WO2012103609A1 - Process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content - Google Patents
Process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content Download PDFInfo
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- WO2012103609A1 WO2012103609A1 PCT/BR2011/000038 BR2011000038W WO2012103609A1 WO 2012103609 A1 WO2012103609 A1 WO 2012103609A1 BR 2011000038 W BR2011000038 W BR 2011000038W WO 2012103609 A1 WO2012103609 A1 WO 2012103609A1
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- 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
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/14—Fungi; Culture media therefor
- C12N1/16—Yeasts; Culture media therefor
- C12N1/18—Baker's yeast; Brewer's yeast
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- 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
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/14—Multiple stages of fermentation; Multiple types of microorganisms or re-use of microorganisms
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- 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 refers to a process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content, especially a process for producing ethanol from the microbiological fermentation of sugars, such as sucrose, glucose and fructose using yeasts, of the genus Saccharomyces sp, under controlled conditions of temperature and of high concentration of ethanol in the fermentation medium.
- sugars such as sucrose, glucose and fructose using yeasts, of the genus Saccharomyces sp
- the current prior art comprises a production process in which sugar sources are converted, through a high- efficiency fermentation process, to ethanol.
- sugar sources which can be converted into fermentable sugars it is possible to point out :
- sucrose (Ci 2 H 22 0n) : sugar cane, beet and sweet sorghum;
- Sources of cellulosics and lignocellulosics are plantous compounds containing hemicellulose and cellulose, which can be chemically, or enzymatically converted to pentoses (not fermentable by Saccharomyces sp) and hexoses, respectively.
- Examples of raw materials that can be used in this route are: bambooous materials, elephant grass fiber, sugar cane fiber, grass sorghum fiber, sugar cane or sweet sorghum straw.
- Starchy sources mainly grains and tubers.
- the sugar sources are the sucrose (Ci 2 H 22 0n) or glucose and fructose (C 6 Hi 2 0 6 ) .
- These microorganisms are able to convert sucrose to glucose and fructose through an exo-enzyme called invertase.
- the equation (1) described below represents the biochemical reaction for converting sucrose, glucose and fructose to ethanol.
- starchy carbohydrate and lignocellulosic sources before serving as substrates for fermentation, must be converted into fermentable sugars (hexoses) .
- the starchy sources can be hydrolyzed by glucose, via acids/enzymes, in which the starch is converted to dextrin and posteriorly to glucose, using the alpha-amylase and glucose oxidase enzymes.
- the cellulose and lignocellulose sources can be partially hydrolyzed to fermentable hexoses and to non- fermentable pentoses, via the concentrated or diluted acid, or via enzymes.
- cellulose enzymatic cocktails based on endo-glucanase , exo-glucanase and beta-glucosidase
- - to hemicellulose hemicellulase, exo- hemicellulase and xylosidase.
- control of fermentation enables obtaining a fermented must with high ethanol content and with high conversion of sugars to ethanol .
- the basic reaction (1) which expresses the biochemical conversion of sugars comprising the sucrose ( ⁇ 2 ⁇ 22 ⁇ ⁇ : ⁇ . ) , glucose (C 6 Hi 2 0 6 ) and fructose (C 6 H 12 0 6 ) to ethanol (C 2 H 5 OH) can be summarized as follows:
- the first part of the reaction comprises the enzymatic conversion of the sucrose to glucose and fructose (reducing sugars) and, the second part, the biochemical conversion of these sugars to ethanol and carbonic gas.
- the reaction is exothermal, in which heat is released.
- sugar cane an important source of this raw material is sugar cane.
- sucrose which contains approximately 99.5% of the contained sugars (dry base) and, the remainder (0.5%), is basically glucose and fructose.
- TRS total reducing sugars
- Brazil is the second largest ethanol producer in the world after the United States.
- 2007/2008 Brazilian harvest there were processed 493 million tons of sugar cane, being produced 22.5 billion liters of ethanol (anhydrous and hydrated) and 30.7 million tons of sugar.
- There are basically two types of mills in Brazil the autonomous mills, which only produce ethanol from sugar cane, and the combined mills, which produce sugar and ethanol, the latter being manufactured from the juice and residual syrup (molasse) coming from the sugar manufacturing process.
- the combined mills on average, the equivalent to about 50% of the processed sugar cane is destined to sugar manufacture and 50% to ethanol manufacture (anhydrous and/or hydrated) .
- the raw material used for manufacturing ethanol and sugar requires several processing steps.
- the juice destined to the ethanol manufacture undergoes a specific physical -chemical treatment and is sent to the fermentation vessels, jointly with the exhausted final run-off syrup (mother liquor) resulting from the sugar manufacture .
- This mixture called must, undergoes an alcoholic fermentation process, in agitated tanks (fermenters or vessels) , using mainly the Saccharomyces cerevisiae yeast, generating a fermented must typically containing from 6% to 11% of ethanol.
- As a byproduct of the fermentation process it is further generated carbonic gas in a mass amount of 1:1 in relation to the ethanol, and the fusel oil (less than 1% in mass) which is separated in a posterior distillation step.
