WO2020114566A1 - The economical method to convert biomass to sugars by concentrated acid hydrolysis process - Google Patents
The economical method to convert biomass to sugars by concentrated acid hydrolysis process Download PDFInfo
- Publication number
- WO2020114566A1 WO2020114566A1 PCT/EG2018/000031 EG2018000031W WO2020114566A1 WO 2020114566 A1 WO2020114566 A1 WO 2020114566A1 EG 2018000031 W EG2018000031 W EG 2018000031W WO 2020114566 A1 WO2020114566 A1 WO 2020114566A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sugars
- acid
- sulfuric acid
- hydrolysate
- evaporating
- Prior art date
Links
Classifications
-
- 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
- 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
-
- 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
Definitions
- Biochemistry using the agricultural wastes to produce sugars.
- the lignocellulosic biomass comprises of cellulose, hemicellulose and lignin.
- Cellulose consists of long chains of beta glucosidic residues linked through the 1,4 positions. These linkages cause the cellulose to have a high crystallinity and thus a low accessibility to enzymes
- Hemicellulose is an amorphous hetero-polymer which is easily hydrolyzed.
- Lignin an aromatic three-dimensional polymer, is interspersed among the cellulose and hemicellulose within the plant fiber cell.
- the concentrated sulfuric acid hydrolysis method has advantages of low reaction temperature, high yield, little by-product, etc., and a shortcoming of high acid recovery cost.
- the method involves mixing the biomass with a solution of between 25% and 90% acid, and more preferably, between 70% and 77%, to effect decrystallization of the cellulose and hemicellulose.
- the acid solution is added to achieve a ratio of pure acid to cellulosic and hemicellulosic material of at least 1 :1. More preferably, the ratio achieved is 1.25 : 1.
- the second step is diluting the acid to a concentration of between 20% and 30%, and heating the mixture.
- the mixture is heated to a temperature of between 80°-100° C. for between 40 and 480 minutes, and the hydrolysis is performed at atmospheric pressure.
- the hydrolysate is then separated from the solid materials, preferably through the pressing of the hydrolyzed biomass.
- the liquid hydrolysate which contains sugars and acid is collected for further processing.
- the concentrated acid hydrolysis process of cellulose includes two stages: ⁇ circle around (1) ⁇ one is main hydrolysis process of hydrolyzing the cellulose into carbohydrates (namely oligosaccharides) in
- the cation exchange resin because of the low adsorption capacity (2 meq/g) of the cation exchange resin, it is usually applicable to absorb and separate a minute amount impurities from a large amount production, or absorb and purity a small amount expensive production, for example the purification of amino acid or enzyme. While the sugars to be separated from the
- the sulfuric acid by extraction comprising: mixing cellulose-containing materials with 70 ⁇ 72% sulfuricacid by weight for 10 min at 50° C.;
- the hydrolysate obtained from the post hydrolysis process contains 55% sulfuric acid, 40.5% water and 4.5% sugar, so the radio of the sulfuric acid to the sugar equates to 12.2.
- the extract phase from the first extraction contains 79.4% heptanol, 14.5% sulfuric acid, 5.3% water and a minute amount of sugar, so the radio of the heptanol to
- the sulfuric acid equates 5.5.
- the problems in this method are 1-low yield of sugars 2-the process will not complete to get the maximum benefit 3-the final product will be carbohydrates ( oligosaccharides) not glucose 4-it is very difficult and needs high energy in the pressing process for commercial scale because in the main hydrolysate the ratio of liquid to solid is very low so it is very difficult to extract the liquid from agricultural wastes because the agricultural wastes have high affinity to absorb water 5-the pressing machine will handle with 60-70% sulfuric acid solution means high capital cost 6-the amount of sulfuric acid left in lignin will be high 7-in the first example in the patent they obtained a byproduct of bio-ethylene and biodiesel ethyl levulinate which consume ethanol that affect in the process to be continuos so that the process in the commercial scale will be difficult and not economical.
- An objective of the present invention is to provide a method to obtain high yield of sugars from lignocellulosic material and rcover the maximum amount of sulfuric acid and the used chemicals
- sugars being precipitated by controlling the amount of water the less the amount of water the higher die efficiency of the process and high amount of sugars will be precipitated.
- sugars may be burned by heat and acid so the evaporation process will stop when the colour starts to go black .
