EP2712936A1 - Sugar products and fabrication method thereof - Google Patents
Sugar products and fabrication method thereof Download PDFInfo
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- EP2712936A1 EP2712936A1 EP20130186469 EP13186469A EP2712936A1 EP 2712936 A1 EP2712936 A1 EP 2712936A1 EP 20130186469 EP20130186469 EP 20130186469 EP 13186469 A EP13186469 A EP 13186469A EP 2712936 A1 EP2712936 A1 EP 2712936A1
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- chloride
- mixing solution
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- sugar product
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- 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
Definitions
- the technical field relates to a sugar product and fabricating method thereof.
- the world is facing problems such as the gradual extraction and depletion of petroleum reserves, and changes to the earth's atmosphere due to the greenhouse effect. In order to ensure the sustainability of human life, it has become a world trend to gradually decrease the use of petrochemical energy and petroleum feedstock and to develop new sources of renewable energy and materials.
- Lignocellulose is the main ingredient of biomass, which is the most abundant organic substance in the world. Lignocellulose mainly consists of 38-50% cellulose, 23-32% hemicellulose and 15-25% lignin. Cellulose generates glucose through hydrolysis. However, it is difficult for chemicals to enter the interior of cellulose molecules for depolymerization due to strong intermolecular and intramolecular hydrogen bonding and Van de Waal forces and the complex aggregate structure of cellulose with high-degree crystallinity. The main methods of hydrolyzing cellulose are enzyme hydrolysis and acid hydrolysis. However, there is significant imperfection in these two technologies, therefore, it is difficult to apply widely.
- enzyme hydrolysis can be carried out at room temperature, which is an environmentally friendly method due to the rarity of byproducts, no production of anti-sugar fermentation substances, and integration with the fermentation process.
- a complicated pretreatment process is required, hydrolytic activity is low, the reaction rate is slow, and cellulose hydrolysis enzyme is expensive.
- Dilute acid hydrolysis generally uses comparatively cheap sulfuric acid as a catalyst, but it must operate in a corrosion-resistant pressure vessel at more than 200°C, requiring high-level equipment; simultaneously, the temperature of the dilute acid hydrolysis is high, the byproduct thereof is plentiful, and the sugar yield is low. Concentrated acid hydrolysis can operate at lower temperature and normal pressure. However, there are problems of strong corrosivity of concentrated acid, complications in the post-treatment process of the hydrolyzed solution, large consumption of acid, and difficulties with recycling, among other drawbacks.
- One embodiment of the disclosure provides a sugar product, comprising: a sugar mixture comprising glucose, xylose, mannose, arabinose and oligosaccharides thereof with a weight ratio of 2-15wt%; an acid compound with a weight ratio of 48-97wt%; and a salt compound with a weight ratio of 1-50wt%.
- One embodiment of the disclosure provides a method for fabricating a sugar product, comprising: mixing formic acid or acetic acid and lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, iron bromide, or heteropoly acid to form a mixing solution; adding a cellulosic biomass to the mixing solution for a dissolution reaction; and adding water to the mixing solution for a hydrolysis reaction to obtain a sugar product.
- a method for fabricating a sugar product comprising the following steps. First, formic acid or acetic acid and lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, iron bromide, or heteropoly acid are mixed to form a mixing solution. A cellulosic biomass is added to the mixing solution for a dissolution reaction. Water is added to the mixing solution for a hydrolysis reaction to obtain a sugar product.
- the lithium chloride or lithium bromide has a weight ratio of about 5-20wt% or 10-20wt% in the mixing solution.
- the calcium chloride or calcium bromide has a weight ratio of about 12-40wt% or 12-30wt% in the mixing solution.
- the amount of water added is larger than the total molar equivalent of monosaccharides hydrolyzed from the cellulosic biomass.
- the hydrolysis reaction has a reaction temperature of about 50-150°C or 60-105 °C and a reaction time of about 30-180 minutes or 30-120 minutes.
- the sugar product fabricated by the method may comprise a sugar mixture, an acid compound, and a salt compound.
- the sugar mixture may comprise glucose, xylose, mannose, arabinose and oligosaccharides thereof with a weight ratio of about 2-15wt% in the sugar product.
- the acid compound may comprise formic acid or acetic acid with a weight ratio of about 48-97wt% in the sugar product.
- the salt compound may comprise lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, or iron bromide with a weight ratio of about 1-50wt% in the sugar product.
- the method further comprises adding inorganic acid to the mixing solution before, during or after the dissolution reaction.
- the inorganic acid may comprise sulfuric acid or hydrochloric acid.
- the inorganic acid has a weight ratio of about 1-2wt% in the mixing solution.
- the adding amount of the chloride salt or the bromide salt may be reduced, for example, the weight ratio of the magnesium chloride, the magnesium bromide, the calcium chloride or the calcium bromide in the mixing solution may be reduced to about 1-10wt%, and the weight ratio of the lithium chloride, the lithium bromide, the zinc chloride, the zinc bromide, the iron chloride or the iron bromide in the mixing solution may be reduced to about 1-5wt%.
- Formic acid and calcium chloride (CaCl 2 ) were mixed and heated to form a mixing solution (75wt% of formic acid, 25wt% of calcium chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (6wt% of Avicel ® cellulose) for a dissolution reaction (65 °C , 90 minutes) to form a yellow, homogeneous, and transparent liquid, as recorded in Table 1.
- Formic acid and magnesium chloride (MgCl 2 ) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (65 °C , 120 minutes) to form an amber, homogeneous, and transparent liquid, as recorded in Table 1.
- Formic acid and magnesium chloride (MgCl 2 ) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride).
