DE1280869C2 - Process for the disproportionation, cyclization, addition or polymerization of acyclic, singly unsaturated olefin hydrocarbons - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4H0SW PATENT OFFICE

Int. Cl .:

C07b

PATENT LETTERING

BOIj 25; C08f -3/00 German class: 12 ο - 27 12o-19/01; Uo- (P 31860) 12 g- 11/06; 39 b4 Number: ] 280 869 File number: P 12 80 869.4-42 Registration date: May 21, 1963 Ausleeetetae: October 24, 1968

Issue date: June 26, 1969

The patent specification corresponds to the patent specification

In the field of hydrocarbon conversion, numerous catalysts have been used for Described conversion of paraffins and / or olefins into various hydrocarbon products. Many of these catalysts are solid substances, and the reactions using these catalysts are heterogeneous in nature. For example, various metals, metal oxides and metal chlorides applied to materials such as silica, aluminum oxide and the like. While with some reactions the carrier has little, if any, effect on the reaction in which the catalyst is used is to be exercised, many carriers themselves show a strong activity for catalyzing the reaction.

The present invention relates to a process for disproportionation, cyclization, addition or Polymerization of acyclic, monounsaturated olefin hydrocarbons, characterized in that one these olefin hydrocarbons under known reaction conditions with a catalyst brings into contact, that of a tungsten or molybdenum carbonyl and silicon dioxide, aluminum oxide or silica-alumina has been produced as a support material, the amount of carbonyl in the range between 0.01 and 20 percent by weight, based on the catalyst mass.

The catalyst used according to the invention can be obtained by directly mixing solid components, by impregnation and the like. For optimal activity it is preferred to heat the carrier material at elevated temperatures and for so long that it is prior to mixing with the metal carbonyl is activated.

The carrier materials used are silicas, aluminum oxides and silicic acid-aluminum oxides with large surface areas which are known and easily synthesized or obtained commercially be able. For example, silica gel can easily be precipitated from water glass solutions by adding an acid such as phosphoric acid. Aluminum oxide can be obtained from solutions of one Aluminum salt can be precipitated. The carrier material is preferably used in porous form, for example as a gel.

The support material is preferably first by heating with air and / or an inert gas such as nitrogen, at a temperature above about 260 ⁰ C, preferably to about ⁰ 82o C, activated at a temperature of about the 400th Activation of the carrier can be done in any desired manner. It is preferred, however, to air the support at elevated temperature or in an atmosphere of some kind of disproportionation, cyclization, addition or polymerization process for acyclic,
monounsaturated olefin hydrocarbons

Patented for:

Phillips Petroleum Company,

Bartlesville, OkIa. (V. St. A.)

Representative:

Dr. F. Zumstein, Dr. E. Assmann

and Dr. R. Koenigsberger, patent attorneys,

8000 Munich 2, Bräuhausstr. 4th

Named as inventor:
Robert Louis Banks,
Bartlesville, OkIa. (V. St. A.)

their suitable gas, such as hydrogen, helium, nitrogen and the like. The length of time the Carrier is kept at the activation temperature,

»5 depends on the temperature used, but generally the time is for at least 5 minutes heated. The substrate should be heated for a sufficiently long ^ time at a sufficiently high temperature to to remove virtually all of the free water present in the carrier.

After the carrier has been activated, the metal carbonyls are then either impregnated or introduced by dry blending with the activated carrier. Preferably, depending on the application method of the metal carbonyl, the carrier is treated so that 0.1 to 10 percent by weight of the metal carbonyl, based on the carrier, applied or introduced. If the activated carrier with the Metal carbonyl is impregnated, the metal carbonyl is preferably used as a solution in a hydrocarbon applied. Examples of solvents that can be used for the metal carbonyls are the aromatic hydrocarbons, such as benzene and toluene, cycloparaffins, such as cyclohexane and methylcyclohexane, and normal paraffinic and isoparaffinic hydrocarbons having 4 to 10 carbon atoms per molecule or mixtures of these hydrocarbons. Suitable paraffins include n-butane, n-pentane, η-hexane, isooctane and n-decane. The concentration of metal carbonyl in the hydrocarbon solvent is generally from about 1 to about 10 weight percent. The solubility of the

909 626/91

3 4

Metal carbonyls are usually in volumes of liquid per volume at room temperature door is quite low, and it is therefore often desirable to use catalyst per hour generally between about the hydrocarbon solvent to a temperature of 0.1 to about 20, preferably between about about 6. Temperature of about 65 to 72 ° C to heat the Me- In a similar way, the throughput rates are all catbonyl to solve. Usually it is necessary to use S ets in volumes of gas per volume of catalyst each maintain sufficient pressure to range from about 50 to about 10,000 hour for gas solution to keep practically completely in the liquid phase. or vapor phase process. The reaction time

