DE1768984C3 - Process for the preparation of carboxylic acid allyl esters - Google Patents

Description

the, for example activated carbon, titanium dioxide, titanium 2000 g per hour and then the oxygen additive, Zirconium oxide, zirconium uicate, zirconium phosphate, gradually increased to 196 Nl in the course of 36 hours Aluminum oxide and silicates such as fired clay increased per hour. A catalyst is obtained or aluminosuicates, silicon carbide and silica gel. performance of an average of 245 g allyl acetate per A silica with 5 liters of contact per hour, which remains even after 1000 a specific surface between 40 and 300 m * / g operating hours does not change. The yield of allyl as well as an average pore radius between 50 and acetate, based on converted propylene 2000 A. 97%; 3% of the converted propylene are clogged

It is advisable to carry out the reaction in the presence of carbon dioxide and water. one or more alkali salts of Example 2 to be reacted

Carboxylic acid carry out. Preferred are the Na-

trium salts and particularly preferably the potassium salts. About 2 1 of a fresh catalyst of the same

The preferred amounts of the carboxylic acid-alkali composition as in Example 1 are included Salts are between 0.1 and 25 percent by weight, 5 atmospheres pressure, 650 Nl nitrogen per hour without acid between 1 and 10 percent by weight, contains and heats the catalyst within one drew on the weight of the carrier material and hour at a temperature of 170 C, where as in catalytically active substances existing mixed Example 1 the gas stream from a temperature of catalyst 100 ° C hourly 140 g acetic acid and from a temperature

A particularly favorable technical execution temperature of 130 ⁰ C hourly added form is to be the alkali metal salts of carboxylic acids 20 1600 Nl propylene. As the temperature rises, the acidic acid is continuously or discontinuously added to the mixed amount according to the vapor pressure until the catalyst is added during the reaction, with an increase of 2000 g per hour, so that after breaking aer the continuous addition of the alkali metal salts of the carbon catalyst end temperature of 170 ° C. about acids between 0.1 and 400 ppm, advantageously between 3.0 Nm ^{3 of} a gas mixture consisting of 21.7 Vo-1 and 100 ppm of the carboxylic acid used. «5 percent by volume nitrogen, 53.5 percent by volume propylene

Even if len and 24.9 percent by volume of acetic acid are not required for the reaction according to the invention, the catalyst flows through the oxygen-transferring redox systems. If this gas mixture is used, the presence of such a gas mixture leads to 195 Nl of oxygen being added within 2 hours. The known organic conditions of Example 1 are suitable, corresponding to a conical and especially inorganic redox system, constant catalyst output of 165 g of allyl acetate per liter of contact per hour due to the reversible change in their oxidation levels 96%, based on the converted Pr ° Py ^{| s;} accelerate catalytic reaction. Suitable about 4% of the converted propylene react to form inorganic redox systems. B. the salts of carbon dioxide and water. Metals that change their valence level reversibly Example 3

can, called, e.g. B. those of copper, iron, _t u *, A _rn * uA hprop

Manganese fcers, vanadiums, antimony, lead, chromium The analogous example J mi ^Wism f ^ ™ ^^ ⁶ ;

and titans. Preference is given in the present case to a special catalyst with a solution of 4U. G and the copper and cerium salts. 4 ° potassium acetate, 21.5 g palladium acetate and 2.8 g copper

^F acetal impregnated in 730 ml of acetic acid and im

Example 1 vacuum dried at 5O ⁰ C. .

Over 2 1 of this catalyst one passes under the in ib Bdi P ^r <W> ^en ^ 'S

About 2 1 of this catalyst

970 g of a silica carrier are impregnated with the conditions described in Example I. P ^r <W> ^en · ^ 'S "solution of 40 g of bismuth nitrate in 735 ml of water and 45 acid. Oxygen and nitrogen After 67 ml of concentrated nitric acid have been reached, the reaction -Endbedingungen has the new ■ l ^ Jysa dried supported catalyst is in a vessel having tor a catalyst efficiency of 285 g Allylace al; per 21 ml brought a 5% potassium hydroxide solution liters contact and hour, the au ^ back "00 ^Stu ^ ™ £ after. The yield of allyl acetate, existing potassium hydroxide solution decanted off and converted into propylene by means of water, amounts to 95%. The catalyst is then filtered off with suction, residual amount of 5 ° _o converts s.ch to carbon dioxide and, dried, with a solution of 40 g of potassium acetate water.

and 21.5 g of palladium acetate in 730 ml of acetic acid in Comparative Example 1

pregnated and finally dried in vacuo at 5O ⁰ C _iV overall ereleichsbeispiel with a bismuth-free contact). The finished mixed catalyst contains about 55 (comparative measures mn c process

