DE1518817C - Process for the complete hydrogenation of olefinic ohgomers from propylene and butylenes - Google Patents

Description

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The work is carried out in a practically stationary hydrogen atmosphere under a pressure of 30 atmospheres, ie without recirculation of the hydrogen gas leaving the reactor. As much as the 180 ° C in the hydrogen atmosphere over the impurities in the hydrogen gas is not reduced by the catalyst. From the gas space above the solution in the liquid reaction product, enough reaction product in the separator 10% of the were removed, a small amount of gas from the hydrogen separator, which has been chemically bonded, is depressurized behind the reactor. One relaxes. The reaction product obtained had worked in the reaction space at temperatures of a bromine choice of 2 mg / 100 cm ³ . C ₄ hydrocarbons about 80 to 250 ° C, advantageously 120 to substances by cleavage had not formed. 200 ° C, and with pressures of approximately 10 to 100 atmospheres ... spheres, advantageously 20 to 50 atmospheres. üei game 2 The hourly throughput is z. B. 1 to 5 kg The catalyst support was in Example 1 per liter of catalyst, advantageously 1 to 3 kg. The reaction chamber expediently consists of a turn of magnesium nitrate instead of cobalt tubes with an inner diameter of 25 to 75 mm, 15 nitrate. The amount of magnesium nitrate used, advantageously 30 to 50 mm, and lengths of 1 to 8 m, corresponded to a spinel formation of 60%, also advantageously 2 to 4 m, whereby the tubes were more expedient. for example in the manner described in Example 1, as well as the water to remove the heat of reaction by carrying out the hydrogenation reaction. The wall was used to surround it. 20 here a C ₈ olefin fraction, which has been found to be particularly useful by Codi-AIs, a merization of i-butene and n-butenes produced _Λ part of the hydrogenation product obtained was immediately. Was carried out at 220 ⁰ C with a "■ '} and without pressure relief in the entrance of the reactor flow rate of 1 kg wet product per liter and the gate due. Advantageously, applies one hour. The recirculation of hydrogenation was feedback quantities of 0.5 to 3 parts by weight hydrogenation 25, the same as in example 1. the hydrogenation product, product per 1 part by weight of fresh feed had a bromine number vori ^"v 10 mg per 100 cm ^3. Spaltan. Although this way the total throughput through the in products could not be proven. Trickle phase working reactor increased significantly. . However, there is practically complete saturation of the olefinic bonds. For the preparation of the catalyst, the active aluminum spheres mentioned in Example 1 generally have a bromine number of less than 20, often less than 5 mg / 100 cm ^{3 of} hydrogenation oxide at ordinary temperature with a solution product. There is practically no formation of fission lithium hydroxide in a mixture of 90 volume products. share methanol and 10 parts by volume of water soaked. Beisoiell ³⁵ was then dried at 15O ⁰ C. Then ^p of the carrier was calcined for 2 hours at 950 ° C. the

The catalyst support was produced in finished supports containing 1.5% lithium and was carried out as follows: spheres with 4 mm according to the X-ray diagram of 100% lithium diameter made of active aluminum oxide with an aluminum spinel. The inner surface area was 288 m ² / g, the usual 40 was 95 m ² / g. The pore size was 694 Å. Licher temperature in such an amount of saturated palladium-aqueous solution soaked with cobalt (II) nitrate was applied to this support, the chlorine. The metal was precipitated by a 60% formation of cobalt spinel. Addition of an aqueous alkaline formaldehyde solution. y <l By heating the impregnated and dried subsequently, the water-soluble salts were removed from spheres to 500 ° C., the cobalt nitrate was washed to give the oxide 45 and the catalyst was dried. The finished one decomposes. This product was then heated to 1050 ° C. for 8 hours. The carrier thus obtained had an inner butylene. Work was carried out at a surface area of 40 m ² / g. The pore size was 760 Å. 220 ° C., 30 atmospheric pressure, with recycling To prepare the catalyst, the support was impregnated with 50 parts by weight of the hydrogenation product in a ratio of 2 parts by weight of palladium chloride. Then the Palla hydrogenation product was added to 1 part by weight of fresh starting medium with an alkaline hydrazine hydrate solution in fine material. The preheating and reaction conditions are reflected on the support. The Palla were the same as in Example 1. The reaction medium content of the finished catalyst was 1.8. Product had a bromine number of 5 mg / 100 cm ³ . Weight percentage. Diisobutene was used as the starting material, 55 cleavage products could not be detected, which was obtained by dimerization of i-butene Ti · · 14. The reaction was carried out in an Example 4 vertical tube with a clear width of 25 mm. For the production of the catalyst, aluminum was 1.60 m long, in which the catalyst was arranged in solid oxide powder with an inner surface area of 300 m ² / g. An aqueous solution of zinc nitrate was introduced into the reactor via a preheater, in which the diisobutene correspond to metric zinc spinel in quantities that were preheated to 150 ° C. to form a stoichiometric material. The resultant in an hourly rate of 1.5 kg / liter reactor mass was dried and heated to 500 ⁰ C, with room tion. From which the nitrate decomposed to oxide in a separator below. The cooled hydrogenation product that had collected in the reaction chamber was converted into 4 mm pills with the addition of 2 percent by weight of product, the same amounts as the fresh zinc stearate used. These pill material is returned to the reactor. The mixture was then ^{heated to 1050 °} C. for 8 hours. The electrolyte product obtained above, introduced into the reaction chamber, was zinc based on the X-ray diagram.

