CN103362009A - Rapid-growth poplar sodium hydroxide anthraquinone pulp biochemical method TCF bleaching process - Google Patents

Rapid-growth poplar sodium hydroxide anthraquinone pulp biochemical method TCF bleaching process Download PDF

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CN103362009A
CN103362009A CN2013103012519A CN201310301251A CN103362009A CN 103362009 A CN103362009 A CN 103362009A CN 2013103012519 A CN2013103012519 A CN 2013103012519A CN 201310301251 A CN201310301251 A CN 201310301251A CN 103362009 A CN103362009 A CN 103362009A
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paper pulp
naoh
bleaching
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陈嘉川
吉兴香
杨桂花
田中建
孔凡功
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Qilu University of Technology
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Abstract

The invention discloses a rapid-growth poplar sodium hydroxide anthraquinone pulp biochemical method TCF bleaching process. The process is characterized in that the process comprises the steps that: (1) steaming is carried out, wherein rapid-growth poplar wood sheets are steamed in a steaming pot, such that an original pulp is obtained; washing and screening are carried out, such that paper pulp is obtained; (2) xylanase pretreatment is carried out; (3) TCF bleaching is carried out, wherein the treated paper pulp is bleached with one of the bleaching sequence selected from OP-Q-P, O1-O2P-Q-P and O1P-O2P-Q-P. According to the invention, paper pulp is pretreated by using xylanase, and bleaching is carried out with one of the three bleaching sequences of XOPQP, XO1O2PQP and XO1PO2PQP, such that paper pulp with higher whiteness and viscosity are obtained. Compared with paper pulp obtained by direct bleaching without xylanase pretreatment, the paper pulp provided by the invention has lower beating whiteness loss. A folding resistance is higher by 30-49 times, a burst index is higher by 0.3-0.6N.m.g<-1>, a breaking length is higher by 0.15-0.36KM, and a tearing index is not significantly changed. When a same or similar beating degree is reached, needed beating revolutions are less, and beating energy consumption can be saved by approximately 17.8%.

Description

The NaOH anthraquinone slurry biochemical process TCF bleaching process of a kind of fast-growing poplar
Technical field
The present invention relates to the NaOH anthraquinone slurry biochemical process TCF bleaching process of a kind of fast-growing poplar, belong to pulp technology for making paper.
Background technology
Owing to produced the foul gas that hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl sulphide etc. have peculiar smell in sulfate pulping and the alkali recovery process, atmosphere around the production unit is existed the problem of pollution and air peculiar smell, therefore in the open type slurrying production procedure of some medium-sized pulp mills, adopted take NaOH anthraquinone as main pulping technique.Because the chemicals of the anthraquinone slurrying of NaOH mainly is NaOH; also contain a small amount of anthraquinone as the boiling protective agent; these two kinds of chemicalss are nontoxic free from extraneous odour all; also do not produce the material of peculiar smell in the pulping digestion process, therefore this soda pulping process technology is used more at part batch (-type) pulping by cooking production line.
The fast-growing poplar is as a kind of good paper making raw material, its yield of producing NaOH anthraquinone slurry is higher, generally about 51%, and the own whiteness of fast-growing poplar is high, former pulp brightness after the anthraquinone slurrying of NaOH exceeds 3-5%ISO than the former pulp brightness of other leaf woods generally about 35%ISO.And the fast-growing poplar is as a kind of broad-leaved wood paper making raw material of high-quality, and the black liquor that produces in its alkaline cooking process has the treatment technology of comparative maturity, and environment is not polluted substantially.
At present, the application study of zytase in the broad-leaved wood sulphate pulp bleaching is a lot, and partly realizes industrialization abroad, and not yet realization is at home used on a large scale.Simultaneously, zytase is studied rarely seen report for technique and the mechanism of the bleaching of NaOH anthraquinone slurry.For this reason, the application has selected three kinds of novel commercial xylanase, adopt the biochemistry method for bleaching, explored the new technology completely without chlorine (TCF) bleaching of a kind of fast-growing poplar NaOH-AQ slurry, for food, medicine etc. require nontoxic package paper, speciality paper etc. fast, sound development provides reality and theoretical foundation.
Summary of the invention
For above-mentioned prior art, the objective of the invention is to change the technique of the simple chemical method association with pulp bleaching of tradition, the method that adopts bio-bleaching to combine with complete free from chloride chemical bleaching technique, when reaching identical pulp brightness, when consuming identical chemical bleaching liquor, more Gao Gengyi making beating of the whiteness that makes paper pulp, when reducing the beating energy consumption of paper pulp to environment substantially without any pollution, thereby realizing that the low consumption of fast-growing poplar NaOH anthraquinone slurry is high efficiency bleaches completely without chlorine (TCF).
The present invention is achieved by the following technical solutions: the concentration of following related slurry is mass percent if no special instructions; Related reagent, the consumption of medicine if no special instructions, all are for oven dry stock.
