Energy efficient methods to produce products

Abstract

The invention relates to processes that efficiently convert carbon-containing materials, such as biomass, into products in such a manner that the energy, carbon, and mass content of the materials are efficiently transferred into such products. Such methods include converting the materials into at least one intermediate by a biological conversion process and at least one intermediate by a thermochemical conversion process and reacting the intermediates to form the product. Such methods have a chemical energy efficiency to produce the product that is greater than the chemical energy efficiency of a solely biological conversion process to produce the product and that is greater than the chemical energy efficiency of a process in which all of the material is initially subjected to a thermochemical conversion step as part of the process to produce the product.

1 . (canceled) 
     
     
         2 . The method of  claim 81 , wherein the chemical energy efficiency of the method is at least about 60%. 
     
     
         3 - 7 . (canceled) 
     
     
         8 . The method of  claim 81 , wherein at least about 70% of carbohydrate substances in the material is converted into the product. 
     
     
         9 - 14 . (canceled) 
     
     
         15 . The method of  claim 81 , wherein essentially no carbon dioxide is produced in the biological conversion process. 
     
     
         16 . The method of  claim 81 , wherein only one mole of carbon dioxide is produced per mole of monosaccharide or monosaccharide unit in the material. 
     
     
         17 . The method of  claim 81 , wherein the material comprises carbohydrate substances and non-carbohydrate substances. 
     
     
         18 . The method of  claim 81 , wherein the material comprises biomass. 
     
     
         19 . The method of  claim 81 , wherein the material is selected from the group consisting of herbaceous matter, agricultural residue, forestry residue, municipal solid waste, waste paper, pulp and paper mill residue, trees, shrubs, grasses, wheat, wheat straw, wheat middlings, sugar cane bagasse, corn, corn husks, corn kernel, corn fiber, municipal solid waste, waste paper, yard waste, branches, bushes, energy crops, fruits, fruit peels, flowers, grains, herbaceous crops, leaves, bark, needles, logs, roots, saplings, short rotation woody crops, switch grasses, vegetables, vines, sugar beet pulp, oat hulls, hard woods, wood chips, intermediate streams from pulping operations and soft woods. 
     
     
         20 - 21 . (canceled) 
     
     
         22 . The method of  claim 81 , wherein the biological conversion process comprises fermentation. 
     
     
         23 . The method of  claim 81 , wherein the biological conversion process comprises culturing at least one microorganism. 
     
     
         24 . (canceled) 
     
     
         25 . The method of  claim 23 , wherein the at least one microorganism is a succinic acid bacteria. 
     
     
         26 . The method of  claim 23 , wherein the at least one microorganism is of a genus selected from the group consisting of  Clostridium, Lactobacillus, Moorella, Thermoanaerobacter, Propionibacterium, Propionispera, Anaerobiospirillum , and  Bacteriodes.    
     
     
         27 . The method of  claim 23 , wherein the at least one microorganism is of a species selected from the group consisting of  Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus delbrukii, Propionibacterium acidipropionici, Propionispera arboris, Anaerobiospirillum succinicproducens, Bacteriodes amylophilus  and  Bacteriodes ruminicola.    
     
     
         28 . The method of  claim 81 , wherein the thermochemical conversion process is selected from the group consisting of gasification, pyrolysis, reforming, and partial oxidation. 
     
     
         29 - 31 . (canceled) 
     
     
         32 . The method of  claim 81 , wherein the at least one thermochemical process-produced intermediate is selected from the group consisting of syngas, a component of syngas, a mixture of syngas components, pyrolysis gas, a component of pyrolysis gas, and a mixture of pyrolysis gas components. 
     
     
         33 . The method of  claim 81 , wherein the at least one thermochemical process-produced intermediate is selected from the group consisting of hydrogen, carbon monoxide, carbon dioxide, and methanol. 
     
     
         34 . The method of  claim 81 , wherein the method further comprises acidifying the succinate salt to form succinic acid prior to the step of reacting. 
     
     
         35 . The method of  claim 34 , further comprising esterifying the succinic acid prior to the step of reacting. 
     
     
         36 . (canceled) 
     
     
         37 . The method of  claim 34 , wherein the step of acidifying comprises introducing carbon dioxide or an acid with a lower pKa than succinic acid to a solution comprising the salt of succinic acid. 
     
