CS199159B1 - Process for preparing saturated and / or unsaturated aliphatic aldehyde / or alcohols having 20 to 100 atoms. carbon - Google Patents

Abstract

The invention relates to a method for the production of both saturated and unsaturated aliphatic aldehydes and 20 to 100 carbon atoms, or the corresponding alcohols based on higher molecular weight petrochemical unsaturated compounds with an average molecular weight of 260 to 100, prepared by homopolymerization and/or copolymerization of alkanes with 2 to 5 carbon atoms and/or diones with 3 to 5 carbon atoms. Higher molecular weight unsaturated compounds containing 1,2 to 4 double bonds in the molecule are hydroformylated and subsequently hydrogenated without or with the use of organic solvents.

Description

, 1

The present invention provides a process for the preparation of a saturated, unsaturated aliphatic aldehyde and from 20 to 100 carbon atoms, optionally with the corresponding alcohols based on the molecular molecular structure of the unsaturated compounds, in the molecule. 81 in macromolecules is more than one double in & zbu. Among the known methods for the preparation of higher molecular weight alcohols are the telomerase and ethylene methane, possibly also with alcohol, with the organic peroxide alkaloid compound (VSA patches 2 668 181 and 2 671 121 {NSR Pat · 1 13963 139a 1 138 751, 2® · Pat 124 970), but a large mixture of high molecular weight alcohols and polyolefins is formed. A disadvantage is also the formation of secondary alcohols and low yields. Of particular interest is the so-called Alfolprooes, but the disadvantage is the high demand for pure ethylene purity and the primary alcohols. The following raw material base and the impossibility of producing more molecular aldehydes and unsaturated alcohols by this prooes. Natural resources are therefore heavily exploited. Synthesen mlt Kohlenmónóxyd. Springer-Verlag, Berlin-Hei-delberg-New York (1967) 1 Asinger F.i Dié Petrolohemisóhe Industrie. Akademle-Verlag, Berlin (1997), Rudkovskij D. M.i, Karbonillrovaaie, ss. Izdat.ohim., Leningrad (1968) J, which is widely applied in the hydroformylation of olefins having 2 to 13 carbon atoms. However, the possibilities for the hydroformylation of 1-alkenes, e.g., residues from ethylene oligomers (over 20 carbon atoms), have not been investigated, probably due to the unavailability of such 1-alkanes as the scales for unclear application of the corresponding aldehydes and alcohols.

Obviously, the available natural resources were sufficient for limited consumption. Where it has been necessary to use higher molecular alcohols, they are usually replaced by an alcohols of 12-18 carbon atoms and paraffins of 20-40 carbon atoms. And similarly, it was with high-molecular aldehydes. However, the drawbacks of the prior art are those of the present invention wherein saturated and / or unsaturated aliphatic aldehydes and / or alcohols having from 20 to 100 carbon atoms are produced. hydroformylation of the olefinic alkyl group with compounds having from 19 to 99 carbon atoms, with catalytic action of cobalt and / or rhodium compounds, at a temperature of 80 to 200 ° C, optionally by hydrotreated hydrogen aldehydes under the catalytic effect of hydrogenation catalysts based on metal II. and / or VIII. groups of the periodic system at a pressure of 0.1 to 35: 1 MPa by hydrophonizing polyolefins or a mixture of polyolefins having a molecular weight of 260 to 1400 with a ratio of 1.2 to 4 double in the macromolecules prepared by the homopolymer and / or polymer alkenes and 2 to 5 carbon atoms and / or 3 to 5 carbon atoms of catalytic action of the ionic and / or complex catalysts, preferably after centrifugation of the residues of the catalyst and / or catalytic system, including those formed therefrom, generally in the presence of organic solvents with a boiling point of -10 to 180 ° C, optionally with simultaneous and / or subsequent hydrogenation on a hydrogenation catalyst, preferably based on a medium of zinc, nickel, cobalt and / or palladium, wherein the aldehydes and / or as a rule, alcohols are refined, preferably after the catalysts and solvent have been removed.

In particular, cobalt and radio compounds are used as the hydroformylation catalyst.