1.95 percent by weight palladium diacetate, 6.5% Ka- over 2 liters of a catalyst from nac " ^{dem V} ^ ^en

lium acetate and 1.56% bismuth in the form of acetates. the German patent 1 296.38 by 2 l of the above-described catalyst are gen a solution of 21 5 g ™ ¹ ** ™haben °? filled into a reaction tube. One passes over potassium acetate and 40 g ^ ?? ⁰ ^? every hour a mixture * heats the catalyst at 5 atm pressure Kieselsäuretragers ° and nac "following Trock of 650 Nl of nitrogen and 20 Nl of oxygen and was assumed w.rd under the ^« ^C ^ JT gJSuie the catalyst within one hour to a tem- in Bei _pi el 1 _c a mixture of propylene, acetic acid at temperature of 170 ⁰ C. During the heating advertising oxygen and ^Sückstoff _ ^ ^a ^ .J ^ ³ ^ _{L? er} to the gas stream after reaching a temperature of Katalysatorle.stung 270 g of allyl acetate P ™ ^ from 100 ⁰ C hourly 140 g acetic acid and after reaching 65 contact and hour the ^^. ^ '^^ "" ^, chen a temperature of 130 ⁰ C hourly 1600 Nl driving hours to 215 g ^{and after} V ™ _t JLF hour _and propylene was added. on further heating the catalogs to 60 g allyl acetate per Li he contact undjätonde lysators to 17O ⁰ C, the acetic acid feed drops down. the yield of allyl acetate amounts to about _95/0,

the rest of about 5% reacts to carbon dioxide and conditions 170 g of allyl propionate per liter of contact Water. and hour. It also functions after 600 hours of operation

v., "i":, i ".i,"; rn · ι ι unchanged. The yield of AUyl propionate, based on

Comparative Example 2 ^ _{ljmgesetztes Propylene is 95} j £

(Comparative example with a bismuth-free contact) ₅ vIf the implementation is carried out with otherwise the same

When using a catalyst which is applied to 0.7 weight conditions with a bismuth-free contact of the composition described in percent palladium metal, 0.3 weight percent gold, comparative example 1 and 4 weight percent potassium acetate, the maximum output is 145 g of a silica carrier, results under otherwise allyl propionate per 1 contact and hour. After 125 identical conditions as in Example 4, for a maximum of 10 hours, the output has already dropped to 110 g per catalyst output of 210 g of allyl acetate per liter of contact per hour.
Contact and hour. The catalyst performance is _R. 17th

after 100 hours of operation only 135 g and according to the example

500 operating hours 45 g of allyl acetate per liter of contact over 21 of the catalyst described in Example 1

and hour. 15 a mixture of 440 Nl is passed per hour at 3 atm

. . Nitrogen and 15 Nl oxygen and heats the catalyst

Example 4 _{sator innerha} i _b 1 hour at 180 ⁰ C. During the

Over 200 ml of the heating described in Example 1 and the gas stream from 100 ° C hourly

catalyst used be at 17O ⁰ C under 180 g butyric acid and from 13O ⁰ C hourly 1000Nl per hour normal pressure nitrogen 13 Nl, Nl 32 Pro added ao propylene. The butyric acid supply is in the

pylene, 40 g of acetic acid and 3.9 Nl of oxygen passed. further course of heating up to 2000 g per

An increased space-time yield of 32 g / l · h per hour is obtained. After reaching the final temperature

Allyl acetate at a converted propylene base of 180 ⁰ C increases the oxygen supply in the ver

A yield of 95%. gradually run from 36 hours to 130 Nl per hour.

. . * 5 Under these conditions the catalytic converter

Example 5 performance 145 g allyl butyrate per liter of contact and

For the continuous implementation of the process hour and the yield of allyl butyrate, based on rens, an apparatus is used which consists of a converted propylene, 96%. The catalyst performance of the reaction tube with a length of 4500 mm and a diameter of 32 mm is unchanged even after 570 hours,
Knife, gas and liquid pumps, a gas 30 If the bismuth-free contact is used, the composition described in the compressor, acetic acid evaporator, condenser and Comparative Example 1 consists of a condensation vessel. The oxygen is added before the acetic acid evaporator is added to the gas cycle under otherwise identical conditions. Catalyst output of 128 g of allyl butyrate per liter; the supply of fresh propylene takes place on the contact and hour, but that in the course of 140 suction side of the compressor. The carbon dioxide produced as a by-product for 35 hours to 65 g of allyl butyrate per liter of contact and the resulting carbon dioxide will fall off as waste gas from the hour.
System so far away that a carbon dioxide. . . "

