DE1280869B - Process for the disproportionation, cyclization, addition or polymerization of acyclic, singly unsaturated olefin hydrocarbons - Google Patents

Description

Process for disproportionation, cyclization, addition or polymerization acyclic monounsaturated olefin hydrocarbons In the field of conversion Numerous catalysts have been used for the conversion of hydrocarbons Paraffins and / or olefins described in various hydrocarbon products.

Many of these catalysts are solid substances and the reactions using these catalysts are heterogeneous in nature. For example, were various metals, metal oxides and metal chlorides on materials such as silica, Aluminum oxide and the like applied. While in some reactions the wearer does not if any effect on the reaction in which the catalyst is used is to be exercised, many supports themselves show a strong activity for catalyzing the reaction.

The present invention relates to a method for disproportionation, Cyclization, addition or polymerization of acyclic, monounsaturated olefin hydrocarbons, characterized in that one of these olefin hydrocarbons is known per se Bringing reaction conditions with a catalyst in contact, which consists of a tungsten or molybdenum carbonyl and silica, alumina, or silica-alumina has been produced as a carrier material, the amount of carbonyl in the range between 0.01 and 20 percent by weight, based on the catalyst mass.

The catalyst used in the present invention can be prepared by direct mixing of solid components, by impregnation and the like. To a To obtain optimal activity, it is preferred to keep the support material under increased Temperatures and heat so long that it is before mixing with the metal carbonyl is activated.

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

The carrier material is preferably first heated with air and / or an inert gas such as nitrogen at a temperature above about 260 "C, preferably activated at a temperature of from about 400 to about 8200.degree. Activating of the carrier can be made in any desired manner. However, it is preferred the carrier with air at an elevated temperature or in an atmosphere of any one at- their suitable gas, such as hydrogen, helium, nitrogen and the like. The length of time the carrier is held at the activation temperature depends on the temperature used, however, generally the vehicle will be used for at least Heated for 5 minutes. The wearer should be at a sufficiently high temperature be heated for a sufficient period of time to remove virtually all of the material present in the carrier remove free water.

After activation of the carrier, the metal carbonyls are then either by impregnation or by dry blending with the activated carrier brought in. Preferably, depending on the method of application of the metal carbonyl, the carrier is treated so that 0.1 to 10 percent by weight of the metal carbonyl is 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 applied in a hydrocarbon. Examples of solvents that can be used for the Metal carbonyls can be used are the aromatic hydrocarbons, such as benzene and toluene, cycloparaffins such as cyclohexane and methylcyclohexane, and n-paraffinic and isoparaffinic hydrocarbons with 4 to 10 carbon atoms per molecule or mixtures of these hydrocarbons. Suitable paraffins include n-butane, n-pentane, n-hexane, isooctane and n-decane. The concentration of metal carbonyl the hydrocarbon solvent is generally from about 1 to about 10 Weight percent. The solubility of the Metal carbonyls are common quite low at room temperature and it is therefore often desirable to use the hydrocarbon solvent to a temperature of about 65 to 72 "C to dissolve the metal caibonyl. It is usually necessary to maintain sufficient pressure to prevent the To keep the solution practically completely in the liquid phase.

The hydrocarbon solution of the metal carbonyl is then with the activated carrier brought into contact in an amount sufficient to produce the desired Amount of metal carbonyl on the carrier or to be introduced into the carrier. One suitable method that can be used is to apply just enough solution to to fully moisten the activated vehicle. The hydrocarbon solvent is then removed from the catalyst, for example by rinsing with an inert one Gas at a temperature below about 150 "C, and then the carbonyl-containing Support at a temperature of about 10 to about 370 "C, preferably 65 to 150" C, held under vacuum, which can be between about 1 to about 100 mm Hg absolute. The heat treatment can generally last from a few seconds to about 10 hours, preferably about 0.5 to about 5 hours, wherein the longer times are used at lower temperatures, and vice versa. When the metal carbonyl is dry blended with the activated carrier, can if desired also a heat treatment under vacuum within the above specified ranges are applied.

Those formed from supported metal carbonyls, according to the invention The catalysts used are for a wide variety of conversion reactions of monounsaturated hydrocarbons valuable, including disproportionation of 1- and 2-olefins, the polymerization of 1-olefins, especially ethylene, to solid polymers, the conversion of ethylene to cyclopropane, the dimerization from ethylene to higher olefins, especially 1-butene.

