CS212920B1 - Catalyst-based catalyst recovery regeneration - Google Patents

Abstract

The method of regeneration of a catalyst based on metal copper (Raney-copper, copper oxides, copper oxides with other catalysts of one-step synthesis), used for the one-step production of carbonyl and/or alcoholic compounds with 3 to 12 carbon atoms in the molecule, at a temperature of 90 to 400 °C, usually in a carrier gas stream, is carried out by washing with a dihydric and/or trihydric alcohol with a number of carbon atoms in the molecule of 2 to 6 at a flow rate of 1 to 10 cm3.cm£3t.h'"'L (3 to 5 cm3.cn^3t. .h”^) at a temperature of 40 to 150 °C (80 to 100 °C).

Description

The invention relates to a process for the regeneration of known copper and other aldolyzation-dehydration-hydrogenation catalysts used in the one-step production of mainly methyl isobutyl ketone, dlisobutyl ketone, and optionally also methyl isobutylcarbinol from acetone and / or isopropyl alcohol. Catalysts, when their activity decreases, are relatively easily regenerated by the action of available petrochemical products.

It is known (5s. Patent 140,306; Macho V .: Chem. Industry 25/50, 253 (1975)) that it is formed from acetone on a nickel chromium catalyst, not only with hydrogen but also with nitrogen as the carrier gas. methyl isobutyl ketone and diisobutyl ketone besides a small amount of mesityloxide and by-products. This is similar in the case of palladium on basic catalysts, as well as on magnesium oxide (British Pat.

015 003), but also palladium on ion exchangers (German Pat. No. 1,193,931) and on a combined catalyst consisting of a medium and / or its oxides and at least one chromium, calcium, barium and zinc oxide, when methylisobutylketone and diisobutylketone are produced from acetone. (Cs. Pat. 145,869). This is similar for a catalyst consisting of a medium, silica and phosphoric acid (U.S. Pat. No. 2,802,876), as well as copper (II) oxide, activated by the addition of tartrate and alumina (Bolotov B.A. et al .:

FROM. prlkl. chim. 28, 414 (1955); 903 (1958): author, attest. USSR 98 414), as well as Raney-copper (CSSR Certificate 188 400), for which methyl isobutyl ketone is formed not only from acetone but also from isopropyl alcohol. However, despite evident positive results, these methods do not solve catalyst regeneration. A similar situation is found with copper-chromium and copper-chromium metallurgical catalysts (USSR Certificate No. 445 263).

There is some improvement in the regeneration of said and other catalysts with hydrogen at a temperature of about 350 ° C (Karimov, Sultanov, A.S., Sharapov, F.S .: C.A. 85, 77589m (1976)). The disadvantage, however, is not only the need for high temperature, but also low efficiency. However, these problems can be solved by the method of the present invention.

According to the invention, a method for regenerating a catalyst based on a metallic medium, preferably Raney-copper and / or cuprous oxide alone, or in combination with β oxides of elements II.A, III.A, IV.A, VA and VIII. groups of the Periodic Table of Elements used for the one-step production of carbonyl and / or alcoholic compounds having from 3 to 12 carbon atoms per molecule, at a temperature of 90 to 400 ° C, typically carried out in a carrier gas stream such that and / or a trivalent alcohol having a carbon number of 2 to 6, preferably in the form of an aqueous and / or alcoholic solution having a carbon number of 1 to 3, having a concentration of 0.1 to 100% by weight, at a flow rate of 1 to 3. 10 cm @ 3 / cm @ 2 / cm @ ² , preferably 3 to 5 cm @ 3 / cm @ 2 / cm @ ² , at a temperature of 40 to 150 DEG C., preferably 80 to 100 DEG C.

The advantage of the process according to the invention is the long life of the catalysts based on the medium, made possible by the light and temperature-saving regeneration of divalent and / or trivalent alcohols, in particular ethylene glycol, diethylene glycol, triethylene glycol, butanedioles, glycerol, trimethylolpropane. Another advantage is technically

212 920 Easily available wide range of copper catalysts. The process according to the invention can also be used with other known catalyst regeneration methods, e.g. in the case of Raney-copper, an aqueous solution of alkali.

