CN1519427A - Mechanical alkaline pulping method using hydrogen dioxide from raw material of grass family - Google Patents
Mechanical alkaline pulping method using hydrogen dioxide from raw material of grass family Download PDFInfo
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- CN1519427A CN1519427A CNA031390307A CN03139030A CN1519427A CN 1519427 A CN1519427 A CN 1519427A CN A031390307 A CNA031390307 A CN A031390307A CN 03139030 A CN03139030 A CN 03139030A CN 1519427 A CN1519427 A CN 1519427A
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Abstract
A process for mechanically preparing the alkaline hydrogen peroxide pulp from raw straw materials includes such steps as immersing raw straw materials in hot water, squeezing for dewatering, chemical pretreating, grinding, enzyme treating with the solution of semi-cellulase or the solution of semi-cellulase and lignin peroxidase, chemical pretreating, and grinding. The resultant pulp features high whiteness and strength and easy treatment of its sewage.
Description
(1) technical field
The present invention relates to the method for a kind of alkaline hydrogen peroxide machinery pulping (APMP), relate in particular to the method for a kind of grass as raw material APMP slurrying.
(2) background technology
Alkaline hydrogen peroxide machinery pulping (APMP) is a kind of new chemical mechanical slurry systeming process that grows up at the late 1980s and the beginning of the nineties, (as CTMP) compares with other chemical mechanical pulp-making method, have and to realize small-scale relatively production, firm location is subjected to that the restriction of raw material resources is little, slurrying and bleaching are carried out simultaneously, advantage such as equipment and capital expenditure are few, raw material wide accommodation, pollution control are easy, thereby be described as the pulping process of " development potentiality is arranged most ".At present, a lot of to the research of APMP slurrying in the world, the raw material of use relates to needlebush (as dragon spruce), leaf wood (as poplar, Eucalyptus etc.) and non-wood fibrous raw material (as bluish dogbane, bagasse etc.).At home, how tame unit such as Chinese pulping and paper-making studying and designing institute, South China Science ﹠ Engineering University, Shandong Light Ind College also carried out research (Chinese papermaking journal, 2003,18 (1): 19 to the APMP slurrying of plurality of raw materials such as bluish dogbane, Eucalyptus, poplar, masson pine; " modern pulping bleaching technology and principle ", work such as Chen Jiaxiang, publishing house of South China Science ﹠ Engineering University, 2000,158-172; International Paper, 2001,20 (1): 29-35).
Grass as raw material as wheat straw, is the main raw material(s) of China's paper industry, and it is raw-material more than 50% to account for China's paper industry.Grass as raw material such as present wheat straw mainly adopt chemical pulping, and as soda processes, sulfate process etc., pulping yield lower (generally being lower than 50%), a large amount of black liquor of Chan Shenging are difficult to reclaim effectively in process of production, have caused the serious environmental pollution problem.According to statistics, COD (COD) accounts for 46% of national industrial COD total release in China's pulp and paper industry waste discharges in 1998, occupy first (International Paper, 2000,5:20), wherein black liquor is the main source of COD.Therefore, the mechanical feedback technology of research paper pulp yield height, grass as raw material that pollution level is low is significant.But owing to compare with timber, the fibre length of grass as raw material such as wheat straw itself is just shorter, as adopt simple mechanical feedback, then owing in the defibrination process, understand excessive cut staple and big macrolesion pulp strength, therefore, the chemical mechanical slurry systeming process that development has Chemical Pretreatment is more suitable in prepare the paper pulp with better strength character with grass as raw material, wherein, because the plurality of advantages that the APMP pulping process is had makes the APMP slurrying of research wheat straw raw material more be of practical significance and environment protection significance.
