WO2005103370A1 - Traitement enzymatique des pates de bois - Google Patents
Traitement enzymatique des pates de bois Download PDFInfo
- Publication number
- WO2005103370A1 WO2005103370A1 PCT/US2005/013216 US2005013216W WO2005103370A1 WO 2005103370 A1 WO2005103370 A1 WO 2005103370A1 US 2005013216 W US2005013216 W US 2005013216W WO 2005103370 A1 WO2005103370 A1 WO 2005103370A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chips
- enzyme
- lignin
- biopulped
- fungus
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
- C12P1/02—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes by using fungi
-
- 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
-
- 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
- D21C3/00—Pulping cellulose-containing materials
Definitions
- the invention relates generally to the field of producing pulp from wood and, more specifically, to a method for producing pulp using biopulping followed by an enzyme treatment.
- Pulp is the fibrous slurry that is fed to a paper machine to produce paper.
- Mechanical, chemical and hybrid methods dominate commercial pulping plants. About 25% of worldwide pulp production is mechanical pulp. It is a high-yield process but suffers from high energy costs and damage to the wood fibers. This damage means lower strength paper.
- These disadvantages cost and quality
- Biopulping prior to mechanical pulping overcomes the aforementioned disadvantages. The production of pulp begins with wood chips.
- the wood chips are 'digested' with one or more fungi types prior to mechanical or chemical pulping.
- the fungi soften the wood chips by degrading or digesting the lignin components of the wood chips.
- the wood chips are mechanically or chemically pulped into individual fibers.
- the fungus and the produced enzymes are destroyed during the thermomechamcal pulping process. Due, in large part, to the biochemical action of the fungi, less energy is now required to convert the chips to fibers. Some investigators claim energy savings of at least 30%.
- the easier conversion from chip to fiber means less damage to the wood fibers.
- the paper formed from these fibers is stronger.
- biopulping there are some drawbacks to biopulping, such as a reduction in the brightness and opacity of the resulting fibers.
- the production of higher quality papers is desirable.
- Use of biopulped fibers for this application will require improvements in brightness and opacity.
- Preliminary bleaching studies with hydrogen peroxide and addition of calcium carbonate to improve both brightness and opacity have met with early success.
- the present invention provides a method for producing pulp that addresses the above and other issues.
- the present invention provides a process of producing thermomechanical pulp using a combined fungus/enzyme process in which the enzymes are produced in situ.
- wood chips are treated with a lignin-degrading fungus using the biopulping process.
- the enzymes that have been produced by the fungus axe extracted from the wood chips in the form of a crude broth.
- the enzymes are used to treat the pulp prior to completing the refining process.
- Biopulping has been shown previously to reduce the energy requirements for mechanical pulping.
- Enzyme treatments have also been shown to be beneficial.
- a method for processing wood chips includes biopulping the chips, extracting at least one enzyme from the biopulped chips, performing a further pulping of the biopulped chips, and re-introducing the at least one extracted enzyme to the further pulped chips.
- Fig. 1 illustrates the lignolytic enzyme activity change for the laccase enzyme, where thermomechanical pulping (TMP) is performed over a six hour treatment time on Picea abies (Norway Spruce) wood chips with fungal treatment using P. subserialis, T. versicolor and C. subvermispora, in accordance with the invention
- Fig. 2 illustrates the lignolytic enzyme activity change for the manganese peroxidase enzyme, for comparison with the results of Fig. 1, in accordance with the invention
- Fig. 3 illustrates a method for processing wood chips, in accordance with the invention.
- the invention employs a fungus treatment and a subsequent enzyme treatment to process wood chips.
- the wood chips are biopulped by inoculating them with a fungal treatment, such as a liquid mixture comprising a lignin-degrading fungus and a corn steep liquor.
- a fungal treatment such as a liquid mixture comprising a lignin-degrading fungus and a corn steep liquor.
- Enzymes which are formed as a result of the fungal inoculation are extracted from the wood chips.