As starting materials for the one-step production of carbonyl and / or alcoholic-; In addition to acetone and isopropyl alcohol alone, their aqueous solutions, mixtures, e.g. aqueous solution of technical isopropyl alcohol directly from its production by hydration of propane, regenerated mixture of acetone with isopropyl alcohol and with admixtures of other organic compounds.

The regeneration of the catalysts based on the medium is carried out by the divalent and / or trivalent alcohols themselves, but preferably in the form of aqueous or alcoholic solutions or acetone solutions, the recovery temperature being from the room temperature to the boiling point of the divalent and / or trivalent alcohol; however, temperatures of about 100 ° C are most preferred. The process can be carried out continuously, semi-continuously and continuously. The regeneration is generally carried out in a carrier gas stream. Such a gas can be hydrogen, nitrogen, helium, argon, carbon monoxide, carbon dioxide, air, methane, ethane, and water vapor can also perform such a function at temperatures above 100 ° C. By-product products are also by-products in addition to the main products that are generally separated and the non-converted feedstocks are recirculated. These main products are methyl isobutyl ketone, diisobutyl ketone, isopropyl alcohol, mesityl oxide, foranes. By-products are mesitylene, dihydroisophorane, dihydrophorone, isophorone, diisopropyl ether, 2-methylpentene, 2-methylpentane, 1,3,5-trimethylcyclohexene, 3,3,5-trimethylcyclohexane, 2,6-dimethyl-2-heptanone, 3-isobutyl -1,5-dimethylbenzene and 3-isobutyl-5-isobutylene-1-methylbenzene. These by-products, which are generally undesirable, reduce the yield of the main products, and are formed in particular at temperatures above 280 ° C or at too long contact times. At the same time, the environment, especially the type of carrier gas, influences selectivity. In the case of nitrogen, e.g. methyl isobutyl ketone and diisobutyl ketone are formed essentially only with isopropyl alcohol as the starting material, but the essential components of the crude acetone products as starting material are mesityloxide, lzomezityloxide and foranes.

In the case of hydrogen, these are, in particular, methylisobutylketone, diisobutylketone, isopropyl alcohol and methylisobutylcerbinol.

Further details of the method and advantages are apparent from the examples.

Example 1 '

To an aqueous solution of sodium hydroxide at a concentration of 20% by weight. with stirring and cooling such that the temperature does not exceed 40 ° C, 110 cm @ 3 of a grain alloy of 0.3 to 0.9 cm (in% by weight) of the following composition are added: me3 »49.6; aluminum = 50.3; calcium = 0.03; traces (or below 0.001% by weight) of silicon, iron, magnesium. Aluminum dissolves. After 1 hour of dissolution, the alkaline solution is decanted and 400 g of aqueous sodium hydroxide solution with conc. 20 wt. and the alloy is allowed to dissolve for 3 h. Then

212 920 Extracted alloy - Raney-meS washes 10-crete of 300 g of distilled 3 · water until neutral and 100 cm of the thus prepared catalyst (loose mass 149 g / 100 cm) in a nitrogen atmosphere is charged to the reactor from pyrex glass. The reactor containing the catalyst was heated to 180-280 DEG C. and at a hydrogen flow rate of 18.5 cm ^ .cm ^ g ^. ^. H "^ acetone was sprayed in an amount of 0.22 g.cm ^ _{t g>.} h ^_1 . The crude product leaving the reactor passes through a condenser and the liquid product is separated.

Depending on the temperature, the products characterized in Table 1 are obtained. The longest, h experiment is carried out at a temperature of 260-2 ° C. Thereafter, the temperature in the reactor is reduced to 240 ° C, and at this temperature for a further 30 hours, the results shown in the penultimate row of Tab. First

Due to the decrease in catalyst activity, this is regenerated by injecting an aqueous solution of ethylene glycol with conc. 50 wt. at 4 cm @ .cm ^-3 .h ^^ · for 2 hours at 125 ° C in a stream of hydrogen in an amount of 18.5 .h''® '.