Less relatively to the research of wheat straw APMP slurrying both at home and abroad, the data of having reported has people such as Canadian Pan G.X. to the research of wheat straw APMP pulping process condition, APMP slurry bleaching performance (Tappi J.2000,83 (7): 49 but so far; 83 (7): 58; 83 (5): 159; Cellulose Chemistry and Technology, 34:537), the Xu E.C. of U.S. Andritz company is to the research of wheat straw APMP slurrying, and the main technique that above-mentioned research is adopted comprises water retting, alkaline H
2O
2Pre-preg, defibrination etc.But above-mentioned research institute prepares the shortcoming of the wheat straw APMP slurry that to be pulp brightness low (generally being lower than 60%ISO) and to be difficult to bleaching.Owing to further improve relatively difficulty of whiteness, make the range of application of wheat straw APMP slurry be restricted, application potential is less.
(3) summary of the invention
The object of the present invention is to provide a kind of method of novel grass as raw material alkaline hydrogen peroxide machinery pulping (APMP), to solve an above-mentioned difficult problem that occurs in traditional APMP pulping process, the grass as raw material bleached pulp of producing high whiteness and having the higher-strength performance.
The objective of the invention is to be achieved through the following technical solutions, mainly comprise Hot water immersion, extrusion dehydration, for the first time Chemical Pretreatment, first section defibrination, enzyme handle, Chemical Pretreatment, second section step such as defibrination for the second time.
(1) raw material is cut off at first that (about 15～40mm), the dedusting of length was handled 1～3 hour with 60～80 ℃ of Hot water immersion then, and the ratio of water volume (milliliter) and raw material oven dry weight (gram) is 10: 1～30: 1.
(2) above-mentioned raw materials (compression ratio was more than or equal to 4: 1) behind extrusion dehydration adds 2～8%NaOH, 0.5～2%H
2O
2, 0.2～1%EDTA carries out the Chemical Pretreatment first time under 50～90 ℃ of conditions, water volume (milliliter) is 8: 1～15: 1 with the ratio of raw material oven dry weight (gram), the processing time is 20～60 minutes.
(3) after the Chemical Pretreatment, raw material carries out first section defibrination with fiberizer, refining concentration 10～25% (W/V), grinding clearance 0.1～0.5mm.
(4) behind the defibrination, coarse particles washes with water, handle with the mixed enzyme solution of hemicellulase crude enzyme liquid or hemicellulase crude enzyme liquid and lignin peroxidase crude enzyme liquid then, the enzyme treatment conditions are: concentration 3～15% (W/V), 30～180 minutes time, 40～70 ℃ of temperature, reaction system pH3.5～6.5, the hemicellulose enzyme dosage is every gram over dry raw material 2～40IU (xylanase activity is as the criterion), and the lignin peroxidase consumption is every gram over dry raw material 0.1～1.0IU.
When above-mentioned enzyme is handled, be good to select following condition: concentration 5～10%, 50～60 ℃ of temperature, 60～120 minutes time, pH4.0～5.5, zytase consumption are every gram over dry raw material 5～20IU, and the lignin peroxidase consumption is every gram over dry raw material 0.5～1.0IU.
The enzyme of above-mentioned various enzyme liquid is lived and is measured as follows:
Xylanase activity is measured: adopt DNS (3, the 5-dinitrosalicylic acid) method to measure reducing sugar, producing 1 μ mol reducing sugar with per minute is a unit of activity (IU).Get the suitably enzyme liquid to be measured of dilution of 0.5ml, add 1ml pH4.8,1% xylan (Oat Spelts Xylan, the Sigma) solution of the preparation of 0.2M acetate buffer solution, shake up, react 30min down at 50 ℃, control temperature, add 2mlDNS reagent stopped reaction after reaction finishes with water bath with thermostatic control, boil 10min, the cooling back is settled to 15ml with distilled water, surveys OD (absorbance) value in 540nm, calculates xylanase activity with reference to the wood sugar calibration curve.
Lignin peroxidase enzyme activity determination: the sodium tartrate buffer solution, 5mM veratryl alcohol, 0.3mL enzyme liquid and the 0.4mM H that contain 80mM, pH3.5 in the 3.0mL reactant liquor
2O
2, 30 ℃ of reactions down detect adding H
2O
2Afterreaction liquid changes in the light absorption at 310nm place, and the enzyme amount that forms 1 micromole's veratraldehyde with the per minute oxidation is an enzyme activity unit.