- ⁇ -cellulose Sigma Corporation, C8002 was added to the mixing solution (5wt% of ⁇ -cellulose) for a dissolution reaction (65°C, 120 minutes) to form an amber, homogeneous, and transparent liquid, as recorded in Table 1.
- Table 1 Examples Salt (wt%) Cellulose (wt%) Dissolution temp.
- Formic acid and lithium chloride (LiCl) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of lithium chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and lithium bromide (LiBr) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of lithium bromide).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 0.5 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and sodium bromide (NaBr) were mixed and heated to form a mixing solution (82wt% of formic acid, 18wt% of sodium bromide).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 9 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and calcium bromide (CaBr 2 ) were mixed and heated to form a mixing solution (88wt% of formic acid, 12wt% of calcium bromide).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and barium bromide (BaBr 2 ) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of barium bromide).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and magnesium chloride (MgCl 2 ) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride (saturated solution)).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (65 °C , 2 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and magnesium chloride (MgCl 2 ) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of magnesium chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 12 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and calcium chloride (CaCl 2 ) were mixed and heated to form a mixing solution (75wt% of formic acid, 25wt% of calcium chloride (saturated solution)).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (65°C, 1.5 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and calcium chloride (CaCl 2 ) were mixed and heated to form a mixing solution (82.5wt% of formic acid, 17.5wt% of calcium chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 2 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and calcium chloride (CaCl 2 ) were mixed and heated to form a mixing solution (88wt% of formic acid, 12wt% of calcium chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and zinc chloride (ZnCl 2 ) were mixed and heated to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (50°C, 0.25 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and zinc chloride (ZnCl 2 ) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of zinc chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (65°C, 0.25 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and zinc chloride (ZnCl 2 ) were mixed and heated to form a mixing solution (95wt% of formic acid, 5wt% of zinc chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Formic acid and iron chloride (FeCl 3 ) were mixed and heated to form a mixing solution (98wt% of formic acid, 2wt% of iron chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 3 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Magnesium carbonate (MgCO 3 ) precipitate was then removed from the mixing solution.
- the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method.
- DNS 3,5-dinitro-salicylic acid
- the yield of the reducing sugar was then calculated.
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 3.
- Formic acid and magnesium chloride (MgCl 2 ) were mixed by stirring and heated to 70°C under 1 atm to form a mixing solution (90wt% of formic acid, 10wt% of magnesium chloride).
- Avicel ® cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 6 hours).
- water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (120 minutes).
- saturated sodium carbonate (Na 2 CO 3 ) aqueous solution was added to neutralize the mixing solution.
- Formic acid and calcium chloride (CaCl 2 ) were mixed by stirring and heated to 50°C under 1 atm to form a mixing solution (85wt% of formic acid, 15wt% of calcium chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (50°C, 4 hours).
- water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (60 minutes).
- saturated sodium carbonate (Na 2 CO 3 ) aqueous solution was added to neutralize the mixing solution.
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 4.
- Formic acid and calcium chloride (CaCl 2 ) were mixed by stirring and heated to 70°C under 1 atm to form a mixing solution (88wt% of formic acid, 12wt% of calcium chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (70°C, 4 hours).
- water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (60 minutes).
- saturated sodium carbonate (Na 2 CO 3 ) aqueous solution was added to neutralize the mixing solution.
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 4.
- Formic acid and calcium chloride (CaCl 2 ) were mixed by stirring and heated to 90°C under 1 atm to form a mixing solution (90wt% of formic acid, 10wt% of calcium chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI
- was added to the mixing solution 5wt% of Avicel ® cellulose
- dissolution reaction 90°C, 4 hours.
- water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (60 minutes).
- saturated sodium carbonate (Na 2 CO 3 ) aqueous solution was added to neutralize the mixing solution.
- Formic acid and zinc chloride (ZnCl 2 ) were mixed by stirring and heated to 50°C under 1 atm to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (50°C).
- water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (30 minutes).
- saturated sodium carbonate (Na 2 CO 3 ) aqueous solution was added to neutralize the mixing solution.
- Zinc carbonate (ZnCO 3 ) precipitate was then removed from the mixing solution.
- the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method.
- DNS 3,5-dinitro-salicylic acid
- the yield of the reducing sugar was then calculated.
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 5.
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- Formic acid and zinc chloride (ZnCl 2 ) were mixed by stirring and heated to 55 °C under 1 atm to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride).
- Dried corn stalks (comprising 44.5wt% of glucan, 12.4wt% of xylan, 4.6wt% of acid-soluble lignin, 24.4wt% of acid-insoluble lignin, 2.7wt% of water and 3.8wt% of ash) was added to the mixing solution (5wt% of corn stalks) for a dissolution reaction (55°C).
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the bagasse.
- the yield of the xylose is the ratio of the moles of the produced xylose and the moles of the xylose monomers contained in the hemicellulose in the bagasse.
- the yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the bagasse. The result is shown in Table 9.
- 98wt% of H 2 SO 4 , iron chloride (FeCl 3 ) and formic acid were mixed by stirring and heated to 55°C under 1 atm to form a mixing solution (1wt% of H 2 SO 4 , 2wt% of iron chloride, 97wt% of formic acid).
- Dried bagasse (comprising 40.7wt% of glucan, 20.5wt% of xylan, 2.9wt% of Arab polysaccharides, 27.4wt% of lignin, 3.3wt% of ash and 5.2wt% of other ingredients) was added to the mixing solution (10wt% of bagasse) for a dissolution reaction (65°C).
- the reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- the yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the bagasse.