The results shown in the last line of Table 4 were obtained on a catalyst thus regenerated at 240 DEG C. for a further 20 hours. First

Example 2

In a similar manner to Example 1, Raney-MeS is prepared as a catalyst for a one-step synthesis of methyl isobutyl ketone and diisobutyl ketone from isopropyl alcohol in a nitrogen stream as well as a hydrogen stream. Thus, the catalyst load of 0.2 g.cm isopropanol ^^ .h ^"1 and a temperature of 205 ° C, the conversion? 83% selectivity to methylisobutylketone 23.0% to acetone 45.6%, diisobutylketone 23.4% and methylisobutylcarbinol

5.8%. At 250 ° C, under otherwise similar conditions, the conversion of isopropyl alcohol is 90.7% and the selectivity to acetone is 64.7% to methylisobuzylketone 33.3%, methylisobutylcarbinol 3.3% and diisobutylketone 0.8%,

On the same catalyst, acetone is further converted at 280 [deg.] C. for 40 h at a catalyst loading of 0.22-0.02 g / cm &^lt; ² > h &^lt; ^-1 > and a hydrogen flow rate of 18.5 cm < 3 > ¹ ha 50 to 60% per catalyst transition, with selectivity to methylisobutyl ketone of 40 to 51%, to diisobutyl ketone of from 30 to 15%, methyl isobutylcarbinol of 4 to 6% and to isopropyl alcohol of about 16 56.

Thereafter, the activity of the catalyst gradually decreases such that, at the indicated load and at a temperature of 250 ° C, the conversion to 30% and the selectivity to methylisobutyl ketone 35% and diisobutyl ketone 1.6%. The catalyst is activated by washing with aqueous solution of conc. 50 wt. at 4 cm @ .cn ^^^. ^h-1 at 100 to 125 ° C and a hydrogen flow rate of 18.5 cm ^ ^^^ .cn. After regeneration on this catalyst, the conversion of acetone at 260 DEG C., a loading of 0.22 e * ^cm @ ^{-1, and 111} @ ^{-1 and a} hydrogen flow rate of 19 .h ^{@ -1} is 60.56; selectivity to isopropyl alcohol 21 56, methyl isobutyl ketone 38 56, diisobutyl ketone 30% and methyl isobutylcarbinol 6%.

: 12,920

Table 1

temperature [° C] Conversion of acetone to 1 catalyst transition Selectivity of acetone conversions in% to: expressway konětanta transformations acetone isopropyl alcohol metylizo- bytylke- ton mezityl- oxide Methyl isobutylcarbinol diigobutyl- ketone ISO 16.9 71.5 9.1 0.0 0.0 0.0 0.0481 208 28.4 45.7 36.1 0.0 1.0 1.3 0.0934 222 31.6 9.2 56.3 0.0 1.3 9.6 0,117 240 34.5 3.5 66.5 0.0 0.3 19.0 0,134 260 39.8 2.7 70.1 0.2 0.3 18.9 0,158 240 21.7 28.9 45.4 0.0 0.0 0.8 0.0687 240 31.1 5.65 68.7 0.0 0.2 12.2 0.1000

In reference experiments, regeneration with water alone and with an aqueous solution of sorbitol is shown to be ineffective.

Example 3

The procedure is similar to that of Example 1 except that the catalyst is replaced with Reney-copper on a support with a bulk density of 1.060 kg.cm and the following composition (in% by weight): copper oxide = 56.7; chromium trioxide = 0.3; iron oxide - 0.2; the remainder being kieselguhr as a carrier. At a temperature of 260 + 2 ° C and an acetone catalyst loading of 0.25 g.cm < ^-1 > h ^-1 and a hydrogen flow rate of 20 cm < ^-1 > cm < ^-1 > h < ^-1 > 53%, diisobutyl ketone 14.3%, isopropyl alcohol 6%; the rest are by-products. When the conversion is reduced to 25%, the catalyst is regenerated by treatment with an aqueous solution of monoethylene glycol with conc. 50 wt. at 100 ° C for 3 h at 3 cnAcm 4 injection. Acetone is then carefully injected, increasing its conversion to 37% under the above conditions.