Aluminum spinel. It had an inner surface ^v ^ n ² 25 mg / g and a pore size of 742 Å. 2 percent by weight of palladium was applied to this support material in the manner described in Example 1.

Tetraisobutene, which was produced, was used

had been by dimerization of diisobutene. Otherwise, the procedure described in Example 3 was followed. The reaction product obtained had a bromine number of 1 mg / 100 cm ³ .

Claims (1)

1 2 Claim to be transferred. Then takes place to bring about the ipinell a heat to about 900 to Further development of the process for full-1300 ° C., for a period of 1 to 10 hours, continuous hydrogenation of olefinic oligomers from. When using lithium as the spinel-forming propylene and butylenes in the corresponding metal, the stoichiometric paraffins can be produced by hydrogenation Soak several times with the hydroxide solution, arranged noble metal catalysts on supports, insofar as the impregnation with salts has been carried out according to the falling film process according to the patent, you can also soak several times under intermediate-1275 525, thereby marked, io circuit of the decomposition stage for the salt. One way of working that is different as a catalyst carrier is aluminum oxide, which is finely used, which has been completely or partially converted into spinel granular aluminum oxide with a large inner surface and then starts out with the inner surface and this with the solution of the metal surfaces of 20 to 120 m ² / g and pore size connection added, whereby one has from 300 to 800 A from the start. x5 can add a lot of solution of the metal compound, like the intended later degree of conversion in ' Spinel equals. After drying you can deform the mass by suitable means, e.g. B. press into strands or pills, if necessary under The subject of patent 1275 525 is a 20 addition of lubricants and - if salts for start-up for complete hydrogenation olefinic turn came - with the interposition of the Zer oligomers from propylene and butylenes in the decomposition stage, as described above, glow. It is Speaking paraffins by hydrogenation under pressure also possible to produce mixing spindles and at elevated temperature in the presence of solid application of multiple spinel-forming metal assemblies Noble metal catalysts on supports 35 compounds. Level of annealing temperatures and duration ' according to the trickle film process, the annealing process that is characterized by it, is shown in the individual spinels is that the hydrogenation in practically dormant products different, but can be by pre-hydrogen atmosphere at pressures of 10 to try to easily determine which conditions at -100 atmospheres and temperatures of 80 to 250 ° C are to be maintained in order to achieve the desired properties is carried out. 30 to achieve the catalyst carrier. In particular, in a further development of the process to have the full level of the annealing temperature and duration of the annealing constant hydrogenation of olefinic oligomers from an influence on the inner surface of the support Propylene and butylenes in the corresponding paraffin and the. Pore diameter. Have as expedient fine by hydrogenation under pressure and with increased dimensions of the catalysts from 3 to 10 mm Temperature in the presence of firmly arranged noble '35 has been proven, e.g. B. in the form of pills, strands or in metal catalysts on supports after the trickle other forms. film process according to patent 1,275,525, the noble metal, in particular palladium or platinum, has now found a process which can be characterized on the support in a manner known per se in that aluminum oxide amounts of 0.1 to 10 percent by weight are advantageously used as the catalyst support which, from 0.5 to 5 weight percent, may be applied wholly or partly in spinel 4 °, has been converted and then inner surfaces of the precious metal, in particular palladium for example, can be from 20 to 120 m ² / g and pore sizes of 300 to the Carrier can be applied by owning the 800 Å. _ · Carrier soaked with an aqueous metal salt solution Beryllium in particular are suitable as spinel-forming metals, and the metal on lithium by reduction, for example with hydrazine-magnesium, zinc, ... manganese, cobalt, nickel and 45 hydrate in alkaline solution. In the case of spinel catalysts, the carrier should precipitate. But one can also Metallverdas alumina advantageously at least bond, for example, palladium nitrate, or 20 ° / _0, preferably to 40% or over, organic and spinel salts ,, such as the presence of palladium. Those carriers have proven to be very suitable acetate, by reduction with hydrogen at elevated temperatures, in which the aluminum oxide is converted into the metal at a temperature of practically 50,
exists entirely as spinel. The spinel catalysts The starting materials for the inventive generator can be produced in various ways. Processes are the oligomers of propylene and a particularly suitable form has been found to be, butylene, which contains 6 to 16 carbon atoms in the molecule, of highly active aluminum oxide in lump form.It is advantageous to start these feedstocks according to their inner surface of un- 55 production in the upstream process steps ferry 200 to 35Om ^z / g having. To protect this lumpy aluminum from the ingress of air. miniumoxide, for example in the form of strands, The hydrogen gas to be used in the hydrogenation Pills or balls, one can use an aqueous containing conveniently at least 50 volume saline solution of the spinel-forming me- percent hydrogen to be used. The reaction space is vortalls or in the case of lithium also with an aqueous 6 ° sometimes arranged vertically, and the hydroxide used Soak the solution and the soaked catalyst material trickles over the fixed catalyst dry. If necessary, the spin blower can be lowered. The hydrogen gas leads one purpose-building Metal compounds, also in organic, moderately in cocurrent with the feedstock, Dissolve solvents such as methanol. but you can also drive in the opposite direction. As far as one has soaked with salts, it is advisable- «5 At the end of the reaction space or after it has taken place moderately, this can be achieved by heating to about 250 to cooling the reaction products 650 ° C, optionally with the addition of an oxygen separator, in which the separation containing or water vapor-containing gases, in oxides of the gas from the liquid reaction product takes place.