Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
  • C12M45/00—Means for pre-treatment of biological substances
  • C12M45/06—Means for pre-treatment of biological substances by chemical means or hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
  • C12M45/00—Means for pre-treatment of biological substances
  • C12M45/20—Heating; Cooling
• • C—CHEMISTRY; METALLURGY
  • C13—SUGAR INDUSTRY
  • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
  • C13K1/00—Glucose; Glucose-containing syrups
  • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C1/00—Pretreatment of the finely-divided materials before digesting
  • D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P19/00—Preparation of compounds containing saccharide radicals
  • C12P19/02—Monosaccharides
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P19/00—Preparation of compounds containing saccharide radicals
  • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

• the present invention relates to the
• CA1096374 and CA141376 describe the pretreatment reactor and the steam explosion process of lignocellulosic matter, which in 60 seconds raises the pressure in the range of 28.1-49.2 kg / cm 2 at a temperature of 180-240 S C, which subsequently has a rapid depressurization and lowering of temperature by being exposed to atmospheric air. Also in the last document is the glucose production stage by impregnating the cellulose with acid solution.
• US2002164730 protects a process that is quite Full production of ethanol, comprising pretreatment by steam explosion, the biomass originating from agricultural residues at low temperatures (200- 220 and C), high pressures and treatment times larger (5 to 10 minutes) .
• the inventors claim that these conditions give rise to better glucose recovery rates.
• US 6,419,788 conducts a steam blasting process of lignocellulosic matter, primarily wood, under known conditions, but which is subsequently treated with alkaline pH (8-13) hot water containing dissolved oxygen. Wash water removes lignin, hemicellulose and inhibitors from the hydrolysis step.
• WO2012060767 and JP2003212888 are intended to separate cellulose and / or oligosaccharides from solid biomass with water under severe conditions, such as temperatures greater than 250 S C and residence times of 1, 5 and 1, 0 seconds respectively. and the extracted phases are rapidly cooled.
• the first process presents a description of possible equipment to be used, however, does not bring the system design, and the experiments take place on a laboratory scale, using pine as biomass and yields of 35% glucose recovery.
• the second case is shown a diagram with the necessary configuration to perform the process, however, the available examples involve the degradation of crystalline cellulose, a situation that does not represent the conditions found in the industry.
• PI0706024 describes process and equipment of biomass hydrolysis, previously minced and placed in contact with water, optionally containing ethanol (2 10%) under high temperature conditions (C 2 140- 180 and 240-280 C for 2 hemicellulose and cellulose degradation, respectively) and pressure in a number of 4 + n or 3 + n pressure reactors, where the various heating, cooling, and other processes can occur. simultaneously.
• the cooling step is by evaporation of water.
• the process can save up to 60% energy with a saccharide yield of approximately 40%.
• an equipment for the treatment of biomass is outlined, however, much differs from that intended to protect and does not yet bring a rapid cooling system of the mixture.
• Patent CN101613377 outlines a biomass degradation system through its pretreatment and hydrolysis, mainly wood, in reactors with water under supercritical (350-400 fi C), and subcritical (200-300 a C) conditions, in sequence. In both situations the respective chillers (100-200 to C and 15-50 to C) from each reactor lower the system temperature. In the present case there is no discussion about the residence time of the biomass in the reactor and still focuses on the biomass disruption to glucose rather than xylose / glucose removal.
• Document JP2009261275 brings a preheating, reaction and cooling system through the use of three reactors for each step, which, according to the inventors, allow a not so abrupt temperature decrease in each unit, which decreases its costs.
• the mixture biomass and water are preheated to 70-120 fi C with recycled steam cooling step, and is transported to the second stage, which occurs treatment with hot water at 140-200 C for 8 extraction of C5 or 240-280 to C for cellulose extraction.
• the last three tanks is decreasing temperature to 140-180 C by evaporation.
• the biomass and solution are separated and solid matter can be returned to the system again.
• a saccharide yield of approximately 40% is obtained.
• the patent describes a process that will take at least 1 minute for each step to occur and has no specific equipment for solid and liquid phase separation.