- the enzymes can be extracted as a crude broth or pressate by applying mechanical pressure to the chips following the fungal treatment. A concentrated broth is then formed.
- a further pulping is performed, such as a first-stage thermomechanical pulping (TMP), to refine the biopulped chips to a coarse pulp.
- TMP thermomechanical pulping
- the resulting pulp is subsequently treated with the concentrated enzyme broth.
- This process has several advantages. First, the enzymes that are re-introduced into the coarse pulp are incubated on the wood and presumably adapted to reacting with the wood. Also, a separate enzyme production process is not necessary since the enzymes that are produced during the biopulping process are utilized. Finally, although mechanical energy is needed to extract the enzymes, the extraction weakens the wood chip structure, which should also reduce the necessary refiner energy in the first stage.
- the growth of the fungi on the wood chips is a relatively slow process compared to the normal processing time scales in the paper industry. The treatment of the wood chips with the lignin-degrading fungi can take anywhere from two to six weeks or longer depending on the degree of treatment desired.
- the treatment time can be shortened by using greater concentrations of fungi initially, but this would come at a higher cost.
- Previous related work has indicated that the inoculation amounts (5g/ton of chips) and treatment time of 2 weeks are reasonably feasible from an economic standpoint.
- the use of a biological agent should not cause a concern of contamination or other health concerns relating to concentrated cultures of microorganisms since the organisms used are all naturaUy-occurring and limit their attacks to lignocelMosic materials.
- Picea abies preparation Picea abies was selected as the softwood for this example.
- different species of woods including hardwoods and/or softwoods, can also be used.
- the invention can be used with virgin wood or waste wood, including, e.g., kiln dried, air-dried and green wood from industrial, residential, sawmill, construction and demolition sources.
- logs from a 79- year old tree were debarked with a 36-cm spoke shave, chipped in a Carthage 10-blade chipper, and air dried to approximately 15% moisture by spreading the chips on a tarp.
- the chips were then screened in a Williams classifier. All fractions were collected and the chips retained on the 15.8, 12.7 and 9.25-mm screens were pooled together and sealed in plastic bags, and stored at room temperature (approximately 24°C) for use throughout this study.
- TAPPI test method T- 257 cm-97 was followed for all subsequent testing and samples were taken from the pooled material as needed.
- TAPPI refers to the Technical Association of the Pulp and Paper Industry, Norcross, Georgia.
- Test Methods consist of a capital T, followed by a space, then a number (assigned sequentially within several Test Method categories), another space, a two-letter designation of classification, a hyphen, and the last two digits of the year published.
- the reactor was then cooled for approximately two hours until the temperature was below 30°C.
- the moisture content was brought up to 55% moisture by the addition 200 ml water collected during steaming plus additional distilled makeup water.
- Fresh fungal inoculum (2.3 ml) and 0.5% (v/v) unsterilized corn steep liquor (CSL) at 50% solids was added to the additional distilled makeup water.
- the chips can be inoculated with the hgnin-degrading fungus by providing a liquid mixture including the fungal inoculum, and applying the liquid mixture to the chips. The inoculated chips were then incubated under conditions favorable to the propagation of the hgnin-degrading fungus through the chips.
- the bioreactor was then placed in the incubation chamber at 27°C with forced continuous flow of warm humidified air at a rate of 0.028 cubic meters per minute.
- House air was measured by a flow meter and humidification was controlled by passing air through two water filled two-liter glass sidearm flasks (in series) through a fritted ground glass sparger. The sidearm flasks were immersed in a 40°C water bath. From the hot water flasks, the warm humidified air passed though a water trap and a final filtering through a 0.2 micron Millipore air filter (for sterilization) before connecting to the individual bioreactors.
- the TMP produced was sealed in a 40-liter Nalgene® carboy and refrigerated at 4°C until use.
- Culture Supernatant Purification Purification involved monitoring laccase and manganese peroxidase activity and harvesting the mycelium from P. subserialis (RLG6074-sp), C. subvermispora (L- 14807 SS-3), and T. versicolor (FP-72074) on the first day after peak laccase activity.
