TR201808167T1 - PREPARATION OF ETHANOL FROM BIOMASS AND SUGAR CANE BASED RAW MATERIALS - Google Patents

Abstract

The invention relates generally to the preparation of ethanol from biomass using yeast fermenting pentose and hexose. In particular, it relates to the use of lignocellulosic biomass such as corn, corn cob, corn stalk, sugar cane pulp or agricultural waste biomass used as partial reinforcement in the conventional ethanol fermentation system to achieve simultaneous conversion of pentose and hexose sugars to ethanol.

Description

DESCRIPTION ETHANOL FROM BIOMASS AND SUGAR CANE-BASED RAW MATERIALS PREPARATION OF TECHNICAL FIELD Biomass in general using yeast that ferments pentose and hexose and the preparation of ethanol from molasses. More specifically, corncob, Efficiency of corn straw, cane pulp or pentose and hexose sugars to ethanol which uses molasses molasses to achieve its timely high-efficiency transformation. agricultural products used as partial supplements in the traditional ethanol fermentation system It is associated with the use of lignocellulosic biomass, such as waste biomass. PRIOR ART The future availability of fossil fuels, especially crude oil Because of their restrictions, many national governments use ethanol in motor vehicles. encourages the use of alternative fuels. Ethanol is widely used in Brazil. It is a used vehicle fuel and is widely used in other countries such as the USA and Europe. while using; It has been significantly promoted in India over the last few years. However, The preparation of the fuel ethanol is mostly used in the form of millet, sugarcane or sugar beet. made from food products, on the non-food use of these nutrients causes great social and economic problems. Therefore, governments to meet the growing demand for renewable energy sources. non-food materials such as lignocellulosic materials for the production of scale fuel ethanol encourages the use of raw materials.

In India, ethanol production is mainly based on sugarcane as raw material. is carried out. For continuous ethanol production, cane sugar (or sugar stable supply of cane juice) as raw material is required. However, most of the time The demand for sugarcane varies depending on the market situation. it's all year The absence of sufficient molasses molasses for the operation of ethanol plants throughout causes. Therefore, an alternative raw material such as LSM (Ignocellulosic material) if used with molasses [without a large additional capital outlay], can provide sufficient raw material for the operation of conventional ethanol plants. This invention It deals with this deficiency in the industry.

Lignocellulosic materials such as molasses molasses [LSM] are ethanol from the agricultural industry. are other waste by-products used in production. Often as an energy source it is used inefficiently or fed to animals; but a big part of it is wasted in this way without being used at all. LSM hemicellulose and Iigninin Compared to other carbohydrate-based materials such as starch, depending on the source cellulose, a compound formed by forming a compound that is resistant to hydrolysis from different angles is the structure. LSM; It forms the structural components of plants and is positioned in the host. or has a variable layout depending on the type of host. high in technique temperature, water, acid, alkali and other chemicals used in many chemicals and thermal LSM hydrolysis methods are available. These processes make LSM xylose and glucose for efficient separation into fermentable sugars such as is applied. These sugars can also be used as a fuel additive in fermentation thanks to yeast. It is converted to ethanol, which is used in many applications, including

In the production of ethanol from LSM, a large part of the sugars required for fermentation One of the obstacles is the existence of the part in the form of ignocellulose. LSM to parse hydraulic stability and structural strength to the cell walls of plants has been evolved to provide. These “disobedience” polysaccharides (cellulose and hemicellulose) cross-linking formed by ester and ether bonds between lignin and and these bonds result in a material that is physically hard to reach. takes out. This means that for the efficient use of these components, the LSM in question is reserved, means it must be split and/or decrystallized.

In the recent past, many effective LSM pretreatment or hydrolysis methods have been used in the art. has been mentioned. After pretreated LSM, both sugars for ethanol production Both pentose and It can be used for the fermentation of the hexose contained in it.

The invention described herein consists of pretreated LSM with ethanol pretreated more efficiently than using biomass alone to make ethanol Provides a method for using to produce say that pre-processed The conversion efficiency of pentose and hexose contained in LSM to sucrose and starch does not reach the level of ethanol-based production processes.

