WO2010077172A1 - Process for pretreatment of wood raw material for saccharification, system and product - Google Patents
Process for pretreatment of wood raw material for saccharification, system and product Download PDFInfo
- Publication number
- WO2010077172A1 WO2010077172A1 PCT/RU2009/000567 RU2009000567W WO2010077172A1 WO 2010077172 A1 WO2010077172 A1 WO 2010077172A1 RU 2009000567 W RU2009000567 W RU 2009000567W WO 2010077172 A1 WO2010077172 A1 WO 2010077172A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- milling
- wood
- pretreatment
- raw material
- stage
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims abstract description 37
- 239000002023 wood Substances 0.000 title claims abstract description 37
- 239000002994 raw material Substances 0.000 title claims abstract description 19
- 238000003801 milling Methods 0.000 claims abstract description 34
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 14
- 230000009471 action Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 description 14
- 235000010980 cellulose Nutrition 0.000 description 14
- 239000001913 cellulose Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 235000000346 sugar Nutrition 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000007071 enzymatic hydrolysis Effects 0.000 description 5
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000004880 explosion Methods 0.000 description 3
- 239000012978 lignocellulosic material Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- CXQWRCVTCMQVQX-LSDHHAIUSA-N (+)-taxifolin Chemical compound C1([C@@H]2[C@H](C(C3=C(O)C=C(O)C=C3O2)=O)O)=CC=C(O)C(O)=C1 CXQWRCVTCMQVQX-LSDHHAIUSA-N 0.000 description 1
- SATHPVQTSSUFFW-UHFFFAOYSA-N 4-[6-[(3,5-dihydroxy-4-methoxyoxan-2-yl)oxymethyl]-3,5-dihydroxy-4-methoxyoxan-2-yl]oxy-2-(hydroxymethyl)-6-methyloxane-3,5-diol Chemical compound OC1C(OC)C(O)COC1OCC1C(O)C(OC)C(O)C(OC2C(C(CO)OC(C)C2O)O)O1 SATHPVQTSSUFFW-UHFFFAOYSA-N 0.000 description 1
- 229920000189 Arabinogalactan Polymers 0.000 description 1
- 239000001904 Arabinogalactan Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 241000222354 Trametes Species 0.000 description 1
- -1 alkaline Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019312 arabinogalactan Nutrition 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- XCGZWJIXHMSSQC-UHFFFAOYSA-N dihydroquercetin Natural products OC1=CC2OC(=C(O)C(=O)C2C(O)=C1)c1ccc(O)c(O)c1 XCGZWJIXHMSSQC-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/02—Pretreatment of the raw materials by chemical or physical means
- D21B1/025—Separating pith from fibrous vegetable materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/06—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods
- D21B1/063—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods using grinding devices
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
- D21D1/28—Ball or rod mills
Definitions
- the present invention relates to an improved process for pretreatment of wood raw material for saccharification. Also the invention relates to a system for carrying out of the process and product obtained by the process.
- US2005069998 describes the pretreatment comprising stages of grinding the lignocellulosic biomass to a size of 15-30 mm, subjecting the product to steam explosion pretreatment at a temperature of 190-230 0 C for 1 to 10 minutes.
- the steam explosion does not always break down lignin completely and some of the compounds produced can be inhibitory to the subsequent fermentation.
- Biological pretreatment can involve applying lignin-solubilizing microorganisms.
- the wood raw material may be subjected to pretreatment with the aim of producing substrates that can be more rapidly and efficiently hydrolyzed to yield mixtures of fermentable sugars; in turn the valuable chemical compounds can be obtained through fermentation from the sugars.
- milling can greatly increase the susceptibility to enzymic depolymerization of cellulose.
- two stage milling firstly a coarse milling to particles ranging in size from 1 mm to 2 mm and then ultraflne milling to particles 1-5 ⁇ m with mechanoactivation
- two stage milling firstly a coarse milling to particles ranging in size from 1 mm to 2 mm and then ultraflne milling to particles 1-5 ⁇ m with mechanoactivation
- Coniferous wood chips are milled in the ball mill (e.g. AS-2M, Novosibirsk) to size of 1 - 2 mm and are dried on hot air to humidity no more than 10%. The operating time of this process is 1 second. Then the obtained wood chips are extracted (e.g. using ultrasound-assisted extraction) with acetone or ethanol; the ratio of solvent to wood chips is in the range of from about 7:1 to about 10:1. The extracted wood chips are milled in the activation mill (AC-2C, Novosibirsk) to the size of l-5 ⁇ m. The total operating time is 3 seconds. The obtained product is mechanoactivated ultrafine powder with the particle size distribution given in the Table 1.