- Mycelium was harvested from the liquid culture by centrifuging for 20 min at 10,000 rpm, followed by treating the crude supernatant with 10% (v/v) acetone and refrigerating for one hour at 4°C to precipitate any extracellular polysaccharide.
- the broth was centrifuged again for 20 minutes at 10,000 rpm and filtered through a Whatman glass microfiber GF/A 42.5-mm diameter filter.
- the resulting supernatant was concentrated in a DC-2 ultrafiltration unit (Amicon Corp., Danvers, Mass.) equipped with a 30-kDa molecular weight cutoff hollow fiber filter from an initial volume of 1000 ml to 100 ml.
- Enzyme activity was monitored at harvest time and after the final concentration.
- Enzyme Treated TMP First-stage coarse thermomechanical pulp was treated with partially purified culture supernatant from P. subserialis, C. subvermispora, and T.
- Duplicate reaction vessels contained 2.0 g OD coarse refiner mechanical pulp that was suspended in 5% (w/v) 50-mM sodium acetate buffer (pH 4.5). The pulp in each reaction vessel was mixed with concentrated enzyme broth at a normalized enzyme activity of approximately 1.50 nkatal ml "1 manganese peroxidase. Laccase activity was measured and monitored throughout the experiment. For each fungus, one reaction vessel was setup in duplicate for analysis at 0, 30, 60, 90, 180 and 360-minute intervals in a constant temperature bath of 30°C.
- Boiling chips were added to the boiling flask with 300 ml of the ethanol-benzene mixture. Samples were extracted for eight hours at brisk boiling with siphoning at approximately ten-minute intervals. After eight hours, the extraction thimbles were removed from the Soxhlet extractors, washed with 100% pure ethanol by placing the thimble in a 100 ml coarse ground glass crucible fitted on a 1000-ml sidearm flask. The thimble was returned to the Soxhlet extractor and extracted for four hours with 100% pure ethanol. The samples were transferred to a Buchner funnel and washed with hot water to remove the ethanol and then allowed to air dry for all subsequent carbohydrate and lignin analyses.
- Picea abies chips were prepared as previously described, inoculated with Phlebia subserialis, Ceriporiopsis subvermispora, and Trametes versicolor, and incubated for 30 days at 27°C with forced warm humidified air at a rate of 0.028 cubic meters per minute. The chips were thus incubated under conditions favorable to the propagation of the lignin-degrading fungus through the chips.
- Duplicate 500-g samples were removed from each bioreactor, and double-bagged in 6x9 zip lock bags. One bottom corner of the double bag was cut off with scissors.
- the stainless steel plates on the top and bottom pressing surfaces of the Williams press (Williams Apparatus Co., Watertown, NY) were cleaned first with soap and water and then dried with ethanol.
- the press was blocked up at a 45° angle and secured.
- the zip lock bag containing the sample was placed between the pressing surfaces and a clean 20-dram vial was placed under the cut corner of the bag. Pressure was applied (1500 psi) to the sample and the pressate was captured in the glass vial as a crude broth. Laccase and manganese peroxidase enzyme assays were performed on each vial to determine the enzyme present and enzyme concentration.
- the enzyme concentration was then adjusted to 1.4 nkatal ml and were used to treat l st -stage TMP as a method to reduce the amount of lignin within the pulp, reducing the electrical refining energy and thereby increasing pulp strength.
- This system can also be used as a first-stage biobleacbing of mechanical pulp.
- the enzyme activity levels were monitored, followed by a lignin analysis of the TMP.
- Table 1 lists the laccase and manganese peroxidase enzyme activity levels throughout the pulp treatment. Initial activity was measured from the concentrated production medium before addition to each sample and then the manganese peroxidase enzyme concentration was normalized to approximately 1.50 nkatal ml "1 for the zero-time condition.
- Laccase from P. subserialis showed a 22% decrease in activity while T. versicolor and C. subvermispora showed much smaller changes in activity, 3.1 and 1.4%, respectively. This difference may not be significant due to the much lower laccase activity in the enzyme broth from P. subserialis.