The hydrocarbon solution of the metal carbonyl generally extends from about 1 second to is then with the activated carrier in one off- about 10 hours or more, preferably from about sufficient amount brought into contact with the ίο 0.5 to 5 hours. When working in the reaction vessel desired amount of metal carbonyl on the support with stirring is, for example, the catalyst or to be introduced into the carrier. A suitable concentration in the reaction zone in general The method that can be used is just enough in the range of about 0.5 to about 40 percent by weight Apply solution to the activated carrier completely of the reaction mixture.

to moisten. The hydrocarbon solvent 15 The above reactions can then be removed from the catalyst, for example, neither in the presence or absence of a dilution by purging with an inert gas with a tempering medium, but the temperature is generally below about 150 ⁰ C, and then the mean Use of a diluent, the carbonyl-containing carrier at a temperature of which is not detrimental to the reaction, preferably about 10 to about 370 ⁰ C, preferably 65 to 150 ⁰ C, 20 of a hydrocarbon diluent, preferably kept under vacuum, which is between about 1 to about To typical hydrocarbon solvents that can be ver-100 mm Hg absolute. The heat treatments that can be applied include the aromatic treatment can generally be carried out for a period of time from a few hydrocarbons such as benzene and toluene, cyclopa seconds to about 10 hours, refines and / or paraffins with up to 12 carbon, preferably about 0.5 to about 5 hours, with the as atoms per molecule, such as cyclohexane and methylcyclol, being used for longer times at lower temperatures anhexane, n-pentane, η-hexane, isooctane, dodecane and the like, and vice versa. If the metal or mixtures thereof. If vercarbonyl diluents are mixed dry with the activated carrier, they can be added from a small amount, if desired also a heat up to about 98 weight percent of the reaction treatment under vacuum within the above-mentioned mixture can be,
applied areas. According to the invention, all conversion reactions

The metal carbonyls provided with supports are either batchwise or continuously formed, Catalysts used in the present invention are conducted using either a solid for the most varied of reactions for the conversion bed catalyst process or in the reaction vessel under treatment of monounsaturated hydrocarbons 35 stirring or another method with moving value, including disproportionation of local catalyst or any of the known 1- and 2-olefins, the polymerization of 1-olefins, contact processes for the conversion of the various in particular Ethylene, to solid polymers, the NEN reactants in the desired products. Conversion of ethylene to cyclopropane, the di- At the end of the reaction, the unreacted merization of ethylene to form higher olefins, including materials and the reaction products special 1-butene. Hydrocarbon solution from the catalyst after loading

Separated from acyclic monounsaturated hydrocarbons known processes and from it the product

substances that are converted into products that contain higher molecular weight carbons, for example by fractionation,

contain hydrogen, transferred according to the invention to liquid or solvent extraction,

can be, include 1- and 2-alkenes, which 2 to 45. The reaction pro-

Contain 16 carbon atoms per molecule. products (solid and liquid polymers, aromatics or

Typical examples of olefinic hydrocarbons - higher olefins), are used in industry, substances according to the invention in products that are higher- So, for example, solid, according to the invention molecular hydrocarbons, for example liquid polymers produced from 1-olefins by their and / or solid polymers, cyclic or olefinic 50 high density and are used to manufacture art products contain, can be transferred, are substance products according to conventional processes, such as ethylene, Propylene, 1-butene, 1-pentene, 2-pentene, for example the injection molding process, vacuum formver-1-hexene, 2-heptene, 1-octene, 2-nonene, 1-dodecene, driving or extrusion are suitable. Many of the invented 2 tetradeces, 1-hexadecene and the like. Higher molecular weight products obtainable according to this,

The reaction conditions used, for example, ^{are a} k intermediates or starting materials

wise temperature, pressure, throughput rates for the production of other valuable products

and the like, usable for the various reactants in question. For example, ethylene can

ions change quite considerably, depending on the particular in higher olefins, especially 1-butene, over-

their catalyst component used, which are carried, and the 1-butene thus obtained can be used for

special desired product and other process- 60 production of butadiene can be used,

variables. However, in general the disproportionation of olefins employed is according to FIG

Temperature in the range of about-18 to about 320 ⁰ C, the present invention gives olefins of both

preferably from about 37 to about 260 ^° C. The lower as well as higher molecular weight than

turning pressure is generally between about the starting olefin. Also takes place in the process

0 and about 210 atm or more, preferably between 65, some isomerization of the double bond,

about 7 and about 70 atm. The extent of double bond isomerization

In a liquid-phase process in which a Ka- depends on the catalyst support used and on the

fixed catalyst bed is used, the throughput reaction temperature is below. For example, the

