DE1767082B2 - METHOD OF DISPROPORTION OF OLEFINS - Google Patents

Description

The olefin disproportionation is a process in which in the presence of a catalyst Feed stream which is one or more hydylenic contains unsaturated compounds in an end product is converted, which contains at least 10 percent by weight of compounds, presumably from at least a primary implementation, as defined below, or a combination of at least a primary reaction and at least one isomerization reaction of an unsaturated bond have arisen. This is the sum of the hydrogen contained in the product obtained of saturated hydrocarbons and compounds. which are presumably caused by gene isomerization, however not formed by one or more of the reactions listed above were less than 25 percent by weight of the total product obtained. Charging components and their unsaturated binding isomers are used in the determination of the above given percentages are not included in the product obtained.

In the olefin disproportionation defined above, the primary reaction is conversion which can be imagined as breaking two unsaturated bonds between first and second carbon atoms or between third and fourth carbon atoms and the formation comprised of two new unsaturation bonds. Here, the first and second carbon atoms and the third and fourth carbon atoms are in the same or different molecules.

Such an olefin disproportionation is illustrated by the following reactions:

1. The disproportionation of an acyclic mono or polyene having at least three carbon atoms to other acyclic mono- or polyenes having both higher as well as lower number of carbon atoms. For example, the result is disproportionation of propylene, ethylene and butenes, the disproportionation of 1,5-hexadiene ethylene and 1,5,9-decatriene.

2. The conversion of an acyclic mono- or polyene with three or more carbon atoms and another acyclic mono- or polyene having three or more carbon atoms for manufacture other acetic olefins. For example, the conversion of propylene and isobutylene yields ethylene and isopentene.

3. The conversion of ethylene and an internal acyclic mono- or polyene with four or more carbon atoms to produce olefins with fewer carbon atoms than those of the acyclic mono- or polyenes. For example, the conversion of ethylene yields and 4-methylpent-2-ene, 3-methyl-but-1-ene and propylene.

4. The conversion of ethylene or an acyclic mono- or polyene with three or more Carbon atoms and a cyclic mono- or cyclic polyene to make an acyclic one Polyene having a number of carbon atoms higher than that of any of the starting materials. For example, the conversion of cyclohexene and but-2-ene gives deca-2,8-diene and of Cycloocta-l.S-diene and ethylene deca-1,5,9-triene.

5. The conversion of one or more cyclic mono- or cyclic polyenes to create a cyclic polyene having a number of carbon atoms higher than that of any of the Source materials. For example, the conversion of cyclop-niene gives cyclodeca-l.o-diene.

6. The conversion of an acyclic polyene with at least 7 carbon atoms and with at least 5 carbon atoms between 2 double bonds each to generate acycic and cyclic ones Mono- and polyenes with fewer carbon atoms than that of the feed. For example, converting Octa yields India Cyclohexene and ethylene or

7. the conversion of one or more acyciischer polyenes with at least 3 carbon atoms between 2 double bonds each to produce acyciischer and cyclic mono- and polyenes, which in general have both higher and fewer carbon atoms than the feedstock. For example, the conversion gives of 1,4-pentadiene and 1,4-cyclohexadiene Ethylene.

From US patent 3 26! 879 is a procedure known for olefin disproportionation, in which in the presence of molybdenum oxide-aluminum oxide or tungsten oxide-aluminum oxide catalysts is being worked on. However, an alternative was sought for a long time, according to the one there The catalysts described are advantageously replaced by other disproportionation catalysts can be.

From the published Dutch patent application 66 118 40 are zirconium, vanadium, niobium Catalysts containing tantalum oxide are known, their use in the disproportionation of Olefins is not very satisfactory.

The process according to the invention produces olefins with 3 to 30 carbon atoms in the molecule disproportionate by being under suitable reaction conditions including temperature and Residence time, with a certain, with regard to the disproportionation of propylene in ethylene and Butene active catalyst are brought into contact. The inventive method for disproportionation of olefins with 3 to 30 carbon atoms in the molecule or their mixtures in the presence a disproportionation catalyst consisting of molybdenum oxide, tungsten oxide or rhenium oxide on a carrier is characterized in that the disproportionation is carried out in the presence of a catalyst whose support is made

Aluminum phosphate, zirconium phosphate, calcium phosphate. Magnesium phosphate or titanium phosphate is made.

The compounds used as carriers, zirconium phosphate, aluminum phosphate, calcium phosphate Magnesium phosphate or titanium phosphate are generally not very expensive and in large quantities Quantities can be easily produced.

