the conversion of butene increased considerably. This shows the overwhelming advantages of the Use of hydrogen.

BAD OWGLAL

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Example 10

It has been found that the catalyst was poisoned the more quickly the higher the diolefin content of the feedstock .jwr _s, ar. For example, it has been found that the catalyst activity when using a starting material with 0.7 % 1,3-butadiene in less than 2 days and when using a starting material with 1.8 % 1,3-eutadiene in less than 2 days Hours completely stopped. Such concentrations were used in the following experiments. The values given in Table 4 show the advantages of adding hydrogen in a process with a starting material containing Q "72 wt. $ 1,3-butadiene. The analyzes were carried out every 24 hours.

Table 4

Catalyst: NiO on silica
35 kg / cm ² , 2.4 vol / vol / h, 100 ° C 12th Clay gel 0
52 14th attempt 0.72
Yes
51.0 , 72
Yes
, 6 Butadiene in the starting material,
Weight %
Addition of hydrogen
Conversion of butene-1 0.72
Yes
52.3

The values show that the catalyst activity decreases a test duration of j) days not decreased, but actually had increased.

109849/1928 ORIGINAL BATHROOM

Example 11

The following table 5 shows the advantages obtained by adding of hydrogen on a feedstock containing 1.8 $ 6 butadiene were achieved. The analyzes were carried out at intervals of 24 hours over an overall period of 4 days carried out. A reaction pressure of 36 kg / cm was maintained in these tests.

table 5

Catalyst: HiO on silica-alumina gel 56 kg / cm ² , 2.4 vol / vol / h. 100 ⁰ C

Attempt 15 16 17 18

Butadiene in the starting material, Qev.fi 1.8 1.8 1.8

Hydrogen yes yes yes

Conversion of butene-1 23.8 26.6 29.9

From the above values it can be seen that the hydrogen is the Catalyst regenerated when the reaction continues.

Example 12

In a further series of tests, propylene and butene-1 mixed in the storage container and then in the reactor under largely the same conditions as in the preceding

1 ,8th Yes 36 ,8th

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play codimerized. Some attempts were made without hydrogen carried out and then iiiit experiments with the addition of hydrogen compared. The results are shown in Table 6.

table 6

Catalyst: NiO on silica-alumina gel 35 teg / en ² . 2.4 vol / vol / h, 100 ^c C

Attempts 19 20 21 22 23 '

Butadiene la starting material, wt Jf 0.02 0.02 0.74 0.74 0.74

Hydrogen addition no no no yes yes

C h / C, ratio im

Ausgöngsmaterial £ 2.11, 11 2.11 2.11 2.11

Conversion to C ₆₊ 41.8 4l, 0 25.6 39 * 3 45.6

From the fourth in experiments 19 and 20, which were obtained after one and two days, respectively, it can be seen that the catalyst is gradually poisoned even with a very low content of 1,4-butadiene. After the second day, the 1 _: 5-butadiene content was increased from 0.02 to 0.74 wt % dropped. By adding hydrogen in experiments 22 and 23, the catalyst was regenerated and its activity was significantly improved.

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BAD ORICifiU.

When the above experiments 19 to 2j> were repeated, but in which the impurities consisted of allene, acetylene, methylacetylene and thyne thyacetylene, similarly advantageous results were obtained by adding hydrogen. Very advantageous results have been achieved even with repetition of the experiments with hexene-1 and butene-2 and hexene-1 as A ~ _US gangs material for the production of dimers and codimers.

1 09849/1 928

Claims (18)

(US 661 225 - prio 17.8.67 US 661 209 - prio 17.8.67 US 683 447 - prio 16.11.67 5632) Essso Research and Engineering Company Elizabeth, N.J., V.St.A. Hamburg, July 18, 1968 Claims 1. A process for the copolymerization of propylene and n-butylene to predominantly straight-chain and singly branched Cg- * C- and Cg-olefins in high yield, characterized in that propylene and n-butylene are used in a molar ratio of butylene to propylene of about 1 : 1 to about 5: 1 and above a nickel oxide-supported catalyst at temperatures in the range of from about 6O ⁰ C to about 149 ° C and a pressure sufficient to maintain a liquid phase reaction pressure reacted together in the presence. 2. The method according to claim 1, characterized in that the starting materials in a molar ratio of n-butylene to propylene from about 2: 1 to about 3.5: 1. 3. The method according to claims 1 and 2, characterized in that that the catalyst used is nickel oxide on a support of silica-alumina-oil used. 1 0 ö ¹ H 9/1 9 2 8 4. The method according to claim ^, characterized in that a catalyst support containing about 10 to about 45% aluminum oxide is used. 5. Process according to claims 1 to 4, characterized in that a supported catalyst is used which, based on the total catalyst, with about 0.1 to about 35 0ew. # % Nickel oxide is impregnated. 6. The method according to claims 1 to 5, characterized in that one carries out the reaction at a temperature in the range of about 79 ⁰ C to about 121 ° C. 7- method according to claims 1 to 6, characterized in that that a pressure of about 10.5 kg / cm to about 70 kg / cm above atmospheric pressure is maintained in the reaction mixture. 8. The method according to claim 7, characterized in that one Maintained pressure of about 14 to about 35 kg / cm above atmospheric pressure. 9. The method according to claim 1, characterized in that one in a first zone propylene with a mixture consisting essentially of butylenes in a molar ratio of n-butylene to propylene 109849/1 928 from about 1.5 «1 b * - ^s about 5il or more in the presence of a nickel oxide supported catalyst at temperatures in the range from about 60 to about 149 ° C and a pressure sufficient to maintain a liquid reaction phase at a predominantly ^C 6 ~ * ^C 7 ^"1 ^ ^C 8" ^olefins and higher olefins-containing reaction product is reacted, separating the Cg and higher olefins from this reaction product, and in a second zone with propylene in a molar ratio of isobutylene to the propylene of from about 0.15: 1 to about 2: 1 in the Oasphase in the presence of a partially dehydrated phosphoric acid containing Tragerkatalysators at temperatures ranging from about 137 to about 288 ⁰ C to give an essentially of CG, CU and Cg to C ₁₂ ^"and higher olefins existing reaction product and the C ₇ - Separates olefins from this. 10. The method naoh claim 9, characterized in that one in the the starting materials in the molar ratio of n-butylene to the first zone Propylene from about 2: 1 to about 3.5: 1 and in the second zone that Starting materials In the molar ratio is isobutylene to propylene from about 0.3: 1 to about 3: 1. 11. The method according to claims 9 and 10, characterized in that that in the first zone a catalyst made of nickel oxide on a support made of silica-alumina oil and in the second Zone uses a catalyst made from a partially dehydrated liquid phosphoric acid on a support made from diatomaceous earth. 109849/1928 12. The method according to claim 11, characterized in that a catalyst support containing about 10 to about 45% aluminum oxide is used in the first zone. Ij5. Process according to Claims 9 to 12, characterized in that that a supported catalyst is used in the first zone, which based on the total catalyst is about 0.1 to about 25 Oew.J * contains nickel oxide. 14. The method according to claims 9 to lj>, characterized in that the reaction in the first zone at a temperature in the range of about 79 ° C to about 121 ° C and in the second zone at a temperature of about I76 to about 2j52 ° C carried out. 15. Process according to claims 1 to 14, characterized in that that the reaction mixture catalyzed by nickel oxide is mixed with hydrogen in order to maintain the catalyst activity. 16. The method according to claim I5, characterized in that the About 1 to 10 moles of hydrogen per mole of acetylenes and diolefins present as impurities are added to the reaction mixture. hb: bb T09849 / 1928