5 6

Isomerization to a greater extent with silica tels to use a polymer solvent. That is Alumina supports than with alumina, and any desired polymerisation method can be used. lysator process or a process in a stirred reactor,

However, it is preferred to use a diluent to the disproportionation according to the present invention. The olefins subject to the invention are straight-chain. The reaction can be batch or continuous 1- and 2-olefins having 3 to 16 carbon atoms. Some of course can be done. Special examples of such olefins are propylene, play of diluent 1-butene, 1-pentene, 2-pentene, 2-heptene, 1-octene, n-pentene, η-hexane, isooctane, 2-nonene, 1-dodecene, 2-tetradecene and 1-hexadecene. io cyclohexane and methylcyclohexane. At the end of the

The disproportionation can either be the polymers after any preparation time be carried out wisely or continuously, obtained with suitable processes. Solid polymers for example by the fixed bed catalyst process, for example by methods such as coagulation or while stirring the bed. The process is obtained at Heren with water, solid precipitation and the like Temperatures from -18 to about 320.degree. C., preferably ≥5. The solid products are for manufacturing 37 to 260 ° G, in particular 90 to 205 ° C, carried out. of plastic objects according to known processes - paraffinic or cycloparaffinic hydrocarbons, such as injection molding, vacuum forming or extruded materials can, if desired, be pressed as a diluent, suitable. The polymerization of 1-olefins be used. If a diluent is applied using catalysts, this makes up to about 95 percent by weight of the supported mop percent, preferably 50 to 90 percent by weight, of the lybdenum hexacarbonyl or tungsten hexacarbonyl be reaction mixture. Some special examples that are activated by an aromatic hydrocarbon for diluents include isobutene, n-pentene, and substance. For examples of! -Olefins, Isohexane, isooctane, cyclohexane or methylcyclohexane. which can be polymerized according to the invention, A particularly useful disproportionation »5 includes ethylene, propylene, 1-butene, 1-hexene and reaction, propylene feed 1-octene. These olefins are made into solid polymers and propane is used as a diluent. transferred, which have technical significance, whereby

Ethylene can be carried out in hydrocarbon mixtures via the process especially on the polymerization of the cyclopropane, methylcyclopropane ethylene is applicable. Suitable aromatic active substances and other hydrocarbons are contained, for example, benzene and toluene. The aromatic compound with the catalysts used according to the invention can be treated in the mixture. To carry out the cyclization different ways are introduced. A suitable reaction is the catalyst and ethylene in amount of a suitable liquid aromatic combiner temperature from -18 to 320 ⁰ C, preferably bond can be entered into the reaction mixture, brought 90 to 260 ° C in contact. This reaction can take place, playing the dual role of either a batch or continuous analytical component, and the reaction using appropriate procedures such as a solid diluent. Optionally, an aroma catalyst bed or a reaction vessel with a stirred connection can be introduced into the mixture by pretreating the catalyst. In addition to a metal carbonyl applied to a carrier, the resulting lower than 40 with an aromatic hydrocarbon, before the molecular cyclopraffins, other carbon catalysts are introduced into the reaction vessel or the hydrogen of reaction is obtained, including the hydrocarbon zone. In these materials, which can be used as feed for various processes, the polymerization reaction can be used without using, among them, for example, 1-butene, the diluent or, if desired, 2-butene and 2-pentene. 45 when using a non-aromatic thinner

High molecular weight polymers and copolymers are carried out by means of. Another method is of 1-olefins having 2 to 8 carbon atoms can be the use of an aromatic compound to impregnate the metal carbonyls on the catalyst by treating one olefin or a mixture of two or more of these olefins with one of them. According to the present erfindungsgemäeinen activated aluminum oxide, silica or s "SEN process, the olefin feed and the silica - alumina -carrier applied catalyst, including the aromatic compo existing chromium hexacarbonyl catalyst component manufacturer, at a temperature from -18 to 320 ⁰ C , to be introduced. Some examples of 1-olefins, preferably 65 to 235 ⁰ C, brought into contact. The polymeric process according to the invention is carried out in the presence or absence of a versieit or can be copolymerized, including thinners, as explained above. Ethylene, propylene, 1-butene, 1-hexene and 1-octene. Although any desired polymerization process can be applied particularly to the polymerization of, such as a fixed-bed catalyst process, ethylene and mixtures of ethylene with others, or a process in the reaction vessel with stirring comonomers, in which ethylene is the main component, however, the use of a diluent is represented , to solid polymers of high density 60 times preferred. The reaction can be applied batchwise or and with high crystallinity. To be carried out continuously for polymerization. At the end of the reaction, the olefin feed and the catalytic reaction can be brought into contact with the polymers by any suitable method, including coagulating at from 55 to 235 ° C. The water, solids precipitation and the like, obtained grazing, driving can be carried out in the presence or absence of a diluent. If they are absent, they are produced and consumed annually, whereby one of the diluents may be necessary, but the production of butadiene is essential for the production of the catalyst and the diluent is separated by dehydrogenation. There were various