On acyclic monounsaturated hydrocarbons that are used in products, which contain higher molecular weight hydrocarbons, are converted according to the invention can include 1- and 2-alkenes containing 2 to 16 carbon atoms per molecule.

Typical examples of olefinic hydrocarbons used according to the invention in products containing higher molecular weight hydrocarbons, for example liquid and / or solid polymers containing cyclic or olefinic products are transferred are ethylene, propylene, 1-butene, 1-pentene, 2-pentene, 1-hexene, 2-heptene, 1-octene, 2-nonene, 1-dodecene, 2-tetradecene, 1-hexadecene and the like.

The reaction conditions used, for example temperature, Pressure, throughput rates, and the like, for the various in question Reactions change quite considerably, depending on the particular catalyst component used, the particular product desired and other process variables. However lies generally the temperature used is in the range of about -18 to about 320 "C, preferably from about 37 to about 260 ° C. The pressure to be used is generally between about 0 and about 210 atmospheres or more, preferably between about 7 and about 70 atm.

In a liquid phase process in which a fixed catalyst bed is used, the throughput speed in volumes of liquid per volume Catalyst per hour generally between about 0.1 to about 20, preferably between about 1 to about 6.

Similarly, throughput rates are in volumes Gas per volume of catalyst per hour in the range from about 50 to about 10,000 for gas or Vapor phase process. The reaction time generally ranges from about 1 second to about 10 hours or more, preferably from about 0.5 to 5 hours. When working in the reaction vessel with stirring, for example, the catalyst concentration is in the reaction zone generally in the range of about 0.5 to about 40 weight percent the reaction mixture.

The above reactions can either be in the presence or In the absence of a diluent, however, is generally carried out the use of a diluent that is not detrimental to the reaction, preferably a hydrocarbon diluent, preferably, To typical K Hydrogen solvents that can be used include the aromatic ones Hydrocarbons such as benzene and toluene, cycloparaffins and / or paraffins with up to 12 carbon atoms per molecule, such as cyclohexane and methylcyclohexane, n-pentane, n-hexane, isooctane, dodecane and the like.

Or mixtures of these. If thinners are used, can from a small amount up to about 98 percent by weight of the reaction mixture be.

According to the invention, all of the conversion reactions can either be carried out in batches or are carried out continuously using either a fixed bed catalyst process or in the reaction vessel with stirring or by another method with movable Catalyst or any of the known contact processes for the conversion of the different reactants into the desired products.

At the end of the reaction there will be the unreacted materials as well the hydrocarbon solution containing the reaction products from the catalyst according to known methods Process separated and the product obtained therefrom, for example by fractionation, Liquefaction or solvent extraction.

The reaction products prepared according to the invention (solid and liquid polymers, aromatics or higher olefins) are used in industry For example, solid ones prepared from 1-olefins according to the invention are distinguished Polymers are characterized by their high density and are used in the manufacture of plastic products by customary processes, such as injection molding, valruumforming or extrusion suitable Many of the higher molecular weight obtainable according to the invention Products are used as intermediates or raw materials for manufacture usable from other valuable products. For example, ethylene can be used according to the invention are converted into higher olefins, in particular 1-butene, and the resultant 1-butene can be used to make butadiene.

The disproportionation of olefins according to the present invention yields olefins of both lower and higher molecular weight than that Starting olefin. There is also some isomerization of the Double bond.

The extent of double bond isomerization depends on the one used Catalyst support and on the reaction temperature. For example the Isomerization to a greater extent with silicic acid / aluminum oxide carriers than with aluminum oxide, and higher reaction temperatures cause more isomerization than lower.

Those subject to disproportionation according to the present invention Olefins are straight-chain 1- and 2-olefins with 3 to 16 carbon atoms. Some specific examples of such olefins are propylene, 1-butene, 1-pentene, 2-pentene, 2-heptene, 1-octene, 2-nonene, 1-dodecene, 2-tetradecene and 1-texadecene.

The disproportionation can be either batchwise or continuously be carried out, for example by the fixed bed catalyst process or under Stirring the bed. The process is carried out at temperatures from -18 to about 320 "C, preferably 37 to 260 ° C, in particular 90 to 2050 C, carried out.