- the resulting fermented must is then submitted to centrifugation, in which the yeast is separated and recycled, and the wine containing ethanol is sent to distillation. Subsequently, the wine is usually brought into direct contact with the steam in distillation columns, generating two streams, an ethanol stream at the top and a vinasse stream at the bottom. Upon using the system of flushing the vapor directly in the column, the vapor is brought into direct contact with the wine, promoting the incorporation of condensate in the vinasse, and the volume generated can be somewhat between 10 and 14 times the volume of alcohol, depending on the wine alcoholic degree. There also exists the distillation process by indirect contact, in which the generated vinasse volume is smaller, being 6 to 8 times the produced ethanol volume.
- the mixed juice destined to sugar manufacture undergoes the operation of separating bagacillo in cush-cush type screens and/or rotary screens, being heated to about 40°C and is conveyed, in case of producing white sugar, to sulfitation (usually in columns or hydro-ejectors) in which, by addition of sulfur dioxide resulting from the sulfur burning in the burners, has its pH reduced to about 4.0 to 4.5.
- the juice After sulfitation, the juice receives the addition ' of lime milk (or calcium saccharate) in which the pH is elevated to about 7.0 to 7.2.
- lime milk or calcium saccharate
- the limed (or dosed) juice is then heated to about 105°C, subsequently undergoing a vaporization process (flash balloon) for removal of dissolved gases, receiving the addition of a flocculating agent, usually a polyacrylamide polyelectrolyte, and is then submitted to the decantation in static decanters, with or without trays. This operation is also commonly known as clarification .
- a flocculating agent usually a polyacrylamide polyelectrolyte
- the clarification process generates two streams: a sludge stream and a clarified juice stream.
- the sludge after being added with bagacillo which is a type of a natural element, receives the addition of lime milk and, eventually, polyelectrolyte, usually a polyacrylamide , and is then filtrated in vacuum rotary filters or belt press filters, thus producing the filter cake which is conveyed to the plantation site, as well as the filtrated juice which is re-conducted to the process.
- the obtained clarified juice is sent to evaporation in multiple effect vacuum evaporators, usually Robert type evaporators with 4 or 5 stages, producing a concentrated juice known as syrup, which has a concentration of about 60-65°Brix.
- pre- evaporation In the first evaporation stage, usually known as pre- evaporation, it is effected the bleeding of vegetal vapor (VI) used in the operations of evaporation and crystallization, heating of the mixed juice and distillation in the ethanol manufacture.
- vegetal vapor V2 and V3 There are mills that carry out the bleedings in the second and third effects, respectively called vegetal vapor V2 and V3 , these vapors being used for heating the juice, or even in the case of the vapor V2 , for the cooking operation.
- the syrup obtained in the evaporation is sent to the posterior crystallization step, which is carried out in vacuum calender type evaporating crystallizers in systems of two or three masses.
- the conventional crystallization process takes from 3 to 5 hours, and the crystal mass obtained is conveyed to horizontal crystallizers provided with a cooling jacket until reaching the ambient temperature. The final mass is then submitted to a centrifugation cycle, in basket centrifuges, in which the crystals are washed upon application of water and steam and then conducted to the drying and bagging steps.
- the run-off syrup obtained in the centrifugation is reused in the cookings for obtaining the second sugar
- the processes for fermenting sugar to ethanol can be continuous or by fed batch.
- the process predominantly adopted is the fed batch fermentation.
- the fed batch process it is initially added, in the fermenter, a yeast fraction from about 8% to 15% of its useful volume. Subsequently, it is gradually added an increasing amount of must as the fermentation activates.
- the heat removal is generally carried out through indirect thermal exchange devices (heat exchanger and coils) between the must in fermentation process and the water coming from a tower or spray cooling system.
- the water effluent from the heat exchanger is sent to a cooling tower in which the heated water resulting from the heat exchange with the fermented must receives a forced air flow. Accordingly, the water is cooled to the wet-bulb temperature of the ambient air, and returns to the cooling process of the fermenters.
- the total reducing sugars (TRS) in the fermenter is maintained between 2% and 4% until the fermentation process is completed.
- the formed foam, resulting from the strong evolution of C02 is controlled through the addition of an antifoaming agent. The process is finished when the useful volume of the fermenter is completed and the TRS is substantially exhausted, taking about 6 to 12 hours on average.
- the continuous fermentation system consists of agitated vessels connected in series, so that the must and the yeast are generally fed in the first stage and, in the outlet of the last reactor of the series, the TRS being maintained in substantially zero values.
- the cooling of the fermenters occurs through the indirect thermal exchange devices, connected in each stage, the cold fluid coming from a spray system or cooling towers, which basically comprises evaporative cooling at ambient temperature.
- an alcoholic content in the fermented must is obtained, generally between 6.0 and 8°GL for non-optimized processes and from about 8.5 to 11°GL for well -optimized and controlled processes.
- the fermented must is then sent to centrifugation for separation of the yeast from the wine, the concentrated yeast ("yeast cream”) being sent to an agitated tank in which it frequently receives an acid treatment (based on sulfuric acid) and then re-used again in the process.
- the resulting wine is sent to distillation, in which the contained ethanol is recovered in its anhydrous and hydrated form, generating from about 5 to 14 L of vinasse/L of produced ethanol.