• Process CA2750754 features a hydrothermal treatment in which water and biomass are extruded countercurrent and the liquid phase is sent to an enzymatic hydrolysis unit, while the solid phase is cooled with lower temperature liquid water to stop hemicellulose degradation, and which is also subsequently sent to the enzymatic hydrolysis unit.
• the process involves a solid and liquid phase separation step for both extractions and a process water recovery step for energy saving.
• the reactor is in a vertical position, which can cause matter loss, since the bagasse, for example, is a light biomass, making it difficult to control its rise. Still the process takes minutes to occur, for example, in the first Pretreatment step, extrusion occurs 3-10 minutes.
• the process WO2011091044 claims a lignocellulosic biomass treatment process where in a first reactor pretreatment, hot water and the cellulosic matter are brought into contact at a temperature of 180-260 9 C, pressure of 50-110 bar and at time 1-10 min. After this step liquid / solid separation occurs and xylose in solution is cooled. The other phase is subjected to hydrolysis under conditions S 275-450 C, 200-250 bar pressure and 1-45 s residence time. The products are separated and cooled. In the two power stages can be added C0 2 as well as in both cooling steps acid may be optionally added. Cellulose recovery from biomass reaches 60% yields, with glucose conversions up to 90%.
• the UHTST process concept can also be applied to broths used in fermentation to obtain ethanol and is widely used in the food industry but with the purpose of thermally inactivating contaminants while preserving maximum nutrients.
• the present invention describes the process for converting sugarcane bagasse using UHTST continuous reactors using superheated liquid water for the bagasse pretreatment and hydrolysis process.
• the proposed pretreatment process is conducted in 2 phases that operate sequentially under different conditions of residence time, temperature and pressure optimized for maximum preservation of monomeric or oligomeric sugars of each of the bagasse hemicellulose and cellulose fractions and consequently minimal formation of inhibitory products.
• the pre-treatment and pre-treatment heating and cooling systems are designed to be conducted equally quickly, lasting less than one and a half minutes or even fractions of seconds.
• the temperature range is wide up to 350 to C depending on whether or not chemicals are capable of creating synergy with heat treatment. Effective residence times during pretreatment are less than 1 minute and may reach fractions of seconds.
• the entire process involving reaction, cooling and transfer to subsequent steps is conducted aseptically, by not contacting the material with outside air to avoid contamination.
• Process steam consumption is less than 20kg / TC while water consumption is less than 4kg / kg of treated bagasse, and with this water consumption the concentration of fraction C-5 from hemicellulose hydrolysis is 75.5g. / L whereas the concentration of the C-6 fraction from cellulose hydrolysis is 120g / L.
• the evaporative cooling system adopted provides thermal regeneration, concentration and rapid cooling in order to preserve the released sugars.
• a drawback of the prior art is that the pretreatment processes generate low concentration hydrolysates ( ⁇ 20g / L) and are energy intensive for concentration at the levels obtained by this technology.
• modules used for the pretreatment do not have a good matter transfer dynamics when it is intended to increase the residence time of the biomass in the reactor. such a varied flexibility of said times of residence.
• the process described herein utilizes superheated water at a temperature and pressure range of 280 fl C / 2 C 64,5barg 350/161, 5barg without the use of chemicals, acids or enzymes, carried out in two stages.
• Overheated water under the conditions of this project has excellent properties, such as high solvency capacity, including organic substances, high reactivity and very low viscosity.
• the process is designed to occur in 2 phases where reactors are designed to separately extract and hydrolyze hemicellulose by releasing sugars of 5 carbon atoms and hydrolyze cellulose by releasing sugars of 6 carbon atoms. Both process steps are conducted with the UHTST concept, meaning Ultra High Temperature Short Time, ultra-fast thermal processes that are conducted at elevated temperatures.
• This process class is widely used in the food industry in sterilization and pasteurization processes with the mutual goal of eliminating microbiological contaminants and preserving food nutrients.