Paraffinic or cycloparaffinic hydrocarbons can if desired can be used as a diluent. If a diluent is used, so this makes up to about 95 percent by weight, preferably 50 to 90 percent by weight, of the reaction mixture. Some specific examples of diluents include isobutene, n-pentene, isohexane, isooctane, cyclohexane or methylcyclohexane.

In a particularly useful disproportionation reaction Propylene was used as a feed and propane as a diluent.

Ethylene can be converted into hydrocarbon mixtures that Cyclopropane, methylcyclopropane and other hydrocarbons contain by it is treated with the catalysts used according to the invention To carry out of the cyclization reaction, the catalyst and ethylene are at one temperature from -18 to 320 "C, preferably 90 to 260" C, brought into contact. This reaction can either batchwise or continuously using appropriate procedures, such as a fixed bed of catalyst or a reaction vessel with a stirred catalyst be performed. In addition to the low molecular weight resulting from this process Cyclopraffins will contain other hydrocarbons, including hydrocarbons, which are useful as a feed for various processes, among them, for example 1-butene, 2-butene and 2-pentene.

High molecular weight polymers and copolymers of 1-olefins with 2 to 8 carbon atoms can be obtained by treating an olefin or a mixture of two or more of these olefins with an activated aluminum oxide, Silicic acid or silicic acid - aluminum oxide - carrier applied chromium hexacarbonyl existing catalyst can be produced. Some examples of 1-olefins, which are polymerized or copolymerized by the process according to the invention can include ethylene, propylene, 1-butene, 1-hexene and 1-octene. The procedure is especially on the polymerisation of ethylene and mixtures of ethylene with others Comonomers, in which ethylene is the main component, to solid polymers of high density and high crystallinity applicable. To be polymerized the olefin feed and catalyst at a temperature of -18 to 3200 C, preferably 55 to 235 "C, brought into contact. The method can be used on arrival or in the absence of a diluent. In the absence of one It may be necessary to separate the catalyst and the diluent Diluent means of using a polymer solvent. 7war can be any you want polymçrisationsmethade be applied, such as a best-bed catalyst process or a process in a stirred reactor, however, it is preferred to use a diluent to use. The reaction can be carried out batchwise or continuously. For specific examples of desired, if applicable, diluents include n-pentene, n-hexane, isooctane, cyclohexane, and methylcyclohexane. At the end of Reaction time, the polymers are obtained by any suitable method. Solid polymers can, for example, by methods such as coagulation with water, Solid precipitation and the like., Can be obtained. The solid products are for manufacturing of plastic objects by known methods such as injection molding, vacuum forming or extrusion, are suitable. The polymerization of 1-olefins can be carried out using carried out by catalysts made from supported molybdenum hexacarbonyl or tungsten hexacarbonyl are made up of an aromatic hydrocarbon to be activated. Examples of 1-olefins which polymerize according to the invention include ethylene, propylene, 1-butene, 1-hexene, and 1-octene. These olefins are converted into solid polymers, which have technical importance, where the process is particularly applicable to the polymerization of ethylene. Suitable aromatic activators are, for example, benzene and toluene. The aromatic compound can be introduced into the mixture in a number of ways. A suitable amount a suitable liquid aromatic compound can be added to the reaction mixture be entered, it having the dual role of both a catalytic component as well as the: reaction diluent plays. Optionally, an aromatic Compound into the mixture by pretreating one applied to a support Metal carbonyls with an aromatic hydrocarbon before the catalyst is transferred into the reaction vessel or the reaction zone. In this case, the polymerization reaction can be carried out without using the diluent or, if desired, using a non-aromatic diluent be carried out. Another method is the use of an aromatic Compound for the impregnation of the metal carbonyl on the catalyst support. To the present inventive process, the olefin feed and the Catalyst, including the aromatic component, at a temperature of -18 to 320 "C, preferably 65 to 235" C, brought into contact. The procedure will in the presence or absence of a diluent, as explained above, carried out.

Any desired polymerization process can be used, such as a fixed catalyst bed process or a process in the reaction vessel below Stir, however, the use of a diluent is preferred. The reaction can be carried out batchwise or continuously. At the end of the reaction you can the polymers by any suitable method including coagulation with water, solid precipitation and the like, obtained from pastures, large amounts of butenes, especially 1-butene, are produced and consumed annually, with a substantial one Uses the manufacture of butadiene by dehydration is, there have been various procedure used to make butene as the main process the dehydration of n-butane. In recent years the manufacturing capacity has increased of Ethylene quickly to. According to the invention, ethylene can be used as a feed material a catalytic synthesis of higher olefins, especially 1-butene, by treatment with one of an activated alumina, silica or silica-alumina carrier applied tungsten hexacarbonyl formed catalyst can be used.

