CS251952B1 - Method of arylalkyl agent preparation - Google Patents

Abstract

Preparation of an arylalkylating agent containing methylphenylcarbinol at 40 up to 100% and generally other ingredients such as styrene, ethylbenzene, acetophenone, propylene glycol, styrene oligomers, C6 to Clfi, hydrocarbons carried out by the raw products epoxidation of alkenes with ethylbenzene hydroperoxide the methylphenylcarbinol extraction is isolated by rectification and / or acetophenone in which it is generally further selectively hydrogenated acetophenone to methylphenylcarbinol. hydrogenation the fraction is carried out in liquid or v vapor phase at 70 to 210 ° C on the catalyst, containing at least one metal or a metal compound I.b, II.b, VI.b and VIII. group of the periodic system.

Description

The present invention relates to the preparation or recovery of an arylalkylating agent containing methylphenylcarbinol and, optionally, other components, particularly suitable for the preparation of 1-phenyl-1- (2-hydroxyphenyl) ethane, 1-phenyl-1- (4-hydroxyphenyl) ethane and optionally 1. phenoxy-1-phenylethane as a mixture of isomers of benzylmethylphenol and di- (benzylmethyl) phenol using as a starting material a by-product from epoxidation of alkenes with ethylbenzene hydroperoxide.

Arylalkylation of phenol with styrene under the catalytic action of aluminum chloride, hydrogen chloride, phosphoric acid, polyphosphoric acid and acid builder has been known for some time in U.S. Pat. 2,247,402; Chem. Abstr. 35, 62676 [1941]; Kurašev M.

V. et al., Nephtechimija 9, 428 (1969); Pauškin J. M. et al., Nephtechimija 9, 842 (1969); Kumok S. Š. and others: Ž. Vsesojuz. Chim. Obšč. 17, 460 (1972)], as well as detailed results of the formation of the individual components under the catalytic action of p-toluenesulfonic acid [Lukasik L. et al., Przem. Chemiczne. 26 / 10,530 (1977)).

However, it requires relatively pure starting monomers - styrene and phenol. In contrast, it is long known that in the so-called. phenol pitch, mainly in the front fraction, in addition to phenol, there is mainly dimethylphenylcarbinol and acetophenone, as well as by-products of epoxidation of alkenes with organic hydroperoxides, in particular ethylbenzene hydroperoxide - methylphenylcarbinol and acetophenone, which are rarely recovered technically and economically. Such a possibility of technical processing and evaluation of the mainly present acetophenone, methylphenylcarbinol and phenol, without a more demanding separation of the secondary components, enables the method according to the invention.

A method of synthesis arylalkylating agent comprising methylphenyl carbinol at 40 ° to 100 ° / o, hereinafter generally styrene in an amount of 0-50% and 0-30% of other components, such as ethylbenzene, acetophenone, propylene glycol, oligomers of styrene and hydrocarbon _Cn to C _1G, the by so doing that from the crude products of epoxidation of alkene or alkenes with ethylbenzene hydroperoxide, preferably from the product of epoxidation of propene with ethylbenzene hydroperoxide to methyloxirane, the fraction containing methylphenylcarbinol and / or acetophenone is isolated by rectification and / or further hydrogenated selectively in liquid and / or vapor phase 70 to 210 ° C on hydrogenation catalyst or catalysts containing at least one metal and / or metal compound Ib, IIb,

VI. b and VIII. groups of the periodic system, preferred honey and silver on carriers and skeletal honey.

An advantage of the process according to the invention is, on the one hand, the raw material availability, whereby the by-products from the epoxidation of alkenes to alkyloxirans, in particular propylene to propylene oxide by epoxidation with ethylbenzene hydroperoxide, are technically and economically exploited.

It is also an advantage that it is not necessary to isolate pure acetophenone or methylphenylcarbinol and other components from the starting material, nor to separate phenol and ethylbenzene, propylene glycol and the like before dosing for selective hydrogenation. Last but not least, the process is complemented by a set of procedures by which the number of technically available arylalkylating reagents and the use of by-products from petrochemical production can be expanded.