• the heating and cooling steps are also extremely fast to prevent sugars from undergoing thermal degradation reactions, thus preserving them, thus preventing the release of organic acids and other inhibitor products to the subsequent process steps.
• Hydrolyzed broths are sent to evaporative cooling vessels ensuring instant cooling to safe temperatures to prevent such thermal degradation reactions.
• Evaporative cooling vessels also ensure thermal regeneration and hydrolyzed broth concentration and are sized for minimal sugar carry-over. Optimum amount of overheated water for the pretreatment process can be used without concern for excessive dilution of sugars in the resulting hydrolyzed broths as the added water will be removed during evaporative cooling and reused as steam.
• the reactors used are pluggable tube modules which, together with varying pump speed, allow the pre-treatment residence time to be varied over a wide range as required for optimization.
• decompression at the exit of the reactor 2 desestrutu mechanical assembly gives biomass feed with consequent increase in its specific surface, which contributes to increase the efficiency of the subsequent enzymatic reaction in the case of this reaction is required.
• the steps of the hemicellulose and cellulose pretreatment and hydrolysis process are designed to occur in separate reactors and also separately extracting the C-5 and C-6 rich hydrolyzed broths in order to provide more flexibility to the subsequent process. With this configuration these streams may be processed separately or premixed for joint processing depending on available technology which is not the subject of this invention.
• the system of the present invention therefore has the advantages of maximum specific surface area for the enzymatic reaction together with maximum hemicellulose removal, maximum cellulose preservation (> 99%), maximum pentose preservation (> 99%) and minimal production. of inhibitory products.
• Figure 1 UHTST PRE-TREATMENT AND SIMULAN CONVERSION OF CANE bagasse in the extraction configurations of C-5, C-6 without enzyme use.
• Bagasse (1) is fed to a mill (2) in which it is processed, here it is noteworthy that processed characterizes the reduction and uniformity of its particle size distribution.
• Said treated bagasse (1) is discharged into a helical conveyor (3) where it receives a small amount of hot water (4) for swelling and formation of the bagasse sludge (5), making the bagasse pumpable.
• the helical conveyor discharges this bagasse sludge (5) into the pump suction (6) which will feed the first reactor module formed by panel pluggable standpipe assembly (7, 8, 9, 10) through the connections (11 , 12, 13, 14) designed to achieve residence times within the range of 0.5 second to 80 seconds.
• Said tubes allow that, if the reaction does not occur completely within a certain residence time, previously stipulated, the raw material, preferably bagasse, may still remain in contact with hot water for a longer time.
• Water superheated to 250-300 C and 40-90barg (15) feeds this first module in co-current with the sludge residue.
• the sludge (43) finds a perforated mesh of 400 to 600 mesh (44) which will be responsible for separating the liquefied hemicellulose (C-5 sugar rich liquor) from the lignocellulosic solid.
• the C-5 high sugar liquor (45) is sent to a set of evaporative coolers (16-21) whose function is to promote instant cooling, where instantaneous refers to cooling performed preferably in milliseconds; liquor concentration; and thermal and water regeneration. This can be achieved by using multiple stages in series. Shown here is a set of 6 stages.
• the cooling temperature will vary depending on the number of stages used in the system. The greater the number of stages, the greater the thermal regeneration.
• the outlet liquor (46) will be rich in C-5.
• stream 22 can ideally be used for energy integration in parallel processes such as the 1G sugar and ethanol production plant.
• Stream 23 represents replacement water for the process.
• the lignocellulosic material (24) from the perforated screen (44) proceeds to the suction of the pump (25) which feeds the second reactor module.
• the second reactor module is also comprised of panel pluggable standpipe assemblies (26-29) through connections (48 to 51) designed to achieve residence times within the range of 0.5 second to 80 seconds.
• Overheated water (30) at 300-370 to C and 90-220 barg feeds the second module in co-current with lignocellulosic sludge (24).
• the lignocellulosic sludge (31) encounters a 400-600 mesh perforated mesh (32) which It will be responsible for the separation of the sugar-rich C-6 liqueur (33) from the lignocellulosic lignin-rich insoluble solid material (34).