According to this process, the catalyst and the ethylene are at one Temperature from -18 to 3200 C, preferably 38 to 205 "C, a pressure from 0 to 210 atmospheres, preferably 7 to 42 atmospheres, brought into contact. The procedure will either carried out 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 can be used, and they include compounds containing 4 to 10 carbon atoms contain. Some specific examples of suitable diluents are isobutane, n-hexane, isooctane, n-decane, cyclohexane and methylcyclohexane. The main one The product of the process according to the invention is 1-butene, but lower levels are also obtained Amounts of propylene and 2-butene. These products can be manufactured using known methods, such as fractional distillation, liquefaction and the like.

The method of the German Auslegeschriftl 142867 describes the Treatment of acetylene compounds.

The method of the German Auslegeschrift 1051003 describes the Polymerization of olefin compounds to high molecular weight polymers in the presence a catalyst composed of a mixture of metal carbonyls and inorganic or organic halogen compounds. The method according to the present invention relates to 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. olefin disproportionation.

In both known methods there is no reference to the Procedure 1, 2 or 4 above.

Although the procedure of the German Auslegeschrift 1 051 003 is based on the Polymerization of ethylene is directed, the data show in the following Example 12 clearly shows that in the absence of an aromatic diluent the on Supported catalyst according to the present invention has no activity for the polymerization of ethylene.

On the other hand, according to the present invention, one gets with one aromatic diluent a polymerization without the use of a halogen compound, as it is mandatory according to the citation. These data prove it the advantages of the catalyst according to the present invention over the known ones Catalysts.

The method of French patent 1,329,207 is disclosed the disproportionation of olefin hydrocarbons with a catalyst that of molybdenum oxide or tungsten oxide, while the present invention is the Relates to the use of tungsten or molybdenum carbonyls located on a carrier; it can also be seen from the following data that by using the Catalysts used according to the invention the possi- there is a possibility of ethylene in To convert cyclopropane or to a solid polymer or to 1-butene, in addition to the ability to disproportionate olefins.

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

Example 1 Ethylene was made according to one embodiment of the invention converted into higher olefins, especially 1-butene.

In this experiment, pelletized aluminum oxide was heated to 5380.degree heated in air and then in nitrogen to activate this carrier, and then activated alumina with a cyclohexane solution of tungsten hexacarbonyl impregnated. Just enough solution of tungsten hexacarbonyl was used to make to completely moisten the carrier, and the concentration (about 5 percent by weight) the solution kept at 66 to 71 "C was dimensioned such that 2 percent by weight on the alumina. Then the cyclohexane was removed from the catalyst by 2 hours Rinse at 121 to 143 "C and remove the catalyst for 2 hours at 121 to 143" C kept absolute under a pressure of 1 mm Hg.

121.8 g of catalyst were then used for the conversion of ethylene into higher olefins arranged as a fixed bed in a tubular reactor and 70 g of ethylene passed through the reaction vessel within 2 hours. Ruled in the reaction vessel during the experiment 121 "C and 32.3 atm. The effluent from the reaction vessel was on Relieved normal pressure, a sample removed and gas chromatographically and mass spectrometrically analyzed.

The conversion rate in this experiment was 40 / o, and the product contained 21 mole percent propylene, 7.9 mole percent 2-butene and 71.1 mole percent 1-butene.

Example 2 In a further experiment carried out according to the method of Example 1 was carried out, 84 g of catalyst, which was made on a support applied W (CO) of Example 4 was formed into a tubular reaction vessel Filled in and ethylene over the catalyst at 173 "C, 39.6 atmospheres and 500 volumes per volume per hour. The conversion in this experiment was 2.72%. That Product contained 33.1 percent by weight propylene, 58.8 percent by weight 1-butene, 6.98 Weight percent 2-butene, 0.73 weight percent cyclopropane and 0.369 weight percent Methylcyclopropane.