- AS-2M Novosibirsk
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Processing Of Solid Wastes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Extraction Or Liquid Replacement (AREA)
- Disintegrating Or Milling (AREA)
Abstract
The present invention relates to a process for pretreatment of wood raw material comprising two stage milling, wherein at the first stage a coarse milling is carried out, followed by an extraction of pitch and at the second stage a ultrafine milling is carried out, moreover the mechanoactivation of the obtained product takes place at the second stage, also the invention relates to a system for carrying out of the process and product obtained by the process.
Description
Process for pretreatment of wood raw material for saccharification, system and product
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an improved process for pretreatment of wood raw material for saccharification. Also the invention relates to a system for carrying out of the process and product obtained by the process.
BACKGROUND OF THE INVENTION
In dry wood cellulose fibers are embedded in a matrix of other structural biopolymers, primarily hemicelluloses and lignin. Crystallinity and presence of lignin in most of the natural celluloses are major impediments towards development of an economically viable process technology for enzymatic hydrolysis of cellulose. Most of β-glycosidic bonds in wood-base material are inaccessible to cellulose enzymes by virtue of the small size of the pores in the multicomponent biomass. The molecules of individual microfibrils in crystalline cellulose are packed so tightly that not only enzymes but even small molecules like water cannot enter the complex structure. Suitable pretreatment to remove these blocks is necessary to obtain hydrolysis rates for the process to be viable. Pretreatment is a process that converts the wood raw material from its native form, in which it is recalcitrant to enzyme systems, into a form for which enzymatic hydrolysis is effective (Ashok Pandey, Handbook of Plant-Based Biofuels, CRC Press, 2008, p. 122). Many different pretreatments have been attempted. Some have been demonstrated to be effective in disrupting lignin cellulose complex, while others are responsible for breaking down the highly ordered cellulose crystalline structure, which is prerequisite for enzyme action.
The known pretreatment techniques include physical, chemical, and biological methods that may be used separately or in combination.
Physical treatments such as grinding, milling, high temperature, radiation and steaming/steam explosion are aimed at size reduction and mechanical decrystallization.
JP55009758 discloses the pretreatment of scrap wood by grinding in a vibration ball mill.
JP63137693 discloses the pulverization of wood wherein roughly crushed wood powder compressed and pulverized under pressure of 50 kg/mm2 and, if necessary, the pulverized material is disintegrated by a disintegrator. Further the obtained product should be classified to separate the fine particles. However these documents do not give due attention to quality of pulverized wood raw material, but finally this factor just defines high sugar yield.
WO2008/073186 discloses a method of changing a molecular structure of a biomass feedstock comprising radiation in the form of an electron beam and/or sonication.
RU2088108 discloses a wood processing method by ionizing radiation providing absorbed ionizing radiation dose of 100-290 kGy and simultaneous drying, grinding and sorting of wood raw material at temperature of drying agent of 413-423K. Though radiation has superior penetrating power and ionization action, which breaks cellulose chains, the method is slow and expensive, sometimes this pretreatment results in oxidation, degradation of molecules, dehydration.
US2005069998 describes the pretreatment comprising stages of grinding the lignocellulosic biomass to a size of 15-30 mm, subjecting the product to steam explosion pretreatment at a temperature of 190-230 0C for 1 to 10 minutes. The steam explosion does not always break down lignin completely and some of the compounds produced can be inhibitory to the subsequent fermentation.
Chemical methods can include pretreatment with dilute acid, alkaline, organic solvent, ammonia, sulfur dioxide, carbon dioxide, ionic liquid.
US4266981 discloses the process in which cellulosic raw material are hydrolyzed by dilute sulfuric acid to remove hemicellulose. Such process significantly increases cellulose hydrolysis, however acid consumption is n expensive part of the method; it requires expensive corrosion-resistant materials and disposal of solid waste generated is a problem.