are used for the production of butene, the main process being the dehydrogenation of η-butane. In recent years the capacity for the production of ethylene has increased rapidly. According to the invention, ethylene can be used as a feed material in a catalytic synthesis of higher olefins, especially 1-butene, by treatment with a catalyst formed from Wolfranjhexacarbonyls applied to an activated alumina, silica or silica-alumina support. According to this method, the catalyst and the ethylene at a temperature of -18 to 320 ° C, preferably 38 to 205 ^c C, a pressure of 0 atm to 210 atm, preferably 7 to 42, brought into contact. The process is carried out either batchwise or continuously, for example by a fixed bed catalyst process or in a reaction vessel with a stirrer. If desired, diluents can be used and they include compounds containing from 4 to 10 carbon atoms. Some specific examples of suitable diluents are isobutane, η-hexane, isooctane, n-decane, cyclohexane and methylcyclohexane. The main product of the process according to the invention is 1-butene, but smaller amounts of propylene and 2-butene also result. These products can be separated by known methods such as fractional distillation, liquefaction and the like.

The method of the German Auslegeschrift 1142867 describes the treatment of acetylene compounds.

The method of the German Auslegeschrtf11051003 describes the polymerization of olefin compounds to high molecular weight polymers in the presence of a catalyst made from a mixture of metal carbonyls and inorganic or organic halogen compounds. The method of the present invention regards

There is also the possibility of converting ethylene into cyclopropane or into a solid polymer or into 1-butene to the ability to disproportionate olefins.

The following examples serve to explain the invention in more detail.

example 1

Ethylene was according to one embodiment of

ίο Invention converted into higher olefins, especially 1-butene.

In this experiment, pelletized aluminum oxide was heated to 538 ° C in air and then in nitrogen, to activate this carrier, and then the activated alumina was treated with a cyclohexane solution impregnated with tungsten hexacarbonyl. Just enough solution of tungsten hexacarbonyl was used to completely wet the wearer, and the concentration (about 5 percent by weight) of the

A solution held at 66 to 71 ^° C. was measured in such a way that 2 percent by weight resulted on the aluminum oxide. The cyclohexane was then removed from the catalyst by flushing for 2 hours at 121 to 143 ° C. and the catalyst was kept at 121 to 143 ° C. for 2 hours under a pressure of 1 mm Hg absolute.

121.8 g of catalyst were then arranged as a fixed bed in a tubular reactor for the conversion of ethylene into higher olefins and 70 g of ethylene were passed through the reaction vessel over the course of 2 hours. The temperature in the reaction vessel during the experiment was 121 ^° C. and 32.3 atmospheres. The effluent from the reaction vessel was let down to normal pressure, a tube was removed and analyzed by gas chromatography and mass spectrometry.

The conversion was in this experiment, 4 ° / _0, and the product contained 21 mole percent propylene, 7.9 mole percent 2-butene and 71.1 mole percent 1-butene.

1. the conversion of ethylene to cyclopropane;

2. the conversion of ethylene to 1-butene;

3. the polymerization of ethylene in the presence of an aromatic hydrocarbon and

4. the olefin disproportionation.

In both known methods there is no reference whatsoever to the above-mentioned methods 1, 2 or 4. Although the method of German Auslegeschrift 1 051 003 is directed to the polymerization of ethylene the data in Example 12 below clearly show that in the absence of an aromatic The supported catalyst of the present invention does not diluent Has activity for the polymerization of ethylene. On the other hand, according to the present invention, one gets a polymerization with an aromatic diluent without the use of a halogen compound, as it is mandatory according to the citation. Dtese data prove the advantages of the catalyst according to the present invention over the known catalysts.

The method of French patent 1 329 207 discloses the disproportionation of Olenn hydrocarbons with a catalyst consisting of mojybdenum oxide or tungsten oxide, while the present invention relates to the use of tungsten or molybdenum carbonyls carried on a carrier regards; it can also be seen from the following data that by using the Catalysts used according to the invention the possi-

Example 2

In a further experiment carried out by the procedure of Example 1, 84 g of catalyst formed from the supported W (CO) of Example 4 were placed in a tubular reaction vessel and ethylene was placed over the catalyst at 173 ⁰ C, 39? 6 atü and 500 volumes per volume per hour. The conversion in this experiment was 2.72%. The product contained 33.1 percent by weight propylene, 58.8 percent by weight 1-butene, 6.98 percent by weight 2-butene, 0.73 percent by weight cyclopropane and 0.369 percent by weight methylcyclopropane.