- spary and vacuum distillation in the evaporation of water especially the hydrolysate in the end of the process will be at 100 °C.
- composition of the hydrolysate before and after the evaporation process is the composition of the hydrolysate before and after the evaporation process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Emergency Medicine (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Saccharide Compounds (AREA)
Abstract
A method for recovering sulfuric acid and obtaining high yield of sugars from the hydrolysate in the concentrated acid hydrolysis process by evaporating the optimum amount of water from hydrolysate to enable the sugars to precipitate when we use precipitant that decreases the solubility of sugars, the concentrated acid hydrolysis uses 70 % acid concentration then diluted to 25% or 30% so at the end of the process the high amount of water prevent sugars from precipitation.The solution is evaporating critical amount of water before the sugars being burned by heat and acid, then adding precipitant like ethanol so that sugars are precipitated and separated from the solution, the precipitant is separated from acid by evaporation and condensation then reuse them.
Description
The economical method to convert biomass to sugars by concentrated acid hydrolysis process
Technical field
Biochemistry, using the agricultural wastes to produce sugars.
BACKGROUND OF THE INVENTION
the lignocellulosic biomass comprises of cellulose, hemicellulose and lignin. Cellulose consists of long chains of beta glucosidic residues linked through the 1,4 positions. These linkages cause the cellulose to have a high crystallinity and thus a low accessibility to enzymes
or acid catalysts. Hemicellulose is an amorphous hetero-polymer which is easily hydrolyzed. Lignin, an aromatic three-dimensional polymer, is interspersed among the cellulose and hemicellulose within the plant fiber cell.
There are two types of processes to hydrolyze the feed stocks which contains cellulose and hemicellulose into monomeric sugar. The hydrolysis methods most commonly used are acid (dilute and
concentrated) and enzymatic.
The concentrated sulfuric acid hydrolysis method has advantages of low reaction temperature, high yield, little by-product, etc., and a shortcoming of high acid recovery cost.
the process described in U.S. Pat. No. 5,562,777 The
concentrated sulfuric acid hydrolysis method for producing sugars from materials containing cellulose and hemicellulose. The method involves mixing the biomass with a solution of between 25% and 90% acid, and more preferably, between 70% and 77%, to effect decrystallization of the cellulose and hemicellulose. In a preferred embodiment, the acid solution is added to achieve a ratio of pure acid to cellulosic and hemicellulosic material of at least 1 :1. More preferably, the ratio achieved is 1.25 : 1. The second step is diluting the acid to a concentration of between 20% and 30%, and heating the mixture. Preferably, the mixture is heated to a
temperature of between 80°-100° C. for between 40 and 480 minutes, and the hydrolysis is performed at atmospheric pressure. The hydrolysate is then separated from the solid materials, preferably through the pressing of the hydrolyzed biomass. The liquid hydrolysate which contains sugars and acid is collected for further processing.
The concentrated acid hydrolysis process of cellulose includes two stages: {circle around (1)} one is main hydrolysis process of hydrolyzing the cellulose into carbohydrates (namely oligosaccharides) in
concentrated acid to obtain main hydrolysate; {circle around (2)} the other is post hydrolysis process of hydrolyzing the carbohydrates into glucose in dilute acid to obtain post hydrolysate described in U.S. Pat.
No. 8,052,953.
The commonly used method of recovering sulfuric acid from the concentrated acid hydrolysate of plant cellulose material is electrodialysis method. However, this method is capital intensive and high in running cost. Then, new methods of recovering acid have been gradually developed . such as the process described in U.S. Pat. No. 5,562,777 , using strong acid cation exchange resins to adsorb sugars in the liquid portion and recover the acid, thereby obtaining 15% sugar by weight and 15% sulfuric acid by weight, finally evaporating water from the recovered dilute sulfuric acid to concentrate the sulfuric acid to a concentration of 70~77% by weight for reuse. However, because of the low adsorption capacity (2 meq/g) of the cation exchange resin, it is usually applicable to absorb and separate a minute amount impurities from a large amount production, or absorb and purity a small amount expensive production, for example the purification of amino acid or enzyme. While the sugars to be separated from the
biomass hydrolysate are a large amount, easily reaching to tens of thousands ton to millions tons per year, therefore the cation exchange resin is incompetent obviously what's more, the absorptive and elution process of the cation exchange resin is very slow. To attain such yield, it is undoubtedly need a large amount of cation exchange resin, and the complex composition in the biomass hydrolysate easily makes the cation exchange resin poisoned and invalid. Thus the process in fact is not practical as described in U.S. Pat. No. 8,052,953.