- the yield of the xylose is the ratio of the moles of the produced xylose and the moles of the xylose monomers contained in the hemicellulose in the bagasse.
- the yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the bagasse.
- Formic acid acetic acid and zinc chloride (ZnCl 2 ) were mixed and heated to form a mixing solution (54wt% of formic acid, 6wt% of acetic acid and 40wt% of zinc chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (60°C, 60 minutes), forming an amber transparent liquid with an uniform phase. The dissolution of cellulose was observed using a polarizing microscope. The cellulose was completely dissolved.
- Formic acid acetic acid and zinc chloride (ZnCl 2 ) were mixed and heated to form a mixing solution (50wt% of formic acid, 10wt% of acetic acid and 40wt% of zinc chloride).
- Avicel ® cellulose Sigma Corporation, Avicel-pH-105-27NI was added to the mixing solution (5wt% of Avicel ® cellulose) for a dissolution reaction (65°C, 60 minutes), forming an amber transparent liquid with an uniform phase. The dissolution of cellulose was observed using a polarizing microscope. The cellulose was completely dissolved.
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Abstract
Description
- This Application claims priority of China Patent Application No.
. This application claims the benefit of2013104350048, filed on Sep 23, 2013 , which claims the benefit of provisional Application No.U.S. Application No. 13/973,072, filed on Aug 22, 2013 , the entireties of which are incorporated by reference herein.61/707,576, filed on Sep 28, 2012 - The technical field relates to a sugar product and fabricating method thereof.
- The world is facing problems such as the gradual extraction and depletion of petroleum reserves, and changes to the earth's atmosphere due to the greenhouse effect. In order to ensure the sustainability of human life, it has become a world trend to gradually decrease the use of petrochemical energy and petroleum feedstock and to develop new sources of renewable energy and materials.
- Lignocellulose is the main ingredient of biomass, which is the most abundant organic substance in the world. Lignocellulose mainly consists of 38-50% cellulose, 23-32% hemicellulose and 15-25% lignin. Cellulose generates glucose through hydrolysis. However, it is difficult for chemicals to enter the interior of cellulose molecules for depolymerization due to strong intermolecular and intramolecular hydrogen bonding and Van de Waal forces and the complex aggregate structure of cellulose with high-degree crystallinity. The main methods of hydrolyzing cellulose are enzyme hydrolysis and acid hydrolysis. However, there is significant imperfection in these two technologies, therefore, it is difficult to apply widely.
- Generally speaking, enzyme hydrolysis can be carried out at room temperature, which is an environmentally friendly method due to the rarity of byproducts, no production of anti-sugar fermentation substances, and integration with the fermentation process. However, a complicated pretreatment process is required, hydrolytic activity is low, the reaction rate is slow, and cellulose hydrolysis enzyme is expensive.
- Dilute acid hydrolysis generally uses comparatively cheap sulfuric acid as a catalyst, but it must operate in a corrosion-resistant pressure vessel at more than 200°C, requiring high-level equipment; simultaneously, the temperature of the dilute acid hydrolysis is high, the byproduct thereof is plentiful, and the sugar yield is low. Concentrated acid hydrolysis can operate at lower temperature and normal pressure. However, there are problems of strong corrosivity of concentrated acid, complications in the post-treatment process of the hydrolyzed solution, large consumption of acid, and difficulties with recycling, among other drawbacks.
- One embodiment of the disclosure provides a sugar product, comprising: a sugar mixture comprising glucose, xylose, mannose, arabinose and oligosaccharides thereof with a weight ratio of 2-15wt%; an acid compound with a weight ratio of 48-97wt%; and a salt compound with a weight ratio of 1-50wt%.
- One embodiment of the disclosure provides a method for fabricating a sugar product, comprising: mixing formic acid or acetic acid and lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, iron bromide, or heteropoly acid to form a mixing solution; adding a cellulosic biomass to the mixing solution for a dissolution reaction; and adding water to the mixing solution for a hydrolysis reaction to obtain a sugar product.
- A detailed description is given in the following embodiments.
- In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing.
- In one embodiment of the disclosure, a sugar product is provided. The sugar product comprises a sugar mixture, an acid compound, and a salt compound. The sugar mixture comprises glucose, xylose, mannose, arabinose and oligosaccharides thereof with a weight ratio of about 2-15wt% in the sugar product. The acid compound may comprise formic acid or acetic acid with a weight ratio of about 48-97wt% in the sugar product. The salt compound may comprise lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, or iron bromide with a weight ratio of about 1-5wt% in the sugar product.
- In one embodiment of the disclosure, a method for fabricating a sugar product is provided, comprising the following steps. First, formic acid or acetic acid and lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, iron bromide, or heteropoly acid are mixed to form a mixing solution. A cellulosic biomass is added to the mixing solution for a dissolution reaction. Water is added to the mixing solution for a hydrolysis reaction to obtain a sugar product.
- The formic acid has a weight ratio of about 50-97wt% in the mixing solution.
- The lithium chloride or lithium bromide has a weight ratio of about 5-20wt% or 10-20wt% in the mixing solution.
- The magnesium chloride or magnesium bromide has a weight ratio of about 10-30wt% or 15-20wt% in the mixing solution.
- The calcium chloride or calcium bromide has a weight ratio of about 12-40wt% or 12-30wt% in the mixing solution.
- The zinc chloride or zinc bromide has a weight ratio of about 5-45wt% or 20-30wt% in the mixing solution.
- The iron chloride or iron bromide has a weight ratio of about 1-50wt% or 5-10wt% in the mixing solution.