The NaOH anthraquinone slurry biochemical process TCF bleaching process of a kind of fast-growing poplar, step is as follows:
(1) boiling: get the quick growth poplar wood sheet, put into the digester boiling, get magma, then wash fully, screen, get paper pulp, the Kappa number of paper pulp is 16～21;
(2) xylanase pretr eatment;
(3) TCF bleaching: the above-mentioned paper pulp of processing through enzyme is bleached, and bleaching process is O P-Q-P, O 1-O 2P-Q-P or O 1P-O 2PThree kinds of-Q-P float one of order, and the step of bleaching process is: at first, the paper pulp of processing through enzyme is carried out the deoxidation lignin or strengthens the deoxidation lignin; Oxygen delignification washs paper pulp after finishing, and then carries out Q section chelation treatment; Q section chelation treatment is washed paper pulp after finishing, and then carries out P section H 2O 2Bleaching is finished.
Further, the concrete mode of described boiling is: get the quick growth poplar wood sheet of length 15～25mm, width 10～20mm, thickness 3～5mm, behind the natural air drying, in 15L electric heating rotating autoclave, carry out boiling, make fast-growing poplar NaOH anthraquinone magma, the condition of boiling is: alkali charge 22%(is to the over dry raw material, and NaOH counts), AQ consumption 0.05%, liquor ratio 1:4,165 ℃ of boiling maximum temperatures are carried out little venting 10-15min in the time of 105 ℃, heating-up time 90min, temperature retention time 90min; The boiling disposed slurry gets paper pulp, the Kappa number 16～21 of paper pulp through fully washing, screening.
Further, the concrete mode of described xylanase pretr eatment is: adjusting pulp density is 10%, then uses zytase X 1, X 2Or X 3Process, in processing procedure, every interval 10～15min rubs once, to guarantee that enzyme mixes with the even of paper pulp; Take out after processing, put into boiling water bath 10min, make zytase inactivation cessation reaction, with entering next step bleaching process behind the running water cleaning paper pulp.
Described zytase X 1Provide (the letter zytase Pulpzyme HC of trade name Novi, article number CKN00117 and CDN00429) by Novozymes Company, liquid state, the cellulose-less enzyme is lived; Zytase X 2, X 3Biological Co., Ltd provides (trade name zytase, article number LV-1 and LV-2) by the green little health in Shenzhen, is the white powder solid, and all cellulase is not lived.
Described zytase X 1, X 2Or X 3The concrete technology condition of processing is as follows: dextranase X 1Process conditions be: enzyme dosage 10IU/L(is for the cumulative volume of paper pulp), temperature 50 C, pH8-9, time 90-120min; Zytase X 2Process conditions be: enzyme dosage 8IU/g(is for the quality of exhausted paper pulp), 55 ℃ of temperature, pH8-9, time 90-120min; Zytase X 3Process conditions be: enzyme dosage 10IU/g(is for the quality of exhausted paper pulp), temperature 50 C, pH8-9, time 120min.
Further, described O PThe concrete mode of the white operation of-Q-P is: Oxygen Delignification of Fast-Growing is: starch dense 10%, NaOH consumption 2.5%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 80min, MgSO 4Consumption 0.5%; The Q section: starch dense 8%, DTPA(Chinese diethylene triamine pentacetic acid (DTPA)) consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
Further, described O 1-O 2PThe concrete mode of-Q-P bleaching process is: first paragraph oxygen delignification and second segment are strengthened the process conditions of oxygen delignification: first paragraph O 1: starch dense 10%, NaOH consumption 2%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, MgSO 4Consumption 0.5%; Second segment O 2P: replenish 0.5% NaOH, add 3% H 2O 2, Na 2SiO 3Consumption 0.7%, oxygen is pressed 0.5MPa, time 60min; The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
Further, described O 1P-O 2PThe concrete mode of-Q-P bleaching process is: two sections process conditions of strengthening oxygen delignification: first paragraph O 1P: starch dense 10%, NaOH consumption 2%, H 2O 2Consumption 1%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%; Second segment O 2P: replenish 0.5% NaOH, add 2.5% H 2O 2, oxygen is pressed 0.5MPa, time 60min; The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
The present invention adopts zytase that paper pulp is carried out preliminary treatment, then passes through XO PQPXO 1O 2PQP, XO 1PO 2PThree kinds of QP float one of order and bleach, and have obtained the higher paper pulp of whiteness and viscosity, (X refers to xylanase pretr eatment) specific as follows:
Fast-growing poplar NaOH-AQ starches XO PQP floats order at H 2O 2In the situation of total consumption 5%, the whiteness of floating rear slurry is up to 83.5%ISO, minimum 83.2%ISO; O PThe whiteness of QP bleached pulp is 81.0%ISO, through enzyme process than not with enzyme process float after the whiteness of slurry exceed 2.2-2.5%ISO, and kept higher pulp viscosity and lower Kappa number;
Fast-growing poplar NaOH-AQ starches XO 1O 2PQP floats order at H 2O 2In the situation of total consumption 5%, the whiteness of bleached pulp is up to 83.3%ISO, minimum 83.0%ISO; O 1O 2PThe whiteness of QP bleached pulp is 80.8%ISO, through enzyme process than not with enzyme process float after the whiteness of slurry exceed 2.2-2.5%ISO, and kept higher pulp viscosity and lower Kappa number;
Fast-growing poplar NaOH-AQ starches XO 1PO 2PQP floats order at H 2O 2In the situation of total consumption 5.5%, the whiteness of bleached pulp is up to 84.0%ISO, minimum 83.6%ISO; O 1PO 2PThe whiteness of QP bleached pulp is 81.8%ISO, through enzyme process than not with enzyme process float after the whiteness of slurry exceed 1.8-2.2%ISO, and kept higher pulp viscosity and lower Kappa number.