Selective hydrogenation of acetophenone with hydrogen to methylphenylcarbinol can be carried out at a pressure of 0.09 to 45 MPa, and can be carried out not only in liquid but also in vapor phase, e.g. on the trickle catalyst. In addition to acetophenone, methylphenylcarbinol, ethylbenzene, styrene, dimethylphenylcarbinol, propylene glycol, and other components may be present in the feedstock for hydrogenation, but it is preferable to remove at least dimethylphenylcarbinol and alpha-methylstyrene, in particular for the purpose of further production. l- (hydroxyphenyl) ethanes. In addition, during the hydrogenation, dimethylphenylcarbinol could be dehydrogenated as little as possible and possibly dehydrated, respectively. hydrogenolyzed to isopropylbenzene. Due to the high selectivity, hydrogenation is preferably carried out at lower temperatures, preferably in the range of 100 to 150 ° C. At temperatures below 70 ° C the hydrogenation rate is already very low and at temperatures above 210 ° C due to the bonding of the hydroxyl group to the secondary carbon and other influences, on the one hand the chemical equilibrium is shifted mainly to the dehydrogenation side and dehydration is easy! for the hydrogenolysis of ethylphenylcarbinol.

Suitable selective catalysts for the hydrogenation of acetophenone to methylenenylcarbinol are media based catalysts and compounds thereof (Raney honey and skeletal honey, media oxides, media oxides on supports, copper chromium and copper chromochemite, as well as copper chromite-barium catalysts and the like), and further] less suitable are already based on zinc and chromium (poorly effective).

However, mixed, mixed and mixed catalysts based on Cu-Zn, Cu-Zn-Cr, Cu-Zn-Fe and the like, whether in the form of alloys, oxides, metals or oxides on supports, are suitable.

Catalysts based on metals VIII. groups can be applied only within the lowest temperature range, possibly after a preliminary partial poisoning, e.g. sulfur compounds. Catalysts based on metals VIII. While these groups are among the most efficient hydrogenation catalysts, but due to their high efficiency in hydrogenation of the C = C double bonds, they are less suitable for this purpose because they catalyze the hydrogenation of the aromatic ring. At higher temperatures they even hydrogenolyz the C-H and C-C bonds. The hydrogenation catalysts are either in bed reactors, in fluid form, or dispersed in a hydrogenation medium.

Hydrogenation may also be carried out in the presence of solvents, and other components of acetophenone fractions may also perform this function. In the case of the use of selective catalysts, the amount of propylene glycol, phenol, or even styrene present will not undergo any changes in the acetophenone hydrogenation, so that the hydrogenate without additional isolation or the addition of the additional phenol needed can be immediately converted to the arylalkylation.

The process according to the invention can be carried out continuously, semi-continuously or discontinuously. Further details of the method of the invention as well as other advantages are apparent from the examples.

Example 1

Z tzv. of phenol pitch, constituting a substantially distillation residue from the production of phenol and acetone by catalytic decomposition of cumene hydroperoxide, is distilled off by differential vacuum distillation of a fraction having a boiling point of 27-160 ° C / 2.67 kPa, after an additional 5.6 wt. phenol has the following composition (in wt.%): acetorenone = 36.9; dimethylphenylcarbinol = 22.4; phenol - 20.9; cumylphenols - = 2.6 and alpha-methylstyrene = 0.7.

This multicomponent mixture is fed to a continuous arylalkylation carried out on a phosphate catalyst on silica gel as carrier (5 millimeter diameter beads containing 22.6% by weight of phosphorus and an acid number of 298 mg KOH / g) under a stream of nitrogen at 160 ° C and catalyst loading 0.4 g. cm ^-3 . h ^_1 . An arylalkylate of the following composition is obtained (in wt.%): Acetophenone = 46.2; dimethylphenylcarbinol = 0.4; phenol = 4.6 and cumylphenols = 32. After separation of cumylphenols through sodium cumylphenates, the distilled acotophenone fraction contains 72 wt. acetophenone and the remainder are the by-products and other more precisely unidentified by-products. This fraction is led to hydrogenation both in the liquid phase and on the scrubbed catalyst and / or the scrubber. in the vapor phase.

The liquid phase hydrogenation of the acetophenone fraction is carried out on an oxide mednochromium catalyst (Akdins catalyst) used in an amount of 10% by weight. at a temperature of 150 + 3 ° C and a hydrogen pressure of 18 to 15 MPa, using a stainless steel rotary autoclave equipped with heating accessories and temperature control. After 4 h, a hydrogenate content of 69 wt. methylphenylcarbinol and 1.2% acetophenone.

The second part of the fraction is hydrogenated continuously on a truncated scaffold copper catalyst (Raney-med) having a particle size of 1 to mm, at a temperature of 110 + 2 ° C, mol. an acetophenone: hydrogen ratio of 1: 7 and a pressure close to atmospheric, with the catalyst being loaded with an acetophenone fraction of 0.28 g. . cm ^_3 .h ^_l . Acetophenone conversion reached 95% and selectivity to methylphenylcarbinol 93%.