An efficient method for molasses fermentation and known for LSM hydrolysis Although there are several methods, high with reduced capital expenditure year-round fermentation, distillation and wastewater treatment to produce valuable chemicals More efficient and economical methods to use existing distillation infrastructures such as need to be found.

DETAILED DESCRIPTION OF THE INVENTION Ethanol pretreated LSM in one embodiment of the disclosed invention It is produced from biomass and molasses molasses. Here is the corn in question such as cob, pulp, stalk or other similar agricultural material. The size of the biomass is reduced to particulate matter. Approximately 40 mm in size This particulate matter is then immersed in water to remove soil or other contaminants. washed to remove materials. Then, immersed in said water high-pressure steam for a period of minutes as a source of energy and water. using a mixture of acids [organic and inorganic]. oxalic acid The acid mixture forming the amount is between 0.1 and 5 percent and the amount of sulfuric acid between 0.1 and 5 percent by weight of said biomass. at the desired time upon carrying out said pre-treatment under the required conditions, repeatedly a hydrolyzed LSM subjected to a neutralization and enzymatic hydrolysis current (first stream) is obtained. Pre-processing on the LSM in question, While secreting xylose from the hemicellulosic part, the crystalline cellulose fibers are relaxed, thus It can be processed with more cellulolytic enzymes. Said hydrolyzed stream is first pH NaOH to increase the value to about 4 to 6 [by creating a neutralized current] or neutralized with an alkali such as MgO and then approximately 10 mg to 100 mg of cellulase. enzyme cocktail is added, and the reaction takes approximately 30 to 120 hours. It is allowed to digest the solid material in question at a temperature of 40°C to 80°C.

Said cellulolytic enzymes are one or more cellulases, a hemicellulase or includes a combination of these. This step is in the created stream (second stream) glucose from cellulose fibers leading to a significant increase in glucose and xylose makes the release. Said second stream is fermented in desired amount by weight. It is mixed with molasses molasses, which contains about 40% to 60% of the available sugars.

Mixing molasses in the second stream is approximately 12% to 12% total by weight. the third stream rich in ethanol, the third stream leading to the formation of ethanol in the final stream Saccharomyces, which ferments both glucose and xylose present in the stream cerevisiae is subjected to fermentation using the recombinant strain. Here Nitrogen source such as urea and diammonium phosphate support the fermentation process is added to the third stream to become

In another embodiment, the cellulase treatment precedes the fermentation of the sugar with the cellulose performed separately. After the separate hydrolysis is complete, molasses molasses is added and concomitant fermentation of xylose and glucose in said stream, simultaneous Saccharomyces sp, which can ferment pentose and hexose sugars carried out using recombinant yeast.

In another embodiment of the invention, a recombinant of Saccharomyces sp. genetics of the xylose metabolism pathway in yeast created by editing. This is xylose isomerization, xylose-1-epimerase, PPP pathway genes or for the conversion of xylose to ethanol with said yeast It also includes the addition of genes related to other necessary genes.

In another embodiment of the invention, molasses-based candies and cellulosic based sugars combined with the same conversion efficiency to produce ethanol fermented. This is about 90% conversion efficiency of hexose sugars and It is 88% less than the conversion efficiency of pentose sugars.

In another embodiment of the invention, the efficiency of enzymatic hydrolysis of cellulose is is at least 60% of the theoretical efficiency of the reaction.

In another embodiment of the invention, the conversion of hexose sugars to ethanol The efficiency is at least 80% of the theoretical efficiency of the reaction.

In another embodiment of the invention, the conversion of pentose sugars to ethanol The efficiency is at least 65% of the theoretical efficiency of the reaction.

In yet another embodiment of the invention, the total amount leading to the formation of ethanol up to 80% of fermentable sugars can consist of molasses molasses.

The examples given below may be considered appropriate by a person skilled in the art. A broader application of the invention without limitation as to the modifications It provides usable area. Preparation of various test results of ethanol advantageous and new aspects of the combination process of molasses molasses and LSM for A non-limiting summary is provided in the illustrative examples.

