Method and apparatus for preparing a dialkyl carbonate, and its use in the preparation of diaryl carbonates and polycarbonates

Abstract

Unexpected corrosion of downstream sections of a dialkyl carbonate manufacturing apparatus has been traced to alkyl chloroformate impurities, which slowly decompose to yield hydrochloric acid. An improved process and apparatus for dialkyl carbonate synthesis reduce corrosion by physically removing or chemically decomposing the alkyl chloroformate impurities within the corrosion-resistant upstream sections of the apparatus.

1 . A method of preparing a dialkyl carbonate, comprising: reacting an alkanol, oxygen, carbon monoxide, and a catalyst to form a mixture comprising a dialkyl carbonate, an alkyl chloroformate, hydrochloric acid, water, carbon dioxide, and carbon monoxide; and passing said mixture through a fluid passageway at a temperature of about 30° C. to about 130° C. and for a residence time of about 0.5 hour to about 10 hours.  
     
     
         2 . The method of  claim 1 , wherein said alkanol comprises a C 1 -C 12  alkanol.  
     
     
         3 . The method of  claim 1 , wherein said alkanol comprises a C 16 -C primary alkanol.  
     
     
         4 . The method of  claim 1 , wherein said alkanol comprises methanol.  
     
     
         5 . The method of  claim 1 , wherein said alkanol, said oxygen, and said carbon monoxide are reacted in a molar ratios of (about 0.5 to about 0.7 alkanol):(about 0.04 to about 0.06 oxygen):(about 0.8 to about 1.2 carbon monoxide).  
     
     
         6 . The method of  claim 1 , wherein said catalyst comprises a metal selected from the group consisting of iron, copper, nickel, cobalt, zinc, ruthenium, rhodium, palladium, silver, cadmium, rhenium, osmium, iridium, platinum, gold, mercury, and combinations comprising at least one of the foregoing metals.  
     
     
         7 . The method of  claim 1 , wherein said catalyst comprises copper.  
     
     
         8 . The method of  claim 1 , wherein said catalyst comprises hydrochloric acid.  
     
     
         9 . The method of  claim 1 , wherein said catalyst comprises hydrochloric acid and copper in a molar ratio of about 0.5 to about 1.5.  
     
     
         10 . The method of  claim 1 , wherein said fluid passageway comprises a heat exchanger.  
     
     
         11 . The method of  claim 1 , wherein said fluid passageway comprises a holding vessel.  
     
     
         12 . The method of  claim 1 , wherein said fluid passageway comprises a plurality of holding vessels.  
     
     
         13 . The method of  claim 1 , wherein said fluid passageway comprises a section having a length to volume ratio of at least about 5.  
     
     
         14 . The method of  claim 13 , wherein passing said mixture through a fluid passageway comprises passing said mixture through at least one section having a length to volume ratio of at least about 5 for at least about 50% of the total residence time spent in said fluid passageway.  
     
     
         15 . The method of  claim 1 , further comprising condensing said mixture prior to passing said reaction mixture through said fluid passageway.  
     
     
         16 . The method of  claim 1 , further comprising removing hydrochloric acid from said mixture.  
     
     
         17 . The method of  claim 16 , wherein said removing hydrochloric acid comprises reducing the concentration of said hydrochloric acid to less than about 1×10 −3  moles per liter.  
     
     
         18 . The method of  claim 16 , further comprising vaporizing said mixture before said removing hydrochloric acid.  
     
     
         19 . The method of  claim 18 , wherein said vaporizing said mixture comprises heating said mixture, reducing the pressure applied to said mixture, or both.  
     
     
         20 . The method of  claim 1 , further comprising removing carbon dioxide and carbon monoxide from said mixture.  
     
     
         21 . The method of  claim 20 , wherein at least about 90% of said carbon dioxide and at least about 90% of said carbon monoxide are removed from said mixture.  
     
     
         22 . The method of  claim 20 , wherein said removing carbon dioxide and carbon monoxide comprises passing said mixture through a plurality of gas-liquid separation vessels.  
     
     
         23 . The method of  claim 22 , wherein said reacting is conducted at a first pressure, and said plurality of gas-liquid separation vessels comprises a first gas-liquid separation vessel having a pressure within about 10% of said first pressure, and a second gas-liquid separation vessel having a pressure less than about 20% of said first pressure.  
     
     
         24 . An apparatus for preparing a dialkyl carbonate, comprising: means for reacting an alkanol, oxygen, carbon monoxide, and a catalyst to form a mixture comprising a dialkyl carbonate, an alkyl chloroformate, hydrochloric acid, water, carbon dioxide, and carbon monoxide; and means for removing alkyl chloroformate from said mixture.  
     
     
         25 . An apparatus for preparing a dialkyl carbonate, comprising: a reactor for reacting an alkanol, oxygen, carbon monoxide, and a catalyst to a produce a mixture comprising a dialkyl carbonate, an alkyl chloroformate, hydrochloric acid, water, and carbon dioxide; and a fluid passageway for removing alkyl chloroformate.  
     
     
         26 . The apparatus of  claim 25 , wherein said fluid passageway comprises a heat exchanger.  
     
     
         27 . The apparatus of  claim 25 , wherein said fluid passageway comprises a holding vessel.  
     
     
         28 . The apparatus of  claim 25 , wherein said fluid passageway comprises a plurality of holding vessels.  
     
     
         29 . The apparatus of  claim 25 , wherein said fluid passageway comprises a section having a length to volume ratio of at least about 5.  
     
     
         30 . The apparatus of  claim 25 , wherein said fluid passageway comprises a section having a length to volume ratio of at least about 10.  
     
     
         31 . The apparatus of  claim 25 , further comprising a condenser in fluid communication with said reactor and said fluid passageway.  
     
     
         32 . The apparatus of  claim 31 , further comprising a gas-liquid separator in fluid communication with said condenser and said fluid passageway.  
     
     
         33 . The apparatus of  claim 25 , further comprising an acid removal column in fluid communication with said fluid passageway.  
     
     
         34 . The apparatus of  claim 25 , further comprising an azeotrope column in fluid communication with said fluid passageway.