With respect to not using xylanase pretr eatment, directly bleach for the paper pulp that obtains, making beating loss of whiteness value of the present invention still less, folding strength exceeds 30-49 time, burst index exceeds 0.3-0.6Nmg -1, fracture length exceeds 0.15-0.36KM, and tear index changes little.When reaching identical or close beating degree, the former required making beating revolution still less can be saved beating energy consumption about 17.8%.Paper pulp after fast-growing poplar NaOH-AQ slurry is processed through enzyme carries out O PQP, O 1O 2PQP, O 1PO 2PThe TCF bleaching of QP, in the situation that consumes identical chemicals, can improve the final whiteness 1.8-2.5%ISO of paper pulp, kept higher pulp viscosity, and the physical indexs such as folding strength, bursting strength, fracture length that become paper all are better than the paper pulp do not processed with enzyme, this shows that these three kinds of enzymes have kept better bleaching selectivity, has improved more significantly the physical property of floating rear slurry, wherein helps to float effect and it would be desirable X 2, X 1And X 3Effect suitable.
Description of drawings
Fig. 1: NaOH-AQ magma fiber properties schematic diagram.
Fig. 2: NaOH-AQ magma is through zytase X 1The paper pulp fiber characteristic schematic diagram of processing.
Fig. 3: NaOH-AQ magma is through zytase X 2The paper pulp fiber characteristic schematic diagram of processing.
Fig. 4: NaOH-AQ magma is through zytase X 3The paper pulp fiber characteristic schematic diagram of processing.
Fig. 5: NaOH-AQ magma is through O PThe paper pulp fiber characteristic schematic diagram of QP bleaching.
Fig. 6: NaOH-AQ magma is through X 1O PThe paper pulp fiber characteristic schematic diagram of QP bleaching.
Fig. 7: NaOH-AQ magma is through X 2O PThe paper pulp fiber characteristic schematic diagram of QP bleaching.
Fig. 8: NaOH-AQ magma is through X 3O PThe paper pulp fiber characteristic schematic diagram of QP bleaching.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
The process optimization of embodiment 1 xylanase treatment fast-growing poplar NaOH-AQ slurry
The research and comparison of zytase aspect leaf wood KP slurry auxiliary bleaching is many, has also obtained good effect.According to pertinent literature, the principal element that affects xylanase treatment paper pulp has enzyme dosage, temperature, pH value and time etc., and these factors have in various degree impact to oxygen delignification effect and follow-up bleaching.At present, because the research rarely seen report of zytase in the bleaching of fast-growing poplar NaOH-AQ slurry, so inquire into the only preliminary treatment fast-growing of different xylanase preparations poplar NaOH-AQ sizing process condition, and utilize various modern Instrumental Analysis means, inquire into Novel xylanase helping of fast-growing poplar NaOH-AQ slurry floated mechanism, have important innovation and realistic meaning.
The below discusses different xylanase preparations in the impact of the factors such as consumption, temperature, pH value, time on fast-growing poplar NaOH-AQ slurry oxygen delignification effect.With reference to the Master's thesis of the lucky emerging perfume (or spice) of inventor, it is as follows to formulate better oxygen delignification condition when the Oxygen Delignification of Fast-Growing condition of selecting in this experiment: starch dense 10%, NaOH consumption 2.5%, oxygen pressure 0.6MPa, 100 ℃ of temperature, time 80min, MgSO 4All drug dosages of consumption 0.5%(are all for oven dry stock, and are as follows).
The used raw material sources of this experiment are:
Experiment is to mix the quick growth poplar wood sheet with the quick growth poplar wood sheet, takes from Shandong sun Paper Co., Ltd.Chip dimensions length 15-25mm, width 10-20mm, thickness 3-5mm, the qualification rate of wood chip is more than 90%, and is after wood chip is fetched from the stock ground, for subsequent use behind the natural air drying equilibrium water conten.
Zytase X 1Provided by Novozymes Company, liquid state, the cellulose-less enzyme is lived; Zytase X 2, X 3All have Shenzhen biological Co., Ltd of green little health to provide, be the white powder solid, all cellulase is not lived.
During experiment, the fast-growing poplar is carried out boiling, obtain paper pulp after, carry out again xylanase pretr eatment.Digestion process is: carry out boiling in 15L electric heating rotating autoclave, make fast-growing poplar NaOH-AQ magma.The condition of boiling is: alkali charge 22%(is to the over dry raw material, and NaOH counts), AQ consumption 0.05%, liquor ratio 1:4,165 ℃ of boiling maximum temperatures are carried out little venting 10-15min, heating-up time 90min, temperature retention time 90min in the time of 105 ℃.The boiling disposed slurry is through fully washing, screening.Paper pulp yield 49.5%, the Kappa number 18.2 of paper pulp, viscosity 881.7mL/g, whiteness 36.0%ISO.
