Propylene acrolein

Vinyl chloride, vinyl alcohol, styrene, acrylic acids, acrylonitrile, the acrylates, propylene, acrolein. 

Russian workers using 14C-labeled propylene, acrolein, and acetaldehyde (29-31) have determined that carbon oxides are formed chiefly through the further oxidation of acrolein and that acetaldehyde and formaldehyde are produced either from acrolein or directly from the symmetrical 7r-allylic intermediate. These two saturated aldehydes can then undergo further oxidation (about 20 times more rapidly than acrolein) to CO and COj. The overall scheme proposed is given in Fig. 4. 

Figure 2. Experimental results from Run 2, Table I. Key X, temperature measured propylene , acrolein A> acrylic acid and CO and CO,.

In order to perform the simulation, components and die physical property package must be specified. The main con nents of this process are water, air, propylene, acrolein, acrylic acid, acetic acid, and acrylic acid dimer. The Peng-Robinson method could be used for example. 

Where xcs xc3, and xo2 are the mole fractions of propane, propylene, and oxygen in the gas phase, kc3°, kacr. and kcox are the rate constants of propylene, acrolein, and COx production, Kc3" is a propylene adsorption constant, and (O2) denotes the zero order oxygen dependence. 

Hexadienal, (E,E)- (E,E)-2,4-Hexadienal (E,E)-2,4-Hexadien-1-al trans,trans-2,4-Hexadien-1-al trans,trans-4-Hexadienal 1,3-Pentadiene-1-carboxaldehyde 3-Propylene acrolein Sorbaldehyde... 

Figure 24.6. Selective oxidation of propane (a) and propylene (b) over a MoVTeNbO catalyst at 380°C and a C3/02/H20/He molar ratio of 4/8/30/58. Symbols , = acrylic acid, = propylene, = acrolein. From Ref. 92.

Industrially, olefins are converted to aldehydes via the 0X0 process (olefin, carbon monoxide, hydrogen, and a catalyst). In addition, olefins can be oxidized to give the aldehyde (propylene- acrolein). 

The Reaction. Acrolein has been produced commercially since 1938. The first commercial processes were based on the vapor-phase condensation of acetaldehyde and formaldehyde (1). In the 1940s a series of catalyst developments based on cuprous oxide and cupric selenites led to a vapor-phase propylene oxidation route to acrolein (7,8). In 1959 Shell was the first to commercialize this propylene oxidation to acrolein process. These early propylene oxidation catalysts were capable of only low per pass propylene conversions (ca 15%) and therefore required significant recycle of unreacted propylene (9—11). 

In 1957 Standard Oil of Ohio (Sohio) discovered bismuth molybdate catalysts capable of producing high yields of acrolein at high propylene conversions (>90%) and at low pressures (12). Over the next 30 years much industrial and academic research and development was devoted to improving these catalysts, which are used in the production processes for acrolein, acryUc acid, and acrylonitrile. AH commercial acrolein manufacturing processes known today are based on propylene oxidation and use bismuth molybdate based catalysts. 

Today the most efficient catalysts are complex mixed metal oxides that consist of Bi, Mo, Fe, Ni, and/or Co, K, and either P, B, W, or Sb. Many additional combinations of metals have been patented, along with specific catalyst preparation methods. Most catalysts used commercially today are extmded neat metal oxides as opposed to supported impregnated metal oxides. Propylene conversions are generally better than 93%. Acrolein selectivities of 80 to 90% are typical. 

The reaction is very exothermic. The heat of reaction of propylene oxidation to acrolein is 340.8 kJ /mol (81.5 kcal/mol) the overall reactions generate approximately 837 kJ/mol (200 kcal/mol). The principal side reactions produce acryUc acid, acetaldehyde, acetic acid, carbon monoxide, and carbon dioxide. A variety of other aldehydes and acids are also formed in small amounts. Proprietary processes for acrolein manufacture have been described (25,26). 