The third part of the fraction is hydrogenated under otherwise similar conditions to the second part, but instead of the scaffold medium, copper oxide on silica is used (bulk density - 1.080 kg. Dm ³ ; CuO = 64.5 wt.%; Kieselguhr = 34.5 wt.%). R ₂ O ₃ - 0.5 wt.%, Annealing losses - 3 wt.%) Reduced in nitrogen atmosphere gradually at 120-180 ° C prior to use.

Hydrogenation is carried out at 140 ° C, the conversion of acetophenone to 65% and the selectivity to methylphenylcarbinol 95%.

Example 2

Acetophenone fraction from so-called hydrogenation is used for liquid phase hydrogenation. phenol pitch after isolation of dimethylphenylcarbinol of the following composition (in wt.%): acetophenone = 44; phenol = 34; dimethylphenylcarbinol - 0.5; alpha-methylstyrene = 1.8; alpha-methylstyrene dimers = 0.8 and other, unidentified products.

300 g of acetophenone fraction and 30 g of copper-chromium-calcium catalyst (Adkins catalyst) are taken for hydrogenation.

The hydrogenation is carried out at a temperature of 100 + 1 ° C and a pressure of 10 MPa. The hydrogenate obtained contains (in% by weight): 0.6 alpha-methylstyrene; 34.3 methylphenylcarbinol; 6.4 acetophenone; 0,9 dimethylphenylcarbinol; 33 phenol; 0.5 dimers of .alpha.-methylstyrene and 4.9 l-phenyl-1- (hydroxyphenyl) ethanes.

Acetophenone conversion for 5 h reached 85.4% and selectivity to methylphenylcarbinol 91.3%. This hydrogenate is led to arylalkylation carried out at 152 + 3 ° C on a phosphate catalyst (4x4 mm grain size, trihydrogenphosphoric and polyphosphoric acid on silica gel, phosphorus content = 22.6% by weight) at a catalyst loading of 0.3 g.cmm. ³ .h '' ¹ wherein the selectivity of l-phenyl-(hydroxyphenyl) ethane was 59% and the 1-fenylxy-l-phenylethanol 27%.

In another variation, the hydrogenation of the acetophenone fraction is performed under otherwise similar conditions but at a temperature of 140 ± 2 degrees Celsius of acetophenone and a selectivity to methylphenylcarbinol of 88%.

Example 3

90 g of ethylbenzene solution of ethylbenzene hydroperoxide at a concentration of 40.7% by weight, 4.8% by weight are weighed into a 1dm ³ stainless steel rotary autoclave.

% of acetophenone and 3.5 wt. metylfenylkarbinolu. Furthermore, 35 g of ethylbenzene and 4.0 g of molybdenum phthenate containing 4.1 wt. molybdenum. After closing the autoclave and removing the air, 40 g of propylene (mol. Excess = 3.65) are passed through, and the contents of the autoclave are rapidly heated to 110 ° C with constant rotation. The total pressure in the autoclave reached 2.6 MPa. At this temperature with an accuracy of + 2 ° C, epoxidation takes place with constant rotation. Attempt after 60 min. The product is stopped, the product is drained through a condenser, weighed, and propylene and propylene oxide are distilled off. The total conversion of ethylbenzene hydroperoxide reaches 99.6%, the selectivity to propylene oxide 53.6% and the methylphenylcarbinol 40.5% and the selectivity of propylene to propylene oxide 94.3%. The distillation residue mainly consists of methylphenylcarbinol (30.3 wt%), acetophenone (9.2 wt%), ethylbenzene (60.3%), propylene glycol, a catalyst and ethylbenzene hydroperoxide.

Example 4

3.671 kg are injected into a continuously operating epoxidation reactor. h ¹ raw materials of the following composition (in% by weight): propylene = 45.0; ethylbenzene - 32.7; acetophenone = 2.3; methylphenylcarbinol - 2.8; ethylbenzene hydroperoxide = 17.1 and epoxidation catalyst = 0.1. The reaction mixture exiting from the epoxidation reactor in an amount of 3.661 kg.h ^-1 is fed to a regeneration ("degassing") column from which unconverted propylene of 1.491 kg.h ¹ is discharged and returned to the feedstock and epoxidation reactor and from below. Crude reaction product in an amount of 2.180 kg.h ^{1 of the} following composition (in wt.%): propylene oxide? = 8.6; ethylbenzene = 55.1; acetophenone = 7.62; methylphenylcarbinol = 25.81; ethylbenzene hydroperoxide = 1.42; propylene glycol - 1.90 and catalyst - 0.15. The crude reaction product is fed to a 2 nd rectification column from which 0.1875 kg is removed. h ¹ propylene oxide and column bed at 1,992 kg.h ¹ composition intermediate (wt.%): ethylbenzene - 60.3; methylphenylcarbinol = 28.1; acetophenone - 7.7; ethylbenzene hydroperoxide = 1.6; propylene glycol - = 2.1 and catalyst = 0.2.