In the first stage, approximately 35% cellulose by weight, approximately 135 kg of solids containing approximately 90% of total solids by weight. Sugarcane pulp was used as raw material. Your size is granular particles smaller than 40 mm, which can cover approximately 122 kg of material It was subjected to mechanical shearing for reduction. This granular material is approx. minutes under water. Then about 30% of the total by weight Approximately 405 kg of slurry containing solid matter was prepared and continuously inserted into a screw-type hydrolyzer with a plug. Here, the slurry is about 180 It was mixed with a mixture of L'acid catalysts. This mixed acid mixture is dry oxalic acid at a rate of approximately 1% by weight on a biomass weight basis and by weight about 1.5% sulfuric acid [approximately 25% total acid by weight] contained. The resulting reaction mixture is then in said hydrolyzer. at a temperature of approximately 150°C and a pressure of approximately 5 bar for approximately 15 minutes. It was hydrolyzed at a pH of approximately 1.2 throughout the period. At the end of this preprocessing, The final state of the approximately 658 kg slurry was determined by HPLC methods. approximately 18% of the total solids; and approximately 0.4% glucose, about 4.0% xylose, as well as undigested cellulose and Iignin It contained approximately 4000 PPM of phenolic components. In this pretreatment, xylanine The efficiency of the conversion was about 90%. In the second stage, C5 solid This precursor, which is rich in C5 sugars as well as cellulose (mainly cellulose) The treated hydrolyzate is subjected to enzymatic hydrolysis by a cellulase mixture. has been retained. Before enzymatic hydrolysis, MgO is needed to raise its pH to about 5. neutralized with. Then a cocktail of cellulase [about 30 mg/g cellulose] cocktail was added to the pre-treated material and heated at 52°C under desired conditions. These solids were left to digest for 72 hours. This enzymatic hydrolysis is approximately 62% by weight with cellulose hydrolysis efficiency. approximately 3.8% glucose and approximately 3.2% xylose by weight containing approximately 790 kg of hydrolyzate. In the third step, this hydrolyzate by weight generating a stream of 13% of total fermentable sugars approximately 189 kg of sugar containing approximately 45% fermentable sugars cane mixed with molasses molasses. To support the fermentation process for urea and diammonium phosphate (each with a nitrogen source of approximately has been added. The aforementioned sugar-rich stream is approximately 6.4% by weight. heme glucose in the stream leading to ethanol concentration in an end stream as well as a recombinant Saccharomyces cerevis/ae that ferments xylose to ethanol was subjected to fermentation using tension. here for about 72 hours The efficiency of conversion of glucose to ethanol after the fermentation period is theoretical. about 90% of maximum, conversion efficiency of xylose to ethanol about 88% [total yield was about 85%]. Here after 120 hours [72 hours enzyme treatment and 48 hours fermentation] conversion efficiency of bagasse to ethanol was approximately 58% at the end. After fermentation, this stream is distilled. processed and approximately 122 kg of dry sugar cane pulp and by weight 189 kg molasses with a total of approximately 45% fermentable sugars extracted approximately 80 L of ethanol from molasses.

In the first stage, approximately 35% cellulose by weight, approximately 135 kg of solids containing approximately 90% of total solids by weight. Sugarcane pulp was used as raw material. Your size is granular to particles smaller than 40 mm, which can cover approximately 122 kg of material It was subjected to mechanical shearing for reduction. This granular material is approx. minutes under water. Then about 30% of the total by weight Approximately 405 kg of slurry containing solid matter was prepared and continuously inserted into a screw-type hydrolyzer with a plug. Here, the slurry is about 180 It was mixed with a mixture of L'acid catalysts. This mixed acid mixture is dry oxalic acid at a rate of approximately 1% by weight on a biomass weight basis and by weight about 1.5% sulfuric acid [approximately 2.5% total acid by weight] contained. The resulting reaction mixture is then in said hydrolyzer. at a temperature of approximately 150°C and a pressure of approximately 5 bar for approximately 15 minutes. It was hydrolyzed at a pH of approximately 1.2 throughout the period. At the end of this preprocessing, The final state of the approximately 658 kg slurry was determined by HPLC methods. approximately 18% of the total solids; and approximately 0.4% glucose, about 4.0% xylose, as well as undigested cellulose and Iignin It contained approximately 4000 PPM of phenolic components. In this pretreatment, xylanine The efficiency of the conversion was about 90%. In the second stage, C5 solid This precursor, which is rich in C5 sugars as well as cellulose (mainly cellulose) The treated hydrolyzate is subjected to enzymatic hydrolysis by a cellulase mixture. has been retained. Before enzymatic hydrolysis, MgO is needed to raise its pH to about 5. neutralized with. Then a cocktail of cellulase [about 30 mg/g cellulose] cocktail was added to the pre-treated material and heated at 52°C under desired conditions. These solids were left to digest for 72 hours. This enzymatic hydrolysis is approximately 62% by weight with cellulose hydrolysis efficiency. approximately 3.8% glucose and approximately 32% xylose by weight containing approximately 790 kg of hydrolyzate. In the third step, this hydrolyzate by weight generating a stream of 14% of total fermentable sugars approximately 127 kg of sugar containing approximately 71% fermentable sugars mixed with cane syrup. This includes urea to support the fermentation process. and diammonium phosphate (each with added nitrogen source as approx.