- Initial manganese peroxidase activity levels were on the same order of magnitude for all three fungal extract applications. The range in overall manganese peroxidase activity loss was from 15.8% forR. subserialis to 8.9 and 25.7% loss for T. versicolor and C. subvermispora, respectively.
- Figures 1 and 2 chart the enzyme activity throughout the experiment and show the decrease in activity over the life of the experiment. In particular, Fig.
- Fig. 1 illustrates the lignolytic enzyme activity change for the laccase enzyme, where thermomechanical pulping (TMP) is performed over a six hour treatment time on Picea abies (Norway Spruce) wood chips with fungal treatment using P. subserialis, T. versicolor and C. subvermispora.
- Fig. 2 illustrates the lignolytic enzyme activity change for the manganese peroxidase enzyme, for comparison with the results of Fig. 1.
- the horizontal axis denotes time, in minutes, from 0 to 400 minutes
- the left hand vertical axis denotes T.v. and C.s. laccase activity
- the right hand vertical axis denotes P.s. laccase activity.
- Fig. 1 illustrates the lignolytic enzyme activity change for the laccase enzyme, where thermomechanical pulping (TMP) is performed over a six hour treatment time on Picea abies (Norway Spruce) wood chips with fungal treatment using P. subse
- the horizontal axis denotes time, in minutes, from 0 to 400 minutes, while the left hand vertical axis denotes manganese peroxidase activity.
- Table 2 outlines the results from lignin analysis on the TMP, showing that the lignolytic enzyme treatment from C. subvermispora removed up to 3.66% of the lignin in the sample over a six-hour period, while P. subserialis and T. versicolor reduced the lignin content by similar amounts, 2.35 and 2.67%, respectively. P. subserialis showed a significant decrease in lignin content at the 90-minute sample; however, no significant change occurred after that time interval. Both T. versicolor and C.
- Table 2 Klason lignin analysis of a Picea abies TMP treated with partially purified enzymes from P. subserialis, T. versicolor and C. subvermispora over 6 hours
- FIG. 3 illustrates a method for processing wood chips, in accordance with the invention.
- wood chips are biopulped by inoculating the chips with a lignin-degrading fungus, and incubating.
- an enzyme is extracted from the biopulped chips as a crade broth and/or pressate.
- a concentrated broth with the enzyme is prepared.
- a further mechanical and/or chemical pulping of the chips is performed.
- the extracted enzyme is re-introduced to the chips by mixing the chips with the concentrated broth.
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Abstract
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/412,593 US8317975B2 (en) | 2004-04-20 | 2006-04-27 | Product and processes from an integrated forest biorefinery |
US13/683,642 US8668806B2 (en) | 2004-04-20 | 2012-11-21 | Product and processes from an integrated forest biorefinery |
US14/198,754 US8940133B2 (en) | 2004-04-20 | 2014-03-06 | Product and processes from an integrated forest biorefinery |
US14/603,663 US9273431B2 (en) | 2004-04-20 | 2015-01-23 | Product and processes from an integrated forest biorefinery |
US15/051,742 US9683329B2 (en) | 2004-04-20 | 2016-02-24 | Methods of producing a paper product |
US15/625,545 US9945073B2 (en) | 2004-04-20 | 2017-06-16 | Methods of producing a paper product |
US15/927,181 US20180245285A1 (en) | 2004-04-20 | 2018-03-21 | Methods of producing a paper product |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US56383704P | 2004-04-20 | 2004-04-20 | |
US60/563,837 | 2004-04-20 |
Related Child Applications (1)
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US11/412,593 Continuation-In-Part US8317975B2 (en) | 2004-04-20 | 2006-04-27 | Product and processes from an integrated forest biorefinery |