Behind the xylanase pretr eatment, carry out oxygen delignification, the oxygen delignification experiment is carried out in JF-DSTE polymerization reaction kettle (have and stir and the automatic constant-temperature function).Its Oxygen Delignification of Fast-Growing is: starch dense 10%, NaOH consumption 2.5%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 80min, MgSO 4Consumption 0.5%.
1.1 the consumption of zytase is on the impact of fast-growing poplar NaOH-AQ slurry oxygen delignification
Because the content of different slurry kind of xylans is different, higher than the content of softwood pulp such as the xylan content of hardwood pulp, and xylan is easier and, so the consumption of enzyme is less.In the suitable situation of pH value and temperature, the consumption with zytase of greater activity just lacks than common zytase consumption.So in order to obtain best enzyme treatment effect, must carry out optimum experimental to the consumption of xylanase treatment fast-growing poplar NaOH-AQ slurry.Present embodiment mainly is to inquire into three kinds of Novel xylanase consumptions to the impact of fast-growing poplar NaOH-AQ slurry oxygen delignification effect.Following table 1,2,3 is three kinds of Novel xylanase X 1, X 2, X 3Consumption to fast-growing poplar NaOH-AQ slurry oxygen delignification experimental studies results.
Table 1 zytase X 1Consumption is on the impact of the oxygen delignification performance of pretreating paper pulp
Figure BDA00003525545500041
Annotate: zytase X 1Other conditions of processing: temperature 50 C, time 120min, starch dense 10%, pH value 8-9.
As can be seen from Table 1, under identical xylanase treatment condition, along with zytase X 1Increase, weaken to some extent after the whiteness of the paper pulp behind the NaOH-AQ slurry oxygen delignification improves first, at X 1When consumption was 10IU/L, the whiteness of paper pulp reached peak 60.5%ISO; The Kappa number of paper pulp is along with X 1The increase of consumption no longer changes after progressively reducing first, at X 1During consumption 10-12IU/L, the Kappa number minimum of paper pulp is 7.6; The viscosity of paper pulp is along with X 1The increase of consumption tends towards stability after progressively raising first, at X 1During consumption 8-10IU/L, the viscosity maximum of paper pulp is 772mL/g.
Also can find out from table 1, be not the consumption that the increases zytase effect that just can always increase pulp oxygen delignification.The factors such as the whiteness of paper pulp, Kappa number, viscosity can draw behind the comprehensive oxygen delignification: zytase X 1The most suitable consumption of processing NaOH-AQ slurry be 10IU/L.
Table 2 zytase X 2Consumption is on the impact of the oxygen delignification performance of pretreating paper pulp
Figure BDA00003525545500042
Annotate: zytase X 2Other conditions of processing: temperature 50 C, time 120min, starch dense 10%, pH value 8-9.
As can be seen from Table 2, along with zytase X 2The increase of consumption slightly reduces after the whiteness of paper pulp increases first behind the NaOH-AQ slurry oxygen delignification and is tending towards gradually constant, and when the zytase consumption was 8IU/g, whiteness reached 60.6%ISO, did not use X 2The whiteness of the oxygen delignification paper pulp of processing improves 1.5%ISO; The viscosity of paper pulp rises first and tends towards stability afterwards or slightly reduction, at zytase X 2When consumption was 6IU/g, the viscosity of oxygen delignification paper pulp remained on 769mL/g, does not use X 2The viscosity of the oxygen delignification paper pulp of processing exceeds 26mL/g; The Kappa number of paper pulp reduces first and is tending towards afterwards constant or slightly rises, at zytase X 2When consumption is 8-10IU/g, paper pulp kappa number minimum 7.7.
Can find out also that from table 2 consumption that neither increase zytase just can increase the effect of pulp oxygen delignification always.Consider the experimental result of table 2, can draw zytase X 2When consumption was 8IU/g, the paper pulp that enzyme is processed was best to the effect of oxygen delignification.
Table 3 zytase X 3Consumption is on the impact of the oxygen delignification performance of pretreating paper pulp
Figure BDA00003525545500043
Annotate: zytase X 3Other conditions of processing: temperature 50, time 120min, starch dense 10%, pH value 8-9.
As can be seen from Table 3, along with zytase X 3The increase of consumption no longer increases on the contrary slightly decline, at X after the whiteness of paper pulp progressively increases behind the oxygen delignification 3When consumption was 10IU/g, the whiteness of paper pulp reached 60.5%ISO, does not use X 3The whiteness of the oxygen-delignified pulp of processing exceeds 1.4%ISO; The Kappa number of paper pulp descends first and is tending towards afterwards no longer changing, at X 3When consumption was 10-12IU/g, the Kappa number of paper pulp was minimum 7.7, and the oxygen-delignified pulp of more processing with enzyme reduces by 0.8 unit; The viscosity of paper pulp is tending towards slightly changing after keeping first rising, at X 3When consumption was 8IU/g, the viscosity of paper pulp reached maximum 762mL/g, and the viscosity of the oxygen-delignified pulp of more not processing with enzyme exceeds 19mL/g.