- the higher the alcoholic content the better the performance of the posterior steps, since there is a higher production of ethanol by reactor volume, higher amount of ethanol produced by distillation column volume, reduction of vapor consumption in the distillation and reduction of the generated vinasse volume.
- the amount to be re-circulated evidently depends on the medium osmotic pressure, which is the factor that limits the amount to be re-circulated. In case of a high amount, it can drastically affect the performance of the yeasts and impair, therefore, the alcoholic fermentation process.
- the re- circulation rates range from about 20% to 60% of the generated volume .
- Prescott e Dunn's (Prescott, S.Dunn's, A. Industrial Microbiology, 4a. ed. CBS Publishers and Distributors, New- Delhi, India, p.541-581, 1987) verified that the optimum temperature for the cell growth and ethanol production is 30°C, higher temperatures (35-38°C) being tolerable, but to the detriment of the alcoholic contents. In this temperature range, the cellular growth rate, the ethanol production and . the death rate can be drastically- affected .
- yeast S.cerevisiae tolerates temperature levels to about 33 °C, in industrial conditions, for production of ethanol.
- the minimum growth range occurs in temperatures from about 10°C to 40°C, the optimum operation temperature being in the range between 28°C and 35°C.
- Dias et al . M.O.S.Dias, R.Maciel Filho and C.E.V Rossel, Efficient cooling of fermentation vats in ethanol production. Proc . Int. Soc . Cane Technol . Vol. 26, 2007) reported that high temperatures in the fermentation affect the yeast metabolism and reduce the concentration of ethanol in the end wine, which increases the consumption of vapor in the distillation.
- the fermentation conducted at 28°C enables operating with higher sugar concentrations in the must, which fact reduces the vapor consumed in the distillation and generates vinasse in levels of 5.76 L/L EtOH.
- the registered temperatures of the fermentation are in the range from 32 °C to 36°C.
- the refrigeration system has the object of reducing the temperature of a fluid at a temperature substantially lower than the ambient temperature.
- the thermodynamic principle which rules this system, teaches that the energy cannot be created nor destroyed, and no system can receive heat at a given temperature and release it to a system at a higher temperature without receiving external work.
- the industrial processes use equipment to generate cold, water, with the purpose of refrigerating heat generating units.
- the choice for efficient systems, at low cost and low energy consumption for producing cold water, as well as the adequate strategy for cooling the must and the fermenters, are determinant to make the application of this system feasible.
- the chillers are basically divided into centrifugal chillers, screw chillers, reciprocating chillers and absorption, machines.
- the three first types are industrial refrigeration technologies which use the principle of vapor compression. Said systems present disadvantages in relation to the absorption system, since they present high electric energy consumption, do not allow using alternative energy sources, use synthetic refrigerants with CFC/HCFC, present high operational cost and high indices of noise and vibration.
- the lithium bromide-based absorption machines allow using thermal sources, such as natural gas or LPG (liquid petroleum gas), exhaust steam from the turbines or generator, low-pressure vegetal vapor from the evaporators, hot water or condensate, alcoholic vapors, vinasse effluent from the distillation column, and even residual gases from the combustion.
- thermal sources such as natural gas or LPG (liquid petroleum gas)
- LPG liquid petroleum gas
- the latter are required to be at a temperature higher than 75 °C.
- the absorption systems employ mainly water, lithium bromide or ammonia.
- the lithium bromide- based absorption refrigeration machines use the vacuum principle and the high capacity of the lithium bromide solution to absorb water vapor.
- the water when maintained under intense vacuum, boils and vaporizes abruptly, besides being cooled to low temperatures.
- the lithium bromide solution is a highly hygroscopic solution, presenting the best solubility-vapor pressure relationship, obtaining a highly efficient cycle therewith .
- An absorption unit by lithium bromide consists, basically, of five main components:
- Cooler Element it comprises a pipe section in which there occurs the return of the cold water which is indirectly cooled by the water pulverized on the tubes.
- the evaporator element is maintained at an absolute low pressure, so that the sprayed water vaporizes and cools the water which passes through the tubes.
- Absorber Element it consists of a concentrated lithium bromide solution which absorbs the water vapor vaporized in the evaporator element.
- the lithium bromide solution is discharged on the tubes through a pumping element.
- the total thermal load (refrigeration load + dilution heat + cooling of the condensed water + sensitive cooling of the solution) is indirectly transferred to the cooling water, which comes from a cooling tower.
- Heat-Exchanger Element of the Solution this component is used to improve the cycle efficiency by exchanging heat between the diluted solution, which leaves the absorber, and the concentrated hot solution, which comes from the generator.
- Generator Element in this compartment, the diluted lithium bromide solution is maintained at the boiling point in the solution, through a hot source (above 75°C) , to eliminate the absorbed vapors.
- Condenser Element in this compartment, the water vapor which was eliminated in the generator element is condensed to posteriorly return to the cooler element.
- the absorption cycle therefore, is a cycle of two pressures in which it is usually maintained, for the effluent cold water, a temperature between 7.2°C and 8.3°C. This water will be used for cooling, at an absolute pressure of 0.27 in of Hg°, in the section of the evaporator-generator elements, and of 3.0 in of absolute Hg° , in the section of the generator-condenser elements.