This is fed to a third rectification column, from which 1,201 kg.h ^{1 of} ethylbenzene is discharged at the top, and 0.791 kg.h ^{1 of the by-} product oxygen-containing organic product of this composition (in% by weight): acetophenone - 19.3; methylphenylcarbinol - 71.1; ethylbenzene hydroperoxide - 4.0; propylene glycol - 5.2 and catalyst = 0.4.

Oxygenated organic by - product of

3. The rectification column is then freed from the catalyst by means of efficient extraction with ammonium hydroxide, which is then regenerated or the oxygen-containing organic product in an amount of 0.791 kg.h ¹ is fed to the catalyst.

Fourth rectification column, which extends in an amount of 0.613 kg · h ¹ leaving acetophenone - metylkarbinolová fraction compositions (% wt.) Acetophenone = 19.9; methylphenylcarbinol = 73.4; propylene glycol and dimethylphenylcarbinol = 6.7.

The heavy distillation residue leaving the bottom of the 4th column at 0.178 kg.h ¹ contains about 65% methylphenylcarbinol, 18% acetophenone, 1.8% catalyst and other unidentified, mainly oxygenated organic products. For selective hydrogenation to produce an arylalkylating agent, either an oxygen-containing organic product is used, notably after deprotection or regeneration of the epoxidizing agent, an " overhead " acetophenone-methylphenylcarbinol fraction which can be used alone as an arylalkylating agent and heavy distillation residue. especially after removal of the epoxidation catalyst.

Example 5

200 g of the by-product oxygen-containing organic product from propylene oxide production by the epoxidation of propylene with ethylbenzene hydroperoxide specified in Example 4 are weighed into a 1 dm ³ rotary stainless steel autoclave. To this is added 20 g of Raney-med copper, air is removed and hydrogen is brought to a pressure of 15 MPa. Hydrogenation is carried out at 115 + 2 ° C for 3.5 h. A hydrogenate is obtained which, after filtering off the catalyst, has the following composition (in% by weight): acetophenone = - 0.5; methylphenylcarbinol = 92.4; propylene glycol - 5.2; styrene = 1.6 and ethylbenzene = 0.7. This hydrogenate is a suitable arylalkylating agent without further refining.

Example 6

The procedure is similar to that of Example 5, except that the acetophenone-methylphenylcarbinol fraction specified in Example 4 is selectively hydrogenated instead of the by-product of the oxygen-containing organic product. The hydrogenate obtained has the following composition (% lnuot): methylienylcarbinol-93.2; acetophenone 0.1; propylene glycol with additional impurities = 6.7.

Example 7

The heavy distillation residue specified in Example 4 is distilled under vacuum, the distillate obtained having the following composition (% by weight: acetophenone = 22.1; methylphenylcarbinol - = 76.8 and styrene = 0.9).

The distillate is then hydrogenated on a trickled tableted copper-chromite-calcium catalyst (Adkins catalyst) at a temperature of 153 + 2 ° C and a molar ratio of acetophenone: hydrogen = 1: 15. However, the hydrogenation catalyst is titrated in a stream of hydrogen at 180 ° prior to hydrogenation. 210 degrees Celsius for 6 h. The hydrogenate obtained has the following composition (in w / w): acetophenone <0.05; methylphenylcarbinol = 94.6;

styrene - 2,8 and ethylbenzene = 2,5,

example

The hydrogenation is conducted with the heavy distillation residue specified in Example 4 and hydrogenated on an activated copper-chromite-calcium catalyst by bubbling hydrogen through the tempered (to 105 + 1 ° C) distillation residue prior to entering the hydrogenation reactor and thereby entraining the reactor. his couples. A similar high hydrogenation efficiency at 153 + 2 ° C as in Example 7 and a long hydrogenation catalyst life are achieved without pre-distillation.