Example 3 In another experiment, the method of previous example 87 g of the catalyst in a tubular reaction vessel introduced and ethylene over the catalyst at 154 "C, 31.5 atü and 50 volumes per volume per hour. The conversion was 3.89% and the products passed of 13.61 percent by weight propylene, 80.3 percent by weight 1-butene, 5.64 percent by weight 2-butene and 0.25 weight percent of each of cyclopropane and methylcyclopropane.

Example 4 Various catalysts were used in a number of experiments checked for disproportionation of olefins.

The catalysts used in these experiments were impregnated made of activated alumina with a cyclohexane solution of Mo (CO). The aluminum support was a granular aluminum oxide that was produced by heating in air and then activated in nitrogen at 538 ° C. This carrier then became impregnated with a solution of M9 (CO) 8 in cyclohexane. The solutions used ranged from about 5 g Mo (CO) each. 100 ml cyclohexane up to about 10 g per 100 ml, the approximate saturation point at a temperature of 66 to 71 ° C that applied to keep the carbonyl in solution during vacuum impregnation. Press from about 1.0 to 10 mm Hg absolute was applied and just enough solution was used to completely wet the carrier. The solution concentration was calculated so that the desired amount of molybdenum hexacarbonyl resulted on the support. Then became the cyclohexane from the catalyst by flushing with N2 for 2 hours at 121 to 143 ° C removed and then the ca- catalyzer for 2 hours under a vacuum of about 1 mm Hg held at 121 to 1430 C.

The catalyst formed from the supported carbonyl was then used to disperse olefins in a reaction vessel as a fixed bed used. The liquid olefins were degassed by heating to their boiling point and at the desired speed through a drying tube by means of a metering pump filled into the tubular reaction vessel. In each attempt, about 100 ml of catalyst introduced into 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 fractionation column severed. The weight of each fraction was determined and a representative sample taken of the composition.

The products were subjected to gas chromatography and mass spectrometry examined. The results. these tests are given in Table I.

Table I. Attempt no. 1 2 3 4 5 6 7 8 feed Olefin ...... propylene 1-butene 1-butene 1-butene 2-butene 1-pentene 1-hexene C.yclo- witches Isobutane as a diluent medium, weight percent. -. 0 0 - 0 0 0 0 68 69 catalyst Weight percent Mo (CO) on support (a) ............... 3.0 1.3 2.0 3.0 1.6 2.0 2.0 2.0 Grams in bed ............... 118.7 103.7 114.9 9 103.7 95.3 96.2 115.3 115, Operating conditions Temperature, ° C .... ... 121 121 232 232 232 121 121 121 Pressure, atü. . . . . . . . . . . . . . . . 35.2 35.2. 35.2 35.2 35.2 35.2 35.2 35.2 Volumes per volume per Hour (b). . . . . . . . . . . . . . . . . 300 1.5 1.9 1.6 1.6 1.6. 1.6 1.7 Duration of the experiment, hours. . . . . 5 5 5 5 5 5 5 5 Conversion,% (c) ... .... 25 10 18 15 16 60 54 0 Isomerization,% (d). . ... 0 19 65 66 5 15 15 Product distribution, mole percent Ethylene. . . . . . . . . . . . . . . . . 42 8 5 7 5 2 5 Propylene ..... ..... - 34 39 33 36 21 13 Butene 55 - - - - 27 12 Pentenes .... .... 2 18 40 38 39 - 15 Witches. 32 (e) 12 14 10 27 - Heptene. . ............... to 1 8 2 4 10 10 55 Octene ... .... 1 8 1 2 10 11 55 Nonene .......... ..... 1 8 1 1 10 1 55 Heavy olefins Butene distribution, mole percent 1-butene - - - - - 33 52 2-butene. . .............. 100 67 48 Pentene distribution, mole percent 1-pentene. . . 2 5 4 6 52 2-pentene. 98 88 80 75 40 Isopentene ............... 7 16 19 8 (a) Amount added to an activated alumina by impregnation.

(b) volumes of liquid per volume of catalyst per hour, except for Tried where volume of gas per volume of catalyst per hour is given.

(c) With the exception of isomerization of the double bonds in the feed, for example 1-butene to 2-butene.

(d)% double bond isomerization of the feed.

(e) Predominantly trans-3-hexene.

In Table I, experiments 1 to 7 represent experiments according to the invention while Run 8 is a control using a cyclic olefin was used. It can be seen that in Run 8, no conversion was obtained. The experiments show that the hexacarbonyl catalysts according to the invention applied to a support are effective for converting a) propylene into predominantly 2-butene and ethylene (experiment 1), b) n-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 predominantly in heptenes, pentenes, butenes and propylene (Verusch 7).