The above-mentioned phosphates can be any conventional ones by methods known per se manufactured materials of catalytic quality. Particularly suitable phosphates include those chemically precipitated and purified water taps Oxides or hydrogels of metal orthophosphates. as these substances are generally relatively highly effective Have surface area. Such melamine orthophosphate hydrogels can by precipitation of a soluble salt of the metal with phosphoric acid or a phosphate salt. For example, aluminum orthophosphate by precipitation of a soluble sodium alumina and fcatrmmphoaphatsalzes with aqueous alkali heraestelli will.

Γ '· ι get the desired activity / u, sufficient accelerator is used ^! If the promotional materials are normally more important than the carrier materials, unnecessarily large amounts are usually not used. In general, the finished catalyst base contains about 0.1 to 30 percent by weight of the selected accelerator larger \ k-hkui used wt den. In most cases, a preferred amount of accelerator is about 1 to 20 " _n .

In the method according to the invention \ oiwcr.dc; cr. Caialyzer compositions can trust me Process are established and activated. For example, molybdenum oxide can be mixed with aluminum phosphate are precipitated together and then to produce an activated catalyst Calcined in air at temperatures of 371 to 871 C for 0.5 to 20 hours. Alternatively, it can Carrier material, e.g. B. zirconium dioxide. with one in that Oxide convertible compound of the accelerator, such as ammonium metatungstate, impregnated and then calcined in air as described above. Magnesium tungstate can also be used and beryllium phosphotungstate with titanium phosphate dry mixed and activated by calcining in air at elevated temperatures.

Fs may be the identity of the catalyst obtained after activation with the accelerator is not completely detectable. Therefore, under the catalytic agent, that is when mixing the carrier component and the accelerator component the catalyst composition under activation conditions to understand reaction product obtained. With the term "phosphate" in the present Catalytic compositions can also be a mixture and or complex Act oxides of the metals in question and phosphorus oxides. So the term "phosphate" includes Substances that essentially consist of phosphorus and oxygen.

The catalysts used in the process of the invention can, depending on the Type of contact process in which the catalyst is used, in the form of fine powder up to urobeii granules as well as in the form of

Agglomerated pellets. Balls, strand ^ pellets or Pearls are present.

The process of the invention can either be batchwise or continuously using a fixed bed catalyst. a stirred batch reactor, carried out a fluidized catalyst chamber or other conventional contacting process will. The process can be carried out in the vapor or liquid phase at temperatures from about 316 to 649 C and at pressures from 1 to 137 atm.abs. carried out will. Temperatures in the range of 427 to 538 "C are most preferred to be optimal Maintain transformation and effectiveness. Although the implementation of the invention is essentially is independent of pressure. generally becomes one suitable for the most economical operation Pressure used. For batch reactions, the catalyst contains 1 to about 40 percent by weight of the Reaction mixture, and reaction times of about 1 minute to 20 hours are used.

In the case of continuous implementation, the optimum compact time range for the inventive device depends Process primarily depends on the activity of the catalyst, which is determined by the surface area, the accelerator concentration and the activation temperature is influenced, and on the working temperature. Generally undesirable Side reactions favored longer contact times. Therefore, the contact time should be in t'accordance with the desired conversion be as short as possible.

Generally / ur continuous implementation Space velocities in the range of about 0.5 to 1000 parts by weight of hydrocarbon feed Parts by weight of catalyst hour suitable, with excellent results in the case of about 1 to 500 can be obtained. The speed ranges given in the examples in the context of the application are in the range from 0.5 to 1000.

The reactions according to the invention can be carried out in The presence or absence of a diluent can be carried out

Suitable diluents are paraffinic and cycloparaffinic hydrocarbons. For this include propane, for example. Cyclohexane, methylcyclohexanone, n-pentane. η-hexane, isooctane, dodecane or mixtures thereof, primarily including those paraffins and cycloparaffins, that contain up to 12 carbon atoms per molecule. The diluent should be below the Reaction conditions will not be reactive.

The olefins having 3 to 30 carbon atoms which can be used in the process according to the invention in the molecule belong acyclic mono- and polyenes including their alkyl and aryl derivatives, cyclic ones Mono- and polyenes with at least 4 carbon atoms per molecule including their alkyl and Aryl derivatives. Mixtures of the foregoing olefins and mixtures of ethylene and the aforementioned Olefins. Many useful reactions can be carried out with olefins containing 4 to 5 carbon atoms contained per molecule.