Example 9

The ecetophenone-methylphenylcarbinol fraction isolated from the epoxidation product of a mixture of 1-butene with 2-butenes ethylbenzene hydroperoxide contains 18.5% acetophenone, 73.9% methylphenylcarbinol and the remainder is butylene glycols and other oxygenated organic products at 200 g and 100 g of ethylbenzene solvent in an autoclave specified in Example 5, on a Raney-med catalyst (21 g) at 140 + 3 ° C for 3 h. Acetophenone is hydrogenated with a conversion of 99% and a selectivity of 84 feathers. to methylphenylcarbinol.

Example 10

The procedure is similar to that of Example 7, except that a copper-zinc-chromium catalyst and a temperature of 160 + 2 ° C are used in place of the oxide copper-chromium-calcium catalyst. The hydrogenation catalyst was also activated in a stream of hydrogen at 180-210 ° C for 6 hours prior to hydrogenation. The hydrogenate obtained has the following composition (in% by weight: acetophenone = 0.0; methylphenylcarbinol - 89.4; styrene - 7.9 and ethylbenzene = 2.6. The hydrogenate is a good arylalkylating agent.

Example 11

The procedure is similar to that in Example 7, except that a skeletal Raney-nickel and a hydrogenation temperature of 85 ± 1 ° C are used in place of the oxide copper-chromite-calcium catalyst. The hydrogenate obtained has the following composition (in% by weight): acetophenone - 0.7; methylphenylcarbinol - 89.9; ethylbenzene and unidentified products - 8,7.

Claims (3)

251952 10 in a stream of hydrogen at 180-210 degrees Celsius for 6 h. The obtained hydrogenate has this composition (in% w / w): aceto-phenone <0.05; methylphenylcarbinol = 94.6; styrene - 2.8 and ethylbenzene = 2.5, Example A heavy distillation residue as specified in Example 4 is fed to hydrogenation and hydrogenated on an activated copper-chromium-calcium catalyst such that hydrogen is bubbled through the hydrogenation reactor. a tempered (to 105 + 1 ° C) distillation residue and thereby pours its steam into the reactor. Similarly, a high hydrogenation efficiency of 153 ° C is obtained without distillation + 2 ° C of Example 7 and the long service life of the hydrogenation catalyst. EXAMPLE 9 Ecetophenone-methyl-phenylcarbinol fraction isolated from the epoxidation product of 1-butene-2-butene-ethylbenzene hydroperoxime contains 18.5% acetophenone, 73.9% methylphenylcarbinol and the remainder is butylene glycols and other oxygenated organic products. 200 g and 100 g of ethylbenzene as solvent are hydrogenated in an autoclave specified in Example 5 on a Raney-med catalyst (21 g) at 140 ° C + 3 ° C for 3 h. Acetophenone is hydrogenated with a conversion of 99% and a selectivity of 84. to methylphenylcarbinol. EXAMPLE 10 A procedure similar to Example 7 was followed, except that the copper-zinc-chromium catalyst and the temperature of 160 + 2 [deg.] C. were used instead of the copper copper chromate catalyst. The hydrogenation catalyst is also activated prior to hydrogenation in a stream of hydrogen at 180-210 ° C for 6 hours. The hydrogenate obtained has this composition (in% by weight): acetophenone = 0.0; methylphenylcarbinol - 89.4; styrene-7.9 and ethylbenzene = 2.6. The hydrogenate is a high quality arylalkylating agent. EXAMPLE 11 A procedure similar to that described in Example 7 was followed, except that a scaffolding Raney-nickel and a hydrogenation temperature of 85 ++ 1 ° C were used instead of the oxide copper chromate foam. The obtained hydrogenate has this composition (in% by weight): acetophenone - 0.7; methyl phenylcarbinol - 89.9; ethylbenzene and more closely identified products - 8.7. SUBJECT A method for preparing arylalkylating agent containing methylphenylcarbinol of from 40 to 100 o / o, more typically styrene in a quantity of 0 to 50% and 0 to 30% of other ingredients such as ethylbenzene, acetophenone, propylene glycol, styrene oligomers and C6 to Cfi hydrocarbons characterized in that the cross-linked products of epoxidation of the alkene or alkenes with ethylbenzene hydroperoxide, preferably from the product of the epoxidation of propene ethylbenzene hydroperoxidium to methyloxirane, are isolated by rectification of a fraction containing methylphenylcarbinol and / or acetophenone which further selectively hydrogenates in a liquid and or vapor phase at 70 to 210 ° C on a hydrogenation catalyst or catalysts containing at least one metal and / or a metal compound Ib, II.b, v.1.b. and VIII. groups of the periodic system, preferred honey and silver · on carriers and ske-flight honey.