- the absorption cycle basically comprises three circuits: one in which the refrigeration water is pumped to the evaporator element, and the lithium bromide, used as absorbent, circulates on the evaporator tubes, through the heat exchanger to the generator; the cooling water flows in series, initially through the . absorber tubes and, partially, through the condenser tubes.
- the water to be cooled is admitted in the bundle of tubes of the cooler, in which it is indirectly cooled by water pulverization.
- the vaporized water is absorbed by a concentrated lithium bromide solution at a low pressure.
- the lithium bromide which absorbed the water vapor is then pumped, through the heat exchanger, from the solution to the generator, so as to reconstitute the diluted solution.
- the water vapor generator operates at low pressure so as to expel the water vapor absorbed in the solution, thus concentrating the salt solution, before re-entering in the absorber element.
- the solution flow which comes from the generator goes to the absorber by difference of gravity and pressure.
- the water which leaves the generator in the form of vapor is then condensed, passes to the liquid state in the condenser element section, and the condensate returns to the evaporator element.
- the thermal sources to be used in the cold water production system must be fluids with temperature superior to 75°C.
- the vinasse effluent from the distillation condensates from the juice evaporation, alcoholic vapors from the distillation, vegetal vapors coming from the juice or vinasse evaporation, exhaust steam from the turbines or bled from the generators, biogas (methane) coming from the biodigestion of vinasse and chimney gases resulting from the bagasse and/or straw burning.
- the process consists of the following steps: (i) preparing a must to feed the fermentation containing a high sugar content, containing between 18% to 35% of TRS, preferably above 22% of TRS; (ii) cooling the must used in the fermentation to temperatures between 8°C and 30°C, preferably from 22°C to 25°C; (iii) feeding the yeast cream constituted of Saccharomyces cerevisiae, to the fermenter, so as to maintain a concentration, on a volumetric basis, of about from 5% to 15%, preferably about 10%; (iv) gradually feeding, at increasing flow rates, the cooled must to be fermented into the fermenter containing the yeast, so as to accompany the progressive increase of the metabolic activity of the microorganism; (v) starting the cooling process of the fermenters, at the stage in which the temperature of the fermentation system surpasses from 28°C to 30°C, preferably 28°C; (vi) maintaining the process of fermentation and must feeding; (vii) maintaining the fermentation until reaching a substantially zero TRS
- a cold water generator system which uses, as thermal source, one of the sources available in the sugar and alcohol industry complex, such as: the vinasse effluent from the bottom of the distillation system, alcoholic vapor condensates from the top of the distillation column, or even vegetal vapors effluent from the juice evaporation for the manufacture of sugar and/or ethanol , or exhaust steam bled from the turbines or generators .
- Figure 1 is a block diagram of the currently employed system for cooling the fermentation and the integration thereof with the distillery.
- the raw materials used for compounding the must such as clarified juice, pre- evaporated juice, syrup and water, are sent to the must preparation unit (1) in controlled quantities. This must, in the temperature range from 45 °C to 95 °C, is conducted to the thermal exchange device (2) to be cooled by the cooling water coming from the cooling system by tower or sprays (6) to the range from 30°C to 34°C.
- the cooled must is fed to the fermentation system (3) which can be either a fed batch fermentation or continuous fermentation.
- the must in fermentation process is continuously cooled in the indirect thermal exchange devices (4) , whose cold fluid is the evaporative cooling water of the evaporative cooling system (6) .
- the fermentation temperature is maintained controlled in the range from 32 °C to 36 °C.
- the end product of the fermentation (3), wine is sent to the distillery (5) for recovery of the ethyl alcohol, generating a second effluent from (5) , which is used in regenerative thermal exchange devices for the pre-heating of the wine, before it is fed to the distillation device.
- the vinasse is then cooled to about 60 °C and conveyed to be used in the sugar cane plantation site.
- FIG. 2 is a block diagram of one of the preferred forms of the invention, in which cold water is used to effect the cooling of the must and of the fermentation system.
- This cooling system consists of absorption chillers, in which the must prepared in the must preparation unit (1) , in the same manner as in the current system described in figure 1, with temperature range from 45°C to 95°C, is sent to the indirect thermal exchange device (2) to be cooled by the cooling water coming from the evaporative cooling system (6) to the range from 30 °C to 34 °C. Then, it follows to the next cooling stage in the thermal exchange device (8) , where it is cooled with cold water at the range from 5°C to 25°C, coming from the absorption chiller (7) .
- This cold water used for cooling the must is refrigerated by the water of the internal circuit of the absorption refrigeration machine.
- the must, then cooled to a temperature range from 7°C to 27 °C, is fed to the fermentation system (3).
- the temperature will be controlled in a temperature range from 20 °C to 32 °C.
- the must in fermentation will be in constant circulation, passing through the indirect thermal exchange device (4), in which the cold water coming from the absorption chiller (7) is maintained in the range from 15 °C to 27 °C.
- the available hot thermal sources for concentrating the lithium bromide solution of the absorption cycle of the chiller (7) in the distillery (5) are: vegetal vapor, condensates, vinasse and alcoholic vapors and exhaust steam, preferably vinasse.
