Resins anionic exchange

Anion exchange resins of the quaternary ammonium hydroxide type (e.g., De-Acidlte FF, IRA-400 or Dowex I) are strong bases and are useful cataly s for the cyanoethylatlon of alcohols and possibly of other active hydrogen compounds. 

Anion-exchange resins contain a basic radical, such as —NH and =NH, and are prepared by the condensation of formaldehj de with amines such as m-phenylenediainine and urea. These resins can absorb acids by the formation of salts, —NH3CI and =NHjCl, and are regenerated by treatment with sodium hydroxide or sodium carbonate. 

The exchange resins 6nd application in (i) the purification of water (cation-exchange resin to remove salts, followed by anion-exchange resin to remove free mineral acids and carbonic acid), (ii) removal of inorganic impurities from organic substances, (iii) in the partial separation of amino acids, and (iv) as catalysts in organic reactions (e.g., esterification. Section 111,102, and cyanoethylation. Section VI,22). 

Anion exchange resins—gel type — Strongly basic- —quaternary ammonium functionality... 

Anion exchange resin-gel type— intermediate basicity... 

Anion exchange resins- —gel type—weakly basic—polyamine functionality ... 

Continuous processes have been developed for the alcohols, operating under pressure with Hquid ammonia as solvent. Potassium hydroxide (206) or anion exchange resins (207) are suitable catalysts. However, the relatively small manufacturing volumes militate against continuous production. For a while a continuous catalytic plant operated in Raveima, Italy, designed to produce about 40,000 t/yr of methylbutynol for conversion to isoprene (208,209). 

Ion-exchange separations can also be made by the use of a polymer with exchangeable anions in this case, the lanthanide or actinide elements must be initially present as complex ions (11,12). The anion-exchange resins Dowex-1 (a copolymer of styrene and divinylben2ene with quaternary ammonium groups) and Amherlite IRA-400 (a quaternary ammonium polystyrene) have been used successfully. The order of elution is often the reverse of that from cationic-exchange resins. 

Although catalytic hydration of ethylene oxide to maximize ethylene glycol production has been studied by a number of companies with numerous materials patented as catalysts, there has been no reported industrial manufacture of ethylene glycol via catalytic ethylene oxide hydrolysis. Studied catalysts include sulfonic acids, carboxyUc acids and salts, cation-exchange resins, acidic zeoHtes, haUdes, anion-exchange resins, metals, metal oxides, and metal salts (21—26). Carbon dioxide as a cocatalyst with many of the same materials has also received extensive study. 

Thisis commonly referred to as a salt splitting reaction. The resin s selectivity for Na" is greater than it is for H". Anions are removed in a similar manner with an anion-exchange resin. 

Strong"Base. Strong base anion-exchange resins have quaternary ammonium groups, - NR OH , where R is usually CH, as the functional exchange sites (see Quaternary ammonium compounds). These resins are used most frequentiy in the hydroxide form for acidity reduction. 

Weak Base. Weak base anion-exchange resins may have primary, secondary, or tertiary amines as the functional group. The tertiary amine -N(CH2)2 is most common. Weak base resins are frequentiy preferred over strong base resins for removal of strong acids in order to take advantage of the greater ease in regeneration. 

Fig. 3. Regeneration of anion-exchange resins using NaOH (14).

The point at which two polymeric chains are joined together by a cross-linker such as divinylbenzene, or sites where tertiary hydrogens are located in the stmcture, are other locations for oxidative attack. In both cation- and anion-exchange resins, oxidative attack results in the removal of cross-linking. 

Boron Removal. Boron [7440-42-8] is occasionaHy present in water suppHes at an unacceptable level. It cannot be removed with the standard anion-exchange resins unless the water is deionized. Selective removal is possible by using an anion exchanger functionalized with /V-methy1g1ucamine [6284-40-8]. This resin is in limited commercial supply. The borate form of conventional strong base anion exchangers is used in some nuclear reactors to adjust the concentration of boron in water used as a moderator. The resin releases boron as the water temperature rises. 

In the three-step process acetone first undergoes a Uquid-phase alkah-cataly2ed condensation to form diacetone alcohol. Many alkaU metal oxides, metal hydroxides (eg, sodium, barium, potassium, magnesium, and lanthanium), and anion-exchange resins are described in the Uterature as suitable catalysts. The selectivity to diacetone alcohol is typicaUy 90—95 wt % (64). In the second step diacetone alcohol is dehydrated to mesityl oxide over an acid catalyst such as phosphoric or sulfuric acid. The reaction takes place at 95—130°C and selectivity to mesityl oxide is 80—85 wt % (64). A one-step conversion of acetone to mesityl oxide is also possible. 

Suitable catalysts include the hydroxides of sodium (119), potassium (76,120), calcium (121—125), and barium (126—130). Many of these catalysts are susceptible to alkali dissolution by both acetone and DAA and yield a cmde product that contains acetone, DAA, and traces of catalyst. To stabilize DAA the solution is first neutralized with phosphoric acid (131) or dibasic acid (132). Recycled acetone can then be stripped overhead under vacuum conditions, and DAA further purified by vacuum topping and tailing. Commercial catalysts generally have a life of about one year and can be reactivated by washing with hot water and acetone (133). It is reported (134) that the addition of 0.2—2 wt % methanol, ethanol, or 2-propanol to a calcium hydroxide catalyst helps prevent catalyst aging. Research has reported the use of more mechanically stable anion-exchange resins as catalysts (135—137). The addition of trace methanol to the acetone feed is beneficial for the reaction over anion-exchange resins (138). 

Early patents indicated that because water inhibits the aldol condensation mechanism, it was necessary to dry recycle acetone to less than 1% water (139—142). More recent reports demonstrate DAA production from waste acetone containing 10—50% water (143), and enhanced DAA production over anion-exchange resins using acetone feeds that contain 3—10% water (144,145). 

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