From the experimental data of table 3, can draw: at X 3When consumption was 8-10IU/g, the oxygen delignification effect of xylanase treatment paper pulp was comparatively desirable.
Can find out from table 1,2 and 3, oxygen-delignified pulp after three kinds of zytases are processed the NaOH-AQ slurry is all along with the increase of enzyme dosage, the whiteness of paper pulp and viscosity all increase first and is tending towards afterwards no longer changing, and is substantially constant after the Kappa number of paper pulp reduces first, just slightly variant on the general effect.Also can find out from top experimental data, the paper pulp of paper pulp behind oxygen delignification that three kinds of enzymes are processed has shown the common feature of higher whiteness, lower Kappa number and higher pulp viscosity, and this shows that also the preliminary treatment that zytase is used for before the NaOH-AQ anthraquinone slurry oxygen delignification is feasible.
In sum, the only consumption of three kinds of enzyme processing NaOH-AQ is: X 1Consumption is 10IU/L, X 2Consumption is 8IU/g, X 3Consumption is 8-10IU/g.
1.2 temperature is on the impact of fast-growing poplar NaOH-AQ slurry oxygen delignification
The activity of zytase is relevant with temperature, and temperature raises can fast reaction speed, Reaction time shorten.Therefore too high or too low for temperature, the relative activity of enzyme can reduce, and must control temperature well.Temperature mainly contains two aspects to the effect of zytase and paper pulp: the one, in the scope of zytase existence temperature, the activity of temperature rising enzyme improves, accelerate with the speed of paper pulp reaction, the 2nd, along with the rising enzyme of temperature loses activity gradually, so that the functioning efficiency of the reaction speed of enzyme and enzyme reduces.Therefore select suitable reaction temperature, the usefulness of giving full play to zytase has important practical significance.Table 4,5, the 6th, temperature is to three kinds of Novel xylanase X 1, X 2, X 3Process the result of study that affects of NaOH-AQ slurry oxygen delignification.
Table 4 temperature is to zytase X 1The impact of the oxygen delignification performance of pretreating paper pulp
Figure BDA00003525545500051
Annotate: enzyme dosage is 10IU/L, time 120min, starch dense 10%, pH value 8-9.
As can be seen from Table 4, along with the rising of temperature, zytase X 1Reduce gradually after the whiteness of the NaOH-AQ slurry oxygen-delignified pulp of processing raises first, when temperature was 55 ℃, pulp brightness reached maximum 60.5%ISO; The Kappa number of paper pulp reduces first rear rising, when temperature is 50-55 ℃, and the Kappa number of paper pulp minimum 7.6; The viscosity of paper pulp raises first and diminishes afterwards, when temperature is 55 ℃, and the highest 767mL/g of viscosity of paper pulp.
The experimental result of consolidated statement 4, zytase X 1Enzyme activity in the time of 50-55 ℃, be more satisfactory.But consider zytase X from actual production 1Select treatment temperature be 55 ℃ relatively good, both can save heat and reduce the water consumption, can reduce production costs and increase economic efficiency again.
Table 5 temperature is to zytase X 2The impact of the oxygen delignification performance of pretreating paper pulp
Figure BDA00003525545500052
Annotate: enzyme dosage is 8IU/g, time 120min, starch dense 10%, pH value 8-9.
As can be seen from Table 5, along with the rising of temperature, zytase X 2Increase afterwards first with the action effect of paper pulp and to weaken.As can be seen from Table 5, along with the rising of pretreatment temperature, the pulp brightness behind the oxygen delignification begins to improve, when 55 ℃ of temperature, and X 2The whiteness of the NaOH-AQ slurry oxygen-delignified pulp of processing reaches 60.6%ISO, and the whiteness of paper pulp begins to reduce behind the oxygen delignification subsequently; The Kappa number of paper pulp reduces along with the rising of temperature, and Kappa number is minimum to 7.7 when 55 ℃ of temperature; The viscosity of paper pulp becomes along with the rising of temperature greatly, but when temperature surpassed 55 ℃, the viscosity of paper pulp was up to 764mg/L; The viscosity of paper pulp descends apparent in viewly when temperature surpasses 60 ℃, shows that the usefulness of excess Temperature zytase performance reduces rapidly.
The experimental result of consolidated statement 5 draws: as zytase X 2The effect of preliminary treatment fast-growing poplar NaOH-AQ slurry is the most desirable when temperature is 55-60 ℃.
Table 6 temperature is to zytase X 3The impact of the oxygen delignification performance of pretreating paper pulp
Figure BDA00003525545500061
Annotate: enzyme dosage is 10IU/g, time 120min, starch dense 10%, pH value 8-9.
As can be seen from Table 6, along with the rising of temperature, zytase X 3The rear reduction that raises first of the whiteness of the oxygen-delignified pulp of processing, when temperature was 50 ℃, whiteness reached 60.5%ISO, and when temperature was 55 ℃, whiteness reached 60.4%ISO; The Kappa number of paper pulp is 7.7 when temperature is 50 ℃, and temperature is 7.8 when being 55 ℃; The rising first increases and then decreases of the viscosity with temperature of paper pulp is 760mg/L when temperature is 50 ℃, is 759mg/L when temperature is 55 ℃.Can draw thus zytase X 3Performance helps that to float performance ideal when temperature is 50 ℃.