(5) coarse particles after the above-mentioned enzyme processing is carried out the Chemical Pretreatment second time, treatment conditions are: 1～3%NaOH, 2～6%H
2O
2, 0.2～1%EDTA, 60～90 ℃, 0.2～2%Na
2SiO
3, 0.1～1%MgSO
4, concentration 5-15% (W/V), the processing time is 30～120 minutes.
(6) with the raw material after above-mentioned second section Chemical Pretreatment, carry out second section defibrination, refining concentration 10～25% (W/V), grinding clearance 0.05～0.3mm with fiberizer.Behind the defibrination, slurry is latent through disappearing again, screening, makes paper pulp.
Grass as raw material in the above-mentioned APMP pulping process can be wheat straw, and one of bagasse, straw, reed, bluish dogbane, Chinese alpine rush or awns stalk relatively are applicable to wheat straw raw material.
Compare with traditional APMP pulping process, excellent results of the present invention is:
(1) Chemical Pretreatment is carried out at twice, can also obtain higher whiteness effectively when guaranteeing that paper pulp has the good strength performance.
(2) enzyme is handled and is positioned at before the Chemical Pretreatment second time, after first section defibrination.Do like this and have the following advantages: the one, raw material through first section defibrination after, fiber is by initial gross separation, specific fiber surface is long-pending to be increased, make enzyme and fiber surface directly carry out the chance that physics contacts and increase, and fiber is through after the Chemical Pretreatment for the first time, the easily molten material stripping of part alkali in the fiber, the porosity of fiber increases, enzyme is strengthened to the diffusion of fibrous inside and osmosis, and directly handle raw material with enzyme and compare, the effect of this two aspect can cause the raising of enzyme functioning efficiency; The 2nd, the raising of enzyme functioning efficiency helps reducing the time of biological treatment; The 3rd, data shows, and when APMP slurrying, chemical treatment for the second time has the greatest impact to whiteness, therefore, enzyme handled being placed on before the chemical treatment for the second time, can bring into play enzyme effectively and handle H
2O
2The facilitation of bleaching is improved the bleachability of Straw Pulp, makes the wheat straw APMP paper pulp of preparation have higher whiteness.
(3) adopt the wheat straw APMP slurry of method for preparing to have higher whiteness and good intensity, the whiteness of wheat straw APMP slurry can reach 65～80%ISO, and fracture length reaches more than 4500 meters; Can satisfy the needs of producing high-grade sheet paper products.
(4) specific embodiment
Embodiment 1:
Wheat straw raw material through cut-out (length is 20～30mm), after the dedusting, by the ratio of water volume (milliliter) and wheat straw oven dry weight (gram) be 10: 1 60 ℃ of ratio addings warm water and flooded 1 hour; Extrusion dehydration (compression ratio 4: 1) after finishing adds 2%NaOH, 0.5%H then
2O
2, 0.3%EDTA, handled 20 minutes down at 50 ℃, the ratio of water volume during processing (milliliter) and raw material oven dry weight (gram) is 15: 1; Carry out first section defibrination, refining concentration 10%, grinding clearance 0.5mm with fiberizer after disposing; After coarse particles washed with water, handled 30 minutes with the hemicellulase crude enzyme liquid under concentration 5%, 40 ℃, system pH3.5 condition, the zytase consumption is a 5IU/g over dry raw material; Slurry after enzyme is handled is through after washing, at 1%NaOH, 2%H
2O
2, 0.2%EDTA, 60 ℃, 2%Na
2SiO
3, 0.2%MgSO
4, handled again 30 minutes under concentration 5% condition; Carry out second section defibrination, refining concentration 10%, grinding clearance 0.1mm with fiberizer then.Slurry is latent through disappearing again, screening, and the whiteness of the wheat straw APMP slurry that makes is 55.2%ISO, and fracture length is 2500 meters.