It can also be seen that the supported Mo (CO) 6 catalyst is active for double bond isomerization. In the following compilation the isomerization values of the experiments from Table I are given: Temperature isomerization Charge product ° C% 1-butene 121 19 2-butene 1-butene 232 65 2-butene 2-butene 232 5 1-butene 1-pentene 121 15 2-pentene 1-hexene 121 15 2-, 3-hexene Next is from table I can see that higher temperatures favor the double bond isomerization.

Example 5 In a further series of tests, those made from Mo (CO) 8 Catalysts formed on supports are used in experiments in stirred vessels.

In these experiments, the catalysts were as in Example 4 described, but in most of the trials the granular was used Aluminum oxide to a particle size of 10 to 100 before impregnation with carbonyl solution grind. A granular catalyst was used in the remainder of the experiments.

About 50 ml of catalyst were used for each experiment in the stirred reaction vessel and 230 to 330 g of olefin are charged into a 1 liter reaction vessel. The internal stirrer was switched on and the reaction vessel heated to the desired temperature.

After 2 to 3 hours at operating temperature, the hydrocarbons were by rinsing the hot reaction vessel into a 1.8 l bomb at dry ice temperature removed. The products were then analyzed as described in Example 4.

The results of these experiments are given in Table II: Table II Attempt no. 9 10 11 12 13 14 15 16 feed Olefin. ............... 1-butene 2-butene isobutene 2-pentene-cis-2- 2- 3- 1- Penten witches hepten octene Grams of olefin ............... 250 250 230 230 330 250 230 230 catalyst Mo (CO) 6, weight percent (a) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Gram. ............... 41.0 39.2 45.9 43, 45.8 45.5 44.4 44.6 Operating conditions Temperature, ° C. . . . . . . . . . . . 121 121 121 121 121 121 121 121 Pressure atü ............... 29.5 25.3 15.5-1.05 10.2 11.2 3.5 1.2 3.5 Duration of the experiment, hours. . . . . 2 2 3 3 3 3 3 3 Conversion,% (b) .......... 7.4 2.3 96 51 46 7 0 41 Isomerization ...... ..... 9.3 1.7 - 1 2 2 @ - - Product distribution, mole percent Ethylene ... ............... 40 Propylene .. ...... .... 19 58 8 7 13 butene ... . - - 58 42 3 Pentenes .. ............... 11 42 - - 26 Witches .. 30 34 51 - 1 Heptene. . ............... 30 34 51 22 10 Octene. . . ............... 30 50 34 51 7 Nonene ............... ......... 30 34 51 3 39 heavier. .. 50 34 51 39 37 Butene distribution,% 1-butene. . ... .... 12 8 2-butene .... 88 92 Distribution of pensions,% 1-pentene. . 2-pentene. ... 100 100 100 (a) Weight percent Mo (CO), in the catalyst during manufacture.

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

In Table II, Runs 11 and 15 are controls while the other attempts fall within the scope of the present invention. Bs is closed see that the polymerization of isobutene was effected in Run 11 while from Experiment 15 it can be seen that 3-olefins, as shown in Example 3-heptene, are not subject to disproportionation with the catalyst according to the invention.

Example 6 In a further series of experiments, catalysts were made Mo (CO), on different supports for their disproportionation activity investigated by olefins.