Can find out that from table 4,5,6 temperature that three kinds of xylanase treatment fast-growing poplar NaOH-AQ slurry is fit to is all 50-55 ℃ of scope, temperature cross low too high all the action effect of enzyme and paper pulp can not be performed to best.But the temperature of three kinds of xylanase treatment effects preferably the time be difference to some extent also: zytase X 1And X 3The effect of enzyme pulp treatment is better when temperature is 50-55 ℃, zytase X 2Effect is better when being 55-60 ℃.
1.3pH value is on the impact of fast-growing poplar NaOH-AQ slurry oxygen delignification
Zytase has different activities under different pH values, thereby the hydrolyzed xylan ability is different.The activity of most of zytase need to competence exertion effect in certain pH value scope, and pH value is crossed to exceed to hang down all can affect the conformation of zymoprotein, even zytase is lost activity, thereby directly has influence on the effect of xylanase treatment paper pulp.Table 7,8, the 9th, the experimental data of the effect of the lower xylanase treatment fast-growing poplar NaOH-AQ slurry of different pH values oxygen delignification.
Table 7 pH value is to zytase X 1Pretreating paper pulp is on the impact of oxygen delignification effect
Figure BDA00003525545500062
Annotate: enzyme dosage is 10IU/L, temperature 50 C, and time 120min starches dense 10%.
As can be seen from Table 7, zytase X 1The whiteness of paper pulp is that 8 o'clock pulp brightness are up to 60.5%ISO along with the increase of pH value increases first rear reduction in the pH value behind the preliminary treatment fast-growing poplar NaOH-AQ slurry oxygen delignification, is that 9 o'clock pulp brightness reach 60.4%ISO in the pH value; The Kappa number of paper pulp is along with the rising of pH value reduces first rear increase, and pH value 8 and 9 o'clock, Kappa number is minimum all to reach 7.6; The viscosity of paper pulp becomes first with the rising of pH value and diminishes after large, and when pH value 8, the viscosity of paper pulp reaches maximum 767mg/L.Therefore, zytase X 1The optimal pH of pulp treatment is 8-9.
As can be seen from Table 8, along with the increase of pH value, X 2Slowly reducing after the whiteness of the fast-growing poplar NaOH-AQ slurry oxygen-delignified pulp of processing improves rapidly first, is 8 o'clock in the pH value, and pulp brightness reaches the highest 60.6%ISO, is 9 o'clock in the pH value, and pulp brightness reaches 60.5%ISO; The Kappa number of paper pulp is to reach 7.7 at 8 o'clock in the pH value, is to reach minimum 7.6 at 9 o'clock in the pH value; The viscosity of paper pulp is to reach 764mg/L at 8 o'clock in the pH value, is to reach maximum 766mg/L at 9 o'clock in the pH value.Can draw thus: X 2The optimal pH of the fast-growing poplar NaOH-AQ slurry of processing is 8-9.
Table 8 pH value is to zytase X 2Pretreating paper pulp is on the impact of oxygen delignification effect
Figure BDA00003525545500071
Annotate: enzyme dosage is 8IU/g, 55 ℃ of temperature, and time 120min starches dense 10%.
As can be seen from Table 9, zytase X 3The whiteness of paper pulp is along with the rising of pH value increases first rear reduction behind the preliminary treatment fast-growing poplar NaOH-AQ slurry oxygen delignification, and when pH value 9, the whiteness of paper pulp is up to 60.5%ISO; The Kappa number of paper pulp is along with the increase of pH value reduces first rear increase, and when pH value 8-9, Kappa number reaches minimum 7.7; The viscosity of paper pulp is along with the increase of pH value increases first rear reduction, and when pH value 8, the viscosity of paper pulp reaches maximum 763mL/g.When the treatment effect of pH value 8 and 9 is substantially suitable, gap is very little, can draw thus zytase X 3The better pH value of pretreating paper pulp is 8-9.
Table 9 pH value is to zytase X 3Pretreating paper pulp is on the impact of oxygen delignification effect
Figure BDA00003525545500072
Annotate: enzyme dosage is 10IU/g, temperature 50 C, and time 120min starches dense 10%.
Can find out that from table 7,8,9 the pH value of three kinds of zytases treatment effect to paper pulp in the 8-10 scope is all more satisfactory.Zytase X 1, X 2And X 3Best pH value all is 8-9.It is different that this and three kinds of enzymes are used for the optimal pH of Aspen KP slurry, also there are differences with the zymologic property of three kinds of zytases.The most suitable pH value of the zymologic property test of these three kinds of zytases all is 8, optimal pH when processing fast-growing poplar NaOH-AQ slurry all is 8-9, this shows that the alkali resistance of three kinds of zytases when processing this slurry increases, and the enzyme that is conducive to after the soda pulping process is processed.