Embodiment 2:
Wheat straw raw material through cut-out (length is 20～30mm), after the dedusting, by the ratio of water volume (milliliter) and wheat straw oven dry weight (gram) be 20: 1 70 ℃ of ratio addings warm water and flooded 2.5 hours; Extrusion dehydration (compression ratio 4: 1) after finishing adds 6%NaOH, 2%H then
2O
2, 0.5%EDTA, handled 40 minutes down at 80 ℃, the ratio of water volume during processing (milliliter) and raw material oven dry weight (gram) is 10: 1; Carry out first section defibrination, refining concentration 20%, grinding clearance 0.3mm with fiberizer after disposing; After coarse particles washed with water, under concentration 10%, 50 ℃, system pH5.0 condition, handled 90 minutes with the mixed enzyme solution of hemicellulase crude enzyme liquid and lignin peroxidase crude enzyme liquid, the zytase consumption is a 15IU/g over dry raw material, lignin peroxidase consumption 1IU/g over dry raw material; Slurry after enzyme is handled is through after washing, at 2%NaOH, 6%H
2O
2, 0.5%EDTA, 90 ℃, 1%Na
2SiO
3, 0.5%MgSO
4, handled again 60 minutes under concentration 10% condition; Carry out second section defibrination, refining concentration 20%, grinding clearance 0.15mm with fiberizer then.Slurry is latent through disappearing again, screening, and the whiteness of the wheat straw APMP slurry that makes is 75%ISO, and fracture length is 5000m.
Embodiment 3:
Wheat straw raw material through cut-out (length is 20～30mm), after the dedusting, by the ratio of water volume (milliliter) and wheat straw oven dry weight (gram) be 30: 1 80 ℃ of ratio addings warm water and flooded 2 hours; Extrusion dehydration (compression ratio 4: 1) after finishing adds 8%NaOH, 1%H then
2O
2, 0.8%EDTA, handled 60 minutes down at 90 ℃, the ratio of water volume during processing (milliliter) and raw material oven dry weight (gram) is 9: 1; Carry out first section defibrination, refining concentration 20%, grinding clearance 0.1mm with fiberizer after disposing; After coarse particles washed with water, handled 180 minutes with the hemicellulase crude enzyme liquid under concentration 15%, 65 ℃, system pH6.0 condition, the zytase consumption is a 30IU/g over dry raw material; Slurry after enzyme is handled is through after washing, at 2.5%NaOH, 4%H
2O
2, 0.5%EDTA, 80 ℃, 0.5%Na
2SiO
3, 0.5%MgSO
4, handled again 120 minutes under concentration 10% condition; Carry out second section defibrination, refining concentration 20%, grinding clearance 0.2mm with fiberizer then.Slurry is latent through disappearing again, screening, and the whiteness of the wheat straw APMP slurry that makes is 70%ISO, and fracture length is 5500 meters.
Claims (4)
1. the method for a grass as raw material alkaline hydrogen peroxide machinery pulping (APMP) is by Hot water immersion, extrusion dehydration, Chemical Pretreatment, first section defibrination, enzyme are handled for the first time, Chemical Pretreatment, second section step such as defibrination are formed for the second time; It is characterized in that described enzyme processing section is positioned at before the Chemical Pretreatment second time, after first section defibrination, used enzyme liquid is the hemicellulase crude enzyme liquid, perhaps is the mixed enzyme solution of hemicellulase crude enzyme liquid and lignin peroxidase crude enzyme liquid; The enzyme treatment conditions are: concentration 3～15%, and 30～180 minutes time, 40～70 ℃ of temperature, reaction system pH3.5～6.5, the hemicellulose enzyme dosage is every gram over dry raw material 2～40IU, the lignin peroxidase consumption is every gram over dry raw material 0.1～1.0IU.
2. the method for a kind of grass as raw material alkaline hydrogen peroxide machinery pulping as claimed in claim 1 (APMP), it is characterized in that, the enzyme treatment conditions are: concentration 5～10%, 50～60 ℃ of temperature, 60～120 minutes time, pH4.0～5.5, zytase consumption are every gram over dry raw material 5～20IU, and the lignin peroxidase consumption is every gram over dry raw material 0.5～1.0IU.
