Chemical Production Processes and Systems

Abstract

Hydrogenolysis systems are provided that can include a reactor housing an Ru-comprising hydrogenolysis catalyst and wherein the contents of the reactor is maintained at a neutral or acidic pH. Reactant reservoirs within the system can include a polyhydric alcohol compound and a base, wherein a weight ratio of the base to the compound is less than 0.05. Systems also include the product reservoir comprising a hydrogenolyzed polyhydric alcohol compound and salts of organic acids, and wherein the moles of base are substantially equivalent to the moles of salts or organic acids. Processes are provided that can include an Ru-comprising catalyst within a mixture having a neutral or acidic pH. A weight ratio of the base to the compound can be between 0.01 and 0.05 during exposing.

1 . A hydrogenolysis system comprising:
 a reactant reservoir configured to contain a polyhydric alcohol compound; and   a reactor coupled to the reactant reservoir, the reactor housing an Ru-comprising hydrogenolysis catalyst and configured to expose the polyhydric alcohol compound to the catalyst, wherein the contents of the reactor is maintained at a neutral or acidic pH during the exposing.   
   
   
       2 . The system of  claim 1  wherein the polyhydric alcohol compound is a C-3 compound. 
   
   
       3 . The system of  claim 1  wherein the polyhydric alcohol compound is glycerol. 
   
   
       4 . The system of  claim 1  further comprising a product reservoir coupled to the reactor, wherein the product reservoir is configured to house a product having a neutral or acidic pH. 
   
   
       5 . The system of  claim 1  wherein the catalyst comprises one or more of Zn, Cd, Se, Te, Cu, Re, and Sn. 
   
   
       6 . The system of  claim 1  wherein the catalyst comprises carbon. 
   
   
       7 . A hydrogenolysis reactor containing a mixture comprising a polyhydric alcohol compound and an Ru-composition wherein a pH of the mixture is neutral or acidic. 
   
   
       8 . The reactor of  claim 7  wherein the mixture further comprises water. 
   
   
       9 . The reactor of  claim 7  wherein the mixture comprises a liquid phase and solid phase, the liquid phase consisting essentially of the polyhydric alcohol compound and water, and the solid phase comprising the Ru-composition. 
   
   
       10 . The reactor of  claim 9  wherein the water is at least about 10% of the liquid phase. 
   
   
       11 . The reactor of  claim 9  wherein the polyhydric alcohol compound is glycerol. 
   
   
       12 . The reactor of  claim 9  wherein the solid phase comprises one or more of Zn, Cd, Se, Te, Cu, Re, and Sn. 
   
   
       13 . The reactor of  claim 9  wherein the Ru-composition comprises one or more of Zn, Au, Cd, Se, Te, Cu and Sn. 
   
   
       14 . The reactor of  claim 9  wherein the Ru-composition comprises carbon. 
   
   
       15 . The reactor of  claim 14  wherein the Ru-composition comprises at least 5% (wt./wt.) Ru. 
   
   
       16 . The reactor of  claim 14  wherein the Ru-composition comprises from about 0.1% to about 5.0% (wt./wt.) promoter. 
   
   
       17 . The reactor of  claim 16  wherein the promoter comprises one or more of Zn, Au, Cd, Se, Te, Cu and Sn. 
   
   
       18 . A hydrogenolysis process comprising exposing a polyhydric alcohol compound to an Ru-comprising catalyst to form a mixture, the mixture having a neutral or acidic pH. 
   
   
       19 . The process of  claim 18  further comprising recovering a polyol from the mixture. 
   
   
       20 . The process of  claim 19  wherein the polyhydric alcohol compound comprises n hydroxyl groups and the polyol comprises n-1 hydroxyl groups. 
   
   
       21 . The process of  claim 20  wherein the polyhydric alcohol compound comprises glycerol and the polyol comprises propylene glycol. 
   
   
       22 . The process of  claim 18  wherein the mixture further comprises a reducing agent. 
   
   
       23 . The process of  claim 22  wherein the reducing agent comprises H 2 . 
   
   
       24 . A process for hydrogenolysing a polyhydric alcohol compound comprising:
 within a reactor, exposing a reactant mixture to an Ru-comprising catalyst; and   while exposing the mixture to the catalyst, maintaining the contents of the reactor at a neutral or acidic pH.   
   