The aforementioned sugar-rich stream has a final result of approximately 6.7% by weight. both glucose and ions present in the stream leading to the concentration of ethanol in the stream. a recombinant strain of Saccharomyces cerevisiae that ferments xycyclose to ethanol was subjected to fermentation. here for about 72 hours The efficiency of conversion of glucose to ethanol after the fermentation period is theoretical. about 90% of maximum, conversion efficiency of xylose to ethanol about 88% [total yield was about 85%]. Here after 120 hours [72 hours enzyme treatment and 48 hours fermentation] conversion efficiency of bagasse to ethanol was approximately 58% at the end. After fermentation, this stream is distilled. processed and approximately 122 kg of dry sugar cane pulp and by weight 120 kg of cane sugar containing approximately 71% fermentable sugars in total approximately 80 L of ethanol was extracted from the syrup.

In the first stage, approximately 38% cellulose by weight, approximately 250 kg of solids containing approximately 40% of total solids by weight. The pulp extract was used as raw material. Then, the total by weight is approx. prepared and inserted into a screw type hydrolyzer with a continuous plug. Here, the aqueous mixture was mixed with a mixture of approximately 135 L of acid catalysts. This mixed acid mixture, approximately 1% by weight, based on dry biomass oxalic acid and approximately 1.5% by weight sulfuric acid [total by weight approximately 25% acid]. The resulting reaction mixture is then a temperature of approximately 165 °C and approximately 5 bar in said hydrolyzer. subjected to hydrolysis at approximately pH 1.2 at pressure for a period of approximately 15 minutes has been retained. At the end of this pre-treatment, the final state of the slurry of approximately 530 kg, Approximately 19% of the total solids as determined from HPLC methods; and approximately 05% glucose, approximately 4.1% xylose, and undigested It contained phenolic compounds of about 3500 PPM, as well as cellulose and lignin. This In the pretreatment, the efficiency of conversion of xylan to xylose was approximately 90%. Second In the next step, C5 solids [mainly cellulose] as well as C5 sugar. This pretreated hydrolyzate, which is rich in subjected to hydrolysis. Prior to enzymatic hydrolysis, it should lower its pH to about 5 neutralized with MgO to raise the total solids of said hydrolyzate. water to reduce the material content from about 19% to about 15% by weight has been added. A cocktail of cellulase [approximately 30 mg/g cellulose] is then prepped. It was added to the treated material and under desired conditions at 52°C for 72 hours. These solids were left to digest throughout. This enzymatic hydrolysis with cellulose hydrolysis efficiency of about 68% by weight approx. yielded approximately 635 kg of hydrolyzate. In the third step, this hydrolyzate approx. by weight, generating a stream of 14.2% of fermentable sugars mixed with molasses molasses. This includes urea to support the fermentation process. and diammonium phosphate (each with added nitrogen source as approx.

The aforementioned sugar-rich stream has a final result of approximately 6.2% by weight. both glucose and ions present in the stream leading to the concentration of ethanol in the stream. a recombinant strain of Saccharomyces cerevisiae that ferments xycyclose to ethanol was subjected to fermentation. here for about 72 hours The efficiency of conversion of glucose to ethanol after the fermentation period is theoretical. about 90% of maximum, conversion efficiency of xylose to ethanol about 88% [total yield was about 85%]. Here after 120 hours [72 hours enzyme treatment and 48 hours fermentation] conversion efficiency of bagasse to ethanol was approximately 58% at the end. After fermentation, this stream is distilled. processed and approximately 100 kg of pulp pulp and by weight total approx. It produced L ethanol.