Acrolein is produced according to the specifications in Table 3. Acetaldehyde and acetone are the principal carbonyl impurities in freshly distilled acrolein. Acrolein dimer accumulates at 0.50% in 30 days at 25°C. Analysis by two gas chromatographic methods with thermal conductivity detectors can determine all significant impurities in acrolein. The analysis with Porapak Q, 175—300 p.m (50—80 mesh), programmed from 60 to 250°C at 10°C/min, does not separate acetone, propionaldehyde, and propylene oxide from acrolein. These separations are made with 20% Tergitol E-35 on 250—350 p.m (45—60 mesh) Chromosorb W, kept at 40°C until acrolein elutes and then programmed rapidly to 190°C to elute the remaining components. 

Virtually all of the acryUc acid produced in the United States is made by the oxidation of propylene via the intermediacy of acrolein. 

Propylene Oxidation. The propylene oxidation process is attractive because of the availabihty of highly active and selective catalysts and the relatively low cost of propylene. The process proceeds in two stages giving first acrolein and then acryUc acid (39) (see Acrolein and derivatives). 

Single-reaction-step processes have been studied. However, higher selectivity is possible by optimizing catalyst composition and reaction conditions for each of these two steps (40,41). This more efficient utilization of raw material has led to two separate oxidation stages in all commercial faciUties. A two-step continuous process without isolation of the intermediate acrolein was first described by the Toyo Soda Company (42). A mixture of propylene, air, and steam is converted to acrolein in the first reactor. The effluent from the first reactor is then passed directiy to the second reactor where the acrolein is oxidized to acryUc acid. The products are absorbed in water to give about 30—60% aqueous acryUc acid in about 80—85% yield based on propylene. 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

Liquid-Phase Oxidation of Acrolein. As discussed before, the most attractive process for the manufacture of acrylates is based on the two-stage, vapor-phase oxidation of propylene. The second stage involves the oxidation of acrolein. Considerable art on the Hquid-phase oxidation of acrolein (17) is available, but this route caimot compete with the vapor-phase technology. 

Since aHyl chloride could be converted to glycerol by several routes, the synthesis of glycerol from propylene [115-07-1] became possible. Propylene can also be oxidized in high yields to acrolein [107-02-8]. Several routes for conversion of acrolein to glycerol are shown in Figure 1. 

Oxidation Catalysis. The multiple oxidation states available in molybdenum oxide species make these exceUent catalysts in oxidation reactions. The oxidation of methanol (qv) to formaldehyde (qv) is generally carried out commercially on mixed ferric molybdate—molybdenum trioxide catalysts. The oxidation of propylene (qv) to acrolein (77) and the ammoxidation of propylene to acrylonitrile (qv) (78) are each carried out over bismuth—molybdenum oxide catalyst systems. The latter (Sohio) process produces in excess of 3.6 x 10 t/yr of acrylonitrile, which finds use in the production of fibers (qv), elastomers (qv), and water-soluble polymers. 

A second process has two steps. The first step is oxidation of propylene [115-07-1] to acrolein and the second step is reduction of acrolein to ahyl alcohol by a hydrogen transfer reaction, using isopropyl alcohol (25). 

Acrolein can be obtained by propylene oxidation in a process similar to ammoxidation (109) (see Acrolein and derivatives). 

Direct Oxidation of Propylene to Propylene Oxide. Comparison of ethylene (qv) and propylene gas-phase oxidation on supported silver and silver—gold catalysts shows propylene oxide formation to be 17 times slower than ethylene oxide (qv) formation and the CO2 formation in the propylene system to be six times faster, accounting for the lower selectivity to propylene oxide than for ethylene oxide. Increasing gold content in the catalyst results in increasing acrolein selectivity (198). In propylene oxidation a polymer forms on the catalyst surface that is oxidized to CO2 (199—201). Studies of propylene oxide oxidation to CO2 on a silver catalyst showed a rate oscillation, presumably owing to polymerization on the catalyst surface upon subsequent oxidation (202). 