The process can be used as a starting material for the formation of the in-house catalyst, cobalt in the form of metal powder, cobalt oxides and cobalt salts formed by weak, in particular organic acids such as cobalt ethane, cobalt laurate, naphtha-benzobalt, cobalt stearate, cobalt salts using mixed acids from oxido-produced high-boilers of oxo-oxides of 4 to 8 carbon atoms. Co-catalysts are cobalt carbonyls, such as octocarbonyl bicobalt, hydrotetracarbonyl co-balt and trialkyl or triarylphosphine-modified cobalt carbonyls, optionally bonded, i.e. "heterogeneous" to the carrier. Among the radio compounds, it is possible to use hydrated dihydrochloride, radium oxides, carbonyl radicals, trans-dihydrogen carbonyl-bis-triphenylphosphine, as well as other complex radium compounds as well as chemically bonded to carriers, i.e. "heterogeneously". In particular, these catalysts catalyze their own hydrophthylase and partially homogeneous hydrogenation of the aldehydes formed, as well as the hydroformylated salt unsaturated to the saturated compounds. However, for the perfect hydrogenation of aldehyde-related alcohols, it is usually desirable to hydrogenate the hydroformylated polyolefin products, especially after removal of the hydroformylation catalyst, by hydrogen, by heterogeneous catalysis, whether in normal or in the absence of hydrogen. a slight increase in pressure, e.g., a scrubbing catalyst or at high pressure. Particularly suitable as hydrogenation catalysts are media-based catalysts such as Haney-copper and other forms of skeletal cadmium, oxazoline, honey and its oxides on copper, calcium chromate, and the like. MeSnato-O-mormite-barium catalyst. In particular zinc catalysts are known based on zinc. From Elements VIII. groups of the periodic system, in addition to the various elements (Pt, Rh, Pb) which are attached to the support, is in particular nickel, in the form of a powdered metal, in the form of Raney-nickel, respectively. skeletal nickel, nickel oxide, nickel or oxides per carrier, further nickel-staggered catalyst, and the like.

The polyolefins are preferably low molecular weight polyethylene, oligomeric ethylene, low molecular weight ethylene-propylene copolymers, low molecular weight polypropylene, so-called polyolefins. polypropylene oil, polyisobutyl, copolymers of the components of the pyrolysis fraction, mainly devoid of the essential part of 1,3-butadiene, thus containing isobutene, n-butenes, isobutene, n-butane and 1,3-butadiene. These are homopolymers and copolymers of the pyrolysis fraction components, mainly isopentene, n-pentones, piperylone, cyclopentadiene and isoprene.

True, it can be used for the homopolymerization and copolymerization of even individually 3 to 5 carbon atoms, especially if it is suitable from the thermo-economical hl'a- diaca. /

Suitable rope and complex catalysts of low molecular weight homopolyphthyrisol, oligomers and copolymers are the so-called Lewis acids, such as aluminum halides, in particular aluminum chloride, aluminum chloride hydrochloride complexes and alkylaroinates, and also halogenated hydrocarbons, trialkyl aluminum, chloroalkyl aluminum with titanium chlorides and the like. . It is also possible to hydroformylate these olefinic unsaturated compounds with 19 to 99 carbon atoms, either alone or in the presence of solvents. In particular, in the case of 19 to about carbon atoms and the presence of 1 solvent, it does not particularly favor. Considering that practitioners are high molecular weight compounds without hydroformylation or hydrogenation, they do not change significantly. melting point, for example in the case of hydroformylation of alkenes and 12 to 16 carbon atoms, when it is necessary to use solvents.

As the solvent, butane, isobutane, heavy and heavy naphtha, individually alkanes, cycloalkanes, benzene, toluene, xylenes, alcohols and 1-8 carbon atoms can be used, in principle also higher alcohols than octanols can be used. but it is disadvantageous from the same game

However, it is desirable to remove polyolefin catalysts and systems from the polyolefins prior to hydroformylation. ioh residues, as both hydrocarbon hydrocarbons and Lewis acids may inhibit or retard hydroformylation (cobalt carbonates) ·