Example 4

The procedure is similar to that of Example 1, except that after the acetone conversion has dropped to 21.7%, catalyst regeneration is carried out in one case by spraying an aqueous solution of conc. 30% of 1,4-butanediol and 10% ethylene glycol at 5 cm ^ ^^^ .cn. H ^"1 · · for 2 hours at 100 ° C in flowing helium in an amount of 19 cm ^ cm ^. .h ”^ and in the second case with a sodium ethanolic solution of diethylene glycol and trimethylolpropene

212 920 o horses. 20 wt. % dletylene glycol and 20 wt. trimethylolpropane in an amount

4.5 cm ³ .cm ^ ³ tí.h ^_1 for 2 hours at 90 ° C in a stream of a mixture of 92% by weight. methane, 6%

O „* 3 ..Π wt. % of carbon dioxide and 2 wt. of nitrogen in an amount of 18 cm. 0.2 g / ^cm @ 2 of cat. ^'1 h, and a hydrogen flow rate of 19 cm ³ .cm N ³ O and H ^3, produces results listed in Table second

rEGENERATION agent Acetone conversion per catalyst transition /% / Selectivity of acetone conversions in% to: isopropyl alcohol mstyl- izobu- tylke- ton mezityl- oxide methylene butyl carbinol diisopropyl butyl ketone aqueous solution 30% 1,4-butanediol and 10% ethylene glycol 32.2 3.3 83.2 0.0 0.1 13.4 ethanolic solution with 20% diethylene glycol and 20% trimethylolpropane 33.4 3.1 82.6 0.0 0.2 14.1

Example 5

The procedure is similar to that in Example 1, except that after the acetone conversion has dropped to 21.7%, the catalyst is regenerated by injecting a solution of triethylene glycol in isopropyl alcohol containing 30% by weight of triethylene glycol. and water 2.3 wt.

at 10 ^cm3 .cm ^ ³ ^, h ^"3 for 3 h at 60 ° C in a nitrogen stream containing 1.5% by weight 3 -3 -1. oxygen in 20 cm • ^cm j _c At · ¹¹ ·

On such regenerated catalyst ea at 245 ° C, acetone feed 0.23 ® ^{, cm 2} cat ^. And a hydrogen flow of 18 cm 2 .cn ^ ³ ^ Λ ¹ " ^3- d, acetone conversion to 31.8% and selectivity to isopropyl alcohol was achieved 3.5%; methylisobutyl ketone 81.8; methylisobutylcarbinol 0.3% and diisobutylketone 14.4%.

Claims (1)

BACKGROUND OF THE INVENTION A method for regenerating a copper metal catalyst, preferably Raney copper and / or copper oxide, alone, or in combination with oxides of elements II.A, III.A, IV.A, V.A and VIII. groups of the periodic array of elements used for the single-stage production of carbonyl and / or alcoholic compounds of from 3 to 12 carbon atoms in the molecule, at a temperature of from 90 to 400 ° C, generally in a carrier gas stream, characterized in that the catalyst is regenerated by washing with a divalent and / or trivalent alcohol with a carbon number of 2 to 6, preferably in the form of an aqueous and / or alcoholic solution with a carbon number in the monovalent alcohol molecule of 1 to 3, at a concentration of 0.1 to 100% by weight, a flow rate of 1 to 10 cm, preferably 3 to 5 cm 2, 40 to 150 ° C, preferably 80 to 100 ° C. Price: 2,40 Kčs Printed by Moravské tiskařské závody, operation 12, Leninova 21, Olomouc