- One of these sources is sent to the absorption chiller (7) and, after passing through the generator element constituent of the chiller (7) , will be disposed in the end disposition unit (9) in the most economical manner.
- the heating fluid is the vinasse, its capture will be effected after passing through the regenerative thermal exchange device, described in figure 1.
- vinasse in a temperature range between 80°C and 90°C, will pass through the generator element of the chiller (7) , indirectly exchanging heat with the diluted lithium bromide solution, leaving with the temperature in the range from 50°C to 70°C.
- the exit temperature thereof in a temperature range from 95 °C to 98°C, the exit temperature thereof will be from about 60°C to 70°C and they can be, therefore, re-used/treated for other purposes in the production process.
- alcoholic vapors as hot source, said vapors will be deviated from their conventional flow and, after passing through the chiller, will return to the conventional flow of the condensed alcoholic vapors.
- FIG 3 is a block diagram of another preferred form of the invention.
- the thermal exchange devices (4) and (8) represented in figure 2 and the water used as thermal exchange fluid in the generator of the chiller (7) was removed and substituted by a fluid of the process.
- the substitution of the water which circulates in the refrigeration system implies eliminating the auxiliary indirect thermal exchange devices, equipment for transport of fluids, pipes and several accessories.
- the must, prepared in the must preparation unit (1) in the same manner as in the current system, in the temperature range from 45°C to 95°C, is sent to the thermal exchange device (2) to be cooled by the cooling water coming from the evaporative cooling system (6) to the temperature range from 30°C to 34 °C.
- the temperature will be controlled at the range from 20°C to 32°C, so that the must in fermentation will be in constant circulation, directly passing through the evaporator of the chiller (7) .
- the hot circuit is the same described in Figure 2.
- the total heat of the absorption cycle of the chiller (7) will be removed by the wine coming from the fermentation (3), at ambient temperature, and will leave the chiller at the temperature range from 30°C to 40°C.
- FIG 4 is a block diagram of the refrigeration cycle of the preferred form of the invention represented in Figure 2, which uses cold water to effect the cooling.
- the refrigerant fluid water coming from the condenser (3) at the liquid state
- the evaporator (1) which is under vacuum of about 6 mmHg° .
- the refrigerant evaporates and cools the water passing through the tubes.
- the refrigerant, in the vapor state, is absorbed in the absorption device (1) in which a concentrated lithium bromide solution is sprayed on the vapors of the refrigerant, absorbing the latter and then diluting.
- the diluted solution is pumped to the generator device (2), where it is heated in an indirect thermal exchange device, by a hot source, provoking the evaporation of the refrigerant fluid.
- Said refrigerant, at the vapor state is sent to the condenser device (3) , where it is condensed to the liquid state in an indirect thermal exchange device, whose cooling fluid comes from an evaporative cooling device, for example, a cooling tower.
- the energy released during the absorption process is removed with cooling water coming from the condenser device (3) .
- FIG. 5 is a block diagram of the refrigeration cycle of the other preferred form of the invention represented in Figure 3- and which does not use cold water to carry out the cooling, but instead fluids available in the fermentation and distillation process.
- the lithium bromide vapor absorption machine presents the following differences in relation to the system schematically represented in Figure 4: the cold water circuit in the evaporator device (1) is substituted by must and fermented must, and the cooling water used in the condenser device (3) ,. as well as the water of the absorber device (1) are substituted by wine.
- the must is prepared from the mixed juice, or clarified juice, or juice pre-evaporated until from about 22% to 30% of dry matter, or syrups and molasse effluent from the manufacturing process of sugar from sugar cane e/or its mixtures, so as to obtain a TRS from 18% to 28%.
- the must is then cooled to from about 15°C to 25°C, preferably from 22 °C to 25°C, in indirect thermal exchange auxiliary devices, whose cold fluid is cold water (from 10°C to 20°C) coming from a refrigeration machine, preferably a lithium bromide-based absorption machine.
- the yeast consisting of Saccharomyces cerevisiae, with a concentration from 30% to 60% (volume/volume) , is fed into the fermenters, in a proportion from 5% to 15% of its useful volume, preferably 10%.
- the fermenter containing yeast is added with must, initially in a small flow rate, which is progressively increased as the metabolic activity for converting sugars to ethanol and C0 2 , of the microorganisms constituent of the yeast, is accelerated.
- the temperature of the must in fermentation process reaches from 28°C to 32 °C, the refrigeration system of the fermenters is activated.
- This system consists of indirect thermal exchange devices, in which the cold fluid is cold water generated in the refrigeration system, in a refrigeration machine, preferably a lithium bromide-based absorption machine, which exchanges heat with the must in fermentation process, so as to maintain in the fermenters a temperature between 28°C and 32°C, preferably 30°C.
- the cold water fed to the indirect thermal exchange devices is usually dosed at a temperature range between 8°C and 12°C and is discharged with a temperature from about 5°C to 8°C above de temperature in which the must in fermentation process is maintained.
- the feeding of the refrigerated must is carried out until reaching the useful volume of the fermenter, being interrupted thereafter.
