Acrolein and acrylonitrile

Aciylonitrile has been an important organic intermediate sinee the 1930s, when it was nsed in a eopolymer for synthetic bntadiene rabbets in Germany. While Bnna-N was not as snccessful as the similar Bnna-S, made with styrene, aciylonitrile is now widely nsed in the prodnction of fibers, and ABS resins. Early prodnction rentes were based on the reaction of ethylene oxide or acetylene with 

Shell CU20/AI2O3 US Patent 2451485 (1948) British Patent 778125 (1948) 

The first use of oxide oxidation catafysts for the production of acrolein from propylene with a cuprous oxide/silica formulation was described by Shell in 1948. This followed an Allied Chemical Company patent describing the potential production of aciylonitrile from propylene. As demand for these products increased during the 1950s, other, more efficient, catalysts based on mixed oxides were developed. The best early catalysts are listed in Table 4.13. 

It was soon realized that commercial units would be based on the use of fluidized beds, which were then being introduced in refineries to produce gasoline. The most successful fluid bed process was introduced by Idol of Soldo in 1960 and used a bismuth phosphomolybdate catalyst supported on silica. Knapsack described a bismuth phosphomolybdate catalyst containing iron for aciylonitrile production in 1962. This rather more complex mixed oxide formulation, Fe7Bi2Moi2052, also supported on silica, foreshadowed improvements in the 1970s and the introduction of multicomponent catalysts. Since then several generations of improved catalysts have been introduced, e.g., by Sohio, as the reaction mechanism has been better understood. 

---

EPA. 1982a. Acrolein and acrylonitrile-method 603. In Longbottom JE, Lichtenberg JJ, eds. Methods for organic chemical analysis of municipal and industrial wastewater. Cincinnati, OFI U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory. EPA-600/4-82-057. 

From the ionization potential data for acrolein and acrylonitrile, it can be deduced that in both cases the major interaction of the ethylenic jt MO is with the n of the CH=0 and C N groups, respectively. 

Determination of Acrolein and Acrylonitrile in Municipal and Industrial Discharges using GC... 

Among the oxide catalysts, bismuth molybdates that catalyse selective oxidation and ammoxidation of propylene to yield acrolein and acrylonitrile have received considerable attention (Grasselli Burrington, 1981) ... 

United States Environmental Protection Agency (1996a) Method 603—Acrolein and acrylonitrile. US Code Fed. Regul., Title 40, Part 136, Appendix A, pp. 55-66... 

Three purge and trap methods are used to determine 29 halocarbons (Method 601), seven aromatics (Method 602, including four of the halo-carbons), and acrolein and acrylonitrile (Method 603). The three methods are distinctly different in the sorbent trap materials, GC columns, and... 

The higher polarity and thus higher water solubility of acrolein and acrylonitrile required an elevated purge temperature (85 °C) to produce acceptable recoveries. The trap composition was initially 24 cm of the porous polymer, Poropak N. It was subsequently changed to 1 cm of 3% OV-1 on Chromosorb W and 23 cm of Tenax-GC. 

Other important parameters in providing successful GC are the column packing, temperature conditions, and selection of a detector as specific to the analyte as possible. Maximum resolution of the halocar-bons is achieved with an 8-ft X 0.1-in. i.d. column of Carbopack-B coated with 1% SP-1000. The initial temperature of 45 °C is held for 3 min and then programmed at 8 °C/min to 220 °C. An organohalogen detector (OHD) is used. The aromatics are best resolved with a 6-ft X 0.085-in. i.d. column of Supelcoport coated with 5% SP-1200 plus 1.75 Bentone-34. They are measured with a photoionization detector. The temperature conditions are as follows 50 °C for 2 min then programmed at 6 °C/min to 90 °C. A 10-ft X 2-mm i.d. Porapak-QS (80-100 mesh) column at a temperature of 110 °C for 1.5 min and rapidly heated to 150 °C is now used for acrolein and acrylonitrile. This method employs a flame ionization detector (FID). 

Additional methods considered for 304(h) rule making and the parameters measured are the following (the numbers in parentheses indicate the number of compounds included in the method) 622, organophosphorus pesticides (19) 623, 4,4 -methylene bis(2-chloroaniline) 626, acrolein and acrylonitrile (2) 627, dinitroaniline pesticides (5) 628, carbofuran 629, cyanazine 630, dithiocarbamates (15) 631, carbendazim and benomyl 632, carbamate and urea pesticides (7) and 633, organonitrogen pesticides (7). Most of these are... 

Although allylie oxidation , yielding products like acrolein and acrylonitrile, is the most important and successful partial oxidation reaction, several other processes are of interest. Table 3 represents a summary of the nature of the various processes and the main partial oxidation products. 

Undecylenyl aldehyde, which can be derived from castor oil, has also been used as CM partner of acrolein and acrylonitrile [73]. C5 (1 mol%) led to 94% isolated yield of the a,co-nitrile-aldehyde by reaction with acrylonitrile in toluene at 80°C. A twofold excess of acrylonitrile was necessary to prevent the production of... 

Scheme 5.23 The /MCD-mediated aza-MBH reaction of aryl tosyl aldimines with acrolein and acrylonitrile. EWG = electron-withdrawing group.

