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United States Patent (19) [11] 3,821,259 Bljumberg et al. (45) June 28, 1974

54) METHOD OF SIMULTANEOUS PRODUCTION OF OLEFINE OXIDES AND 56) References Cited ACETIC ACD , FOREIGN PATENTS OR APPLICATIONS 76 Inventors: Erna Albertovna Bjumberg, 1376,471 9/1964 France...... 260/348.5 V Leninsky prospekt, 57, kv. 10; 1,057,398 2/1967 Great Britain...... 260/348.5 V Demid Vasilievich Ivanjukov, 1,080,462 8/1967 Great Britain...... 260/348.5 V Karmanitsky pereulok, 10, kv. 4; 1,143,577 2/1969 Great Britain...... 260/348.5 V Sergei Alexeevich Maslov, Smolensky bulwar, 14/22, kv. 9; OTHER PUBLICATIONS Jury Dmitrievich Norikov, prospekt Malinovski, M. S., and Their Derivatives, Vernadskogo, 113, kv. 91; Nikolai (1965), pp. 64, 65, 68. Markovich Emanuel, Vorobieuskoe, shosse 2 "b', kv. 44; Vladimir Primary Examiner-Norma S. Milestone Vasilievich Boiko, Kaptonya, 1 Attorney, Agent, or Firm-Eric H. Waters kvartal, dom 12, kv. 2, all of Moscow, U.S.S.R. (57) ABSTRACT 22 Filed: May 26, 1972 A method for the simultaneous production of olefin oxides and consisting in concurrent oxida 21 Appl. No.: 257,349 tion of olefins and acetaldehyde with an oxygen containing gas in the presence of a catalyst in the form (52) U.S. Cl...... 260/348.5 V of a silver compound or vanadium oxides. 51 Int. Cl...... C07d 1/08 58 Field of Search...... 260/348.5 V 3 Claims, No Drawings 3,821,259 2 METHOD OF SIMULTANEOUS PRODUCTION OF hyde with an oxygen-containing gas at a temperature of OLEFINE OXDES AND ACETIC ACED 40-150° C and under a pressure of 50 atm in the pres ence of a catalyst, consisting of silver compounds or va The present invention relates to a method for simul nadium oxides. The silver compounds may be em taneous production of olefin oxides and acetic acid. 5 ployed either in the form of silver salts, for example Ag Olefin oxides, particularly ethylene and propylene OX NO, AgCl, Ag, AgBr, or in the form of silver oxides. ides are important products of organic synthesis and Air, as the most inexpensive raw material, is preferably they are widely used in the chemical industry. Olefin used as an oxygen-containing gas. Other oxygen oxides are employed for producing polyurethane, gly containing gases may be used, such as nitrogen-oxygen cols, polyglycols and their esters, capillary active sub O mixtures containing at least 10 percent of oxygen. stances, antifreeze compounds, lubricating oils, plasti In practice the process is carried out as follows. The cizers, humidifiers, and other products. Acetic acid and initial reagent - olefins, for example propylene and ac acetoacetates are used as solvents in manufacture of etaldehyde are dissolved in benzene and charged into artificial fibre, synthetic dyes, ; they are also a metal autoclave along with a quantity of catalyst used in the food industry and as an initial material for 15 which is usually equal to 1-10g per litre of the solution. producing acetone. At present, there are no industrial methods of pro The reaction is generally effected in the presence of ducing propylene oxide without the application of chlo excess olefin. The reactor is hermetically sealed, the rine. In the known industrial process of producing pressure is brought up to 50 atm; and the reaction mix propylene oxide 1 ton of propylene oxide is obtained by ture is brought to the desired temperature while agitat consuming about 3 tons of chlorine and alkali. The re ing it with a mechanical stirrer and applying heat with action is effected in two stages: (1) production of prop the heater of the reactor, both of which are switched ylene chloro-hydrine and (2) its saponification with al on. After attaining a desirable temperature, the oxy kali to propylene oxide. The chief disadvantage of this gen-containing gas is bubbled at a rate of 10-12 litres method consists in the formation of a huge amount of 25 per hour into the reaction mixture (the rate of bubbling wastes of chlorine and alkali which are hazardous for is measured with a rheometer). After completing the the vegetable and animal kingdoms. These wastes prac reaction, the reactor is cooled and the pressure therein tically cannot be destroyed or utilized, and this fact is reduced to atmospheric pressure in order to isolate makes the chloro-hydrine method unsuitable for the the non-reacted propylene. The maximum concentra development of production of propylene oxide on an 30 tion of olefin oxide is attained 1 to 3 hours after the be industrial scale. Attempts have been made in some ginning of the reaction, depending on the nature and countries to produce propylene oxide by catalytic concentration of the catalyst. epoxidation of propylene with the hydroperoxide of The proposed method has substantial advantages as . compared with the process of non-catalytic simulta This method results in a low yield of propylene oxide, 35 neous oxidation of olefins and acetaldehyde. namely, 10-15 kg/m per hour. The process is also dis Due to the use of the above mentioned catalysts the advantageous, in that it is effected in three subsequent rate of formation of propylene oxide is increased from stages, each requiring special conditions and different 0.3 mole? 1 hour to 1.3 molell hour, while the yield of catalysts. This hinders the provision of a continuous propylene oxide for the reacted acetaldehyde is in process and also control thereof. In addition, in this 40 creased from 360 kg/t to 850 kg/t. The yield of carbon process production of 1 ton of propylene oxide is asso dioxide for the reacted acetaldehyde is reduced from ciated with production of 3 tons of a by 200 kg/t to 30 kg/t, while the concentration of peroxide product. compounds in the reaction mixture is reduced by a fac Known also in the art is a promising industrial tor of 10 and does not exceed 0.08 mole/1. method based on the simultaneous oxidation of liquid 45 The invention will be better understood from the fol propylene and acetaldehyde with air at a temperature lowing description of some particular examples of car of 70° C and under a pressure of 50 atm. The process rying the invention into effect. is effected in a single stage and is featured by simple technology. However, the yield of propylene oxide is EXAMPLE I equal to 360 kg per ton of the reacted acetaldehyde, 50 A metal reactor is filled with 40 ml (24 g) of liquid which corresponds to 30 percent of the theoretical propylene, 5-10-15 ml (4-8-12 g) of acetaldehyde dis yield. In the process of simultaneous oxidation, up to solved in 40 ml (35 g) of benzene, 1.0, 5.0 or 10.0 g of 25 percent of the initial acetaldehyde is converted into catalyst being added per litre of this solution. The appa carbon dioxide. Furthermore, a considerable amount ratus is hermetically sealed, the pressure is brought up of explosion-hazardous peroxide compounds is accu 55 to 50 atm, the mixture is heated to a temperature of 70 mulated in the reaction mixture. C, and an oxygen-containing gas is bubbled through the A specific object of the subject invention is to pro mixture at a rate of 10-12 l/hour with simultaneous vide a method for simultaneously oxidizing olefins and mechanical stirring of the mixture. The composition of acetaldehyde which makes it possible to increase the the reaction mixture is analyzed by the gas-liquid chro rate of oxidation, the yield of olefin oxides for the re 60 matography method with the use of a stationary phase acted aldehyde used and the concentration of olefin ox in the form of polyethylene glycol disatearate applied ides in the reaction mixture, as well as eliminating the to a carrier (celite) in an amount of 15 percent of the formation of carbon dioxide and reducing the concen weight of the carrier, as well as by chemical methods tration of explosive peroxide compounds. 65 (iodometry, alkalimetry). The maximum concentration This and other objects are attained in a method for of propylene oxide with various catalysts is attained 1 the simultaneous production of olefin oxides and acetic to 3 hours after the beginning of the reaction. The con acid by concurrently oxidizing olefins and acetalde centration and yield of the products at this moment of 3,821,259 3. 4 time after removing the non-reacted propylene are follows: propylene oxide, 75g acetic acid, 130 g; and given in Table I. carbon dioxide, 8 g.