- the fermentation is considered finished when the TRS of the must in fermentation process reaches the substantially zero value.
- the fermenters are closed vessels, the gas (C0 2 ) emitted in the fermentation process being collected and washed with water in towers for recovery of the ethanol dragged jointly with the gas stream.
- the concentration of ethanol in the fermented must lies in the range from 8 to 16°GL, preferably above 10°GL.
- the fermentation process becomes complete in a time interval of 6-12 hours, depending on the end ethanol content in the fermented must, presenting a typical value of about 10 hours.
- the fermented must is then sent to a system for separating the yeast and the wine.
- the obtained wine is then conducted to the distillation and, the yeast, containing a concentration of 30% to 60%, returns to an acid treatment system and, subsequently, to the fermentation process.
- the must is prepared from the mixed juice, or clarified juice, or juice pre-evaporated until from about 22% to 30% of dry matter, or syrups and molasse effluent from the manufacturing process of sugar from sugar cane e/or its mixtures, so as to obtain a TRS from 18% to 28%.
- the must is then cooled to from about 15°C to 25°C, preferably from 22 °C to 25°C, in an indirect thermal exchange device constituent of the refrigeration system, preferably a lithium bromide-based absorption machine.
- temperatures from about 3°C to 4°C (temperature corresponding to water in the vapor state at a pressure of 6.0 mmHg°) in the inner side containing water in high- vacuum evaporation process.
- Saccharomyces cerevisiae yeast with a concentration between 30% and 60% (volume/volume) , is fed to the fermenters in a proportion of 5% to 15% of its useful volume, preferably 10%.
- the fermenter containing yeast is then added with the must, initially in a small flow rate which is progressively increased as the metabolic activity for conversion of sugars to ethanol and C0 2 , of the microorganisms constituent of the yeast, is accelerated.
- the refrigeration system of the fermenters is activated. In this system, the must in fermentation process is pumped to an indirect thermal exchange device constituent of the preferred refrigeration system (lithium bromide-based absorption machine) .
- the water of the internal circuit is sprayed over the thermal exchange area which, since it is submitted to a high-vacuum evaporation process, allows obtaining temperatures, in the internal side, from about 3°C to 4°C (temperature corresponding to water in the vapor state at a pressure of 6.0 mmHG°) .
- the now cooled must in fermentation process returns to the fermenters and, as such, allows maintaining a temperature from 28 °C to 32 °C, preferably 30°C.
- the vapors produced by evaporation of the water are absorbed by the lithium bromide which is thus diluted.
- the lithium bromide solution exchanges heat, above 75°C, with one of the hot sources which can be vinasse, condensates, vegetal vapor, alcoholic vapors and exhaust steam.
- the water vapor is sent to an indirect condensation device, in which the condensing fluid is the deyeasted wine effluent from the fermentation.
- the wine is heated and conducted to distillation, completing the refrigeration cycle by adsorption.
- the other operations are identical to the ones described for the other preferred form of the invention.
- the auxiliary indirect thermal exchange devices, used in the other form of the invention are eliminated, leading to a more cost- effective fermentation system.
- the process object of the present invention differs from the conventional process by the aspects described below.
- the must is prepared from molasse, water and clarified juice and, in the case of an autonomous distillery, the must is prepared from pre-evaporated sugar cane juice.
- the must temperature lies in the range from 70°C to 100°C. This must is then cooled using water from the cooling tower, or from the spray system, to be then conveyed to the fermentation process.
- the alcoholic fermentation it is necessary to remove the energy released in the form of heat, in the proportion of about 150 kcal/kg TRS (equation 1) , so as to maintain stable the fermentation temperature.
- the must cooling and the fermentation temperature control are carried out by using raw water/treated water from the mill circuit, which can be an open our closed system.
- the cooling of the water is made through the evaporative system, using equipment such as cooling towers or ambient air spray systems.
- the evaporative cooling process comprises, basically, two mechanisms. A first mechanism, in which the heat transfer results from the vaporization of a small water portion, and a second one, in which the sensible heat transfer is caused by the difference of temperatures between the water and the air.
- the heat to be removed from the water, in the cooling tower depends on the air temperature and humidity content. An indication of the air humidity content is its wet -bulb temperature.
- Wet-bulb temperature is the dynamic equilibrium temperature reached by a water surface when the heat transfer rate to the surface, by convection, becomes equal to the heat consumption by mass transfer from the surface to the ambient. That is, the wet-bulb temperature depends on the air temperature and humidity.
- the wet-bulb temperature will determine the minimum possible temperature in the evaporative cooling.
- the evaporative cooling devices are designed to provide an approximation around 5°C. Hence, for example, a region with a wet-bulb temperature of about 24°C, at a certain season of the year, will provide a minimum temperature for the cooled water around 29°C. This will represent, therefore, the lowest temperature existing in the sugar and ethanol manufacturing process.
- the cooling processes in the sugar and alcohol industry are limited to the climatic conditions and, accordingly, suffer a natural variation.
- the registered fermentation temperatures . lie in the range from 32°C to 36°C.
- the yeast can adopt distinct metabolic routes for the production of different compounds.
- the glucose can be converted to ethanol, acetic acid, lactic acid and carbonic gas, which reduces the ethanol produced by TRS unit.