The hydroformylation catalyst is best removed or removed. to regenerate the raw product, right, true, can also be kept in the raw product. The hydroformylation can be selected selectively, for example, only the carbonyl groups or the carbonyl groups and the double non-hydroformylated double bonds can be hydrogenated. For the first variant, catalysts based on zinc and zinc are the most suitable, for metals on the other hand, the metal or co-metals II. and VIII, groups. The solvents are most conveniently removed after the hydrogenation, eventually combining the solvent of the solvent with the separation and refining of the product according to the invention can be carried out discontinuously. semi-continuous and continuous. The advantage of producing the high molecular weight aldehydes and / or alcohols of this invention is the wide availability of polyolefins, especially the primary alcohols, which are suitable for other synthesis and production as well as high thermal stability. Last but not least, the flexibility of the procoes, depending on the needs, to selectively hydroformylate the ages of the most available double loading and difficult to cure or hydrogenate, eventually utilizing less reactivity with less voluminous atoms and molecules. (For example, high molecular weight bromaldehydes, bromoalcohols, alcohols, etc.) can be produced. Further advantages and details of the present invention will be apparent from the examples of embodiment. Example 1

In a 1 dmJ stainless steel rotary autoclave, 16 g of oyfluohexene (solvent) were weighed together with 1.6 g of cocarbonyl bicarbonate Co2 (C0) and 320 g of polypropylene oil prepared by propylene polymerization under the catalytic action of aluminum chloride complex with toluene and with ethyl chloride pr1, heat 70 ° C with a molecular weight of 4β6, the bromine number of «58.9 g · Br ^ / QQO g, so that 1 macromolecule is the average-1.6 double in & d remaining at 20 ° C. J 8 kg 8 kg / l n = = = 90 dynam = = = = = 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 17 17 17 ; After the air has been closed and removed from the autoclave, synthesis gas (42 vol.% Of carbon monoxide; 57 $> vol. Hydrogen) of 0.6 vol. Nitrogen Ó, 1 vol. 0.3% by volume of methane by carbon dioxide) to a total pressure of 22 MPa. Thereafter, while continuously rotating the autoclave, its content is heated to 150 ° C. At this temperature, the hydroformylation proceeds for 2 h, then after increasing the temperature to 16 ° C for an additional 5 h. The total pressure in the autoclave during hydroformylation drops from 29.5 MPa to 20 MPa. Thereafter, the autoclave is discharged from the autoclave to bring the synthesis gas and hydrogen to a pressure of 3 MPa. Thus, at 160 ° C for 1 hour, cobalt carbonyls cobalt powder is deposited. Hydrogen is then discharged from the autoclave and a sample of the crude hydroformylation product (bromine number 22 g Br.sub.2 / 100 g) is removed, corresponding to the conversion of polypropylene oil or double portions 43.9 which is 0.7 double bond ηη molecule} CHO = 0.85 wt.% OH e 0.55 wt.%. Next, 45 g of copper-calcium-calcium catalyst (Adkl's catalyst) are added to the autoclave; and 20 g of manganese oxide and conducting hydrogen to 18 MPa. The hydrogenation is also carried out at a temperature of 50 ° C for 4 h. 512 g of crude product are obtained, from which removal of a substantial part of the catalysts by centrifugation and cyclohexane as solvent by distillation under reduced pressure yields the product of this composition: bromine number s: 25.4 g Br = 100 g OH = 1.35 wt% CHO 0.14 wt% Then the selectivity to alcohols is 81.3%. EXAMPLE 2 A polypropylene oil prepared in a manner similar to that described in Example 1 was distilled off under reduced pressure at a temperature of 180 DEG C./40 mbar. The average molecular weight of this oil is 314 g bromine number 98 g Br2 / 100 g, so that an average of 1.92 double bond per 1 molecule is} density at 20 ° C is 820 kg.m -1 and refractive index (n ^ °) 1,462 .