WO2008065433 discloses a process for the fermentative production of ethanol from solid lignocellulosic material comprising a step of treating the solid lignocellulosic material with alkaline solution in order to remove the lignin. All the lignin and part of hemicellulose are removed but this method is not able to disrupt the crystallinity of cellulose.
US2008227162 discloses the pretreatment of biomass by incubating the biomass in an ionic liquid for approximately from 5 minutes to 8 hours at 50 to 200 C.
Biological pretreatment can involve applying lignin-solubilizing microorganisms.
JP2008006372 discloses the wood-based biomass pretreatment method which comprises grinding processing using white-rot fungi having lignin-decomposing activity. The white-rot fungi are Trametes hirsute. Biological pretreatments appear to have the advantages of requiring no chemicals (if nutrient supplementation is not required) and low energy input. However, biological pretreatments are relatively slow processes, and most lignin-solubilizing microorganisms also solubilize or consume hemicellulose and cellulose (David M. Mousdale, Biofuels: biotechnology, chemistry and sustainable development, CRC Press, 2008, pp. 56-63).
The shortcomings of the known methods are low enzymatic hydrolysis rate and low sugar yield. It should to be noted that because of the increased awareness of, and emphasis on, human health and environmental protection, effective pretreatment that use few or no (hazardous) chemicals are likely to gain research, development, and deployment momentum. This trend is believed to be crucial in guiding future research and development efforts (Handbook on Bioethanol: production and utilization, Edited by Charles E. Wyman, Applied Energy Technology series, p.194).
Therefore the efforts of inventors have been oriented to an improved pretreatment process which does not requre use of chemicals and provides high productivity of the enzymatic hydrolysis of wood-base material to soluble sugars.
BRIEF SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a process for pretreatment of wood raw material comprising two stage milling, wherein at the first stage a coarse milling is carried out, followed by an extraction of pitch and at the second stage a ultrafine milling is carried out, moreover the mechanoactivation of the obtained product takes place at the second stage. In one embodiment the first stage is carried out at temperature no more than 130 0C and during the mechanoactivation the material subjected to CO2 action.
The present invention also relates to a system for carrying out of the process comprising a device for a coarse milling of wood raw material, an extractor, a device for an ultrafine milling and mechanoactivation. Additionally the device for an ultrafine milling and mechanoactivation comprises a device for CO2 gas supply. The present invention also relates to products obtained by the claimed process.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a system for carrying out the claimed process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The wood raw material may be subjected to pretreatment with the aim of producing substrates that can be more rapidly and efficiently hydrolyzed to yield mixtures of fermentable sugars; in turn the valuable chemical compounds can be obtained through fermentation from the sugars.
It is known that milling can greatly increase the susceptibility to enzymic depolymerization of cellulose.
However two stage milling (firstly a coarse milling to particles ranging in size from 1 mm to 2 mm and then ultraflne milling to particles 1-5 μm with mechanoactivation) has given rather surprising results.
We have discovered that in result of two-step mechanical activation of the wood-base material cellulose crystallinity index is decreased from 65-70% to 10%. Also the time of saccharifϊcation of such raw material at pH 5-6 and temperature of 50 0C is only 12-13 hours, and in column process 3-7 hours. The sugars yield is 50% from the weight of wood raw material.
Mechanoactivation of wood-base material per se is known (Kuznetsova S.A., et al. Obtaining Arabinogalactan, Dihydroquercetin and Microcrystalline Cellulose Using Mechanochemical Activation, Chemistry for Sustainable Development 13 (2005) 261-268, Mikushina I.V., Changes in the Chemical Composition of Wood during Mechanochemical Treatment, Chemistry for Sustainable Development 10 (2002), 441-445), but these documents do not teach, disclose or suggest the possibility to use the mechanoactivation in the pretreatment process for saccharifϊcation.
It should to be noted that the ultrafine wood powder has specific properties; particularly it is watered rapidly and goes down immediately compared to conventional wood chips that float awash. It is clear that such properties give option to enzymes to contact efficiently with cellulose material. Also the saccharification process of such activated material takes less water, it is very important on an industrial scale. It gives option to improve the mixing with water, using ratio 1:6 (in case of untreated raw material 1:10). Such activated layers of the material surface have anomalously high chemical activity and sorption capacity but very low diffusion resistance. Large energy store accumulated in the disordered structure of the surface layers and low diffusion resistance may be used in low-temperature chemical reactions and define mechanochemical and mechanosorption processes. These factors results in increasing external surface that promotes the uniform dispersion of the fine powder in liquid during saccharification.
