Pulping Liquors and Uses Thereof

Abstract

The present invention relates generally to the generation of bio-products from organic matter feedstocks. More specifically, the present invention relates to the use of pulping liquors in the hydrothermal/thermochemical conversion of lignocellulosic and/or fossilised organic feedstocks into biofuels (e.g. bio-oils) and/or chemical products (e.g. platform chemicals).

1 . A method for producing a bio-product from organic matter feedstock, the method comprising:
 providing a reaction mixture comprising the organic matter feedstock, a solvent, and green pulping liquor (green liquor), wherein the green liquor was generated independently of the organic matter feedstock;   treating the reaction mixture in a reactor vessel at a reaction temperature and pressure to thereby convert all or a portion of the organic matter feedstock into a product mixture comprising the bio-product; and   depressurising and cooling the product mixture;   wherein the reaction mixture and product mixture move in continuous flow through the reactor vessel during said treating.   
     
     
         2 . The method of  claim 1 , wherein the organic matter feedstock comprises or consists of:
 (i) lignite feedstock;   (ii) lignocellulosic feedstock; or   (iii) a mixture of lignocellulosic and lignite feedstock.   
     
     
         3 . The method of  claim 1 , wherein the organic matter feedstock comprises or consists of lignocellulosic feedstock. 
     
     
         4 . The method of  claim 1 , wherein the pulping liquor further comprises black pulping liquor (black liquor). 
     
     
         5 . The method of  claim 4 , wherein the black liquor comprises:
 (i) between about 4 wt % and 10 wt % sodium hydroxide (NaOH), between about 10 wt % and 30 wt % sodium sulfide (Na 2 S), between about 25 wt % and about 50 wt % sodium carbonate (Na 2 CO 3 ), between about 5 wt % and about 15 wt % sodium sulfite (Na 2 SO 3 ), between about 8 wt % and about 20 wt % sodium sulfate (Na 2 SO 4 ), between about 10 wt % and about 25 wt % sodium thiosulfate (Na 2 S 2 O 3 ), and between about 10 wt % and about 90 wt % organic solids or between about 30% and about 70% organic solids; or   (ii) between about 15 wt % and 25 wt % sodium sulfide (Na 2 S), between about 25 wt % and about 45 wt % sodium carbonate (Na 2 CO 3 ), between about 5 wt % and about 15 wt % sodium sulfite (Na 2 SO 3 ), between about 10 wt % and about 15 wt % sodium sulfate (Na 2 SO 4 ), between about 13 wt % and about 20 wt % sodium thiosulfate (Na 2 S 2 O 3 ), and between about 40 wt % and about 90 wt % organic solids or between about 50% and about 80% organic solids, or between about 60% and about 75% organic solids.   
     
     
         6 . The method of  claim 1 , wherein the green liquor comprises:
 (i) between about 4 wt % and 12 wt % sodium hydroxide (NaOH), between about 15 wt % and 25 wt % sodium sulfide (Na 2 S), between about 50 wt % and about 70 wt % sodium carbonate (Na 2 CO 3 ), between about 1 wt % and about 7 wt % sodium sulfite (Na 2 SO 3 ), between about 2 wt % and about 10 wt % sodium sulfate (Na 2 SO 4 ), and between about 1 wt % and about 5 wt % sodium thiosulfate (Na 2 S 2 O 3 ); or   (ii) between about 5 wt % and 10 wt % sodium hydroxide (NaOH), between about 17 wt % and 23 wt % sodium sulfide (Na 2 S), between about 55 wt % and about 65 wt % sodium carbonate (Na 2 CO 3 ), between about 1 wt % and about 4 wt % sodium sulfite (Na 2 SO 3 ), between about 3 wt % and about 9 wt % sodium sulfate (Na 2 SO 4 ), and between about 1 wt % and about 5 wt % sodium thiosulfate (Na 2 S 2 O 3 ).   
     
     
         7 . The method of  claim 1 , wherein the pulping liquor further comprises white pulping liquor (white liquor). 
     