The hydroformylation experiments of this polypropylene oil (after 160 g in one experiment) were carried out at temperatures ranging from 14 ° to 170 ° C using a half-liter rotary blower. autoclave (82 rpm), 80 g of toluene as solvent, 0.4 g of bicarbonate octocarbon as catalyst at an initial synthesis gas pressure (CO + Hg) of 19 MPa. In order to know the hydrophonsyic cinema at different temperatures, the catalyst can be fed with a portion of the solvent to the reaction medium until the desired reaction temperature is reached. The hydroformylation treatment is monitored from the pressure drop values, the total conversion of the polypropylene oil from the bromine number, the selectivity to aldehyde determination of the aldehyde groups by infrared absorption spectroscopy, and the oximation method when boiling for 1 h the hydroxyl group content by the acetylation method. For dependence of the gravity constant k ^ mitt "1 ^ and the absolute value of the temperature T (K), the dependence" log k = (3,148 - O, 3é5) 2365 - 158, therefore, the selectivity for the corresponding

The T-molecular aldehydes reach 40 to 70% and the corresponding molecular alcohols from 29 to 15%; the residual up to 100% is due to the homogeneously catalyzed hydrogenation of the double bonds and, to a lesser extent, to the subsequent reactivation of the high molecular weight aldehydes and alcohols. for high molecular weight alcohols and decreased aldehydes. Example 3

The polymerization in a substantially butadieneized pyrolysis fraction is carried out. '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' " Eo remove the air in the autoclave. weigh 250 µg of a dark brown solution of aluminum chloride complex (Al = 5 (8901 ()) with 25.9%; ash = 11.14%) with dodecylbenzene admixed with both chlorinated n-alkones and 11-13 carbon atoms disposed in the production of dodoyl benzene by alkylation of the 11 to 13 carbonated n-alkanes with a catalytic action of granulated aluminum, from which "aluminum" forms an aluminum complex, a catalytic complex.

Thereafter, 10 kg of fracoe of this composition (in weight%) of 1.5 1,3-butadiene are weighed; 43.7 isobutene; 33,5 1-butene; 2,5 o-2-butene; 6.9 trans-2-butene; 8.5 n-butane; 2.4 isobutene; 0.2 propylene; 0.1 propane and 0.3 pentanes. The polymerization is carried out at a temperature of 60 DEG C., 1 hour from a temperature of 60 DEG C. and an additional 150 g of a talc complex is added. After 6 h, a gas sample is collected from the gas phase and a sample of gas (1,3-butadiene; 37.6% isobutene; 37.6 $ 1-butene; 2.5 ois-2-butene; # Trans-2-butene, 9.8 n n-butane, 4.2 iz isobutene, 0.3% propane, 0.2% propylene and 0.3 pent penta-nav), the autoclave content is degassed and recovered 4.8 kg of polybutylene oil is refined with active clay, filtered and analyzed. The bromine number of this polybutylene oil is 71.2 g Brg / 100 g and the average molecular weight * 632, so that on average 1 mac-romolecule is 2.8 doubles in & From this amount, 320 g of polybutylene oil are weighed into a 1 liter spinning autoclave together with 200 g of cyclohexane and 1.8 g of bicarbonate octocarbonyl. After removal of the air, the synthesis gas is conducted up to an overpressure of 20 MPa and hydrophomnyl is carried out for 9 hours at 160-2 ° C. At this temperature, the aspen pressure at that time drops to 27.5 MPa to 22.7 MPa. The decomposition of the cobalt carbonyls is carried out by weathering under a hydrogen pressure of 2.5 MPa at 164 ° C. This gives 529 g of crude oxo product, the bromo number of which is 23.3 g Br.sub.1 / 100 g, which corresponds to the conversion of the polybutylene oil and the polybutylene oil. converting the double bond to approximately 32%, which is almost 1 double in the macromolecule (0.9 double bond); CHO b0, 26 wt .; OH with 0.62 wt.% Of this amount is taken up in the hydrogenation with 500 g, together with 50 g of the rononato-ohromite-catalyst together with 20 g of nickel oxide. The hydrogenation is carried out in a 1 liter rotary autoclave at 160-2 ° C and a hydrogen pressure of 21 MPa for 4 h. The crude hydrogenate is obtained from which the product has the following composition after separation of catalyst and solvent: bromine number - 34.35 S Br 2/10 g; OH = 1; 27 wt%; CHO and 0.31 wt. Example 4

Similar to Example 2, a 0.5 liter rotary autoclave of hydroformylation of polypropylene oil is performed at 160 g in the presence of 80 g of a solvent and 0.3 S of HCl (a) (PAr 2) 2 as a catalyst at a temperature of 10 ° C. and a total synthesis gas initial pressure of 14 MPa. the double in & e reaches 30 selectivity for high molecular weight and alcohols are not present. Example 5