- one of the most important factors listed in the preferential yeast reaction is the temperature.
- temperatures below 32 °C as being optimum values for the maximum conversion to ethanol .
- the water which is sent to the condensers is the water flowing after passing through the indirect thermal exchange devices of the fermenters, that is, water already at a temperature above 29°C.
- the water which will be sent to the condensers presents a temperature of about 32°C-35°C coming from the evaporative cooling system;
- the present process has the object of allowing effecting the biochemical fermentation from sugars to ethanol, at low temperature and with high sugar concentrations, resulting in low production of carboxylic acids and glycerol and in high conversion rates from TRS to ethanol, so as to obtain ethanol contents, in the end fermented must, superior to about 10-11°GL.
- the present process is carried out in several steps, starting with the preparation of a must for feeding the fermentation with high sugar content, containing from 16% to 30% of TRS, preferably above 22% of TRS, posterior cooling, fermentation, etc.
- the must is prepared from mixed juice, or clarified juice, or pre- evaporated juice until about from 22% to 30% of dry matter, or syrups and molasse effluent from the process for manufacturing sugar from sugar cane and/or its mixtures, so as to obtain a TRS from 18% to 35%.
- the process claimed in the two preferred forms differs from the conventional process, regarding a combined mill, in that the must is prepared from molasse, water and clarified juice and, in the case of an autonomous distillery, in that the must is prepared from pre- evaporated sugar cane juice.
- the must was prepared from clarified juice and molasse (residual syrup from a three-mass cooking system) . After the preparation, the must presented the following characteristics: pH of 5.5; 0.30% of impurities; 52.90% of Brix; 54.26% of TRS; 82.37% of purity and 2.5g of acidity/ml.
- molasse residual syrup from a three-mass cooking system
- yeast cream and water was added in such a proportion as to obtain a yeast cell concentration of about 30%.
- the yeast cream received the addition of sulfuric acid until reaching a pH of 2.1.
- the volume of 23m 3 of yeast cream contained in the starter was pumped to the fermenter of 100m 3 (volumetric percentage of yeast of about 7%) , at an average flow rate of 45m 3 /h. Subsequently, it was initiated the feeding of the must, maintained at the temperature of 36°C in a controlled flow rate, for maintaining the fermentation medium with a concentration of 11% Brix.
- the must feeding average temperature was maintained at about 36°C and the fermentation temperature at 29°C.
- the control of the fermentation temperature was carried out by means of a control loop actuating in the cold water circuit, maintained at 20°C, exchanging heat in the indirect form (plate heat-exchanger) .
- the volume of the fermented must in circulation was of about 85m 3 /h.
- the wine resulting from the process presented an alcoholic content of 15.90 v/v of ethanol ; 10.96% of cells; 4.22 g of acidity/mL; pH of 4.8; 0.390% of glycerol; less than 1.0% of TRS and 73.37% of cell feasibility .
- the must was prepared from liquor and water, as typically occurs in an autonomous ethanol plant. After the preparation, the must presented the following characteristics: pH of 6.01; 0.20% of impurities; 31.60% Brix; 33.18% of TRS ; 92.53% of purity and 0.72g of acidity/mL.
- pH of 6.01 pH of 6.01
- 0.20% of impurities 31.60% Brix
- 33.18% of TRS 92.53% of purity and 0.72g of acidity/mL.
- yeast cream and water were added in such a proportion as to obtain a yeast cell concentration of about 30%.
- the yeast cream received an addition of sulfuric acid until reaching a pH of 2.1.
- the volume of 26m 3 of yeast cream contained in the starter was pumped to the fermenter of 100m 3 , at an average flow rate of 45m 3 /h. Subsequently, it was initiated the feeding of the must, maintained at 29°C, in a controlled flow rate so as to maintain the fermentation medium with a concentration of 11% Brix.
- the must feeding average temperature was maintained at about 29°C and the fermentation temperature at 30°C.
- the control of the fermentation temperature was carried out by means of a control loop actuating in the cold water circuit, maintained at the temperature of 20°C, exchanging heat in the indirect form (plate heat-exchanger.) .
- the volume of the fermented must in circulation was of about 85m 3 /h.
- the wine resulting from the process presented an alcoholic content of 14.40 v/v of ethanol; 11.33% of cells; 2.41g of acidity/mL; pH of 4.5; 0.620% of glycerol; less than 0.169% of TRS and 73.37% of cell feasibility.
- the must was prepared from liquor and water, as typically occurs in an autonomous ethanol plant .
- the must presented the following characteristics: pH of 5.65; 0.10% of impurities; 35.90% Brix; 39.07% of TRS ; 94.17% of purity and 1.37g of acidity/mL.
- a previously cleaned vessel with hot mass phlegm, vapor and heated water it was added yeast cream and water in such a proportion as to obtain a yeast cell concentration of about 28%.
- the yeast cream received an addition of sulfuric acid until reaching a pH of 2.0.
- the volume of 27m 3 of yeast cream contained in the starter was pumped to the fermenter of 100m 3 , at an average flow rate of 45m 3 /h. Subsequently, it started the feeding with must, maintained at the temperature of 31°C, in a controlled flow rate, with the purpose of maintaining the fermentation medium with a concentration of 11% Brix.