     
         38 . The method of  claim 34 , wherein said step of acidifying comprises introducing a tertiary amine with carbon dioxide to form an acid/amine complex. 
     
     
         39 . The method of  claim 37 , further comprising contacting the acid/amine complex with a water immiscible solvent to form an ester of the water immiscible solvent and the carboxylic acid. 
     
     
         40 . The method of  claim 81 , wherein the step of reacting the at least one biological process-produced intermediate and the at least one thermochemical process-produced intermediate is selected from the group consisting of chemical conversion and biological conversion. 
     
     
         41 - 43 . (canceled) 
     
     
         44 . The method of  claim 81 , wherein the step of reacting the at least one biological process-produced intermediate and the at least one thermochemical process-produced intermediate is a process selected from the group consisting of hydrogenation, hydrogenolysis and reduction. 
     
     
         45 - 47 . (canceled) 
     
     
         48 . The method of  claim 81 , further comprising fractionating the material to form a carbohydrate-containing fraction for conversion to an intermediate by a biological conversion process, and to form a residue fraction comprising lignin for conversion to an intermediate by a thermochemical conversion process. 
     
     
         49 . The method of  claim 48 , wherein the step of fractionating is selected from the group consisting of physical treatment, metal ion treatment, ultraviolet light treatment, ozone treatment, oxygen treatment, organosolv treatment, steam explosion treatment, lime impregnation with steam explosion treatment, lime impregnation without steam treatment, hydrogen peroxide treatment, hydrogen peroxide/ozone (peroxone) treatment, acid treatment, dilute acid treatment, and base treatment. 
     
     
         50 . The method of  claim 81 ,
 (a) wherein the at least one biological process-produced intermediate is produced by fermentation of carbohydrate substances in the material,   (b) wherein the at least one thermochemical process-produced intermediate is produced by thermochemical conversion of non-carbohydrate substances in the material, and   (c) wherein the at least one biological process-produced intermediate of (a) and the at least one thermochemical process-produced intermediate of (b) are chemically reacted to produce 1,4-butanediol.   
     
     
         51 . The method of  claim 81 ,
 (a) wherein a portion of at least one biological process-produced intermediate is produced by fermentation of carbohydrate substances in the material,   (b) wherein the at least one thermochemical process-produced intermediate is produced by thermochemical conversion of non-carbohydrate substances in the material,   (c) wherein a portion of at least one biological process-produced intermediate is produced by fermentation of at least a portion of at least one thermochemical process-produced intermediate of (b), and   (d) wherein the at least one biological process-produced intermediate of (a) and the at least one biological process-produced intermediate of (c) and at least a portion of the remaining at least one thermochemical process-produced intermediate of (b) are chemically reacted to produce 1,4-butanediol.   
     
     
         52 . The method of  claim 81 ,
 (a) wherein the material is fermented to produce at least one biological process-produced intermediate and a fermentation residue comprising non-fermented components of the material,   (b) wherein the at least one thermochemical process-produced intermediate is produced by thermochemical conversion of the fermentation residue, and   (c) wherein the at least one biological process-produced intermediate of (a) and the at least one thermochemical process-produced intermediate of (b) are chemically reacted to produce 1,4-butanediol.   
     
     
         53 - 80 . (canceled) 
     
     
         81 . A method for producing 1,4-butanediol from a material comprising carbon-containing compounds, wherein less than about 75% by weight of the carbon-containing compounds are carbohydrate substances, comprising:
 converting the material into at least two intermediates,
 wherein at least one intermediate is produced by a biological conversion process and comprises succinic acid, a succinate ester, a succinate salt, or a mixture of succinic acid, succinate ester and succinate salt, and 
 wherein at least one intermediate is produced by a thermochemical conversion process and comprises a reductant, and 
   chemically reacting the reductant and the succinic acid, succinate ester, succinate salt, or mixture of succinic acid, succinate ester and succinate salt to produce 1,4-butanediol,   
       wherein the chemical energy efficiency of the method to produce 1,4-butanediol from the material is greater than the chemical energy efficiency of a solely biological conversion process to produce 1,4-butanediol and is greater than the chemical energy efficiency of a process in which all of the material is initially subjected to a thermochemical conversion step as part of the process to produce 1,4-butanediol. 
     
     
         82 - 88 . (canceled)