• the C-6 high sugar liquor (33) is shipped to an evaporative cooler system (35-40) whose function is to promote instant cooling, where instantaneous refers to milliseconds, liquor concentration and thermal and water regeneration. . This can be achieved by using multiple stages in series. The greater the number of stages, the greater the thermal regeneration. Shown here is a set of 6 stages.
• stream 41 can ideally be used for energy integration in parallel processes such as the 1G sugar and ethanol production plant.
• Stream 42 represents replacement water for the process.
• the reactor is designed with modules with lead times of 1, 5s, 4s, 12s and 40s. These modules can be used in combination or separately and varying the reactor feed rate achieves a wide range of treatment times ranging from 0.5 to 80 seconds.
• Figure 2 represents each module that is formed by a set of standby reactors with different residence times, which can be easily configured by choosing panel connections, where the inputs (52, 53, 54 are available). , 55) and outputs (56, 57, 58, 59) of each reactor. Additionally the tubular reactor has excellent characteristics for reactions involving solids because it enables easy cleaning and no energy consumption in the mixture.
• 40 kg of raw bagasse with 50% humidity / 80 kg of water (1) is fed to a mill (2) and processed to a particle size of less than 1 mm. Said pulp is discharged into a screw conveyor (3) which receives small amount of hot water (4) at approximately 100 C.
• the S auger that discharges pulp sludge (5) in the suction of the pump (6) which will feed the first module of reactors formed by a set of standby tubes (7, 8, 9 and 10) with residence time of 0.5 to 80 seconds.
• 80 kg of overheated water at 300 2 C and 88 barg (15) feeds this first module in co-current with the pomace sludge.
• the sludge meets a perforated 400 mesh screen (44) which will be responsible for separating the liquefied hemicellulose (C5 sugar rich liquor) from the lignocellulosic solid.
• the C-5 high sugar liquor (43) is shipped to a set of 6 evaporative coolers (16 to 21) whose function is to provide instant cooling to 70-80 s C and 75.7g / L in milliseconds. Additionally the chain (22) provides 38 kg of water at 286 C. The second stream (23) represents 42 kg of makeup water for the process.
• the liquor at the end of the last stage (45) has a C-5 sugar concentration in the order of 75.4 g / L and a temperature of 80 2 C.
• Lignocellulosic material (24) from the perforated web is fed to the pump suction (25) feeding the second reactor module (26, 27, 28, 29) with residence time of 0.5 to 80 seconds.
• 80kg of overheated water (30) at 350 to C and 170barg feeds the second module in co-current with lignocellulosic sludge (24).
• the lignocellulosic sludge encounters a 400 mesh perforated mesh (32) which will be responsible for separating the C-6 sugar rich liquor (33) from the lignocellulosic lignin rich insoluble solid material (34).
• the C-6 high sugar liquor is shipped to a set of 6 evaporative coolers (35 to 40) whose function is to provide instant cooling to 65-80 s C and 119.5g / l in milliseconds, liquor concentration and regeneration.
• thermal and water The chain (41) has 46 to 300 kg of water S C.
• the stream (42) represents 34 kg of makeup water for the process.
• the liquor at the end of the last stage (46) has a C-6 sugar concentration of 119,5 g / L and 75 S C.
• the process steam consumption is 0.1 kg steam / kg pretreated bagasse resulting in 24 kg steam / TC.
• This low steam consumption can be absorbed by sugarcane processing units without major energy optimization efforts at the units.
• the use of multiple effect evaporative cooling in conjunction with the energy integration of modules 1 and 2 provides zero vapor consumption in the first module. This fact results in additional possibilities for energy optimization when implementing a biomass conversion process in sugarcane processing units, as these two energy-rich streams can be used in the process of processing units and contribute to the reduction of consumption.
• Total water consumption is 3.8 kg water / kg pretreated bagasse, 2.1 kg / kg in the first module and 1.7 kg / kg in the second module.

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• 2013
  • 2013-03-18 BR BRBR102013006389-4A patent/BR102013006389A2/pt not_active Application Discontinuation
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