The coarse milling of the lignocellulosic material is carried out in mills, preferably in ball-mills to particles ranging in size from 1 mm to 2 mm with simultaneous drying by hot air blowing with temperature of 120-130 0C. The process gives option to dry the raw material and prepare it for the ultrafine milling.
The ultrafine milling is carried out in vibro energy, colloid or jet mill that provides the shearing force, the ultrafine milling is carried out to particles ranging in size from 1 μm to 4 μm. During ultrafine milling of wood raw material the destruction occurs mainly by "flaking off"
(fatigue failure) because of surface fracture of milling particles. Therefore the ultrafϊne milling is carried out by high frequency action into the material with relatively light shocks. The ultrafine milling process relies on the discrete character of the process through time (alternation of stress field and its relaxation) and the local character of the mechanical action into substance. It is important that the stress field arises only on the contact of one particle with another particle or a working element.
In result of such ultrafine milling the destruction of the fibrillar nature is accompanied by a mechanical rupture of the cellulose chain molecules, an increase in the moisture adsorption (resulting in better watering).
Mechanoactivation process is accompanied by the saturation of CO2 at supercritical pressure, resulting in producing of carbonic acid that blocks conglomeration of particles and secondary crystal formation.
When naturally-occurring wood extractives (pitch and volatile organic compounds) are found in both resin canals within the structure of the wood, as well as within the parenchyma cells of the wood, the removal of pitch is preferable before the ultrafine milling. More particularly, wood chips are subjected to a solvent extraction process, preferably with acetone, and ethanol (ratio 1 :7 - 1 : 10) for pitch removal.
The process may be more easily understood with reference to FIG.l, where the schematic view of the system for carrying out of the claimed process is shown. The pretreated wood raw material (wood chips with the natural moisture of 28-37% and size of 2-200 mm), e.g. wood scrap 1 or off grade wood 2 are processed in a device for a coarse milling 3, which can be a ball-mill. Then 1-2 mm particles of wood chips from the device 3 are charged to an extractor 4 to remove pitch. The extracted particles are subjected to the ultrafine milling in a device for fine milling and mechanoactivation 5, which can be vibro energy, colloid or jet mill.
The invention may be further understood by the following non-limiting examples.
Example 1
Coniferous wood chips are milled in the ball mill (e.g. AS-2M, Novosibirsk) to size of 1 - 2 mm and are dried on hot air to humidity no more than 10%. The operating time of this process is 1 second. Then the obtained wood chips are extracted (e.g. using ultrasound-assisted extraction) with acetone or ethanol; the ratio of solvent to wood chips is in the range of from about 7:1 to about 10:1. The extracted wood chips are milled in the activation mill (AC-2C, Novosibirsk) to the size of l-5μm. The total operating time is 3 seconds.
The obtained product is mechanoactivated ultrafine powder with the particle size distribution given in the Table 1.
Table 1 Particle size distribution of the ultrafine powder
Therefore the claimed pretreatment process, system and product have got the following advantages: the pretreatment of the raw material does not requre use of chemicals, it results in high productivity of the enzymatic hydrolysis of wood material to soluble sugars.
Claims
1. A process for pretreatment of wood raw material comprising two stage milling, wherein at the first stage a coarse milling is carried out, followed by an extraction of pitch and at the second stage a ultrafine milling is carried out, moreover the mechanoactivation of the obtained product takes place at the second stage.
2. The process of claim 1 wherein the coarse milling is carried out with simultaneous drying by hot air blowing with temperature of 120-130 0C.
3. The process of claim 1 wherein during the mechanoactivation the material subjected to CO2 action.
4. System for carrying out of the process of claims 1-3 comprising a device for a coarse milling of wood material, an extractor, a device for an ultrafine milling and mechanoactivation.
5. System of claim 17 wherein the device for an ultrafine milling and mechanoactivation comprises a device for CO2 gas supply.