Some of the catalysts were vacuum impregnated of example 4 produced, while a catalyst by vacuum impregnation and subsequent heat treatment under nitrogen was produced. In two others The activated catalyst support was mixed dry with Mo (CO) and mixed thereafter the composition is heat treated 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. In the two remaining trials, Trials 21 and 22, 2-butene was used as the feed. Some of the experiments were carried out using the fixed bed method as in Example 4, while the others were carried out using the stirred reactor method as in Example 5. The results of these tests are given in Table III below: Table III Versllch no. 17 18 19 20 21 22 23 24 25 Charging ... 1-butene 1-butene 1-butene 1-butene 2-butene 2-butene 1-butene 1-butene 1-butene catalyst Mo (CO), weight percent. . . . . . . . . . . 1.3 3 6 3 1.3; 3 6 4 100 Carrier. . . . . ........... A1203 A1203 A1203 Al203 Al2O3 SiO2 / sioa active-none So, coal Treatment (1). Imp-Vak Imp-Vak TM Imp-Vak Imp-N2 Imp-Vak TM Imp-Vak Treatment temperature, ° C .... ..... ...... 138 138 154 260 538 138 154 138 none Grams used .... 103.7 46.5 47.5 41.7 not not 31.6 16.9 measured measured Operating conditions Type of reaction vessel (2) fixed bed under under under fixed bed fixed bed under fixed bed under Stir Stir Stir Stir Stir Temperature, ° C ..... 121 121 121 121 121 121 121 121 121 Pressure, atü. . . . . . . . . . 35.2 27.1 28.1 26.4 35.2 35.2 26.4 35.2 26.7 Test duration, Hours ............... 5 4 3 3 3 5 2 5 2 Conversion,% .... 10 3 15 6 0 57 13 1 0 Isomerization, ° / 0. 19 19 10 19 75 12 3 Product distribution, Mole percent Ethylene ............... 8 8 30 17 Propylene. . . . . . .... 34 47 17 17 10 38 28 Butene ............... - - - - - - - Pentenes ..... .... 18 19 14 15 5 37 24 Witches ... ...... 32 23 39 51 25 16 heavier 8 3 l 8 | 3 85 32 (1> The term Imp-Vak means that the impregnation, as described in Example 1, and a subsequent vacuum treatment were carried out at the specified temperature. Imp-N, means an impregnation, as described in Example 1, and a subsequent treatment with N2 at the specified temperature, TM means dry mixing of Mo (CO) 6 with the carrier and subsequent heating to the specified temperature.

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

In Table III, the experiments 17 to 20 experiments according to the invention are which show that various types of catalyst preparation can be used.

Run 21 is a control run showing that a temperature of 538 ° C is too high for the treatment of the catalyst. The experiments 22 and 23 show that silica-alumina and silica are useful carriers, while Experiments 24 and 25 show that a catalyst on activated carbon and a Unsupported catalysts are not useful.

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

Example 7 Two experiments are carried out using a catalyst from W (CO) 8 on a support was used for the disproportionation of olefins.

The catalysts were made according to the impregnation procedure of the example 4 using activated alumina 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. One experiment was carried out without a diluent, while isobutene was used as the diluent in the other experiments. The results of these experiments are given in Table IV below: Table IV Attempt no. 26 27 catalyst Charbonyl. . .. W (CO) 6 W (CO) 6 Weight percent 2, 0. . . . . 2, 2.0 Carrier * ... Al203 Al203 Grams .. .. 108.8 104.8 feed Olefin ............... 1-butene - 1-pentene Isobutane thinner, Weight percent .... 0 66 Gram Olefin + thinner. 690 440 Operating conditions Temperature, ° C. . 121 121 Pressure, atü. . ..... 35.9 35.2 Duration of the experiment, Hours ............... 5 3 Conversion,% (a). . . 7 44 Isomerization,% ...... to 8 20 (a) Feed isomerization only.

Table IV (continued) Attempt no. 26 1 27 Product distribution, Mole percent Ethylene. . Propylene. . 28 34 Butene - 18 Penten 28 - Witches. . ... 40 13 Hepten .... ...... 1 10 Octene. ... ... 3 24 heavier. ...... 3 1 Butene distribution,% 1-butene ............... 3 2-butene. 97 Pentent distribution, ° / 0 1-pentene 2 2-pentene .. .. 92 Isopentene .. ......... 6 Isomerization product .. 2-butene 2-pentene Example 8 Ethylene was converted to a mixture of hydrocarbons including cyclopentane and methylcycloplopane.

A granular aluminum catalyst was heated to 3580C in air and then heated in nitrogen to activate this carrier, then the activated one Aluminum oxide impregnated with a cyclohexane solution of molybdenum hexacarbonyl. It just enough solution was used to completely wet the support, and the concentration of the solution was adjusted so that the desired amount the carbonyl compound on the carrier, as shown in the table below, revealed. The cyclohexane was then removed from the catalyst by rinsing at 121 for 2 hours up to 143 ° C away. The composition was then placed under £ 21 to 143 ° C for 2 hours kept absolute under a pressure of 1 mm Hg.