Concentration of about 20 percent by volume in the circular example 5

running gas (without acetic acid) is maintained. Over 200 ml of the contact mentioned in Example 1

The reactor is filled with 3.6 l of the catalyst described in Example 1 at 185 ^° C. and normal pressure, 23 NI hourly. At 18O ⁰ C and propylene, 29 g of 2-Äthylcapronsäure and 16 NlLuft. a pressure of 7 atmospheres per hour 8.5 Nm ^3. A space-time output of 16 g of 2-ethyl cycle gas, consisting of about 72 percent by volume of allyl caproate per liter of contact and hour, is obtained.
Propylene, 8 percent by volume oxygen and 20 percent by volume .... . _Q

percent carbon dioxide, as well as 6.29 kg acetic acid over 45 H ei play y

passed the catalyst. This gives 7.05 kg per hour over 1 1 fresh contact of beKondensat in Example 1 with a 22.0 Allylacetatgehalt overall composition are registered at 180 ⁰ C under weight percent, corresponding to a catalyst performance atmospheric pressure per hour 95 Nl nitrogen 95 Nl Propyvon 430 g of allyl acetate per liter of contact per hour. len, 64 g of cyclohexanecarboxylic acid and 17 Nl of oxygen. The output is still under 50 after 2500 hours of operation. A space-time yield of changed is obtained. The yield is 98% of allyl acetate, 17 g of allyl cyclohexanecarboxylate per Liier Kon, while the remainder is converted into carbon dioxide and water per hour.

is set. _T,. . . , _Λ

Example 10

Example 6 55 over 200 ml of fresh contact of the in Example 1

About 1 1 of a fresh catalyst of the inscribed in Example 1 composition is introduced at 185 ⁰ C

The composition described is passed hourly at 4 atmospheres and normal pressure? .5 Nl propylene, 10 g

hourly a mixture of 540 Nl nitrogen and 20 Nl phenylacetic acid, 13 Nl nitrogen and 3 Nl oxygen.

Oxygen and heats the catalyst within 1 hour. The space-time yield is 14 to 15 g of phenyl

de to a temperature of 180 ° C. During the 60 acetic acid allyl ester per liter of contact and hour.

Heating up the gas flow after reaching. . ·, ,,

a temperature of 100 ⁰ C per hour 150 g propion Example 11

acid and from 130 ⁰ C hourly 1350 Nl züge- propylene is passed over 200 mL of contact of the example 1

puts. With further heating of the catalyst to the described composition at 185 ° C below

180 ⁰ C, the propionic acid feed is up to 2J0O g per 65 normal pressure 35 Nl propylene, 17 Nl air and hour

Hour and then the oxygen supply in the amount of 12 g benzoic acid. The space-time yield is included

run gradually from 36 hours to 160 Nl per hour 12 to 14 g of allyl benzoate per liter of contact

elevated. The catalyst performance below this is and hours.

Claims (2)

