DE1768436B - Process for the production of decene-5 from propylene - Google Patents

Description

The invention relates to a process for converting propylene into decene-5 via a disproportionation reaction and a combination of disproportionation and isomerization steps for practical complete conversion of propylene to decene-5.

Disproportionation is the conversion of an acyclic mono- or polyene with at least 3 carbon atoms to other acyclic mono- or polyenes with both higher and lower Understood carbon atom number.

Biodegradable detergents are made from linear olefins, and decene-5 is one particularly preferred linear olefin for alkylating a phenol to produce a nonionic one biodegradable alkylate detergent. So far the only source of decene-5 has been mixtures of hydrocarbons, which contained decene-5 and it was recovered therefrom by using more tedious Separation process, e.g. B. by extraction.

The process according to the invention is characterized by the following combination of known process steps: Catalytic disproportionation of propylene into ethylene and 2-butene, catalytic isomerization of the 2-butene obtained in 1-butene, catalytic disproportionation of the 1-butene obtained in ethylene and 3-hexene, catalytic Isomerization of the obtained hexene-3 into hexene-1, catalytic disproportionation of the obtained Hexene-1 in ethylene and decene-5 and extraction of decene-5.

In a preferred embodiment of the invention, the ethylene is derived from each disproportionation product recovered and in a known manner in the presence of a known dimerization catalyst converted into normal butene and the normal butene in the conversion stage of butene-2 headed in butene-1.

The catalysts which can be used for the process according to the invention are those which have an activity for the disproportionation of propylene into ethylene and butenes.
Some examples of these catalysts are

1. Silica or thorium dioxide, which is converted into an oxide by an oxide or by calcining Oxide convertible compound of tungsten or molybdenum or by tungsten sulfide or Molybdenum sulfide or convertible into an oxide by an oxide or by calcining Compounds of rhenium, vanadium, niobium, tellurium or tantalum have been activated;

2. Aluminum oxide which has been activated with an oxide or a compound of molybdenum, tungsten or rhenium which can be converted into an oxide by calcination, by a sulfide of tungsten or molybdenum or by an alkali metal salt, ammonium salt, alkaline earth metal salt or bismuth salt of phosphomolybdic acid;

3. one or more from the group of zirconia ₅ dioxide, aluminum phosphate, zirconium phosphate,

Calcium phosphate, magnesium phosphate, or titanium phosphate, made by a sulfide of molybdenum or or and tungsten or an oxide or one which can be converted into an oxide by calcining Connection of molybdenum, tungsten, vanadium, niobium, tantalum or rhenium or with magnesium tungstate or beryllium phosphotungstate have been activated and

4.Silica, alumina, zirconia, aluminum phosphate, zirconium phosphate, Calcium phosphate, magnesium phosphate or titanium phosphate, which is replaced by a hexacarbonyl of Molybdenum or tungsten are activated.

The catalysts mentioned under 1. can be prepared and activated by customary processes, for example by combining a catalyst silica with suitable tungsten, molybdenum, Rhenium, vanadium, niobium, tellurium or tantalum compounds by a conventional method, for example by impregnation, dry mixing or joint precipitation. The ones applied to carriers Oxides are activated by calcining in air and the sulfides applied to supports are activated by heating in an inert atmosphere.

The catalysts mentioned under 2 can be prepared and activated by conventional methods, for example by combining catalyst aluminum oxide with an oxide or a compound of molybdenum, tungsten or rhenium which can be converted into an oxide by calcination and calcining the mixture obtained after removing any at the Impregnation solvent used. The sulfides of tungsten or molybdenum or the salts of phosphomolybdic acid can be used to impregnate a catalyst alumina by dissolving them in a solvent, then evaporating the solvent and heating the resulting mixture to prepare the catalyst.
The catalyst compositions mentioned under 3