6. Product obtained by the process of claims 1-5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2008151902 | 2008-12-29 | ||
| RU2008151902/13A RU2405832C2 (en) | 2008-12-29 | 2008-12-29 | Method of preparing wood raw material to obtain sugars, installation for realising said method and product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010077172A1 true WO2010077172A1 (en) | 2010-07-08 |
Family
ID=42008538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/RU2009/000567 WO2010077172A1 (en) | 2008-12-29 | 2009-10-22 | Process for pretreatment of wood raw material for saccharification, system and product |
Country Status (2)
| Country | Link |
|---|---|
| RU (1) | RU2405832C2 (en) |
| WO (1) | WO2010077172A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240076831A1 (en) * | 2020-12-29 | 2024-03-07 | Mm Board & Paper Gmbh | Method for producing products based on wood as a raw material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2475540C1 (en) * | 2011-07-19 | 2013-02-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Иркутский государственный технический университет" (ФГБОУ ВПО "ИрГТУ) | Method of preparing lignocellulose material for producing sugar and apparatus for realising said method |
| WO2014012030A1 (en) * | 2012-07-13 | 2014-01-16 | Renmatix, Inc. | Supercritical hydrolysis of biomass |
| RU2577066C2 (en) * | 2013-07-19 | 2016-03-10 | Открытое акционерное общество "Восточно-Сибирский комбинат биотехнологий" (ОАО "ВСКБТ") | Plant for pretreatment of cellulose-containing plant material |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB891152A (en) * | 1957-11-21 | 1962-03-14 | Peter Willems | A method and apparatus for continuously changing the structure of substances or mixtures of such substances |
| GB1543274A (en) * | 1976-05-18 | 1979-03-28 | Mitsubishi Corp | Paper from mechanical treated hardwood pulp stock |
| GB1553296A (en) * | 1975-09-05 | 1979-09-26 | Asplund Arne J A | Process and an apparatus for the production of fibrepulp from ligno-cellulose materials |
| JPS559758A (en) | 1978-07-06 | 1980-01-23 | Agency Of Ind Science & Technol | Saccharification of wood |
| US4266981A (en) | 1978-03-08 | 1981-05-12 | Purdue Research Corporation | Process for recovering and utilizing cellulose using sulfuric acid |
| JPS63137693A (en) | 1986-11-28 | 1988-06-09 | Kobe Steel Ltd | Pulverization of wood |
| US4995943A (en) * | 1985-12-27 | 1991-02-26 | Rehberg Karl H | Pretreatment of cellulosic material with carbon dioxide |
| RU2088108C1 (en) | 1995-08-16 | 1997-08-27 | Ленинградская атомная электростанция им.В.И.Ленина | Method of producing wood powder |
| US6364999B1 (en) * | 1995-12-27 | 2002-04-02 | Weyerhaeuser Company | Process for producing a wood pulp having reduced pitch content and process and reduced VOC-emissions |
| US20050069998A1 (en) | 2000-02-24 | 2005-03-31 | Centro De Investigaciones Energeticas Medioambientales Y Tecnologicas (C.I.E.M.A.T.) | Procedure for the production of ethanol from lignocellulosic biomass using a new heat-tolerant yeast |
| US20070131361A1 (en) * | 2003-08-05 | 2007-06-14 | Klaus Doelle | Method for charging a fiber suspension, and arrangement for carrying out said method |
| JP2008006372A (en) | 2006-06-29 | 2008-01-17 | Oji Paper Co Ltd | Pretreatment method for woody biomass |
| WO2008065433A1 (en) | 2006-11-30 | 2008-06-05 | Petroleo Brasileiro S.A.-Petrobras | Process for the fermentative production of ethanol from solid lignocellulosic material comprising a step of treating a solid lignocellulosic material with alkaline solution in order to remove the lignin |
| WO2008073186A2 (en) | 2006-10-26 | 2008-06-19 | Marshall Medoff | Processing biomass |
| US20080227162A1 (en) | 2007-03-14 | 2008-09-18 | Sasidhar Varanasi | Biomass pretreatment |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1518123A1 (en) * | 1988-02-09 | 1989-10-30 | Кировский Политехнический Институт | Method of producing wood flour |