- The heteropoly acid may comprise H3PW12O40, H4SiW12O40, H3PMo12O40 or H4SiMo12O40 with a weight ratio of about 1-5wt% or 2-5wt% in the mixing solution.
- The cellulosic biomass may be derived from wood, grass, leaves, algae, waste paper, corn stalks, corn cobs, rice straw, rice husk, wheat straw, bagasse, bamboo, or crop stems. The cellulosic biomass may comprise cellulose, hemicellulose, or lignin with a weight ratio of about 1-20wt% or 5-15wt% in the mixing solution.
- The dissolution reaction has a reaction temperature of about 40-90 or 50-70 and a reaction time of about 20-360 minutes or 30-120 minutes.
- In the hydrolysis reaction, the amount of water added is larger than the total molar equivalent of monosaccharides hydrolyzed from the cellulosic biomass.
- The hydrolysis reaction has a reaction temperature of about 50-150°C or 60-105 °C and a reaction time of about 30-180 minutes or 30-120 minutes.
- The sugar product fabricated by the method may comprise a sugar mixture, an acid compound, and a salt compound. The sugar mixture may comprise glucose, xylose, mannose, arabinose and oligosaccharides thereof with a weight ratio of about 2-15wt% in the sugar product. The acid compound may comprise formic acid or acetic acid with a weight ratio of about 48-97wt% in the sugar product. The salt compound may comprise lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, or iron bromide with a weight ratio of about 1-50wt% in the sugar product.
- In one embodiment, the method further comprises adding inorganic acid to the mixing solution before, during or after the dissolution reaction. The inorganic acid may comprise sulfuric acid or hydrochloric acid. The inorganic acid has a weight ratio of about 1-2wt% in the mixing solution. When the inorganic acid is added, the adding amount of the chloride salt or the bromide salt may be reduced, for example, the weight ratio of the magnesium chloride, the magnesium bromide, the calcium chloride or the calcium bromide in the mixing solution may be reduced to about 1-10wt%, and the weight ratio of the lithium chloride, the lithium bromide, the zinc chloride, the zinc bromide, the iron chloride or the iron bromide in the mixing solution may be reduced to about 1-5wt%.
- In the disclosure, formic acid or acetic acid (weak acid) is mixed with lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, or iron bromide to be utilized as a solvent with the characteristic of dissolving cellulose under low temperature (<90°C) and rapid reaction time (<6 hours) to generate a homogeneous liquid. In the disclosed method, cellulose is dissolved in the solvent formed by chloride salt or bromide salt and formic acid or acetic acid to generate a homogeneous liquid at 40-150°C, and a sugar product is further obtained through hydrolysis. This method achieves the technical goals of low temperature, normal pressure, rapid reaction time and high sugar yield and without use of a strong acid corrosion-resistant reactor.
- Examples
- Example 1-1
- Formic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (15wt% of Avicel®cellulose) for a dissolution reaction (50 , 20 minutes) to form a yellow, homogeneous, and transparent liquid, as recorded in Table 1.
- Example 1-2
- Formic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). α-cellulose (Sigma Corporation, C8002) was added to the mixing solution (15wt% of α-cellulose) for a dissolution reaction (50°C, 20 minutes) to form an amber, homogeneous, and transparent liquid, as recorded in Table 1.
- Example 1-3
- Formic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (75wt% of formic acid, 25wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (6wt% of Avicel®cellulose) for a dissolution reaction (65 °C , 90 minutes) to form a yellow, homogeneous, and transparent liquid, as recorded in Table 1.
- Example 1-4
- Formic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (75wt% of formic acid, 25wt% of calcium chloride). α-cellulose (Sigma Corporation, C8002) was added to the mixing solution (6wt% of α-cellulose) for a dissolution reaction (65°C, 90 minutes) to form an amber, homogeneous, and transparent liquid, as recorded in Table 1.
- Example 1-5
- Formic acid and magnesium chloride (MgCl2) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (65 °C , 120 minutes) to form an amber, homogeneous, and transparent liquid, as recorded in Table 1.
- Example 1-6
- Formic acid and magnesium chloride (MgCl2) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride). α-cellulose (Sigma Corporation, C8002) was added to the mixing solution (5wt% of α-cellulose) for a dissolution reaction (65°C, 120 minutes) to form an amber, homogeneous, and transparent liquid, as recorded in Table 1.