tongues can drive manufactured according to conventional methods. It can be produced and activated synthetically. For example, molybdenum or from a naturally occurring mine oxide can be precipitated together with aluminum phosphate, z. B. brucite are obtained. It can be calcined in the form and then in air to produce a fine powder to coarse granules. Presentation of an activated catalyst. Alternatively 5 lying a. The finished catalysts can after the carrier material, for example zirconium dioxide, calcination also in the form of powder or granules with a compound of the convertible into the oxide and in other forms, e.g. B. aggregates, pellets, promoters, e.g. B. ammonium tungstate, impregnated balls, extrudates, pearls and the like. Depending on and then calcined in air. The type of process in which the catalyst is used is the preparation of a sulfide-containing catalyst xo. The magnesium oxide should have a surface can be a sulfide of the promoter with a carrier size of at least about 1 m ^s jg . Before the zirconium phosphate, for example, is ground in the ball mill use in the process according to the invention and then in an inert atmosphere, the magnesium oxide is calcined, for example sphere, e.g. B. nitrogen can be heated. Magnesium tungstate in a current through heating and for 30 hours 1 to about 15 can Berylliumphosphorwolframat an oxygen containing gas at 260 to 816 ° C, for example with titanium phosphate dry blended preferably at about 316-538 ⁰ C.
and by calcining in air at elevated temperatures. In general, contact of the olefinic temperatures will be activated. Sending with the magnesium oxide at temperatures

The catalysts mentioned under 4. together in the range from about 66 to 593 ° C, preferably at

Settlements can be prevented by impregnating a previously 20 about 149 to 538 ° C, at a suitable pressure and

caicinated carrier material, for example calcium - a common residence time or throughput

phosphate, with a solution of hexacarbonyl of the speed that the desired degree of conversion

Promoter in an organic solvent. Excellent results will be

for example benzene and subsequent drying often obtained with an hourly weight average

in vacuum or in an inert atmosphere at 25 set speeds from about 10 to about 30. Die

about 10 to 371 ⁰ C are produced and activated. Implementation is essentially independent of pressure and

The catalytic agent is believed to have pressures from atmospheric to about 36.2 atm. Section.

that are often used when the carrier material is mixed together.

and the promoter material obtained conversion die for use in the invention

product, the mixing of the 30 processes converting suitable dimerization catalysts

Is subjected to activation treatment. hold common catalysts that are known to

It is sometimes desirable, especially with, that they have an activity for the dimerization of

Oxide activated olefin disproportionation catalysis possess ethylene. Preferred catalysts are

gates, the selectivity of the implementation by those that dimeric ethylene with high selectivity

To improve the base treatment of the catalyst. 35 can size. Some examples of usable

This can expediently take place in that the catalysts are nickel-

a smaller amount of an inorganic base oxide catalysts, such as those in the

in the catalyst composition shortly before US Patents 3,045,054, 2,581,228, 2,606,940,

Activation heating step incorporated. 2 949 429, 2 881233, 2 904 608 and 2 985 598

The working temperature for the 40 according to the invention is based on the nickel process applied to a carrier when using catalysts based on sulfate catalysts, as for example in 1. is in the range from about 204 to 593 ° C. The USA. Patent 2,749,842 are described, applied to the invention method using the carrier Palladiumoxydkatalysatoren as catalysts according to the second is at Einei temperature, for example, in the USA. Patent 2,656,398 in the range of about 66-260 ⁰ C accomplished. Are described at 45, and supported Phos use of the catalysts according to 3 is the phosphorus pentoxide catalysts, as they are described in the USA.-inventive method at a temperature of Patent Specification 2,282,602. Besides these carried out from about 316 to 649 ° C. When using solid catalysts, homogeneous catalyst of catalysts according to 4., the erfindungsge- systems such as the Äthylalumäße from a mixture of process at a temperature of about 5 ° miniumsesquichlorid and a Triphenylphosphin-- 18 to +316 ⁰ C. In the case of the catalyst according to the invention, such as the process according to the invention, the nickel carbonyl complex, pressures are not critical; Section. is to be used.