Table Taken Obtained Propylene oxide acetic acid peroxide CO, yield yield g per yield g per compounds, in g per Time of reac quantity of Acetalde- concentra- 100 g of concentra- 100 g of concentra- 100 g of tion and oxi catalyst catalyst, gll hyde, molell tion, molell aldehyde tion, motell aldehyde tion, molell aldehyde dizing gas without Cait. 3.56 0.20 30.0 ... O 125 0.80 19.6 hour; AgO O 3.56 30 72.0 2.0 133 0.80 3.9 aid AgO 10.0 356 0.81 55.0 1.60 129 S AgO 1.0 78 0.47 83.0 0.78 132 3.0 oxidizer AgO O 534 147 555 3.40 32 s do. WOs 5.0 3.56 0.95 550 2.10 24 0.09 3.6 2 hours; V.O. 0.0 3.56 0.90 490 80 O2 0.06. 2.5 air Ag) 5.() 3.56 0.80 500 70 106 0.08 5.5 do. AgNO, 50 3.56 0.75 36.0 18O 84 O.2 6.7 3 hours; AgCl 5.0 3.56 0.73 400 180 OO 0.10 6.0 air AgO ..) 3.56 20 70.0 1.90 23 ().07 36 hour; mixture of 2% O, and 88% of N,

EXAMPLE 2 We claim: A reactor having a volume of 2 litres equipped with 25 1. A method for the simultaneous production of a stirrer for stirring a liquid and catalyst mixture pres propylene oxide and acetic acid comprising the steps of ent therein is charged with 1 g of AgO, and 2 of ben concurrently oxidizing a mixture of propylene and ac Zene containing 20 per cent by weight of acetaldehyde. etaldehyde dissolved in benzene with an oxygen The reaction mixture is heated to a temperature of 100' containing gas in the presence of catalyst C, and air, propylene and acetaldehyde dissolved in at a temperature of 40°-150° C and a pressure of 50 benzene are continuously added to the mixture under atm and recovering propylene oxide and acetic acid, a pressure of 50 atm. The vapour-phase mixture from said propylene being employed in an amount in excess the upper portion of the reactor is fed into a cooler and of said acetaldehyde. is collected in a special apparatus, where the quantity 2. A method as defined in claim 1 wherein the oxy and composition of the condensate are taken into ac gen-containing gas is air. count. The liquid mixture from the bottom portion of 3. A method as defined in claim 1 wherein the cata the reactor is taken-off continuously, and samples ther lyst is employed in an amount in a range of 1 to 10 eof are analyzed. The yield of the reaction products as grams per liter of solution. calculated for 100 g of the reacted acetaldehyde is as 40 ck k k k :

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