| RU2318655C1 (en) * | 2006-06-29 | 2008-03-10 | Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук (ИХТТМ СО РАН) | Method for production of wood flour |
-
2008
- 2008-12-29 RU RU2008151902/13A patent/RU2405832C2/en not_active IP Right Cessation
-
2009
- 2009-10-22 WO PCT/RU2009/000567 patent/WO2010077172A1/en active Application Filing
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB891152A (en) * | 1957-11-21 | 1962-03-14 | Peter Willems | A method and apparatus for continuously changing the structure of substances or mixtures of such substances |
| GB1553296A (en) * | 1975-09-05 | 1979-09-26 | Asplund Arne J A | Process and an apparatus for the production of fibrepulp from ligno-cellulose materials |
| GB1543274A (en) * | 1976-05-18 | 1979-03-28 | Mitsubishi Corp | Paper from mechanical treated hardwood pulp stock |
| US4266981A (en) | 1978-03-08 | 1981-05-12 | Purdue Research Corporation | Process for recovering and utilizing cellulose using sulfuric acid |
| JPS559758A (en) | 1978-07-06 | 1980-01-23 | Agency Of Ind Science & Technol | Saccharification of wood |
| US4995943A (en) * | 1985-12-27 | 1991-02-26 | Rehberg Karl H | Pretreatment of cellulosic material with carbon dioxide |
| JPS63137693A (en) | 1986-11-28 | 1988-06-09 | Kobe Steel Ltd | Pulverization of wood |
| RU2088108C1 (en) | 1995-08-16 | 1997-08-27 | Ленинградская атомная электростанция им.В.И.Ленина | Method of producing wood powder |
| US6364999B1 (en) * | 1995-12-27 | 2002-04-02 | Weyerhaeuser Company | Process for producing a wood pulp having reduced pitch content and process and reduced VOC-emissions |
| US20050069998A1 (en) | 2000-02-24 | 2005-03-31 | Centro De Investigaciones Energeticas Medioambientales Y Tecnologicas (C.I.E.M.A.T.) | Procedure for the production of ethanol from lignocellulosic biomass using a new heat-tolerant yeast |
| US20070131361A1 (en) * | 2003-08-05 | 2007-06-14 | Klaus Doelle | Method for charging a fiber suspension, and arrangement for carrying out said method |
| JP2008006372A (en) | 2006-06-29 | 2008-01-17 | Oji Paper Co Ltd | Pretreatment method for woody biomass |
| WO2008073186A2 (en) | 2006-10-26 | 2008-06-19 | Marshall Medoff | Processing biomass |
| WO2008065433A1 (en) | 2006-11-30 | 2008-06-05 | Petroleo Brasileiro S.A.-Petrobras | Process for the fermentative production of ethanol from solid lignocellulosic material comprising a step of treating a solid lignocellulosic material with alkaline solution in order to remove the lignin |
| US20080227162A1 (en) | 2007-03-14 | 2008-09-18 | Sasidhar Varanasi | Biomass pretreatment |
Non-Patent Citations (8)
| Title |
|---|
| DAVID M. MOUSDALE: "hemistry and sustainable development", 2008, CRC PRESS, article "Biofuels: biotechnology", pages: 56 - 63 |
| DUSHKIN A: "Potential of Mechanochemical Technology in Organic Synthesis and Synthesis of New Materials", CHEMISTRY FOR SUSTAINABLE DEVELOPMENTS, NAUKA PUBLISHERS, NOVOSIBIRSK, RU, vol. 12, 1 January 2004 (2004-01-01), pages 251 - 273, XP007912356, ISSN: 1023-8603 * |
| IRINA V MIKUSHINA ET AL: "Changes in the Chemical Composition of Wood during Mechanochemical Treatment", CHEMISTRY FOR SUSTAINABLE DEVELOPMENTS, NAUKA PUBLISHERS, NOVOSIBIRSK, RU, vol. 10, 1 January 2002 (2002-01-01), pages 441 - 445, XP007912354, ISSN: 1023-8603 * |
| JÜRGEN BLECHSCHMIDT AND SABINE HEINEMANN ED - HERBERT SIXTA: "Chap. 4, Mechanical Pulping Processes", vol. 2, 1 January 2006, HANDBOOK OF PULP, WILEY-VCH, DE, ISBN: 9783527309993, pages: 1100 - 1101, XP007912357 * |
| JÜRGEN BLECHSCHMIDT AND SABINE HEINEMANN ED - HERBERT SIXTA: "Chap. 4, Mechanical Pulping Processes", vol. 2, 1 January 2006, HANDBOOK OF PULP, WILEY-VCH, DE, ISBN: 9783527309993, pages: 1110, XP007912358 * |