The catalyst prepared above was then used for a trial Ethylene used in the fixed catalyst bed. In this fixed bed system, 100 ml of catalyst placed in a tubular reaction vessel, and gaseous ethylene was passed through the reaction vessel at the desired rate. That The reaction vessel was heated to the desired temperature for each experiment. Of the The effluent from the reaction vessel was let down to atmospheric pressure and the products then examined by gas chromatography and mass spectrometry.

The results of these tests are given in Table V below: Table V Nersuch No. 1 2 3 4 5 6 7 8 9 catalyst Weight percent Mo (CO), ............... 2 2 2 2 2 2 3 3 5 conditions Temperature, ° C. .... 138 232 66 121 121 121 121 121 atü ...... ..... .. ...... 35.2 31.6 31.6 33.0 32.3 32.3 0 64.7 33.7 Volumes per volume per hour .... 250 140 250 330 140 110 270 300 200 Duration of experiment, hours ............... 4 4 4 2 4 2 3 3 2 Conversion, 0 / o (2). . . . . . . . . . . . . 2.7 3.0 0.0 0.6 3.2 5.0 0.3 2.0 1.3 Product distribution, percent by weight Propylene ... ............... 28 62 57 58 64 67 52 54 1-butene. ............ ..... 26 6 9 27 8 33 26 31 2-butene ... ..... .......... 26 25 29 8 18 8 15 2-pentene .... .............. 4 Neopentane. .. ............... 1 Cyclopropane .......... ..... 8 5 3 8 6 lane Methylcyclopropyne ............... 12 | @ 4 2 4 track n-butane 2 ..... 2 1-pentene ............... .. 1 @ 4 (1) Gas volumes per volume of catalyst per hour.

(2) Exclusively a very small amount of solid ethylene polymer, that was formed.

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. Run 7 is also a control run showing that atmospheric pressure not sufficient if you want to get cyclopropane and methylcyclopropane. It is it can also be seen that the conversion is extremely low in this attempt. attempt Figure 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 using ethylene to one solid polymer is polymerized by reaction on a catalyst that consists of Molybdenum hexacarbonyl aluminum oxide is formed, with stirring in the reaction vessel is being worked on. The polymerization was carried out in the presence of benzene, however, other aromatic hydrocarbons, including toluene, of xylenes and the like can be used.

A quantity of 246 grams 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 and then preactivated in nitrogen for 2 hours) was in 155 cc a cyclohexane solution containing 7.8 g of molybdenum hexacarbonyl at 60 to 66 "C. The cyclohexane solvent was then carried off by the slurry 2 hours of heating at 1380 ° C. in the presence of nitrogen and then further Holding at this temperature for 2 hours under reduced pressure.

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

A similar attempt that is practically identical to the one above The procedure described was carried out as a control experiment, with only Cyclohexane was used as the reaction solvent in place of benzene. at Practically no solid polymer was found in this control experiment.

Claims (6)

Claims: 1. Process for disproportionation, cyclization, Addition or polymerization of acyclic, monounsaturated olefin hydrocarbons, d a -characterized in that one of these olefin hydrocarbons per se known reaction conditions with a catalyst in contact, which from a tungsten or molybdenum carbonyl and silicon dioxide, aluminum oxide or silicon oxide-aluminum oxide has been produced as a carrier material, the amount of carbonyl in the range between 0.01 and 20 percent by weight, based on the catalyst mass. 2. The method according to claim 1, characterized in that one Catalyst support used, which is produced by heating in an oxygen-containing gas has been activated to a temperature above 2600 C. 3. The method according to claims 1 and 2, characterized in that that one as acyclic, monounsaturated olefin is a 1-alkene or 2-alkene with 2 up to and including 16 carbon atoms are used. 4. The method according to claims 1 to 3, characterized in that that the cyclization of ethylene to cyclopropane in the presence of a molybdenum hexacarb onyl supported catalyst at a temperature in the range from 93 to 260 "C performs. 5. The method according to claims 1 to 3, characterized in that that the addition of ethylene to 1-butene in the presence of a tungsten supported hexacarbonyl catalyst at a temperature in the range of 38 to 204 "C. 6. The method according to claims 1 to 3, characterized in that that the polymerization of ethylene in the presence of an aromatic hydrocarbon at a temperature in the range from 66 to 2320 ° C. Documents considered: German Auslegeschrift No. 1,051,003, 1,142,867; French patent specification No. 1 329 207.