1 · the mixed catalysts described above with high D »! N 7At performances yields of over 96% to patent claims: gSÄSSS». based on the implemented pro 1. Process for the production of carboxylic acid pyjes. _{b} the} process according to the Erfinallylestern in the gas phase by conversion of 5 "■». ^W _{in the} form. Propylene, oxygen or oxygen-containing oung is to be prepared in situ _{in «""{" J ™ ^ wisnl utsalz.} Gases and the corresponding carboxylic acids at However ^ ™™ * "· -" _ebnisse be achieved if the elevated temperatures in the presence of catalysis J ¹ '™ ™ * "- _ne f bismuth salt catalysts particularly one consisting of an inert support material . ^ ^{mu 'n} ^ ™ ^^ S ^ · This carboxylates köneinem.oder more salts of one or more ^WMUtc i ". 5S2KSinritu on the contact erEdelmetalle of transition group VIII of the periodicity new S ^ ^e ^" * ⁿ * - * _{ielsweise From} bismuth hydroxide, systems, possibly salts of metals, look like bismuth and oxy! of the first and second main or subgroups of peno-bismuth oxide or dic system and, if necessary, redox systems dationsnu ^tteln j ... _f - _{ts if} the bismuth in consist, characterized, x ₅ 1 ^ g «SSbSÄ ^^ WtautMioxyd that the reaction in the presence of a catalyst of such a form, oeisp _{under the Rgak} _ conductors, which also 0.01 to 20 Ge or Wamutoxyd, vorhg ^ o _Q ^ Weight percent bismuth, based on the mixing conditions em basiscnes oo catalyst. oxylat b'Wen Can saturated aliphatic, 2. The method of claim 1, marked by *> ^ f ^ f ^^ ^ ZZhfTdcr omaLhc Ca ^ leans that the catalysts ¹ ^ _{one or more} of the metal or a salt containing bismuth in the form cydoahphatische "J'P ^. SSS ^ SSSiSw ^ public, however, is that dfe entering carboxylic acid under the reaction It is known that allyl acetate can be produced by reacting "5 condin _s unger" ^^ rji ^ rtSAXS allyl alcohol with acetic acid. Furthermore, ^Do PPf ^lbin ^ _e ⁿ f "1" ¹ ^ _Ηγ ^ s ίο carbon atoms, know, allyl acetate by- reaction of propylene with in general ^ mcht mete « _{ätti te al} , _ha _ Acetic acid in the presence of compounds of the noble group. Preference is given to "» * » ^e | \ | _{4 κ} * _η1εη J _toff . Metals of Group VIII of the Periodic Table t -sche M ^ rbon ^ anden nut ^ ^ di U Grt 3 ton * ' ^e J " ^p £" ^ metals of Group VIII of the Periodic Sy ^^ ^ ^ produce by n is the reaction in the presence 30 * * * tor ^'e _n J ^"p £" ^ _E "igsäure implemented of molecular oxygen and of redox systems, acidic, particularly preferably hssigsa * made from salts of the metals of the I main and secondary The oxygen can be converted into pure « J * ™haben ^m of molecular oxygen and y from salts of the metals of the I. main and secondary group of the periodic table, which or auc> '"^ * XS under the reaction conditions, their valence level in the form of air or an a change leversibel, carries out. This procedure can be 35 ^ y ^ i "!« ^ ' ¹ "«? ^^ For example, in the liquid phase at temperatures see execution of the ^^^. g ^ * ™ ^ between 60 and 160 ° C and propylene partial pressures moderate, that the «« "^" ΪεΪΖα from 5 to 50 kg / cm *. However, mix outside of the known explosion areas only 7 to 30 mol. _Ar f _n iirt so vor7uesweise Percent of the propylene converted to allyl acetate Der 4 < > The use of the ^ «^^^« 'iStiSS Rest is in propenyl or isopropenyl, and that in the Anfangspenode the Sauer ° ^{s "Pa} _m f ^ ^{r" ck} other by-products, such as acrolein, acetone and slowly increasing. By the ' ^an J ^sam ^ / ¹ ^ f ⁶ Carbon oxides, over. Furthermore, the establishment of the oxygen pressure is the initial penode Allyl acetate from propylene, oxygen and acetic acid to a much higher ^ eToShS UUtUnJ Palladium-metal catalysts at temperatures of 45 Manufacture »f '^^ SSS 50 to 250 ⁰ C in the liquid and gas phase known in the production of ^ "» J ^ n ^ S ^ however, considerable amounts of acetone as a result of the formation of a J ^ ™ ** J "*" crodukt arise form of the catalyst explain the faster The füidieΪ production of carboxylic acid aryl esters increase in the oxygen pressure in the shortened hitherto known catalysts have only a period of time is not obtained. _{tprhni "hen} through rings life, which makes them particularly advantageous for technical is at J '^ ^1" ^^. engineering methods do not. guide the process, the kontinuttrii ^ eRuckfuh The object of the invention is now a process for the preparation of the unconverted input products according to the Production of allyl carboxylic acid esters in the total or partial removal of the gaseous substances phase by converting propylene, oxygen or products into the reactor. The proportion of the Oxygen-containing gases and the corresponding input products _WI rd each replaced, the carboxylic acids bet elevated temperatures suitable for the reaction S_alze ^d "Precious Metals Presence of catalysts from an inert of the VIII. Subgroup ^ Periodic System Support material, one or more salts of one or more salts of ruthenium, rhodium, indium, platinum several noble metals of the VIII. subgroup of the 60 and in particular of the Palladmms. Also "£ *" * «£ Periodic system, optionally salts of the metals, noble metal-salt-Gem.sche can emge with advantage of the I. and II. main or subgroup of the periodic are set. ^ Is particularly preferred. ^ e noble see systems and possibly redox systems metal in the form of the salts of the "^^ J" stand, which is characterized in that the carboxylic acid is used. In the F ^ d "^ u« teung of Reaction in the presence of catalysts through 6 ₅ propylene with acetic acid ,, st therefore -du ; ^ν ί ^ "* ^ ^νοη leads that 0.01 to 20 percent by weight, based on the Paltadium acetate as a catalyst particularly favorable Mixture catalyst contains bismuth. The process As carrier material for the KaUüysator tons of d e According to the invention, when working with a wide variety of inert materials,