Gas-phase oxidation of propylene using oxygen in the presence of a molten nitrate salt such as sodium nitrate, potassium nitrate, or lithium nitrate and a co-catalyst such as sodium hydroxide results in propylene oxide selectivities greater than 50%. The principal by-products are acetaldehyde, carbon monoxide, carbon dioxide, and acrolein (206—207). This same catalyst system oxidizes propane to propylene oxide and a host of other by-products (208). 

Propylene oxide is also produced in Hquid-phase homogeneous oxidation reactions using various molybdenum-containing catalysts (209,210), cuprous oxide (211), rhenium compounds (212), or an organomonovalent gold(I) complex (213). Whereas gas-phase oxidation of propylene on silver catalysts results primarily in propylene oxide, water, and carbon dioxide as products, the Hquid-phase oxidation of propylene results in an array of oxidation products, such as propylene oxide, acrolein, propylene glycol, acetone, acetaldehyde, and others. 

Other important uses of stannic oxide are as a putty powder for polishing marble, granite, glass, and plastic lenses and as a catalyst. The most widely used heterogeneous tin catalysts are those based on binary oxide systems with stannic oxide for use in organic oxidation reactions. The tin—antimony oxide system is particularly selective in the oxidation and ammoxidation of propylene to acrolein, acryHc acid, and acrylonitrile. Research has been conducted for many years on the catalytic properties of stannic oxide and its effectiveness in catalyzing the oxidation of carbon monoxide at below 150°C has been described (25). 

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Mixed Metal Oxides and Propylene Ammoxidation. The best catalysts for partial oxidation are metal oxides, usually mixed metal oxides. For example, phosphoms—vanadium oxides are used commercially for oxidation of / -butane to give maleic anhydride, and oxides of bismuth and molybdenum with other components are used commercially for oxidation of propylene to give acrolein or acrylonitrile. 

After the preliminary tests are made on a promising catalyst and some insight gained on the process, it is time to do a kinetic study and model development. The method of a kinetic study can be best explained on an actual industrial problem. Because more can be learned from a failure than from a success, the oxidation of propylene to acrolein is an instructive attempt at process development. (Besides, to get permission to publish a success is more difficult than to solve the problem itself) Some details of the development work follow in narrative form to make the story short and to avoid embarrassing anyone. 

Degenerate Explosion it was a free radical autocatalytic process and control was difficult, but manageable. The main disadvantage was that it produced as much or more acrolein as propylene oxide. Because no market existed for acrolein at that time, the project was abandoned. Within two years, the acrylic market developed and a new project was initiated to make acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene. 

Efficiency means component 1 made per component 3 converted, all in molar units. Data show that 89.7% of the converted propylene was accounted for by the formed acrolein. An additional 9.8% efficiency is indicated for acrylic acid. Efficiency to total useftil product was 99.5% as long as ignition of homogeneous reaction could be avoided... 

Flammable gases and vapors include acetylene, hydrogen, butadiene, ethylene oxide, propylene oxide, acrolein, ethyl ether, ethylene, acetone, ammonia, benzene, butane, cyclopropane, ethanol, gasoline, hexane, methanol, methane, natural gas, naphtha, and propane. 

Attenlion should be drawn to ihe use of tin oxide systems as heterogeneous catalysts. The oldest and mosi extensively patented systems are the mixed lin-vanadium oxide catalysis for the oxidation of aromatic compounds such as benzene, toluene, xylenes and naphthalene in the. synthesis of organic acids and acid anhydride.s. More recenily mixed lin-aniimony oxides have been applied lo the selective oxidaiion and ammoxidaiion of propylene to acrolein, acrylic acid and acrylonilrile. 

Exception No. 2 Group C equipment shall be permitted to be used for atmospheres containing ethylene oxide, propylene oxide, and acrolein if such equipment is isolated in accordance with Section 501-5(a) by sealing all conduit /2 -in. size or larger. 

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