1.4 the time is on the impact of fast-growing poplar NaOH-AQ slurry oxygen delignification effect
There is certain influence time to xylanase treatment fast-growing poplar NaOH-AQ slurry.If the time is too short, the effect of zytase and paper pulp is abundant not, can not bring into play its usefulness.If overlong time is unfavorable for enhancing productivity.Based on this, in immobilized enzyme consumption, temperature, pH value with starch and studied the time under the dense condition to the impact of NaOH-AQ slurry pretreating effect.Experimental result sees Table 10,11,12.
Table 10 time is to zytase X 1Pretreating paper pulp is on the impact of oxygen delignification effect
Figure BDA00003525545500073
Annotate: enzyme dosage is 10IU/L, temperature 50 C, and pH value 8 starches dense 10%
As can be seen from Table 10, along with the prolongation of time, zytase X 1The NaOH-AQ slurry of processing is tending towards constant or slightly reduces after the pulp brightness behind the oxygen delignification progressively raises.When the processing time was 120min, the whiteness of paper pulp reached peak 60.5%ISO, and the paper pulp of more not processing with enzyme exceeds 1.4%ISO; The Kappa number of paper pulp is tending towards constant after progressively reducing first, and the processing time, the Kappa number of paper pulp was down to 7.6 when being 120min, and more untreated paper pulp hangs down 0.9 unit; The viscosity of paper pulp is along with the prolongation of time is tending towards substantially constant after progressively raising, and when the processing time was 120min, the viscosity of paper pulp reached maximum 767mL/g.Can find out that from table 10 time of enzyme pulp treatment is when being 90min, effect is not best but has kept higher whiteness, lower Kappa number and higher viscosity yet, meets the needs of production to a certain extent yet.Therefore, zytase X 1The time 90-120min of pulp treatment is advisable.
As can be seen from Table 11, along with the prolongation of time, zytase X 2Fast-growing poplar NaOH-AQ slurry after the processing is behind oxygen delignification, and the whiteness of paper pulp also is the rear reduction that raises first, and when the time was 120min, the whiteness of paper pulp reached the highest 60.6%ISO; After descending first, the Kappa number of paper pulp raises to some extent, when the time is 120min, and paper pulp kappa number minimum 7.7; After raising first, the viscosity of paper pulp descends to some extent, when the time is 90min, and the highest 765mL/g of viscosity of paper pulp.The experimental result of consolidated statement 11, zytase X 2The time of pulp treatment is that 90-120min is comparatively desirable.
Table 11 time is to zytase X 2Pretreating paper pulp is on the impact of oxygen delignification effect
Figure BDA00003525545500081
Annotate: enzyme dosage is 8IU/g, 55 ℃ of temperature, and pH value 8-9 starches dense 10%.
As can be seen from Table 12, along with the prolongation of time, zytase X 3Fast-growing poplar NaOH-AQ slurry after the processing is behind oxygen delignification, and the viscosity of paper pulp raises first and omits afterwards reduction, and when the processing time was 120min, the viscosity of paper pulp reached maximum 760mL/g; The whiteness of paper pulp also is the rear reduction that raises first, and when the processing time was 120min, the whiteness of paper pulp reached maximum 60.5%ISO; It is large that the Kappa number of paper pulp reduces first rear change, and when the processing time was 120min, the Kappa number of paper pulp was down to minimum 7.7.Also can find out zytase X from table 12 3The pulp treatment time, the whiteness of paper pulp was the highest, Kappa number is minimum, viscosity is the highest when being 120min, surpassed this time treatment effect and just began to weaken.
Table 12 time is to zytase X 3Pretreating paper pulp is on the impact of oxygen delignification effect
Figure BDA00003525545500082
Annotate: enzyme dosage is 10IU/g, temperature 50 C, and pH value 8-9 starches dense 10%.
Comprehensive above-mentioned experimental technique analysis result can draw the process conditions that three kinds of better processing fast-growing poplar NaOH-AQ of zytase starch: zytase X 1The preferred process condition be: enzyme dosage 10IU/L, temperature 50 C, pH8-9, time 90-120min; Zytase X 2The preferred process condition be: enzyme dosage 8IU/g, 55 ℃ of temperature, pH8-9, time 90-120min; Zytase X 3The preferred process condition be: enzyme dosage 10IU/g, temperature 50 C, pH8-9, time 120min.
The optimization of embodiment 2 bleaching conditions
2.1.1 raw material
Experiment is to mix the quick growth poplar wood sheet with the quick growth poplar wood sheet, takes from Shandong sun Paper Co., Ltd.Chip dimensions length 15-25mm, width 10-20mm, thickness 3-5mm, the qualification rate of wood chip is more than 90%, and is after wood chip is fetched from the stock ground, for subsequent use behind the natural air drying equilibrium water conten.
Zytase X 1Provided by Novozymes Company, liquid, the cellulose-less enzyme is lived; Zytase X 2, X 3All have Shenzhen biological Co., Ltd of green little health to provide, be the white powder solid, all cellulase is not lived.
2.1.2 boiling experiment
In 15L electric heating rotating autoclave, carry out boiling, make fast-growing poplar NaOH anthraquinone magma.The condition of boiling is: alkali charge 22%(is to the over dry raw material, and NaOH counts), AQ consumption 0.05%, liquor ratio 1:4,165 ℃ of boiling maximum temperatures are carried out little venting 10-15min, heating-up time 90min, temperature retention time 90min in the time of 105 ℃.The boiling disposed slurry is through fully washing, screening.Paper pulp yield 49.8%, the Kappa number 18.5 of paper pulp, viscosity 912ml/g, whiteness 36.1%ISO.