- the must feeding average temperature was maintained at about 31°C and the fermentation temperature at 30°C.
- the control of the fermentation temperature was carried out by means of a control loop actuating in the cold water circuit, maintained at 20°C, exchanging heat in the indirect form (plate heat-exchanger) .
- the volume of the fermented must in circulation was of about 85m 3 /h.
- the wine resulting from the process presented an alcoholic content of 14.84 v/v of ethanol; 13.3% of cells; 1.72g of acidity/mL; pH of 4.5; 0.720% of glycerol; less than 0.085% of TRS and 90% of ' cell feasibility.
- the must was prepared from liquor and water, as typically occurs in an autonomous ethanol plant. After the preparation, the must presented the following characteristics: pH of 5.53; 0.80% of impurities; 33.0% Brix; 36.32% of TRS ; 96.41% of purity and 0.59g of acidity/mL.
- pH of 5.53 0.80% of impurities; 33.0% Brix; 36.32% of TRS ; 96.41% of purity and 0.59g of acidity/mL.
- yeast cream and water in such a proportion as to obtain a yeast cell concentration of about 28%.
- the yeast cream received an addition of sulfuric acid until reaching a pH of 1.90.
- the volume of 22.4m 3 of yeast cream contained in the starter was pumped to the fermenter of 100m 3 , at an average flow rate of 45m 3 /h. Subsequently, it started the feeding with must, maintained at the temperature of 26°C, in a controlled flow rate, with the purpose of maintaining the fermentation medium with a concentration of 11% Brix.
- the must feeding average temperature was maintained at about 26°C and the fermentation temperature at 30°C.
- the control of the fermentation temperature was carried out by means of a control loop actuating in the cold water circuit, maintained at the temperature of 20°C, exchanging heat in the indirect form (plate heat- exchanger) .
- the volume of fermented must in circulation was of about 85m 3 /h.
- the wine resulting from the process presented an alcoholic content of 16.78 v/v of ethanol; 16.67% of cells; 2.13g of acidity/mL; pH of 4.3; 0.49% of glycerol; less than 0.216% of TRS and 88.5% of cell feasibility.
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PCT/BR2011/000038 WO2012103609A1 (en) | 2011-01-31 | 2011-01-31 | Process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content |
AU2011357643A AU2011357643A1 (en) | 2011-01-31 | 2011-01-31 | Process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content |
MX2013005496A MX2013005496A (en) | 2011-01-31 | 2011-01-31 | Process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content. |
ZA2013/03503A ZA201303503B (en) | 2011-01-31 | 2013-05-14 | Process for producing ethanol from the fermentation of sugar sources in a fermentation medium with high ethanol content |
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CN113502234A (en) * | 2021-05-28 | 2021-10-15 | 劲牌有限公司 | Saccharomyces cerevisiae Y12 and application thereof in brewing of pure wheat whisky wine base |
CN114423504A (en) * | 2019-07-12 | 2022-04-29 | 巴克曼实验室国际公司 | System and method for optimizing fermentation process |
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CN103266139A (en) * | 2013-04-11 | 2013-08-28 | 清华大学 | Production method of solid alcohol fermentation |
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US4487785A (en) * | 1981-10-30 | 1984-12-11 | Epchtein Jacques S | Continuous process for the fermentation of must to produce wine or ethanol |
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2011
- 2011-01-31 MX MX2013005496A patent/MX2013005496A/en not_active Application Discontinuation
- 2011-01-31 WO PCT/BR2011/000038 patent/WO2012103609A1/en active Application Filing
- 2011-01-31 AU AU2011357643A patent/AU2011357643A1/en not_active Abandoned
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2013
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US4487785A (en) * | 1981-10-30 | 1984-12-11 | Epchtein Jacques S | Continuous process for the fermentation of must to produce wine or ethanol |
Non-Patent Citations (10)
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BOSCARIOL, F.C.: "Alcoholic fermentation with temperature controlled by ecological absortion chiller - Ecochill", XXVII ISSCT CONGRESS, VERACRUZ, MEXICO. MARCH 7-11, 2010, March 2010 (2010-03-01), pages 1 - 20, XP002659836, Retrieved from the Internet <URL:http://www.dedini.com.br/web/index.php?option=com_docman&task=doc_view&gid=15&Itemid=40&lang=pt> [retrieved on 20110921] * |
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DIAS ET AL.: "M.O.S.Dias, R.Maciel Filho and C.E.V Rossel, Efficient cooling of fermentation vats in ethanol production", PROC. INT. SOC. CANE TECHNOL., vol. 26, 2007 |
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Cited By (2)
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CN114423504A (en) * | 2019-07-12 | 2022-04-29 | 巴克曼实验室国际公司 | System and method for optimizing fermentation process |
CN113502234A (en) * | 2021-05-28 | 2021-10-15 | 劲牌有限公司 | Saccharomyces cerevisiae Y12 and application thereof in brewing of pure wheat whisky wine base |
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MX2013005496A (en) | 2013-12-12 |
AU2011357643A1 (en) | 2013-06-06 |
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