The invention is particularly illustrated by references to the configurations listed in the examples. and, although described, the above-described and other features and desirable functions, or alternatives, as many other different systems or applications. can be combined as indicated. Also, unpredictable and predictable for the moment. Various alternatives that cannot be stated and tried to be explained in the following claims, modifications, variations or improvements are made by persons skilled in the art. can be done. With reference to particular preferred embodiments of the invention Although it is described, it is clear that it is not limited to this, more precisely, in technique unqualified persons regarding the invention within the scope of the invention and claims. Consider also that various variations and modifications can be made. they will keep. The advantages of the disclosed invention are listed below: 1. In this process, it is obtained from molasses molasses and biomass raw materials. Compared to the second generation cellulosic fermentation process, the sugars produced Fermentation with the same efficiency as greatly improved sugar conversion efficiency is being done. 2. This process is generally less expensive than the second generation cellulosic ethanol processing plant 3. The process will also allow the ethanol plants to run for about 160 days per year. Compared to its current seasonal operation, molasses molasses-based It helps distillation units operate for more than 300 days. 4. Capital investments required to implement the process, greenfield cellulosic significantly less compared to the establishment of ethanol plants.

Claims (10)

REQUESTS 1. A process for the preparation of ethanol, comprising: (a) converting a dry biomass to particulate matter; (b) preparing an aqueous mixture of said substance in water; (c) contacting said aqueous mixture with an acid mixture for a desired period of time at a desired temperature by applying xylose to produce a first stream; (d) adjusting the pH of said first stream with a base to obtain a neutralized stream; (e) contacting said neutralized stream with cellulotic enzymes for a desired time at a desired temperature, releasing glucose to produce a second stream; (f) adding the desired amount of molasses molasses or cane syrup to said second stream to produce a third stream; (g) subjecting said third stream to pentose and hexose fermenting yeast to obtain a fermented stream; and (h) separating ethanol from said fermented stream by distillation. 2. The process of claim 1, characterized in that (a) said acid mixture contains oxalic acid and sulfuric acid (b) said amount of oxalic acid is between 0.1 and 5 percent, and said sulfuric acid amount is 0.1 percent by weight of said biomass. between 'i' and '5'; (c) said cellulotic enzymes comprise one or more of a cellulase, a hemicellulase, or a combination thereof; (d) said enzymes are used from 10 mg to 100 mg per gram of cellulose in said neutralized stream; (e) said enzymes are used from 10 mg to 100 mg per gram of cellulose in said neutralized stream; (f) said desired temperature to obtain said first stream is between 140°C and 210°C; (g) said desired time to obtain said first stream is between 5 minutes and 120 minutes; (h) said desired temperature to obtain said second stream is between 40°C and 80°C; (i) said desired time to obtain said second stream is between 20 hours and 120 hours; and (j) adjusting the pH of said first stream to be between 4 and 6. 3. The process of claim 1, characterized in that said first stream contains xylose obtained from thermo-chemical hydrolysis of the hemi-cellulose portion of said biomass. 4. The process of claim 1, characterized in that the efficiency of hydrolysis of hemi-cellulose is at least 80% of the theoretical efficiency. 5. The process of claim 1, characterized in that said second stream contains hexose sugars obtained from the enzymatic hydrolysis of the cellulose portion of said biomass. 6. The process of claim 1, characterized in that the efficiency of enzymatic hydrolysis of cellulose is at least 60% of the theoretical efficiency. 7. The process of claim 1, characterized in that the conversion efficiency of hexose sugars to ethanol is at least 80% of the theoretical efficiency. 8. The process of claim 1, characterized in that the conversion efficiency of pentose sugars to ethanol is at least 65% of the theoretical efficiency. 9. The process of claim 1, characterized in that said third stream contains hexose sugars provided by molasses molasses up to 80% of the total fermentable sugars. 10. The process of claim 1, characterized in that said pentose and hexose fermenting yeast is a recombinant of Saccharomyces sp.