Some specific examples of acyclic olefins which are suitable for the reactions according to the invention, include propylene, 1-butene. Isobutene, but-2-ene, Buta-l, 3-diene, pent-l-en, pent-2-en, isoprene, hex-l-en, Hexa-1,4-diene, hept-2-en. Oct-l-ene, octa-2,5-diene, Octa-2,4,6-triene, non -? .- en, 1-dodecene, 2-tetradecene,

1-hexadecene. 5.6-dimethyl-octa-2.4-diene, 2-methylbut-1-en, 2-methyl-hut-2-en. Dodeca-U-dien. Dodeca-1.3,6-trien, 3-methyl-but-1-ene. 1-phenylbut-2-ene-7.7 - diethyldeca -1.3.5 -1rien. Octadeca -1.3.5.7.9 - pentaen, Eicosa-1.3-diene. Oct-4-en.3-eicosen and 3-heptene and mixtures thereof.

Some specific examples of cyclic olefins used for the reactions according to the invention are suitable are cyclobutene. Cyclopentene, cyclohexene, 3-methylcyclopentene, 4-ethylcyclohexene, 4-benzylcyclohexene. CycloocUiL, S-n-propylcyclooctene, cyclodecene. Cyclododecene, 5,5,4,4-tetramethylcyclononen, 3.4.5.6.7-pentaethylcyclodecene, Cycloocta-l.S-diene, cyclododeca - 1,5,9 - triene, cyclododeca - 1.4,7.10 - tetraene. 2-methyl-6-ethyl-cyclocta-1,4-diene and mixtures: s from it.

example 1

A catalyst that contains about 90% zirconium phosphate by weight and contains 10 percent by weight \ Volframox \ d is manufactured. A quantity of 50 g of circu nitrate is dissolved in 2 l of methanol. A quantity of 50 ml of phosphoric acid is added with stirring: h -, Γϊ. <^ Crhalienc thick white gel is filtered and washed with 2 l of methanol and dried in a steam bath. 23.18 g of the dried gel with a Particle diameters from 0.84 to 0.42 mm are increased with increasing amounts of a solution of 3.0 g Ammonium metatungstate in about 25 ml \ Va: »e; mixed. The solid is dried on a steam bath between growing additions.

A 5 ml quantity of the catalyst composition prepared above is placed in a reaction tube introduced from glass. A 2 ml bed of glass beads goes over the catalyst bed in the fixed bed reactor in advance. Using an electric heater that surrounds the glass reaction tube is the catalyst bed in place by heating at 538 ° C for 4 hours in a drier flowing stream Air activated. After activation, the system is flushed with nitrogen and cooled.

Propylene is at atmospheric pressure with a space velocity of 10 vol. Vol., Minutes in fed into the reactor. The results of the experiment are presented as an analysis of the effluent through the with The weight obtained by vapor phase chromatography is given in the table below:

Tabel AndKso 1 4: 7 c 482 ^y Ethylene, percent by weight 0.5 0.6 Propylene, weight percent 95.9 96.8 1-butene, weight percent 2.3 1.3 trans-but-2-ene, Weight percent 0.7 0.5 cis-but-2-en, Weight percent 0.6 0.8 Conversion (%) 4.1 3.2

Example 2

A catalyst is prepared which is about 95 weight percent calcium phosphate and about 5 weight percent Contains tungsten oxide. 21.87 g tribasic calcium phosphate powder with a Solution created containing 1.28 g of ammonium metatungstate and about 100 ml of water. The slurry is dried on a steam bath and the resulting cake is broken and opened sieved a particle size of 0.84 to 0.42 mm.

Using a reactor identical to that described in Example 1. becomes the catalyst activated and to disproportionate propylene in essentially the same way and was used under the same conditions as described in the previous example. the Results are shown in the following Table II:

^ thvlen. Table Il as: c 5.'X " Anahse Weight percent j 427 "C Propylene. ! .0 1.1 Weight percent Bui -! - en. I ° -0 97.5 ^ 7.3 Weight percent trans-but-2-ene. '98.6 0.5 0.5 Weight percent cis-but-2-ene. C.3 0.6 0.6 Weight percent Conversion ('·] : 0.3 0.4 0.5 ! "· S 2.7 i 0.2 1.4

Example 3

A catalyst is produced which is 45 percent by weight Contains magnesium phosphate and about 5 percent by weight tungsten oxide. 16.26 g of the magnesium phosphate are aufc'-slurried with a solution containing 1.01 g of ammonium metatungstate in contains about 25 ml of water. The slurry is dried in a steam bath, the resulting cake broken, and it becomes a faction with one Particle diameters from 0.84 to 0.42 mm retained for further use.