U.S. Pat. No. 4,608,245 discloses a method of recovering
the sulfuric acid by extraction comprising: mixing cellulose-containing materials with 70~72% sulfuricacid by weight for 10 min at 50° C.;
keeping the radio of sulfuric acid to cellulose greater than 7.2; adding water to dilute the acid to a concentration of 40~50% by weight; keeping temperature at 90° C. for 2 min; separating the liquid portion from the solid portion to obtain lignin and hydrolysate; extracting the
cooled hydrolysatefor the first time with C4~C7 alcohols, such as heptanol, as the first extraction solvent to obtain a glucose-rich raffinate phase and an extract phase rich in the acid and the first extraction solvent; extracting the extract phase rich in the acidand the first extractant for the second time with a second extraction solvent, such as benzene, carbon tetrachloride or toluene, to obtain a raffinate phase containing water and sulfuric acid and an extract phase containing the first and the second extraction solvents; separating the first and the second extraction solvents by distillation with result that the recovered sulfuric acid, the first and the second extraction solvents are reusable; and finally neutralizing the small amount of residual sulfuric acid still contained in the glucose-rich phase with lime and then filtrating to obtain the glucose-rich phase without the sulfuric acid. According to the preferred embodiment of this invention, the hydrolysate obtained from the post hydrolysis process contains 55% sulfuric acid, 40.5% water and 4.5% sugar, so the radio of the sulfuric acid to the sugar equates to 12.2. The extract phase from the first extraction contains 79.4% heptanol, 14.5% sulfuric acid, 5.3% water and a minute amount of sugar, so the radio of the heptanol to
the sulfuric acid equates 5.5. In the second extraction, the radio of benzene to heptanol equates 5. If 1 kg glucose needs to be extracted, the amount of benzene to be distilled is: 12.2x5.5x5=335.5 kg, and the burning energy is: 335.5 kgx434 kJ/kg=145607 kJ. However the energy produced by oxygeno lysis of the 1 kg glucose is only 15945 kJ, which is far less than the burning energy for distillation the benzene. Obviously it is a process in which the output energy is far less than the input energy, therefore has no practical value. What's more, this process utilizes organic solvent as the second extraction solvent to separate the alcohol and the acid, so a large amount of the second extraction solvent needs to be recovered which, in turn, lead to high energy consumption described in U.S. Pat. No. 8,052,953.
U.S. Pat. No. 8,052,953 discloses a method of recovering
the sulfuric acid from concentrated acid hydrolysate of plant cellulose material (l)stop the process at the middle before diluting the acid to a concentration of between 20% and 30% and mixing the
concentrated acid main hydrolysate of plant cellulose material with a
liquid organic precipitant which has a property of precipitating sugars, thereby precipitating sugars from the main hydrolysate;(2) conducting solid-liquid separation, thereby obtaining a sugar precipitate and an organic precipitant solution containing sulfuric acid;(3) separating the organic precipitant solution into a sulfuric acid solution and the liquid organic precipitant. the problems in this method are 1-low yield of sugars 2-the process will not complete to get the maximum benefit 3-the final product will be carbohydrates ( oligosaccharides) not glucose 4-it is very difficult and needs high energy in the pressing process for commercial scale because in the main hydrolysate the ratio of liquid to solid is very low so it is very difficult to extract the liquid from agricultural wastes because the agricultural wastes have high affinity to absorb water 5-the pressing machine will handle with 60-70% sulfuric acid solution means high capital cost 6-the amount of sulfuric acid left in lignin will be high 7-in the first example in the patent they obtained a byproduct of bio-ethylene and biodiesel ethyl levulinate which consume ethanol that affect in the process to be continuos so that the process in the commercial scale will be difficult and not economical.