Example 3

In another run, following the procedure of the previous example yielded 87 grams of the catalyst placed in a tubular reaction vessel and ethylene over the catalyst at 154 ° C, 31.5 atmospheres and 50 volumes per volume per hour. The conversion was 3.89%, and the products consisted of 13.61 percent by weight propylene, 80.3 percent by weight 1-butene, 5.64 percent by weight 2-butene and 0.25 percent by weight of each of cyclopropane and methylcyclopropane.

B e i s ρ i e 1 4

In a number of attempts, various catalysts have been used on the disproportionation of olefins checked.

ίο

The catalysts used in these experiments were prepared by impregnating activated alumimoxide with a cyclohexane solution of Mo (CO) ₆ . The aluminum support was a granular aluminum oxide that had been activated by heating in air and then in nitrogen at 538 ° C. This support was then impregnated with a solution of Mo (CO) _e in cyclohexane. The solutions used ranged from about 5 g of Mo (CO) ₄ per 100 ml of cyclohexane to about 10 g per 100 ml, the approximate saturation point at a temperature of 66 to 71 ° C, which was used to impregnate the carbonyl in Hold solution. Pressures of about 1.0 to 10 mm Hg absolute were used and just enough solution was used to completely wet the support. The solution concentration was calculated to give the desired amount of molybdenum hexacarbonyl on the support. Cyclohexane was then removed from the catalyst by flushing with 2stündiges N ₂ at 121-143 ⁰ C and then the catalyst is maintained for 2 hours under a vacuum of about 1 mm Hg at 121-143 ⁰ C.

The catalyst formed from the supported carbonyl was then used to disproportionate olefins in a reaction vessel used as a fixed bed. The liquid olefins were degassed by heating to their boiling point and with the desired speed through a drying tube by means of a metering pump into the tubular reac tion vessel filled. With each attempt were about 100 ml of catalyst placed in the reaction vessel. The effluent from the reaction vessel was let down to atmospheric pressure and the gaseous fraction from the liquid fraction in a fractionating column severed. The weight of each fraction was determined and a representative sample of the composition was taken.

The products were examined by gas chromatography and mass spectrometry. The results

ao of these experiments are given in Table I.

Table I.

Attempt no. 4 I S

feed Olefin

Propylene

Isobutane as a diluent, percent by weight

catalyst Weight percent Mo (CO),

on carrier (a)

Grams in bed

1-butene

Operating conditions Temperature, ° C

Pressure, atü

Volumes per volume per

Hour (b)

Test duration, hours Conversion,% (c) ... isomerization, ° / ₀ (d) ..

Product distribution, mole percent

Ethylene

Propylene '

Butene

Pentenes

Witches

Heptene,

Octene

Nonene

Heavy olefins Butene distribution, mole percent

1-butene

2-butene

3.0

118.7

121 35.2

300 5

25 0

42

55 2

1 1 1

100

1.3 103.7

121 35.2

10 19

8 34

18 32 (e)

Pentene distribution, mole percent

1-pentene

2-pentene

Isopentes

2 98 1-butene

2.0 114.9

232 35.2

1.9

18th 65

5 39

40 12th

1-butene

2-butene

3.0 103.7

232 35.2

1.6

15th 66

7th 33

38

14th

1.6 95.3

232 35.2

1.6 5

16 5

5 36

39 10 10 10 10

1-pentene 1 witches 0 68 2.0 2.0 96.2 115.3 121 121 35.2 35.2 1.6 1.6 5 5 60 54 15th 15th 2 5 21 13th 27 12th __ 15th 27 10 55 11th 55 1 55

Cyclohexene

69

2.0 115.3

121 35.2

88 7th

4th 80 16

6th 75 19th

33 67

(a) Amount added to an activated alumina by impregnation.

(b) Volume of liquid per volume of catalyst per hour, except for experiment 1, where volume of gas per hour is specified per hour.

(c) Except for the isomerization of the double bonds in the feed, e.g. 1-butene to

(d)% double bond isomerization of the feed.

(e) Predominantly trans-3-hexene.

52 48

52

40

Volume of catalyst · 2-butene.