Using the same apparatus, this catalyst is activated and disproportionated of propylene under essentially the same conditions as used in Example 1, used. The results are shown in the following Table III:

Table III

Analysis of the product

Ethylene. Weight percent
Propylene. Weight percent
1-butene. Weight percent
trans-but-2-ene, weight percent
cis-but-2-ene, weight percent
other components
Conversion (%)

4X2 C

0.9
97.6
0.5
0.6
0.4

traces
2.4

Example 4

A catalyst is produced that is about 95 weight percent Contains titanium phosphate and about 5 percent by weight tungsten oxide. 11.23 grams of titanium phosphate powder are mixed with increasing amounts of a solution containing 0.69 g of ammonium metatungstate in

contains about 25 ml of water. The slurry will dried over a steam bath between growing additions. No dried amount of the Catalytic converter with a pressure gauge 0. S4 to 0.42 mm is recovered.

The KaUilysaloi produced above is activated and / ur disproportionation of propylene into one essentially identical to the previous examples Kind of used. The results of this investigation are given in the following table:

Propylene used. The results are in the given in Table V below:

Table V

Table IV Example 5 «Rc Analysis of the product
"~ ~ ~" 0.4 Ethylene, percent by weight 98.8 Propylene, weight percent 0.3 But-1-cn, percent by weight 0.3 trans-but-2-ene, weight percent 0.2 cis-but-2-ene, weight percent traces other components 1.2 Conversion (%)

20th

A catalyst is prepared containing about 95 weight percent aluminum phosphate and 5 weight percent molybdenum oxide. 8.72 g of ammonium molybdate are dissolved in about 50 ml of deionized water dissolved and then slurried with 68.63 g of powdered crystalline aluminum orthophosphate. The slurry is then dried on a hot plate. The resulting solid is then broken up and it becomes when carrying out propylene disproportionation, a fraction with a particle size of 0.84-0.42mm used.

Using the same apparatus and the same conditions as in Example 1, the catalog is lysator activated and used to disproportionate Τι) | χ. Γ.ιΙιιγ. C.

Ethylene,

Weight percent Propylene.

Weight percent 1-butene,

Weight percent trans-but-2-ene,

Weight percent

cis-but-2-en » Weight percent

Conversion (%)

A catalyst is prepared by mixing together aqueous solutions of aluminum nitrate and dibasic ammonium phosphate and drying the solid obtained, which contains about 92% by weight of aluminum phosphate and 8% by weight of tungsten oxide and has a surface area of 135 m ² / g. This solid is an aluminum phosphate! with a surface finish of 135 nr / g. It is then impregnated with ammonium metatungframite as described in Example I.

The catalyst is fed into a reactor, activated and used to convert propylene under the conditions given in Table VI below were used. The catalyst is used between experiments 1 and 2 for 4 hours at 538 ° C reactivated in dry air.

By S pi e I 6 94.6 94.5 I.I 1.2 \ 2 1.2 0.9 0.9 0.9 1.0 5.4 5.5 0.8 4.8

Table VI Conversion of Propylene

attempt

Dwell time in stream (min.) 45 85 155 205 Pressure, atm-abs. 7.8 7.8 7.8 7.8 Temperature, ⁰ C 427 482 538 538

Space velocity in weight / weight hour *) .. 7.5 7.5 7.5 15 Product analysis, weight percent

Ethylene 1.4 53 9.2 7.7

Propylene 96.2 85.6 66J 77.5

1-butene 0.6 2.6 5.8 3.7

trans-2-butene 1.0 3.6 7.1 5.1

cis-2-butene 0.8 2 » 5.6 4.1

Pents - - 05 03

Witches - - 5.1 0.6

Conversion,% 4 14 34 22 Yield of ethylene and butenes. % - - 82 96

*) Weight parts of the charge of the catalyst per S.dndc.

The above results show that Prop j! Cn through more effectively and faster in ethylene and butenes Aluminum phosphate catalysts with a higher surface area is disproportionated.

309526/52!

Attempt 2

30th 60 90 7.8 7.8 7.8 538 538 538 15th 15th 15th 6.3 12th 7.9 81.1 79.4 78.1 12th 34 3.6 4.1 4.6 4.9 3.1 3.5 3.8 0.3 02 0.3 1J9 1.6 1.4 19th 21 22nd 88 91 92

Claims (1)

Claim: Process for the disproportionation of olefins with 3 to 30 carbon atoms in molecule 5 or mixtures thereof in the presence of one of molybdenum oxide, tungsten oxide or rhenium oxide supported disproportionation catalyst, characterized in that that the disproportionation is carried out in the presence of a catalyst whose support is made of aluminum phosphate, zirconium phosphate, Calcium phosphate, magnesium phosphate or titanium phosphate consists '5