| KUZNETSOVA S ET AL: "Obtaining Arabinogalactan, Dihydroquercetin and Microcrystalline Cellulose Using Mechanochemical Activation", CHEMISTRY FOR SUSTAINABLE DEVELOPMENTS, NAUKA PUBLISHERS, NOVOSIBIRSK, RU, vol. 13, 1 January 2005 (2005-01-01), pages 261 - 268, XP007912355, ISSN: 1023-8603 * |
| KUZNETSOVA S.A. ET AL.: "Obtaining Arabinogalactan, Dihydroquercetin and Microcrystalline Cellulose Using Mechanochemical Activation", CHEMISTRY FOR SUSTAINABLE DEVELOPMENT, vol. 13, 2005, pages 261 - 268 |
| MIKUSHINA LV.: "Changes in the Chemical Composition of Wood during Mechanochemical Treatment", CHEMISTRY FOR SUSTAINABLE DEVELOPMENT, vol. 10, 2002, pages 441 - 445 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240076831A1 (en) * | 2020-12-29 | 2024-03-07 | Mm Board & Paper Gmbh | Method for producing products based on wood as a raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2405832C2 (en) | 2010-12-10 |
| RU2008151902A (en) | 2010-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | The role of pretreatment in improving the enzymatic hydrolysis of lignocellulosic materials | |
| Diaz et al. | Evaluation of microwave-assisted pretreatment of lignocellulosic biomass immersed in alkaline glycerol for fermentable sugars production | |
| Barakat et al. | Dry fractionation process as an important step in current and future lignocellulose biorefineries: a review | |
| Wang et al. | Effects of hydrothermal treatment on enhancing enzymatic hydrolysis of rapeseed straw | |
| AU2009308624B2 (en) | Sugar production process and ethanol production process | |
| JP4958166B2 (en) | Treatment of plant biomass with alcohol in the presence of oxygen | |
| Haque et al. | Effect of dilute alkali pretreatment on structural features and enhanced enzymatic hydrolysis of Miscanthus sinensis at boiling temperature with low residence time | |
| JP5136984B2 (en) | Method for producing sugar | |
| Lomovsky et al. | Mechanical pretreatment | |
| Sul’man et al. | Effect of ultrasonic pretreatment on the composition of lignocellulosic material in biotechnological processes | |
| JP2011523349A (en) | Biomass processing method | |
| Sambusiti et al. | One-pot dry chemo-mechanical deconstruction for bioethanol production from sugarcane bagasse | |
| Ji et al. | Production of xylose from diluted sulfuric acid hydrolysis of wheat straw | |
| Wu et al. | Combination of hydrothermal and chemi-mechanical pretreatments to enhance enzymatic hydrolysis of poplar branches and insights on cellulase adsorption | |
| Saadon et al. | Pretreatment of fiber-based biomass material for lignin extraction | |
| JP5621528B2 (en) | Enzymatic saccharification method of lignocellulosic material | |
| JP4619917B2 (en) | Pretreatment method of lignocellulose | |
| WO2010077172A1 (en) | Process for pretreatment of wood raw material for saccharification, system and product | |
| Nlandu et al. | Flax nanofibrils production via supercritical carbon dioxide pre‐treatment and enzymatic hydrolysis | |
| JP5951181B2 (en) | Method for saccharification of lignocellulosic biomass | |
| KR101556547B1 (en) | Manufacturing Method Of Saccharides From Biomass Using Immobilized Enzyme | |
| WO2011002330A1 (en) | Method for utilization of palm oil production waste by its reprocessing in lignocellulose flour with its subsequent application for liquid and solid fuel production | |
| Abd-Talib et al. | Silica removal by alkaline hydrogen peroxide treatment to enhance the conversion of rice straw to sugars | |
| Laxman et al. | Bioethanol lignocellulosic biomass | |
| Bahena-Molina et al. | Pretreatment technologies for second-generation bioethanol production |
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: 09807511 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 09807511 Country of ref document: EP Kind code of ref document: A1 |