909 626/91

11th

In Table I, experiments 1 to 7 represent experiments according to the invention, while experiment 8 represents a control experiment using a cyclic olefin. It can be seen that in experiment 8 there was no conversion was obtained. The tests show that the invention applied to a carrier Hexacarbonyl catalysts are effective for converting

a) propylene in predominantly 2-butene and ethylene (experiment 1),

b) η-butene in predominantly 2-pentene, hexene, propylene and ethylene (experiments 2, 3, 4 and 5),

c) 1-pentene predominantly in hexenes and butenes,

d) 1-hexene mainly in heptenes, pentenes, butenes and propylene (Verusch 7).

It can also be seen that the supported Mo (CO) _e catalyst is active for double bond isomerization. The isomerization values of the experiments from Table I are given in the following table:

feed temperature
⁰ C Isomerization
· / · product 1-butene
1-butene
2-butene
1-pentene
1-hex 121
232
232
121
121 19th
65
5
15th
15th '2-butene
2-butene
1-butene
2-pentene
2-, 3-hexenes

It can also be seen from Table I that higher temperatures favor the double bond isomerization.

S B e i s ρ i e 1 5

In a further series of tests, the catalysts formed from Mo (CO) J on supports were in Experiments used in stirred vessels.

In these experiments, the catalysts were prepared as described in Example 4, however, in most of the experiments the granular alumina was reduced to particle size from 10 to 100 before the impregnation

Grind t5 with Carbony! solution. A granular catalyst was used for the remainder of the trials used.

About 50 ml of catalyst and 230 to 330 g of olefin were used for each experiment in the stirred reaction vessel

»Ο filled into a 1-1 reaction vessel. The internal stirrer was switched on and the reaction vessel was heated to the desired temperature. After 2 to 3 hours at operating temperature, the hydrocarbons were flushed from the

The hot reaction vessel was removed into a 1.8 l bomb at dry ice temperature. The products were then, as described in Example 4, analyzed. The results of these tests are given in Table II:

Table II

10

11 attempt no.

12 I 13

14th

15th

feed
Olefin

Grams of olefin

catalyst

Mo (CO) ₆ , weight percent (a) grams

Operating conditions

Temperature, ⁰ C

Pressure atü

Duration of the experiment, hours

Conversion,% ( ^D )

Isomerization

Product distribution, mole percent

Ethylene

Propylene

Butene

Pentenes

Witches

Heptene

Octene

Nonene

heavier

1-butene 250

3.0 41.0

121 29.5 2

7.4 9.3

40 19

11 30 30 30 30

Butene distribution, ° / o

1-butene

2-butene

Distribution of pents, ° / o

1-pentene

2-pentene

100

2-butene 250

3.0 39.2

121 25.3 2

2.3 1.7

58

42

Isobutene 230

3.0 45.9

121 15.5-1.05
3
96

50 50

100 2-pentene
230

3.0
43.1

121
10.2
3

51
1

58

34
34
34
34
34

12th

cis-2-pentene

330

3.0
45.8

121
11.2

3
46

2.

7th
42

51
51
51
51
51

8th
92

2 witches

250

3.0 45.5

121
3.5 3
7th

3
26th

22nd
7th
3

3-heptene

230

3.0 44.4

121 1.2 3 0

100

1-octene

230

121 3.5 3 41

(a) Weight percent Mo (CO), in the catalyst during manufacture.

(b) Excluding isomerization of double bonds in the olefin feed.

In Table II, Trials 11 and 15 are control trials, while the other trials are in the frame of the present invention. It can be seen that the polymerization of isobutene is being attempted 11 was effected, while experiment 15 shows that 3-olefins, as shown in Example 3-heptene is not subject to disproportionation with the catalyst according to the invention.

Example 6

In a further series of experiments, catalysts made from Mo (CO) ₆ on various carriers were investigated with regard to their activity in the disproportionation of olefins.

Some of the catalysts were prepared using the vacuum impregnation method of Example 4,

while a catalyst by vacuum impregnation and subsequent heat treatment under nitrogen was produced. In two other experiments the activated catalyst support was dry with Mo (CO), mixed and then heat treated the composition at an elevated temperature. One try was carried out without a carrier.

1-butene was used as the olefin feed in all but two of the runs. With the two remaining ones Trials, Trials 21 and 22, 2-butene served as the feed. Some of the attempts have been made under application of the fixed bed process carried out as in Example 4, while the others according to the process in the stirred reaction vessel, as in Example 5, were carried out. The results of these trials are given in Table III below:

