Production of polyols using distillers grains and proteins and lignin extracted from distillers grains

Abstract

Processes for the production of polyols from sources such as dried distillers grains plus solubles (DDGS) make use of a two-stage reaction scheme. In the first stage, the proteinaceous starting material is reacted with an aminating agent, such as diethanolamine (DEOA), to generate amino-amides and amides. These products are then reacted with an alkoxylating agent, preferably a substituted or unsubstituted epoxide to yield polyols. These polyols may be further reacted with isocyanates to give low-cost rigid polyurethane foams. In alternate forms, lignin may be directly converted to polyols by reaction with an alkoxylating agent, optionally followed by reaction with an isocyanate to produce polyurethanes.

We claim: 
     
         1 . A process for the production of polyols comprising the steps of:
 reacting a proteinaceous component selected from the group consisting of distillers grains, polyamides, and mixtures thereof, with an amine under reaction conditions to generate amino-amides and amides; and   reacting said amino-amides and amides with an alkoxylating agent to generate polyols.   
     
     
         2 . The process of  claim 1 , said distillers grains being dried distillers grains with solubles. 
     
     
         3 . The process of  claim 1 , said amine selected from the group consisting of primary amines, secondary amines, and mixtures thereof. 
     
     
         4 . The process of  claim 3 , said amine selected from the group consisting of amines having the formula 
       
         
           
           
               
               
           
         
       
       wherein R1 is selectively and individually selected from the group consisting of H, C2-C12 straight and branched chain alkyl and alkenyl groups each having at least one hydroxyl group, and R2 is selectively and individually selected from the group consisting of C2-C 12 straight and branched chain alkyl and alkenyl groups each having at least one hydroxyl group. 
     
     
         5 . The process of  claim 4 , wherein R1 and R2 are selected from the group consisting of C2-C12 alkanols and alkenols. 
     
     
         6 . The process of  claim 5 , each R1 and R2 being selected from the group consisting of C2-C4 alkanols. 
     
     
         7 . The process of  claim 6 , each R1 and R2 being —CH2CH2OH. 
     
     
         8 . The process of  claim 1 , said proteinaceous component comprising DDGS, the ratio of said DDGS and said amine being from about 0.5-3. 
     
     
         9 . The process of  claim 8 , said ratio being from about 1-1.2. 
     
     
         10 . The process of  claim 1 , said proteinaceous component and said amine being reacted at a temperature of from about 150-250° C. 
     
     
         11 . The process of  claim 10 , said temperature being from about 190-200° C. 
     
     
         12 . The process of  claim 1 , said proteinaceous component and said amine being reacted at a pressure of from about 400-700 psi. 
     
     
         13 . The process of  claim 12 , said pressure being from about 450-500 psi. 
     
     
         14 . The process of  claim 1 , said alkoxylating agent selected from the group consisting of substituted and unsubstituted epoxides, and mixtures thereof. 
     
     
         15 . The process of  claim 14 , said alkoxylating agent selected from the group consisting of epoxides having the formula 
       
         
           
           
               
               
           
         
       
       wherein R3 is selected from the group consisting of H, and C1-C6 straight or branched chain alkyl and alkenyl groups. 
     
     
         16 . The process of  claim 15 , said alkoxylating agent being selected from the group consisting of propylene oxide, ethylene oxide, and mixtures thereof. 
     
     
         17 . The process of  claim 1 , said amino-amide-alkoxylating agent reaction being carried out at a temperature of from about 80-150° C., and a pressure of from about 25-80 psi. 
     
     
         18 . The process of  claim 17 , said amino-amide-alkoxylating agent reaction being carried out at a temperature of from about 100-120° C., and a pressure of from about 40-60 psi. 
     
     
         19 . The process of  claim 1 , said proteinaceous component comprising protein. 
     
     
         20 . The process of  claim 1 , said protein being a grain protein. 
     
     
         21 . The process of  claim 1 , said protein being extracted from distillers grains. 
     
     
         22 . A process for producing polyurethane, comprising the steps of:
 reacting a proteinaceous component selected from the group consisting of distillers grains, polyamides, and mixtures thereof, with an amine under reaction conditions to generate amino-amides;   reacting said amino-amides with an alkoxylating agent to generate polyols; and   reacting said polyols with isocyanate to generate polyurethane.   
     
     
         23 . The process of  claim 22 , said distillers grains being dried distillers grains with solubles. 
     