Polymerizáoia, respectively. copolymerization of 1400 g of substantially butadieneized pyrolysis fractions of the composition (in% by weight): 0.07 propane; 2.35 isobutane with propylene; 8.45 n-butane; 33,50 1-butene; 43.58 isobutane; 7.19 trans-2-methane with isopentane; 3.29 ois-2-butone and 1.53 1,3-bu tadiene, together with 400 g crude, pyrolysis fractions of (in wt): 0.61 propane; 2.24 isobutane and propylene; 10.2 n-butene; 18,35 1-butene; 25.57 isobutene; 4.95 trans-2-butyl, with isopentane; 3,42 ois-2-butone; 34.26 1.3-bu of tadiene and 0.36 of methylaethylene, is carried out in a stainless steel rotary autoclave of 5 dm for catalytic action of 90 g of the AlCl 3 catalyst complex with alkyl aromatic halohydrocarbon; resp. The hydrogen carbon black specified in Example 3. The soot autoclave is continuously heated to 62 ° C for 15 minutes, at which time it is maintained for 30 minutes. and then at 80 ° C for 300 min. Thereafter, the contents of the autoclave are cooled to the stirrer temperature and degassed. The composition of the released gas is also (v / w): 2.82 propane; 23.76 isobutane with optional propylene; 52.74 n-butane; 7.51 1-butene; Isobutene 0.0; 12.89 trans-2-butene with isopentane; 0.37 cis-2-butene and 0.0, 1,3-butadiene. 1,662 g of a liquid product are obtained, which is refined with a 2 wt. the active clay and, after filtration, is analyzed (bromine number with 83.68 g of Br 2/100 g of sample; acid number with 0.0; average molecular weight with 374; viscosity at 20 ° C e 92.8 mPa.s at 30 ° C = 52.5 mPa · s and at 50 ° C = 22.7 mPa · s). Thus, per molecule is on average 2 (1.96) double bonds.

Such a product is used on the hydroformylate which is carried out using a rotary autoclave from stainless steel. 500 g of said liquid product are hydroformylated with 4 g of cobalt double carbonyl carbonate at an initial synthesis gas pressure (CO + H2) of 20 MPa. The hydroformylation is carried out for 2 h at 150 ° C, with the total pressure dropping from a pressure of 26.5 MPa to 21 MPa. At that time, the synthesis gas is pressurized with 29.5 MPa and dropped to 22 MPa for another 5 h. The synthesis gas is then discharged from the autoclave to a pressure of 0.15 MPa and hydrogen is supplied to a pressure of 3 MPa. Decomposition of cobalt carbonyls takes place over 1 h at 160 ° C. The crude oxo product has the following composition: '

Claims (2)

A process for the production of saturated and / or unsaturated aliphatic aldehydes and / or alcohols having 20 to 100 carbon atoms, hydroformylated olefinic unsaturated compounds of 19 to 99 carbon atoms, and a catalytic effect of cobalt and / or rhodium compounds at 80 ° C. optionally by subsequent hydrogenation of the aldehydes formed with the catalytic effect of the metal-based hydrogenation catalysts II. and / or VITI. groups of the periodic system at a pressure of from 1 to 35 MPa, characterized in that hydroforms are present. Polyolefins or a mixture of polyolefins having an average molecular weight of 260 to 1400 and having a diameter of 1.2 to 4 double bonds in macromolecules prepared by the homopolymerization and / or copolymerization of C2-C5 alkenes and / or C3-C5 dienes having a catalytic content the effect of ionic and / or complex catalysts, preferably after removal of the catalyst and / or catalytic system residues, including from them. vortex residues, generally in the presence of organo-organic solvents boiling at -10 to 180 ° C, optionally with simultaneous and / or subsequent hydrogenation on the hydrogenation catalyst, preferably on the basis of medium, zinc, nickel, cobalt and / or palladium, the aldehydes formed and / or alcohols are generally refined, preferably after removal of the catalysts from the solvent. 2. The method according to claim 1, wherein the solvent is alkanes, cycloalkanes, aromatics, alkyl aromatics and aliphatic alcohols having 1 to 6 carbon atoms.