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WO2005103370A1 true WO2005103370A1 (fr) | 2005-11-03 |
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PCT/US2005/013216 WO2005103370A1 (fr) | 2004-04-20 | 2005-04-20 | Traitement enzymatique des pates de bois |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007035481A1 (fr) * | 2005-09-16 | 2007-03-29 | Enzymatic Deinking Technologies, L.L.C. | Traitement de copeaux de bois au moyen d'enzymes |
US20110073264A1 (en) * | 2009-08-13 | 2011-03-31 | The Research Foundation Of State University Of New York | Kraft-Pulping of Hot Water Extracted Woodchips |
US8317975B2 (en) * | 2004-04-20 | 2012-11-27 | The Research Foundation Of The State University Of New York | Product and processes from an integrated forest biorefinery |
CN103159865A (zh) * | 2013-02-01 | 2013-06-19 | 北京林业大学 | 半纤维素及其制备方法 |
CN111454690A (zh) * | 2020-05-21 | 2020-07-28 | 南宁雄晋生物科技有限公司 | 一种利用酶法改性制备木质素基胶黏剂的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US5055159A (en) * | 1990-05-16 | 1991-10-08 | Wisconsin Alumni Research Foundation | Biomechanical pulping with C. subvermispora |
US5081027A (en) * | 1989-03-16 | 1992-01-14 | Kabushiki Kaisha Kobe Seiko Sho | Method for producing pulp by treatment using a microorganism, and its related enzymes |
US5620564A (en) * | 1994-08-11 | 1997-04-15 | Wisconsin Alumni Research Foundation | Method of enhancing biopulping efficacy |
US5705383A (en) * | 1993-03-19 | 1998-01-06 | Clariant Finance (Bvi) Limited | Pitch and lignin degradation with white rot fungi |
-
2005
- 2005-04-20 WO PCT/US2005/013216 patent/WO2005103370A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5081027A (en) * | 1989-03-16 | 1992-01-14 | Kabushiki Kaisha Kobe Seiko Sho | Method for producing pulp by treatment using a microorganism, and its related enzymes |
US5055159A (en) * | 1990-05-16 | 1991-10-08 | Wisconsin Alumni Research Foundation | Biomechanical pulping with C. subvermispora |
US5705383A (en) * | 1993-03-19 | 1998-01-06 | Clariant Finance (Bvi) Limited | Pitch and lignin degradation with white rot fungi |
US5620564A (en) * | 1994-08-11 | 1997-04-15 | Wisconsin Alumni Research Foundation | Method of enhancing biopulping efficacy |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8317975B2 (en) * | 2004-04-20 | 2012-11-27 | The Research Foundation Of The State University Of New York | Product and processes from an integrated forest biorefinery |
US8668806B2 (en) | 2004-04-20 | 2014-03-11 | The Research Foundation Of The State University Of New York | Product and processes from an integrated forest biorefinery |
US8940133B2 (en) | 2004-04-20 | 2015-01-27 | The Research Foundation For The State University Of New York | Product and processes from an integrated forest biorefinery |
US9273431B2 (en) | 2004-04-20 | 2016-03-01 | The Research Foundation For The State University Of New York | Product and processes from an integrated forest biorefinery |
US9683329B2 (en) | 2004-04-20 | 2017-06-20 | The Research Foundation For The State University Of New York | Methods of producing a paper product |
US9945073B2 (en) | 2004-04-20 | 2018-04-17 | The Research Foundation For The State University Of New York | Methods of producing a paper product |
WO2007035481A1 (fr) * | 2005-09-16 | 2007-03-29 | Enzymatic Deinking Technologies, L.L.C. | Traitement de copeaux de bois au moyen d'enzymes |
US20110073264A1 (en) * | 2009-08-13 | 2011-03-31 | The Research Foundation Of State University Of New York | Kraft-Pulping of Hot Water Extracted Woodchips |
CN103159865A (zh) * | 2013-02-01 | 2013-06-19 | 北京林业大学 | 半纤维素及其制备方法 |
CN111454690A (zh) * | 2020-05-21 | 2020-07-28 | 南宁雄晋生物科技有限公司 | 一种利用酶法改性制备木质素基胶黏剂的方法 |
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