Table 1 Examples Salt (wt%) Cellulose (wt%) Dissolution temp. (°C) Dissolution time (min) Solution appearance 1-1 zinc chloride (40) Avicel®cellulose (15) 50 20 yellow, homogeneous and transparent liquid 1-2 zinc chloride (40) α-cellulose (15) 50 20 amber, homogeneous and transparent liquid 1-3 calcium chloride (25) Avicel®cellulose (6) 65 90 yellow, homogeneous and transparent liquid 1-4 calcium chloride (25) α-cellulose (6) 65 90 amber, homogeneous and transparent liquid 1-5 magnesium chloride (20) Avicel®cellulose (5) 65 120 amber, homogeneous and transparent liquid 1-6 magnesium chloride (20) α-cellulose (5) 65 120 amber, homogeneous and transparent liquid - Example 2-1
- Formic acid and lithium chloride (LiCl) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of lithium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-2
- Formic acid and lithium chloride (LiCl) were mixed and heated to form a mixing solution (95wt% of formic acid, 5wt% of lithium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 12 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-3
- Formic acid and sodium chloride (NaCl) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of sodium chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 19 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-4
- Formic acid and lithium bromide (LiBr) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of lithium bromide). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 0.5 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-5
- Formic acid and sodium bromide (NaBr) were mixed and heated to form a mixing solution (82wt% of formic acid, 18wt% of sodium bromide). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 9 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-6
- Formic acid and calcium bromide (CaBr2) were mixed and heated to form a mixing solution (88wt% of formic acid, 12wt% of calcium bromide). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-7
- Formic acid and barium bromide (BaBr2) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of barium bromide). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-8
- Formic acid and magnesium chloride (MgCl2) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (65 °C , 2 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-9
- Formic acid and magnesium chloride (MgCl2) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of magnesium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 12 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-10
- Formic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (75wt% of formic acid, 25wt% of calcium chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (65°C, 1.5 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-11
- Formic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (82.5wt% of formic acid, 17.5wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 2 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-12
- Formic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (88wt% of formic acid, 12wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-13
- Formic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 12 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-14
- Formic acid and barium chloride (BaCl2) were mixed and heated to form a mixing solution (85wt% of formic acid, 15wt% of barium chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, >6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-15
- Formic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (50°C, 0.25 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-16
- Formic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (65°C, 0.25 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-17
- Formic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (95wt% of formic acid, 5wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-18
- Formic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (98wt% of formic acid, 2wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C , >6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-19
- Formic acid and iron chloride (FeCl3) were mixed and heated to form a mixing solution (95wt% of formic acid, 5wt% of iron chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 1 hour). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-20
- Formic acid and iron chloride (FeCl3) were mixed and heated to form a mixing solution (98wt% of formic acid, 2wt% of iron chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 3 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-21
- Formic acid and iron chloride (FeCl3) were mixed and heated to form a mixing solution (99wt% of formic acid, 1wt% of iron chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-22
- Formic acid and ammonium chloride (NH4Cl) were mixed and heated to form a mixing solution (90wt% of formic acid, 10wt% of ammonium chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, >12 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-23
- Formic acid and aluminum chloride (AlCl3) were mixed and heated to form a mixing solution (98wt% of formic acid, 2wt% of aluminum chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70 °C , 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-24
- Formic acid and tin chloride (SnCl3) were mixed and heated to form a mixing solution (95wt% of formic acid, 5wt% of tin chloride (saturated solution)). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70 °C , 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-25
- Formic acid and calcium sulfate (CaSO4) were mixed and heated to form a mixing solution (80wt% of formic acid, 20wt% of calcium sulfate). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
- Example 2-26
- Formic acid and heteropoly acid (H3PW12O40) were mixed and heated to form a mixing solution (99wt% of formic acid, 1wt% of heteropoly acid). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). The dissolution of cellulose was observed using a polarizing microscope, as recorded in Table 2.
Table 2 Examples Salt wt% Dissolution temp. (°C) Dissolution time (hour) Dissolution of cellulose 2-1 lithium chloride 10 70 6 complete dissolution 2-2 5 70 12 no dissolution 2-3 sodium chloride 10, saturated 70 19 no dissolution 2-4 lithium bromide 10 70 0.5 complete dissolution 2-5 sodium bromide 18 70 9 no dissolution 2-6 calcium 12 70 6 complete bromide dissolution 2-7 barium bromide 20 70 6 no dissolution 2-8 magnesium chloride 20, saturated 65 2 complete dissolution 2-9 10 70 12 no dissolution 2-10 calcium chloride 25, saturated 65 1.5 complete dissolution 2-11 17.5 70 2 complete dissolution 2-12 12 70 6 complete dissolution 2-13 10 70 12 no dissolution 2-14 barium chloride 15, saturated 70 >6 no dissolution 2-15 zinc chloride 40 50 0.25 complete dissolution 2-16 20 65 0.25 complete dissolution 2-17 5 70 6 complete dissolution 2-18 2 70 >6 no dissolution 2-19 iron chloride 5 70 1 complete dissolution 2-20 2 70 3 complete dissolution 2-21 1 70 6 complete dissolution 2-22 ammonium chloride 10, saturated 70 >12 no dissolution 2-23 aluminum chloride 2, saturated 70 6 no dissolution 2-24 tin chloride 5, saturated 70 6 no dissolution 2-25 calcium sulfate 20 70 6 no dissolution 2-26 heteropoly acid (H3PW12O40) 1 70 6 complete dissolution - Example 3-1
- Formic acid and magnesium chloride (MgCl2) were mixed by stirring and heated to 70°C under 1 atm to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 2 hours). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (120 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Magnesium carbonate (MgCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 3.
- Example 3-2
- Formic acid and magnesium chloride (MgCl2) were mixed by stirring and heated to 70°C under 1 atm to form a mixing solution (90wt% of formic acid, 10wt% of magnesium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 6 hours). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (120 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Magnesium carbonate (MgCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 3.
Table 3 Examples Cellulose (wt%) Mixing solution (magnesium chloride: formic acid) (wt%) Dissolution temp. (°C) Dissolution time (hour) Hydrolysis temp. (°C) Hydrolysis time (min) Yield of reducing sugar (%) 3-1 5 20: 80 70 2 100 120 97.9 3-2 5 10: 90 70 6 100 120 75.3 - Example 4-1
- Formic acid and calcium chloride (CaCl2) were mixed by stirring and heated to 50°C under 1 atm to form a mixing solution (85wt% of formic acid, 15wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (50°C, 4 hours). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (60 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Calcium carbonate (CaCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 4.
- Example 4-2
- Formic acid and calcium chloride (CaCl2) were mixed by stirring and heated to 70°C under 1 atm to form a mixing solution (88wt% of formic acid, 12wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (70°C, 4 hours). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (60 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Calcium carbonate (CaCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 4.