     
         8 . The method of  claim 7 , wherein the white liquor comprises:
 (i) between about 40 wt % and 65 wt % sodium hydroxide (NaOH), between about 10 wt % and 30 wt % sodium sulfide (Na 2 S), between about 8 wt % and about 22 wt % sodium carbonate (Na 2 CO 3 ), between about 1 wt % and about 6 wt % sodium sulfite (Na 2 SO 3 ), between about 2 wt % and about 10 wt % sodium sulfate (Na 2 SO 4 ), and between about 1 wt % and about 5 wt % sodium thiosulfate (Na 2 S 2 O 3 ), or   (ii) between about 45 wt % and 60 wt % sodium hydroxide (NaOH), between about 15 wt % and 25 wt % sodium sulfide (Na 2 S), between about 10 wt % and about 20 wt % sodium carbonate (Na 2 CO 3 ), between about 2 wt % and about 5 wt % sodium sulfite (Na 2 SO 3 ), between about 2 wt % and about 7 wt % sodium sulfate (Na 2 SO 4 ), and between about 1.5 wt % and about 4 wt % sodium thiosulfate (Na 2 S 2 O 3 ).   
     
     
         9 . The method of  claim 1 , wherein the treating comprises treating the reaction mixture at
 a temperature of between 200° C. and 450° C., and a pressure of between 100 bar and 300 bar.   
     
     
         10 . The method of  claim 1 , wherein the method comprises preparing a slurry comprising the organic matter and the green liquor, generating subcritical or supercritical steam independently of the slurry, and contacting the slurry with the subcritical or supercritical steam in at least one vessel or chamber of said reactor vessel. 
     
     
         11 . The method of  claim 1 , wherein the reaction mixture comprises between 30% and 90%, between 5% and 20%, or less than 5%, of the pulping liquor by weight. 
     
     
         12 . The method of  claim 1 , wherein the solvent is an aqueous solvent, an oil solvent, or a mixture of an aqueous solvent and an oil solvent, and
 the reaction mixture comprises less than 30% or between 30% and 95%, of the solvent by weight.   
     
     
         13 . The method of  claim 1 , wherein the aqueous solvent comprises: water, water only, or water and an alcohol. 
     
     
         14 . The method of  claim 1 , wherein the organic matter comprises a combination of lignocellulosic feedstock and lignite feedstock. 
     
     
         15 . The method of  claim 1 , wherein the organic matter comprises lignocellulosic feedstock that comprises at least 10% lignin, at least 35% cellulose, and at least 20% hemicellulose. 
     
     
         16 . The method of  claim 1 , wherein the reaction mixture further comprises a solid substrate that is solid or substantially solid at the reaction temperature and pressure, sequesters organic and/or inorganic matter that de-solubilises within the reaction mixture or the product mixture, and/or alters one or more flow characteristics of the reaction mixture and/or the product mixture in the reactor vessel,
 wherein the solid substrate is chemically inert or substantially chemically inert at the reaction temperature and pressure, and   wherein the solid substrate inhibits development of a pressure gradient in the reactor vessel during the conversion of the organic matter feedstock into the bio-product.   
     
     
         17 . The method of  claim 16 , wherein the solid substrate is present in the reaction mixture at a concentration of more than 10% by weight. 
     
     
         18 . The method of  claim 1 , wherein the reaction mixture further comprises an oil additive, the oil additive being selected from the group consisting of paraffmic oil, gas-oil, crude oil, synthetic oil, coal-oil, bio-oil, shale oil, kerogen oil, mineral oil, white mineral oil, aromatic oil, tall oil, distilled tall oil, plant or animal oils, fats and their acidic forms and esterified forms, and combinations thereof,
 wherein the oil additive is mixed with the feedstock and/or solvent prior to the treating.   
     
     
         19 . The method of  claim 1 , comprising dissolving bio-oil from the bio-product in a purifying solvent and filtering the dissolved bio-oil to remove particulates and solid material. 
     
     
         20 . The method of  claim 1 , wherein the treating comprises treating the reaction mixture at a temperature of between 300° C. and 400° C., and a pressure of between 180 bar and 350 bar.