Fish and sediment Add water containing acrolein and acrylonitrile to sample freeze sample, extract in vacuum GC/MS 0.025 /Jg/8 Sediment matrix 1011 recovery. Fish matrix 90% recovery Hiatt 1981... 

More commonly, uranium has been used as a catalyst component for mixed-metal oxide catalysts for selective oxidation. Probably the most well known of these mixed oxide catalysts are those based on uranium and antimony. The uranium-antimony catalysts are exceptionally active and selective and they have been applied industrially. An interpretation of the catalyst structure and reaction mechanism has been reported by GrasselU and coworkers [42, 43] who discovered the catalyst The USb30io mixed oxide has been extensively used for the oxidation/ammoxida-tion reaction of propylene to acrolein and acrylonitrile. The selective ammoxida-tion of propylene was investigated by GrasseUi and coworkers [44], and it has been demonstrated that at 460 °G a 62.0% selectivity to acrolein with a conversion of 65.2% can be achieved. Furthermore, Delobel and coworkers [45] studied the selective oxidation of propylene over USb30io, which at 340 °C gave a selectivity to acrolein of 96.7%. 

Cuprous halide complexes have also been obtained with acrolein (330) and various unsaturated nitriles (519, 523). In general, the infrared spectra of the 1 1 complexes indicate a primary coordination through the double bond with some evidence for participation of the other donor group in the molecule. With acrolein and acrylonitrile the enthalpy change for complexing of the gaseous molecule with solid CuCl was found to be —11.8 and —14.9 kcal/mole, respectively. 

These codimerization reactions are mainly limited by the degree of n-bond strength of the electron deficient alkenes to Pd(0). Strongly bonded ligands may prevent any interaction of the metal with the methylenecyclopropane. Typical examples of too strongly bonded alkenes are maleic anhydride, acrolein and acrylonitrile. On the other hand, too weak interactions may result in cyclodimerization of the methylenecyclopropane rather than codimerization. 

Although, as stated above, olefin epoxidation is commonly referred to as an electrophilic oxidation, recent theoretical calculations suggest that the electronic character of the oxygen transfer step needs to be considered to fully understand the mechanism [451]. The electronic character, that is, whether the oxidant acts as an electrophile or a nucleophile is studied by charge decomposition analysis (CDA) [452,453]. This analysis is a quantitative interpretation of the Dewar-Chatt-Dimcanson model and evaluates the relative importance of the orbital interactions between the olefin (donor) and the oxidant (acceptor) and vice versa [451]. For example, dimethyldioxirane (DMD) is described as a chameleon oxidant because in the oxidations of acrolein and acrylonitrile, it acts as a nucleophile [454]. In most cases though, epoxidation with peroxides occurs predominantly by electron donation from the 7t orbital of the olefin into the a orbital of the 0-0 bond in the transition state [455,456] (Fig. 1.10), so the oxidation is justifiably called an electrophilic process. 

The content of acrylonitrile in the fraction of acrylonitrile plus acrolein increased with time on stream (see Figure 2). It can be assumed that acrolein and acrylonitrile are both formed via the common 7i-allyl intermediate, which can undergo either oxygen or NH-insertion [9,12,13]... 

Another example which is directly related to industrial catalysis is the adsorption and decomposition of propene from a mixed oxide, namely FeSbOj- This material is used for the industrial production of acrolein and acrylonitrile (Yoshino et al., 1971). If the surface is dosed with both propene and ammonia, then all the reaction products in the industrial process are seen to evolve as shown in fig. 24 (Hutchings et al., 1991). Some intact propene desorbs at low temperatures, while the selective ammoxidation... 

Encouraged by the success with fluoral, fluoroketones have also been investigated systematically in the MBH reaction. Since 1,1,1-trifluoroacetone is known to trimerize in the presence of amines, lower yields of MBH adducts were obtained at lower temperature when treated with acrolein and acrylonitrile. With methyl acrylate and MVK, however, only a polymeric material was isolated under the MBH reaction conditions. 

The MBH reactions of non-enolizable a-diketones precursors (Figure 1.4) with the activated olefins, e.g. acrolein, methyl acrylate and acrylonitrile, have been investigated systematically. The reaction of 3,3,5,5-tetramethyl-cyclopentane-l,2-dione (162) with acrolein and acrylonitrile, but not methyl acrylate, afforded the mono-a-hydroxyalkylation products in high yields. Other nonenolizable a-diketones, such as camphorquinone (159), homo-adamantane-2,3-dione (160) and bicyclo[ 3.3.2]decane-9,10-dione (161) reacted only with acrylonitrile, probably due to the hindered nature of the a-dicarbonyl compounds and the difference in steric demand between nitrile and ester. 

Nickel(I) and nickel(II) olefin compounds are rare. Examples are [Ni(acac) (COD)], [NiX(COD)] (X = Br, and [NiR(olefm)(bipy)], Alkyl complexes most probably have trigonal-bipyramidal structures. They are formed as unstable intermediate compounds during reactions of [NiR2(bipy)] with olefins. Compounds containing acrolein and acrylonitrile " were also isolated ... 

Industrial catalysts for the synthesis of acrolein and acrylonitrile are based on these simple mixed oxides (ie, bismuth molybdate and iron antimonate) but. 

---