DISCLOSURE OF INVENTION
An objective of the present invention is to provide a method to obtain high yield of sugars from lignocellulosic material and rcover the maximum amount of sulfuric acid and the used chemicals
1- finishing the The concentrated acid hydrolysis process the whole process and get the hydrolysate 2-evaporating the optimum amount of water before sugars being burned by heat and acid 3-adding ethanol to decrease the solubility of sugars to precipitate 4-separating sugars from solution 5 -evaporating the ethanol from sulfuric acid and from separated sugars after adding some water 6-reuse them and repeat the process to be continuos.
In this invention sugars being precipitated by controlling the amount of water the less the amount of water the higher die efficiency of the process and high amount of sugars will be precipitated. during evaporating water from hydrolysate which has a dark yellow colour the sugars may be burned by heat and acid so the evaporation process will stop when the colour starts to go black .
And we can use spary and vacuum distillation in the evaporation of water especially the hydrolysate in the end of the process will be at 100 °C.
The experimental work
Weighting 200 g of rice straw and prepared 70% concentrated sulfuric acid solution mixing 70% sulfuric acid solution with rice straw the ratio of pure acid to rice straw is 1 : 1 for 20 minutes with stiring. adding water to dilute the acid to a concentration of 25 % by weight and heating at 100 °C for one hour after finishing the process separating hydrolysate from solid by pressing . weighting 51.3 g of hydrolysate with dark yellow colour and heating to evaporate water . evaporation process continues till the colour starts to go black this point will be the end of the evaporation process. Amount of water evaporated before the colour going black equals .35-.4 from the mass of hydrolysate and it will change if we diluted the acid to another concentration . after the evaporation process adding 70 g of ethanol about 6 times the amount of water in the remained hydrolysate .after 30 minutes the sugars will be precipated then separating sugars from solution for the solution, evaporating ethanol from sulfuric acid for the sugars , adding small amount of water and heating to rcover the remained ethanol and neutralizing the acid by lime. Finally 70% of acid is recovered at concentration of 50% easy to reuse again in the process, 99%of ethanol is recovered to reuse, the yield of sugars is 80% of the theoretical yield with high concentration so that the process will be economical and applicable in the commercial scale.
The composition of the hydrolysate before and after the evaporation process
The advantages of the invention
1- completing the process of the concentrated acid hydrolysis to the end as described in U.S. Pat. No. 5,562,777 to get the maximum benefit.
2- high yield of sugars 80% of the theoretical yield.
3- recovery 70% of the used sulfuric acid.
4- recovery of 99% of the used ethanol.
5- easy to separate liquid from solid because the pressing process will be after dilution so less energy will be required.
6- the pressing machine will handle with 20-25% sulfuric acid solution the corrosion will decrease.
7- the final product of sugars will be glucose and xylose easy to use not oligosaccharides.
8- the concentration of the recovered sulfuric acid will be 50% easy to reuse because the process starts with 70% sulfuric acid.
9- there is no byproducts.
10- the process will be economical and applicable in the commercial scale.
The applications of the invention
Sugars will be used in the food industries. REFERENCES
Claims
Claims
An economical method to produce sugars from agricultural wastes by concentrated acid hydrolysis process with recovering of the used chemicals and get high yield of sugars, said method comprises the following steps:
1- finishing the The concentrated acid hydrolysis process the whole process and get the hydrolysate
2- evaporating the optimum amount of water before sugars being
burned by heat and acid to enable the sugars to precipitate when we use precipitant that decreases the solubility of sugars.
3- adding ethanol to decrease the solubility of sugars to precipitate
4- separating sugars from solution
5- evaporating the ethanol from sulfuric acid and from separated
sugars after adding some water
6- reuse them and repeat the process to be continuos.
The second claim:the method according to claim 1 , wherein
evaporating the optimum amount of water before sugars being burned by heat and acid to enable the sugars to precipitate when we use precipitant that decreases the solubility of sugars has these advantages
1-high yield of sugars 80% of the theoretical yield.
2-recovery 70% of the used sulfuric acid.
3-recovery of 99% of the used ethanol.
4-easy to separate liquid from solid because the pressing process will be after dilution so less energy will be required.
5-the pressing machine will handle with 20-25% sulfuric acid solution the corrosion will decrease.
6-the final product of sugars will be glucose and xylose easy to use not oligosaccharides.
7-the concentration of the recovered sulfuric acid will be 50% easy to reuse because the process starts with 70% sulfuric acid.