- Example 4-3
- Formic acid and calcium chloride (CaCl2) were mixed by stirring and heated to 90°C under 1 atm to form a mixing solution (90wt% of formic acid, 10wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (90°C, 4 hours). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (60 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Calcium carbonate (CaCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 4.
Table 4 Examples Cellulose (wt%) Mixing solution (calcium chloride: formic acid) (wt%) Dissolution temp. (°C) Dissolution time (hour) Hydrolysis temp. (°C) Hydrolysis time (min) Yield of reducing sugar (%) 4-1 5 15: 85 50 4 100 60 78.4 4-2 5 12: 88 70 4 100 60 70.6 4-3 5 10: 90 90 4 100 60 67.3 - Example 5-1
- Formic acid and zinc chloride (ZnCl2) were mixed by stirring and heated to 50°C under 1 atm to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (50°C). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (30 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Zinc carbonate (ZnCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 5.
- Example 5-2
- Formic acid and zinc chloride (ZnCl2) were mixed by stirring and heated to 50°C under 1 atm to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (50°C). After the complete dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (45 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Zinc carbonate (ZnCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 5.
Table 5 Examples Cellulose (wt%) Adding amount of water (wt%) Hydrolysis time (min) Yield of reducing sugar (%) 5-1 5 50 30 65 5-2 5 50 45 89 - Example 6
- Formic acid and zinc chloride (ZnCl2) were mixed by stirring and heated to 55 °C under 1 atm to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). Dried bagasse (comprising 43.58wt% of glucan, 24.02wt% of xylan, 12.45wt% of acid-soluble lignin, 18.12wt% of acid-insoluble lignin and 1.71wt% of ash) was added to the mixing solution (5wt% of bagasse) for a dissolution reaction (55°C). After the dissolution of the bagasse, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (120 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Zinc carbonate (ZnCO3) precipitate was then removed from the mixing solution. Next, the yields of glucose and xylose were analyzed using high performance liquid chromatography (HPLC) and the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the bagasse. The yield of the xylose is the ratio of the moles of the produced xylose and the moles of the xylose monomers contained in the hemicellulose in the bagasse. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the bagasse. The result is shown in Table 6. After the hydrolysis reaction, a hydrolyzed solution comprising 25.3wt% of zinc chloride, 33.2wt% of water, 38.2wt% of formic acid, 2.3wt% of reducing sugar (comprising 43.2wt% of glucose and 30.4wt% of xylose), 0.4wt% of acid-soluble lignin and 0.6wt% of acid-insoluble lignin was formed.
Table 6 Examples Bagasse (wt%) Amount of water added (wt%) Hydrolysis time (min) Yield of glucose (%) Yield of xylose (%) Yield of reducing sugar (%) 6-1 5 50 30 36.3 88.5 93.3 6-2 5 50 60 53.3 94.2 97.9 6-3 5 50 120 70.4 89.9 105.2 - Example 7
- Formic acid and magnesium chloride (MgCl2) were mixed by stirring and heated to 50°C under 1 atm to form a mixing solution (80wt% of formic acid, 20wt% of magnesium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (50°C, 2.5 hours). After the dissolution of the cellulose, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (90 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Magnesium carbonate (MgCO3) precipitate was then removed from the mixing solution. Next, the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the weight of the cellulose. The result is shown in Table 7.
Table 7 Examples Cellulose (wt%) Mixing solution (magnesium chloride: formic acid) (wt%) Dissolution temp. (°C) Dissolution time (hour) Hydrolysis temp. (°C) Hydrolysis time (min) Yield of reducing sugar (%) 7 5 20: 80 50 2.5 100 0th 46 100 90th 89 - Example 8
- Formic acid and zinc chloride (ZnCl2) were mixed by stirring and heated to 55 °C under 1 atm to form a mixing solution (60wt% of formic acid, 40wt% of zinc chloride). Dried corn stalks (comprising 44.5wt% of glucan, 12.4wt% of xylan, 4.6wt% of acid-soluble lignin, 24.4wt% of acid-insoluble lignin, 2.7wt% of water and 3.8wt% of ash) was added to the mixing solution (5wt% of corn stalks) for a dissolution reaction (55°C). After the dissolution of the corn stalks, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction (90 minutes). Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Zinc carbonate (ZnCO3) precipitate was then removed from the mixing solution. Next, the yields of glucose and xylose were analyzed using high performance liquid chromatography (HPLC) and the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the corn stalks. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the corn stalks. The result is shown in Table 8.
Table 8 Examples Corn stalks (wt%) Amount of water added (wt%) Hydrolysis time (min) Yield of glucose (%) Yield of reducing sugar (%) 8 5 50 90 85 96 - Example 9-1
- 37wt% of HCl, zinc chloride (ZnCl2) and formic acid were mixed by stirring and heated to 55°C under 1 atm to form a mixing solution (1wt% of HCl, 5wt% of zinc chloride, 94wt% of formic acid). Dried bagasse (comprising 40.7wt% of glucan, 20.5wt% of xylan, 2.9wt% of Arab polysaccharides, 27.4wt% of lignin, 3.3wt% of ash and 5.2wt% of other ingredients) was added to the mixing solution (10wt% of bagasse) for a dissolution reaction (65°C). After the dissolution of the bagasse, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction. Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Zinc carbonate (ZnCO3) precipitate was then removed from the mixing solution. Next, the yields of glucose and xylose were analyzed using high performance liquid chromatography (HPLC) and the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the bagasse. The yield of the xylose is the ratio of the moles of the produced xylose and the moles of the xylose monomers contained in the hemicellulose in the bagasse. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the bagasse. The result is shown in Table 9.