3. the method for a kind of grass as raw material alkaline hydrogen peroxide machinery pulping as claimed in claim 1 (APMP) is characterized in that, grass as raw material can be wheat straw, one of bagasse, straw, reed, bluish dogbane, Chinese alpine rush or awns stalk.
4. the method for a kind of grass as raw material alkaline hydrogen peroxide machinery pulping as claimed in claim 3 (APMP) is characterized in that, grass as raw material is a wheat straw.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03139030 CN1254583C (en) | 2003-09-02 | 2003-09-02 | Mechanical alkaline pulping method using hydrogen dioxide from raw material of grass family |
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| CN 03139030 CN1254583C (en) | 2003-09-02 | 2003-09-02 | Mechanical alkaline pulping method using hydrogen dioxide from raw material of grass family |
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| CN1519427A true CN1519427A (en) | 2004-08-11 |
| CN1254583C CN1254583C (en) | 2006-05-03 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101046072B (en) * | 2006-03-28 | 2010-09-22 | 天津科技大学 | Pre-treatment process for producing bleached slurry with cotton stalk material |
| CN101613976B (en) * | 2009-07-17 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing bleached chemi-mechanical pulp by using whole straw of mulberry tree branch |
| CN102174760A (en) * | 2011-03-14 | 2011-09-07 | 山东轻工业学院 | Process for preparing pulp by using salix mongolia by chemical mechanical method |
| CN102399843A (en) * | 2011-11-21 | 2012-04-04 | 华南理工大学 | Biomass enzymolysis saccharification pretreatment method |
| CN102400405A (en) * | 2010-09-15 | 2012-04-04 | 永丰馀造纸股份有限公司 | Method for manufacturing non-lumber fiber stuff |
| CN103898789A (en) * | 2012-12-27 | 2014-07-02 | 东莞市绿微康生物科技有限公司 | Bio enzyme preparation for improvement of paper forming strength of alkaline peroxide mechanical pulp (APMP) and application thereof |
| CN106269818A (en) * | 2016-11-11 | 2017-01-04 | 无限极（中国）有限公司 | The processing method of a kind of Chinese medicine dreg and application |
| CN111304943A (en) * | 2019-04-04 | 2020-06-19 | 南京工业大学 | Straw pulp fiber reinforced cement board and preparation method thereof |
-
2003
- 2003-09-02 CN CN 03139030 patent/CN1254583C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101046072B (en) * | 2006-03-28 | 2010-09-22 | 天津科技大学 | Pre-treatment process for producing bleached slurry with cotton stalk material |
| CN101613976B (en) * | 2009-07-17 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing bleached chemi-mechanical pulp by using whole straw of mulberry tree branch |
| CN102400405A (en) * | 2010-09-15 | 2012-04-04 | 永丰馀造纸股份有限公司 | Method for manufacturing non-lumber fiber stuff |
| CN102174760A (en) * | 2011-03-14 | 2011-09-07 | 山东轻工业学院 | Process for preparing pulp by using salix mongolia by chemical mechanical method |
| CN102174760B (en) * | 2011-03-14 | 2012-02-08 | 山东轻工业学院 | Process for preparing pulp by using salix mongolia by chemical mechanical method |
| CN102399843A (en) * | 2011-11-21 | 2012-04-04 | 华南理工大学 | Biomass enzymolysis saccharification pretreatment method |
| CN103898789A (en) * | 2012-12-27 | 2014-07-02 | 东莞市绿微康生物科技有限公司 | Bio enzyme preparation for improvement of paper forming strength of alkaline peroxide mechanical pulp (APMP) and application thereof |
| CN103898789B (en) * | 2012-12-27 | 2016-08-24 | 东莞市绿微康生物科技有限公司 | Improve biological enzyme formulation and the application thereof of APMP paper strength |
| CN106269818A (en) * | 2016-11-11 | 2017-01-04 | 无限极（中国）有限公司 | The processing method of a kind of Chinese medicine dreg and application |
| CN111304943A (en) * | 2019-04-04 | 2020-06-19 | 南京工业大学 | Straw pulp fiber reinforced cement board and preparation method thereof |
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|---|---|
| CN1254583C (en) | 2006-05-03 |
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