17th 18th Table III 20th Attempt no 22nd 23 24 25th 1-butene 1-butene 1-butene 21 2-butene 1-butene 1-butene 1-butene 19th 2-butene feed 1.3 3 1-butene 3 3 6th 4th 100 catalyst Al ₈ O ₃ Al ₂ O ₃ Al ₂ O ₃ 1.3 SiO ₂ /
Al ₂ O ₃ SiO ₂ active
money none Mo (CO) ₈ weight
percent Imp-Vac Imp-Vac 6th Imp-Vac Al ₂ O ₃ Imp-Vac TM Imp-Vac carrier 138 138 Al ₂ O ₃ 260 Imp-N ₂ 138 154 138 none 103.7 46.5 TM 41.7 538 not 31.6 16.9 Treatment (1) 154 not measured Treatment temperature,
⁰ C Fixed bed under
stir 47.5 under
stir measured Fixed bed under
stir Fixed bed under
stir Grams used .... 121 121 121 Fixed bed 121 Ul 121 121 Operating conditions 35.2 27.1 under
stir 26.4 121 35.2 26.4 35.2 26 7 Type of reaction
eepot (2) ** · * »* ■
5 4th 121 3 35.2 5 2 5 •
2 10 28.1 6th 3 57 13th 1 0 Temperature, ° C. 19th 19th 3 19th O 75 12th 3 Pressure atü 15th Test duration,
hours 8th 8th 10 17th Conversion,% 34 47 17th 10 38 28 Isomerization, ° / ₀ ... 30th Product distribution,
Mole percent 18th 19th 17th 15th 5 37 24 Ethylene 32 23 51 25th 16 Propylene 8th 3 14th 85 32 Butene 39 Pentenes Witches heavier

C) The term Imp-Vac means that the impregnation, as described in Example 1, and a subsequent vacuum treatment were carried out at the specified temperature. Imp-N means impregnation as described in Example 1 and subsequent treatment with N ₁ at the specified temperature. TM means dry mixing of Mo (CO) with the carrier and subsequent heating to the specified temperature.

( ^a ) Fixed bed process identical to example 1, stirred bed process identical to example 2.

In Table III, runs 17 to 20 are runs according to the invention showing that different types the catalyst production can be used. Run 21 is a control run showing that one The temperature of 538 ° C is too high for the catalyst to be treated. Tests 22 and 23 show that silica-alumina and silica are useful carriers, while Experiments 24 and 25 show that a charcoal catalyst and an unsupported catalyst are not useful.

Other carriers which were examined and found to be unusable were tuff, zinc oxide, zirconium oxide, titanium oxide, cobalt-thorium oxide and brucite.

Example 7 »5

Two experiments are carried out using a supported W (CO) catalyst to disproportionate olefins.

The catalysts were prepared according to the impregnation process of Example 4, with activated Alumina was used as a carrier. The impregnated supports were vacuum treated at 138 ° C. The disproportionation tests were carried out according to the fixed bed method of Example 4. An as The experiment was carried out without a diluent, while isobutene was used as the diluent in the other experiments. The results these tests are given in Table IV below:

Table IV catalyst

Carbonyl

Weight percent

carrier

Gram

feed

Olefin

Isobutane thinner, Weight percent

Gram Olefin + thinner ..

Operating conditions Temperature, ^c C

Pressure, atü

Test duration, hours

Conversion, ° / ₀ (a) Isomerization,%

Attempt no. 26 I 27

W (CO),

2.0 A1.O, 108.8

1-butene 0

690

121 35.9

5 7th 8th

W (CO),

2.0 Al ₁ O, 104.8

1-pentene 66

440

121 35.2

44
20th

Table IV (continued)

Product distribution, Mole percent

Ethylene

Propylene

Butene

Pents

Witches

Hepten

Octene

heavier

Butene distribution,%

1-butene

2-butene

Distribution of pents, ° / o

1-pentene

2-pentene

Isopentes

,. Isomerization product

Attempt no.

26th

27

28

28

40

92 6

2-butene

34 18

13 10 24

3 97

2-pentene

(a) Feed isomerization only.

Example 8

Ethylene has been converted into a mixture of hydrocarbons including cyclopentane and methylcyclopiopane.

A granular aluminum catalyst was heated to 358 ° C in air and then in nitrogen to produce the same To activate the carrier, then the activated alumina was impregnated with a cyclohexane solution of molybdenum hexacarbonyl. It was getting straight enough solution used to completely wet the support, and the concentration of the solution

so it was adjusted to give the desired amount of the carbonyl compound on the support as shown in the table below. The cyclohexane was then removed from the catalyst by rinsing at 121 to 143 ³ C for 2 hours removed. The composition was then held at 121 to 143 ^° C under a pressure of 1 mm Hg absolute for 2 hours.

The catalyst prepared above was then used for a test with ethylene in the fixed catalyst bed used. In this fixed bed system, 100 ml of catalyst was placed in a tubular reaction vessel, and gaseous ethylene was passed through the Reaction vessel passed at the desired speed. The reaction vessel was used with each attempt heated to the desired temperature. The effluent from the reaction vessel was reduced to atmospheric pressure relaxed and the products then examined by gas chromatography and mass spectrometry.