Other suitable catalysts are in the French. Preferred dimerization catalysts are

French patents 1 511 381 and 1 516 853 and 55 supported nickel oxide catalysts,

in Patent 3,261,879. These catalysts contain support materials such as

The isomerization catalyst, kieselguhr, activated clays and the like that can be used in carrying out the silicon dioxide, aluminum oxide, silicon dioxide-aluminum process according to the invention, and analyzers include magnesium oxide, silicon dioxide - these are made up of about 0.1 to about 10 percent by weight of aluminum oxide , zeolitic silica-alumi- 60 cent nickel oxide activated. In general, magnesium oxides are used either alone or in combination with these catalysts by impregnating a suitable one of the transition metals and the like. The magnesium oxide suitable for use in the inventive salting and subsequent 0.1 to 20 hour reduction process, sometimes referred to as magnesia heating the impregnated and dried composition, can be used in a stream of air to 427 to 621 ° C or activated magnesia produced more catalytically.
The drawing represents a schematic diagram

5 6

a preferred embodiment of the invention reactor 3 contains a catalyst that is the same or

is similar to that in reactor 2. The isomerization

In it, the propylene is passed through line 10 in reactors containing an isomerization catalyst, the disproportionation reactor 1 and the z. B. Magnesium Oxide. The dimerization reactor j effluent through line 11 into the distillation 5 contains a dimerization catalyst, e.g. B. nickel zone 12 passed, which oxide a single distillation zone on silica-alumina.
or a series of distillation columns. Although the invention is primarily directed to the production of the propylene through line 13 from the distillation position of decene-5, it should be noted that lation zone 12 is removed and through line 13 in the distillation zone 31 practically pure hexene-3 den Disproportionation reactor 1 recycled. The io is produced and, if desired, at least ethylene is removed through line 14 and can be recovered in part through line 27a. Ethylene dimerization zone, to which reference is made below. If desired, ethylene may also be passed as a minor. The butene-1 is obtained by product.
Line 15 in the disproportionation reactor 2 and

the butene-2 through lines 16 and 17 in the 15 example
Isomerization reactor 18 passed. The effluent from

In a system shown in the drawing, the isomerization reactor 18 is passed through the device 19 into the distillation zone 20, from which the first reactor contains a catalyst which removes about 8 butene-2 through line 21 and contains tungsten oxide by weight Silica de-isomerization reactor is recycled, and that holds 20, and the reactor operates at a temperature butene-] is through line 22 to line 15 of 427 ° C, a pressure of 25 atm. Section. and one passed into and thence into the disproportionation reactor 2 space velocity of 40 parts feed per. The effluent from the disproportionation part catalyst per hour to achieve a reactor 2 is through line 23 in the distillation conversion of about 45 ° / ₀ . The first isomerization zone 24 passed, from which the ethylene was removed through line 25 containing a magnesium oxide catalyst and also passed into the dimerization stage. It works at 427 ⁰ C, 25 atm. Section. and one will. The butene-1 is passed through line 26 to the space velocity line of 20 parts by weight of Beschik-15 and from there to the disproportionation reactor 2 kung per part by weight of catalyst per hour to and through line 23 to the distillation zone 24 to achieve an equilibrium distribution of the iso. The hexene-3 is merged through lines 27 and 28. The second disproportionation reactor is passed into the isomerization reactor 29. The effluent holds a catalyst which, similar to the catalyst from the isomerization reactor 29, is passed through that in the disproportionation reactor 1 with the outlet 30 into the distillation zone 31. That would assume that it has been treated with a base and heavy by-products are withdrawn from the distillation additive containing 0.5 percent by weight sodium, zone 24, through line 33. The hexene-1 35 The disproportionation reactor operates at 538 ° C, is removed through line 34 from distillation zone 31 at atmospheric pressure and space velocity, and the hexene-2 and hexene-3 are removed at 35 parts by weight of feed per weight through line 35 and recycled through line 28 in part of catalyst per hour to achieve a conversion of the isomerization reactor 29. The conversion of about 22 ° / ₀ . The second isomerization-hexene-1 is passed through line 34 in the disproportionation reactor 40 contains a magnesium oxide catalyst, he nierungsreaktor 3 and the effluent from which works at 538 ° C, at atmospheric pressure and a disproportionation reactor 3 is through line 36 space velocity of 20 parts by weight Beschik led to the distillation zone 37. The ethylene is drawn off overhead through line 38 per part by weight of catalyst per hour. The hexene-1 attainment of near equilibrium distribution is removed through line 39 and through line 45 the isomers. The third disproportionation reactor 39 is returned to the disproportionation reactor 3. contains a catalyst which is similar to that of the second. The heavy by-products are withdrawn from the distillation zone 37 by the disproportionation reactor rr.with the A "v line 40. Assuming that it is only 0.25% by weight of sodium. The decene-5 is carried out as a product line 48 on which tungsten oxide on silica support contains 50. The disproportionation reactor is working