   
       25 . The process of  claim 24  further comprising after exposing the mixture to the catalyst removing a product mixture from the reactor, the product mixture having a neutral or acidic pH. 
   
   
       26 . The process of  claim 24  wherein during the exposing, the reactor is maintained at a temperature of at least 170° C. 
   
   
       27 . The process of  claim 26  wherein during the exposing, the reactor is maintained at a pressure of at least about 600 psi. 
   
   
       28 . The process of  claim 26  wherein the reactant mixture comprises both a polyhydric alcohol compound and a reducing agent. 
   
   
       29 . The process of  claim 28  wherein a mole ratio of the reducing agent to the polyhydric alcohol compound is at least about 1:1. 
   
   
       30 . The process of  claim 28  wherein reactant mixture comprises at least about 35% (wt./wt.) polyhydric alcohol compound. 
   
   
       31 . A hydrogenolysis system comprising a reactant reservoir coupled to a reactor, the reservoir configured to confine a reactant mixture, the reactant mixture comprising a polyhydric alcohol compound and a base, wherein a weight ratio of the base to the compound is less than 0.05. 
   
   
       32 . The system of  claim 31  wherein the reactant mixture comprises less than about 40% of the polyhydric alcohol compound. 
   
   
       33 . The system of  claim 31  wherein the reactor confines a catalyst and the reactor is configured to expose the reactant mixture to the catalyst. 
   
   
       34 . The system of  claim 33  wherein the catalyst comprises one or more of Re, Co, Pd, and Ni. 
   
   
       35 . The system of  claim 34  wherein the catalyst comprises Re, Pd, and Co. 
   
   
       36 . The system of  claim 35  wherein the catalyst comprises at least about 2.5% Co. 
   
   
       37 . The system of  claim 35  wherein the catalyst comprises at least about 0.5% Pd. 
   
   
       38 . The system of  claim 35  wherein the catalyst comprises at least about 2.5% Re. 
   
   
       39 . The system of  claim 31  wherein the reactor is configured to maintain the catalyst between a temperature of from about 170° C. and 240° C. 
   
   
       40 . The system of  claim 39  wherein the catalyst comprises Re and Ni. 
   
   
       41 . The system of  claim 40  wherein the catalyst comprises at least about 1% Re. 
   
   
       42 . The system of  claim 40  wherein the catalyst comprises at least about 5% Ni. 
   
   
       43 . A hydrogenolysis process comprising:
 providing a reactant mixture comprising a polyhydric alcohol compound and a base, wherein a weight ratio of the base to the compound compound is between 0.01 and 0.05; and   exposing the mixture to a catalyst to at least partially hydrogenolyze a portion of the polyhydric alcohol compound.   
   
   
       44 . The process of  claim 43  wherein the base comprises from about 0.5% to about 2.1% of mixture. 
   
   
       45 . The process of  claim 43  wherein the base comprises less than about 1.0% of the mixture. 
   
   
       46 . The process of  claim 43  wherein the base comprises from about 0.5% to about 1.0% of the mixture. 
   
   
       47 . The process of  claim 43  further comprising prior to exposing the mixture to the catalyst, depassivating the catalyst in the presence of a reducing atmosphere at a temperature less than about 210° C. 
   
   
       48 . A hydrogenolysis system comprising:
 a reactor coupled to both a reactant reservoir and a product reservoir;   a reactant mixture within the reactant reservoir, the reactant mixture comprising a polyhydric alcohol compound and a base;   a product mixture within the product reservoir, the product reservoir comprising a hydrogenolyzed polyhydric alcohol compound and salts of organic acids; and   wherein the carbon molar selectivity to organic acids and salts of organic acids is less than 2% and the carbon molar selectivity to hydrogenolyzed polyhydric alcohol compound is at least 30%.   
   
   
       49 . The system of  claim 48  wherein the polyhydric alcohol compound comprises glycerol. 
   
   
       50 . The system of  claim 49  wherein at least one of the salts of organic acids comprises lactate and the base comprises Na and/or K. 
   
   
       51 . The system of  claim 48  wherein a weight ratio of the base to the polyhydric alcohol compound within the reactant mixture is less than 0.05.