- Example 9-2
- 37wt% of HCl, iron chloride (FeCl3) and formic acid were mixed by stirring and heated to 55°C under 1 atm to form a mixing solution (1wt% of HCl, 2wt% of iron chloride, 97wt% of formic acid). Dried bagasse (comprising 40.7wt% of glucan, 20.5wt% of xylan, 2.9wt% of Arab polysaccharides, 27.4wt% of lignin, 3.3wt% of ash and 5.2wt% of other ingredients) was added to the mixing solution (10wt% of bagasse) for a dissolution reaction (65°C). After the dissolution of the bagasse, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction. Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Iron carbonate (Fe2(CO3)3) precipitate was then removed from the mixing solution. Next, the yields of glucose and xylose were analyzed using high performance liquid chromatography (HPLC) and the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the bagasse. The yield of the xylose is the ratio of the moles of the produced xylose and the moles of the xylose monomers contained in the hemicellulose in the bagasse. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the bagasse. The result is shown in Table 9.
- Example 9-3
- 98wt% of H2SO4, iron chloride (FeCl3) and formic acid were mixed by stirring and heated to 55°C under 1 atm to form a mixing solution (1wt% of H2SO4, 2wt% of iron chloride, 97wt% of formic acid). Dried bagasse (comprising 40.7wt% of glucan, 20.5wt% of xylan, 2.9wt% of Arab polysaccharides, 27.4wt% of lignin, 3.3wt% of ash and 5.2wt% of other ingredients) was added to the mixing solution (10wt% of bagasse) for a dissolution reaction (65°C). After the dissolution of the bagasse, water was added to the mixing solution (50wt% of water) and the mixing solution was heated to 100°C for a hydrolysis reaction. Next, saturated sodium carbonate (Na2CO3) aqueous solution was added to neutralize the mixing solution. Iron carbonate (Fe2(CO3)3) precipitate was then removed from the mixing solution. Next, the yields of glucose and xylose were analyzed using high performance liquid chromatography (HPLC) and the total weight of the reducing sugar was measured using 3,5-dinitro-salicylic acid (DNS) method. The yield of the reducing sugar was then calculated. The reducing sugar comprised glucose, xylose, mannose, arabinose and oligosaccharides thereof. The yield of the glucose is the ratio of the moles of the produced glucose and the moles of the glucose monomers contained in the cellulose in the bagasse. The yield of the xylose is the ratio of the moles of the produced xylose and the moles of the xylose monomers contained in the hemicellulose in the bagasse. The yield of the reducing sugar is the ratio of the total weight of the reducing sugar and the total weight of the cellulose and hemicellulose in the bagasse. The result is shown in Table 9.
Table 9 Examples Hydrolysis time (min) Yield of glucose (%) Yield of xylose (%) Yield of reducing sugar (%) 9-1 90 67.5 82.7 94.5 9-2 90 57.5 78.3 76.6 9-3 90 50.5 85.3 75.1 - Example 10-1
- Formic acid, acetic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (54wt% of formic acid, 6wt% of acetic acid and 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (60°C, 60 minutes), forming an amber transparent liquid with an uniform phase. The dissolution of cellulose was observed using a polarizing microscope. The cellulose was completely dissolved.
- Example 10-2
- Formic acid, acetic acid and calcium chloride (CaCl2) were mixed and heated to form a mixing solution (72wt% of formic acid, 8wt% of acetic acid and 20wt% of calcium chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (60°C, 180 minutes), forming an amber transparent liquid with an uniform phase. The dissolution of cellulose was observed using a polarizing microscope. The cellulose was completely dissolved.
- Example 10-3
- Formic acid, acetic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (50wt% of formic acid, 10wt% of acetic acid and 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (65°C, 60 minutes), forming an amber transparent liquid with an uniform phase. The dissolution of cellulose was observed using a polarizing microscope. The cellulose was completely dissolved.
- Example 10-4
- Formic acid, acetic acid and zinc chloride (ZnCl2) were mixed and heated to form a mixing solution (40wt% of formic acid, 20wt% of acetic acid and 40wt% of zinc chloride). Avicel®cellulose (Sigma Corporation, Avicel-pH-105-27NI) was added to the mixing solution (5wt% of Avicel®cellulose) for a dissolution reaction (65°C, 60 minutes), forming an amber transparent liquid with an uniform phase. The dissolution of cellulose was observed using a polarizing microscope. The cellulose was completely dissolved.
- It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims and their equivalents.
Claims (31)
- A sugar product, comprising:a sugar mixture comprising glucose, xylose, mannose, arabinose and
oligosaccharides thereof with a weight ratio of 2-15wt%;an acid compound with a weight ratio of 48-97wt%; anda salt compound with a weight ratio of 1-50wt%. - The sugar product as claimed in claim 1, wherein the acid compound comprises organic acid compounds or inorganic acid compounds.
- The sugar product as claimed in claim 1 or 2, wherein acid compound comprises formic acid, acetic acid or a mixture thereof.
- The sugar product as claimed in one of the preceding claims, wherein the salt compound comprises lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide or iron bromide.
- A method for fabricating a sugar product, comprising:mixing an acid compound and lithium chloride, magnesium chloride, calcium
chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide, iron bromide or heteropoly acid to form a mixing solution;adding a cellulosic biomass to the mixing solution for a dissolution reaction;
andadding water to the mixing solution for a hydrolysis reaction to obtain a sugar
product. - The method for fabricating a sugar product as claimed in claim 5, wherein the acid compound comprises formic acid, acetic acid or a mixture thereof.