17 18

The results of these tests are given in Table V below: Table V

Experiment No. 5

7th 8th 3 3 121 121 0 64.7 270 300 3 3 0.3 2.0 67 52 33 26th 8th 6th 4th 4th

Catalyst weight percent Mo (CO) ₈ ....

conditions Temperature, ⁰ C

atü

Volumes per volume per hour Duration of the experiment, hours Conversion, ° / ₀ (2) Product distribution, percent by weight

Propylene

l-butene

2-butene

2-pentene

Neopentane

Cyclopropane Methylcyclopropyn

η-butane

1-pentene

138 232 35.2 31.6 250 140 4th 4th 2.7 3.0 28 62 26th 6th 26th 25th 4th 1 8th 12th 2

66 31.6 250

0.0

121 33.0 330

0.6

57

29

121 32.3 140

3.2

58

27

3 4th

32.3 110 2 5.0

121 33.7 200 2 1.3

Trace trace

C) Gas volumes per volume of catalyst per hour.

C) Excluding a very small amount of solid ethylene polymer that was formed.

45

Experiment 3 in the table is a control experiment which shows that a temperature of 66 ° C. is not sufficient for the process according to the invention. The attempt 7 is also a control experiment showing that atmospheric pressure is insufficient when using cyclopropane and wants to obtain methylcyclopropane. It can also be seen that in this attempt the conversion is extremely low. Run 9 shows the results obtained when a higher percentage of Molybdenum carbonyl is used in the catalyst composition.

Example 9

An experiment was carried out in which ethylene is polymerized to a solid polymer by reaction on a catalyst formed from molybdenum hexacarbonyl aluminum oxide, with stirring in the reaction vessel. The poly so merization was carried out in the presence of benzene, but other aromatic substances can also be used Hydrocarbons including toluene, xylenes and the like can be used.

A quantity of 246 g of aluminum oxide with a particle size of about 1.65 to 0.15 mm clear mesh size (previously at 538 ° C in air for 5 hours long and then preactivated in nitrogen for 2 hours) was in 155 ecm of a cyclohexane solution with a content of 7.8 g of molybdenum hexa- carbonyl distributed at 60 to 66 ° C. The cyclohexane solvent was then removed from the slurry by heating at 138 ° C for 2 hours in the presence of nitrogen and then for a further 2 hours Keep at this temperature under reduced pressure.

45.9 g of this catalyst were placed together with 182 g of benzene in a 1-1 reaction vessel with a stirrer brought in. The reaction mixture was heated to 121 ° C. and then with the addition of about 33 g of ethylene brought to a pressure of 33.7 atmospheres. After 2 hours the reaction vessel was cooled to 26.7 ° C and 0.9 g of solid polymer obtained.

A corresponding experiment, which was practically identical to the procedure described above, was called Control experiment carried out using only cyclohexane as the reaction solvent instead of benzene has been used. In this control experiment, practically no solid polymer was found.

Claims (6)

Patent claims: 1. Process for disproportionation, cyclization, addition or acyclic polymerization Monounsaturated olefin hydrocarbons, characterized in that they are Olefin hydrocarbons under known reaction conditions with a catalyst in Brings contact that consists of a tungsten or molybdenum carbonyl and silicon dioxide, aluminum oxide or silicon oxide-aluminum oxide as Support material has been produced, the amount of carbonyl in the range between 0.01 and 20 percent by weight, based on die.Katalysatormasse is. 2. The method according to claim 1, characterized in that one uses a catalyst support which has been activated by heating in an oxygen-containing gas · to a temperature above 26O ⁰ C. 3. Process according to Claims 1 and 2, characterized in that the acyclic, monounsaturated olefin a 1-alkene or 90 * 626/91 2-alkene with 2 up to and including 16 carbon atoms is used. 4. The method according to claims 1 to 3, characterized in that a Molybdänhexacarbonylträgerkatalysators performing the cyclization of ethylene to Cydopropan in the presence at a temperature in the range 93-260 ⁰ C. 5. Process according to claims 1 to 3, characterized in that the addition of Ethylene to 1-butene in the presence of a tungsten supported hexacarbonyl catalyst at a temperature in the range from 38 to 204 ⁰ C carries out. 6. Process according to claims 1 to 3, characterized in that the polymerization of ethylene in the presence of an aromatic hydrocarbon at a temperature in the range from 66 to 232 ° C. Considered publications:
German Auslegeschrift No. 1 051 003, 1 142 867;
French patent specification No. 1 329 207. M9S2S / 1714 10. » O Bindetdruckcrei Berlin