8 -there is no byproducts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EG2018/000031 WO2020114566A1 (en) | 2018-12-02 | 2018-12-02 | The economical method to convert biomass to sugars by concentrated acid hydrolysis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EG2018/000031 WO2020114566A1 (en) | 2018-12-02 | 2018-12-02 | The economical method to convert biomass to sugars by concentrated acid hydrolysis process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020114566A1 true WO2020114566A1 (en) | 2020-06-11 |
Family
ID=70974910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EG2018/000031 WO2020114566A1 (en) | 2018-12-02 | 2018-12-02 | The economical method to convert biomass to sugars by concentrated acid hydrolysis process |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2020114566A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188673A (en) * | 1987-05-15 | 1993-02-23 | Clausen Edgar C | Concentrated sulfuric acid process for converting lignocellulosic materials to sugars |
| US20140170721A1 (en) * | 2012-12-14 | 2014-06-19 | Purevision Technology, Llc | Methods for producing sugars from biomass |
| EP2635712B1 (en) * | 2010-11-05 | 2014-07-02 | Shell Oil Company | Treating biomass to produce materials useful for biofuels |
-
2018
- 2018-12-02 WO PCT/EG2018/000031 patent/WO2020114566A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188673A (en) * | 1987-05-15 | 1993-02-23 | Clausen Edgar C | Concentrated sulfuric acid process for converting lignocellulosic materials to sugars |
| EP2635712B1 (en) * | 2010-11-05 | 2014-07-02 | Shell Oil Company | Treating biomass to produce materials useful for biofuels |
| US20140170721A1 (en) * | 2012-12-14 | 2014-06-19 | Purevision Technology, Llc | Methods for producing sugars from biomass |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8052953B2 (en) | Method for recovering sulfuric acid from concentrated acid hydrolysate of plant cellulose material | |
| US7670813B2 (en) | Inorganic salt recovery during processing of lignocellulosic feedstocks | |
| US7585652B2 (en) | Recovery of inorganic salt during processing of lignocellulosic feedstocks | |
| US8247200B2 (en) | Method of obtaining inorganic salt and acetate salt from cellulosic biomass | |
| JP5520822B2 (en) | Biomass component separation process | |
| US20140106426A1 (en) | Separation of lignin from hydrolyzate | |
| US20150259709A1 (en) | Processes for producing fluff pulp and ethanol from sugarcane | |
| HUT72177A (en) | Method of producing sugars using stong acid hydrolysis of cellulosic and hemicellulosic materials | |
| CN100577674C (en) | Method for producing high-purity crystallized xylose by hydrolyzing corn skin | |
| EP2118294A1 (en) | Method of producing xylitol using hydrolysate containing xylose and arabinose prepared from byproduct of tropical fruit biomass | |
| CN102690899A (en) | Method for hydrolyzing lignocellulose raw material by concentrated phosphoric acid and recovering phosphoric acid | |
| EP2173941A1 (en) | A single step process for separating biomass components | |
| WO2016086078A1 (en) | Processes for producing lignin-based enzymatic hydrolysis enhancers, and compositions produced therefrom | |
| CN101628922B (en) | Oligosaccharide ferulic acid ester preparation method | |
| WO2013071180A1 (en) | Lignocellulose processing methods and related products | |
| CA2565433A1 (en) | Inorganic salt recovery during processing of lignocellulosic feedstocks | |
| WO2020114566A1 (en) | The economical method to convert biomass to sugars by concentrated acid hydrolysis process | |
| EP2294229A1 (en) | Method for glycosylating and separating plant fiber material | |
| US20220325365A1 (en) | Process for treating lignocellulosic biomass | |
| JP6951048B2 (en) | Methods for Isolating Fermentable Sugars from Acid Hydrolysates of Substances Containing Cellulose, Hemicellulose and Lignin | |
| CN100577675C (en) | Process for producing crystallized xylose by hydrolyzing corn skin | |
| CN103074454B (en) | Method for preparing D-xylose and L-arabinose by recycling phosphoric acid | |
| AU2017201901B2 (en) | Method of producing saccharified solution from biomass | |
| CN116804089A (en) | Method for extracting lignin by using inorganic acid to strengthen maleic acid | |
| AU2006233172A1 (en) | Inorganic salt recovery during processing of lignocellulosic feedstocks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18942189 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 22/09/2021) |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 18942189 Country of ref document: EP Kind code of ref document: A1 |