     
         24 . The process of  claim 22 , said amine selected from the group consisting of primary amines, secondary amines, and mixtures thereof. 
     
     
         25 . The process of  claim 24 , said amine, selected from the group consisting of amines having the formula 
       
         
           
           
               
               
           
         
       
       wherein R1 is selectively and individually selected from the group consisting of H, C2-C12 straight and branched chain alkyl and alkenyl groups each having at least one hydroxyl group, and R2 is selectively and individually selected from the group consisting of C2-C12 straight and branched chain alkyl and alkenyl groups each having at least one hydroxyl group. 
     
     
         26 . The process of  claim 25 , wherein R1 and R2 are selected from the group consisting of C2-C12 alkanols and alkenols. 
     
     
         27 . The process of  claim 26 , each R1 and R2 being selected from the group consisting of C2-C4 alkanols. 
     
     
         28 . The process of  claim 27 , each R1 and R2 being —CH2CH2OH. 
     
     
         29 . The process of  claim 22 , said proteinaceous component comprising DDGS, the ratio of said DDGS and said amine being from about 0.5-3. 
     
     
         30 . The process of  claim 29 , said ratio being from about 1-1.2. 
     
     
         31 . The process of  claim 22 , said proteinaceous component and said amine being reacted at a temperature of from about 150-250° C. 
     
     
         32 . The process of  claim 31 , said temperature being from about 190-200° C. 
     
     
         33 . The process of  claim 22 , said proteinaceous component and said amine being reacted at a pressure of from about 400-700 psi. 
     
     
         34 . The process of  claim 33 , said pressure being from about 450-500 psi. 
     
     
         35 . The process of  claim 22 , said alkoxylating agent selected from the group consisting of substituted and unsubstituted epoxides, and mixtures thereof. 
     
     
         36 . The process of  claim 35 , said alkoxylating agent selected from the group consisting of epoxides having the formula 
       
         
           
           
               
               
           
         
       
       wherein R3 is selected from the group consisting of H, and C1-C6 straight or branched chain alkyl and alkenyl groups. 
     
     
         37 . The process of  claim 36 , said alkoxylating agent being selected from the group consisting of propylene oxide, ethylene oxide, and mixtures thereof. 
     
     
         38 . The process of  claim 22 , said proteinaceous component comprising protein. 
     
     
         39 . The process of  claim 38 , said protein being a grain protein. 
     
     
         40 . The process of  claim 39 , said protein being extracted from distillers grains. 
     
     
         41 . A process for producing polyols comprising the steps of reacting lignin with an alkoxylating agent. 
     
     
         42 . The process of  claim 41 , said alkoxylating agent selected from the group consisting of epoxides having the formula 
       
         
           
           
               
               
           
         
       
       wherein R3 is selected from the group consisting of H, and C1-C6 straight or branched chain alkyl and alkenyl groups. 
     
     
         43 . The process of  claim 42 , said alkoxylating agent being selected from the group consisting of propylene oxide, ethylene oxide, and mixtures thereof. 
     
     
         44 . The process of  claim 41 , said reaction being carried out at a temperature of from about 100-120° C., and a pressure of from about 40-60 psi. 
     
     
         45 . The process of  claim 41 , said lignin derived from distillers grains, wood, cooking liquors generated in wood pulp processing, and plants. 
     
     
         46 . The process of  claim 45 , said lignin being a part of dried distillers grains with solubles. 
     
     
         47 . A process for producing polyurethane, comprising the steps of:
 reacting lignin with an alkoxylating agent to generate polyols; and   reacting said polyols with isocyanate to generate polyurethane.   
     
     
         48 . The process of  claim 47 , said alkoxylating agent selected from the group consisting of epoxides having the formula 
       
         
           
           
               
               
           
         
       
       wherein R3 is selected from the group consisting of H, and C1-C6 straight or branched chain alkyl and alkenyl groups. 
     
     
         49 . The process of  claim 48 , said alkoxylating agent being selected from the group consisting of propylene oxide, ethylene oxide, and mixtures thereof. 
     
     
         50 . The process of  claim 47 , said reaction being carried out at a temperature of from about 100-120° C., and a pressure of from about 40-60 psi. 
     
     
         51 . The process of  claim 47 , said lignin derived from distillers grains, wood, cooking liquors generated in wood pulp processing, and plants. 
     
     
         52 . The process of  claim 51 , said lignin being a part of dried distillers grains with solubles. 
     
     
         53 . The process of  claim 47 , said isocyanate being diisocyanate.