The ethylene in the line 38 is together with at 510 ⁰ C, 1.7 atm. Section. and a space velocity of the ethylene in lines 14 and 25 by the lceit of 15 parts by weight of feed per line 41 by weight in the ethylene dimerization reactor 42 parts of catalyst per hour to achieve a bypass, from which the ethylene and the butenes by conversion of about 21 * / ₀ . The dimerization unit removes line 43 and into distillation zone 55 42 contains a catalyst which is fed to 4 percent by weight 44. The ethylene is returned to the line 41 through the nickel oxide on Sfliriumdioxyd-Aluminumoxyd entLeitung 45, which holds heavy, and works at 38 ° C, 21.4 atm. abs, and any byproducts are withdrawn through line 46 sufficient to provide a 56% space velocity and the butenes are withdrawn through line 47 to the butenes-containing effluent.
Line 21 and from there to the isomerization reactor 60. The material balance during the implementation is given in the following table, in which the amounts in

The reactor 1 contains a disproportionation parts by weight are indicated, and it should be noted

catalyst, for example about 8 percent by weight that from 1000 parts by weight of propylene 555 weight

Tungsten oxide on silicon dioxide, the reactor 2 parts decene-5 are made,

preferably contains a highly selective, base 65 The above example shows that propylene is effective in

acted disproportionation catalyst, for example decene-5 is converted. The inventive

wise tungsten oxide on silica, treated process also provides a source if desired

with up to about 1 percent by weight sodium, and that for hexene-3 and / or ethylene.

table
Streams in parts by weight

10 11th 15th 14th 13th 16 21 47 22nd 23 26th 1000 333
1220
173
493 173 333 1220 493 2507 390 883 238
3804 3804 710 1000 2219 173 333 1220 493 2507 390 883 108
4860 3804

Ethylene

Propylene

Butene-1

Butene-2

Butene

Witches-1

Witches

Witches-3

Decene-5

Total byproducts

108 108

Ethylene

Propylene

Butene-1

Butene-2

Butene

Witches-1

Witches

Witches-3

Decene-5

Total byproducts

table
Streams in parts by weight (continued)

27 25th 35 34 39 36 40 De
cen-5 38 41 43 238 111 111 682 20th 710 5750 711 3400 3400 390 710 238 5750 711 3400 555
45
4111 45
45 555
555 111 682 292
702

292 292

1 sheet of drawings

Claims (2)

Patent claims: 1. A process for the preparation of decene-5 from propylene, characterized by the the following combination of known process steps: Catalytic disproportionation of propylene in ethylene and butene-2, catalytic isomerization of the butene-2 obtained in butene-1, catalytic disproportionation of the 1-butene obtained in ethylene and 3-hexene, catalytic Isomerization of the obtained hexene -3 into hexene-1, catalytic disproportionation of the obtained Hexene-1 in ethylene and decene-5 and extraction of decene-5. 2. The method according to claim 1, characterized in that the ethylene from each disproportionation product and obtained in a known manner in the presence of a known dimerization catalyst converted into normal butene and the normal butene passed into the conversion stage from butene-2 to butene-1.