- The method for fabricating a sugar product as claimed in claims 5 or 6, wherein the formic acid or acetic acid has a weight ratio of 50-97wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 7, wherein the lithium chloride or lithium bromide has a weight ratio of 5-20wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 8, wherein the magnesium chloride or magnesium bromide has a weight ratio of 10-30wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 9, wherein the calcium chloride or calcium bromide has a weight ratio of 12-40wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 10, wherein the zinc chloride or zinc bromide has a weight ratio of 5-45wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 11, wherein the iron chloride or iron bromide has a weight ratio of 1-50wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 12, wherein the heteropoly acid comprises H3PW12O40, H4SiW12O40, H3PMo12O40 or H4SiMo12O40.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 13, wherein the heteropoly acid has a weight ratio of 1-5wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 14, wherein the cellulosic biomass comprises cellulose, hemicellulose or lignin.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 15, wherein the cellulosic biomass is derived from wood, grass, leaves, algae, waste paper, corn stalks, corn cobs, rice straw, rice husk, wheat straw, bagasse, bamboo or crop stems.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 16, wherein the dissolution reaction has a reaction temperature of 40-90°C.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 17, wherein the dissolution reaction has a reaction time of 20-360 minutes.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 18, wherein the amount of water added is larger than the total molar equivalent of monosaccharides hydrolyzed from the cellulosic biomass.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 19, wherein the hydrolysis reaction has a reaction temperature of 50-150°C.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 20, wherein the hydrolysis reaction has a reaction time of 30-180 minutes.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 21, wherein the sugar product comprises a sugar mixture, an acid compound and a salt compound.
- The method for fabricating a sugar product as claimed in claim 22, wherein the sugar mixture comprises glucose, xylose, mannose, arabinose and oligosaccharides thereof.
- The method for fabricating a sugar product as claimed in claim 22 or 23, wherein the sugar mixture has a weight ratio of 2-15wt% in the sugar product.
- The method for fabricating a sugar product as claimed in one or more of claims 22 to 24, wherein the salt compound comprises lithium chloride, magnesium chloride, calcium chloride, zinc chloride, iron chloride, lithium bromide, magnesium bromide, calcium bromide, zinc bromide or iron bromide.
- The method for fabricating a sugar product as claimed in one or more of claims 22 to 25, wherein the salt compound has a weight ratio of 1-50wt% in the sugar product.
- The method for fabricating a sugar product as claimed in one or more of claims 5 to 26, further comprising adding inorganic acid to the mixing solution.
- The method for fabricating a sugar product as claimed in claim 27, wherein the inorganic acid comprises sulfuric acid or hydrochloric acid.
- The method for fabricating a sugar product as claimed in claim 27 or 28, wherein the inorganic acid has a weight ratio of 1-2wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 27 to 29, wherein the magnesium chloride, the magnesium bromide, the calcium chloride or the calcium bromide has a weight ratio of 1-10wt% in the mixing solution.
- The method for fabricating a sugar product as claimed in one or more of claims 27 to 30, wherein the lithium chloride, lithium bromide, the zinc chloride, the zinc bromide, the iron chloride or iron bromide has a weight ratio of 1-5wt% in the mixing solution.
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| US201261707576P | 2012-09-28 | 2012-09-28 | |
| US13/973,072 US20140090641A1 (en) | 2012-09-28 | 2013-08-22 | Sugar products and fabrication method thereof |
| CN201310435004.8A CN103710472B (en) | 2012-09-28 | 2013-09-23 | Sugar products and methods of making the same |
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| TW201803884A (en) * | 2015-12-10 | 2018-02-01 | 財團法人工業技術研究院 | Solid catalysts |
| CN106938196A (en) | 2015-12-10 | 2017-07-11 | 财团法人工业技术研究院 | Solid catalyst and preparation method of saccharide using the same |
| CN107034317A (en) * | 2016-02-04 | 2017-08-11 | 财团法人工业技术研究院 | Method for separating biomass hydrolysate |
| MY186792A (en) | 2016-02-04 | 2021-08-20 | Ind Tech Res Inst | Method for separating hydrolysis product of biomass |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452640A (en) * | 1982-05-11 | 1984-06-05 | Purdue Research Foundation | Quantitative hydrolysis of cellulose to glucose using zinc chloride |
| WO2006007691A1 (en) * | 2004-07-16 | 2006-01-26 | Iogen Energy Corporation | Method of obtaining a product sugar stream from cellulosic biomass |
| US20080102502A1 (en) * | 2006-10-25 | 2008-05-01 | Brian Foody | Inorganic salt recovery during processing of lignocellulosic feedstocks |
| WO2010104371A1 (en) * | 2009-03-12 | 2010-09-16 | Universiti Malaya | A conversion of cellulosic materials into glucose for use in bioethanol production |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452640A (en) * | 1982-05-11 | 1984-06-05 | Purdue Research Foundation | Quantitative hydrolysis of cellulose to glucose using zinc chloride |
| WO2006007691A1 (en) * | 2004-07-16 | 2006-01-26 | Iogen Energy Corporation | Method of obtaining a product sugar stream from cellulosic biomass |
| US20080102502A1 (en) * | 2006-10-25 | 2008-05-01 | Brian Foody | Inorganic salt recovery during processing of lignocellulosic feedstocks |
| WO2010104371A1 (en) * | 2009-03-12 | 2010-09-16 | Universiti Malaya | A conversion of cellulosic materials into glucose for use in bioethanol production |
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|---|---|---|---|---|
| WO2016099273A1 (en) | 2014-12-18 | 2016-06-23 | Avantium Knowledge Centre B.V. | Process for the preparation of a saccharide-containing solution from a torrefied cellulosic biomass |
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| EP2712936B1 (en) | 2015-10-07 |
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