2.1.3 xylanase pretr eatment
Three kinds of xylanase pretr eatment experiments are all finished in polyethylene plastic bag.The fast-growing poplar NaOH-AQ slurry good washing after the boiling mixes in plastic bag with enzyme, enzyme treatment process condition and experimental procedure according to embodiment 1 optimization, regulate the pH value and starch zytase liquid that dense rear handle modulates put into bag and evenly mix after, put into the water-bath that sets temperature and carry out constant temperature and process.In processing procedure, every interval 10-15min rubs once with hand, to guarantee that enzyme mixes with the even of paper pulp.Slurry takes out after processing the stipulated time, then puts into boiling water bath 10min, makes zytase inactivation cessation reaction, with entering the following bleaching operation behind the running water cleaning paper pulp.
2.1.4 oxygen delignification and the experiment of reinforcement oxygen delignification
The experiment of fast-growing poplar NaOH-AQ slurry oxygen delignification is carried out in JF-DSTE polymerization reaction kettle (have and stir and the automatic constant-temperature function).Its Oxygen Delignification of Fast-Growing is: starch dense 10%, NaOH consumption 2.5%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 80min, MgSO 4All drug dosages of consumption 0.5%(are all for oven dry stock, and are as follows).
The process conditions of two sections oxygen delignifications: first paragraph O 1: starch dense 10%, NaOH consumption 2%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, MgSO 4Consumption 0.5%; Second segment O 2: replenish 0.5% NaOH, oxygen is pressed 0.5MPa, time 60min.
Fast-growing poplar NaOH-AQ slurry is strengthened oxygen delignification O pProcess conditions be: starch dense 10%, NaOH consumption 2.5%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, MgSO 4Consumption 0.5%, Na 2SiO 3Consumption 0.7%, H 2O 2Consumption 3%, time 80min.
First paragraph oxygen delignification and second segment are strengthened the process conditions of oxygen delignification: first paragraph O 1: starch dense 10%, NaOH consumption 2%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, MgSO 4Consumption 0.5%; Second segment O 2P: replenish 0.5% NaOH, add 3% H 2O 2, Na 2SiO 3Consumption 0.7%, oxygen is pressed 0.5MPa, time 60min.
Two sections process conditions of strengthening oxygen delignification: first paragraph O 1P: starch dense 10%, NaOH consumption 2%, H 2O 2Consumption 1%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%; Second segment O 2P: replenish 0.5% NaOH, add 2.5% H 2O 2, oxygen is pressed 0.5MPa, time 60min.
2.1.5 the bleaching experiment of paper pulp
The bleachings such as D, E, Q, P or processing section carry out in polyethylene plastic bag respectively.Get the 30g oven dry stock at every turn, according to the experimental procedure of drafting, pour in the plastic bag after required liquid evenly mixed, put into thermostat water bath after slurry and liquid are mixed and bleach or process.In the process of bleaching or processing, every interval 15min takes out and rubs even mixing once with hand, guarantees paper pulp and the even mixing of floating agent.
2.1.6 analytical method
The mensuration of viscosity: the method according to standard GB/T 1548-1989 regulation is carried out.
Kappa number must be measured: according to the GB1546-1989 standard test
The mensuration of whiteness: paper pulp is discongested after device discongests through fiber, copies into the scraps of paper at Buchner funnel, air-dry measure with YQ-Z-48B whiteness instrument afterwards
Folding number: domestic MIT folding strength tester is measured in using.
Burst index: use swedish company L﹠amp; The bursting strength tester that W produces is measured.
Fracture length: use swedish company L﹠amp; The anti-tester that W produces is measured.
Tear index: measure with the tearability tester that the TMI of u s company produces.
2.1.7 the mensuration of making beating and beating energy consumption
Slurry behind the defibrination adopts KRK company to produce the PFI mill and pulls an oar, and beating consistency is 10%, and beater roll(er) and beater chamber gap are 0.2mm, and beating pressure is 3.4Nmm -1The beating degree of making beating disposed slurry is measured and is adopted Xiao Baier-Rui Gele YQ-Z-13 beating degree analyzer to measure.
The revolution of making beating specific energy consumption: PFI mill is linear with beating energy consumption within the specific limits [119], this experiment required making beating revolution when reaching identical beating degree calculates can loss-rate.Bleached pulp making beating revolution * 100% of the beating energy consumption reduction rate in this experiment=(enzyme is processed the bleached pulp making beating revolution of after bleaching slurry making beating revolution-do not process with enzyme)/do not process with enzyme.
2.1.8 ESEM
To under the identical experiment condition of embodiment 1 " oxygen delignification experiment ", carry out respectively oxygen-delignified pulp from magma through the paper pulp that different enzymes are processed, carry out the different orders of floating subsequently and bleach gained paper pulp etc., after the running water washing, utilizing the quick handshcet former of triumphant match to copy the formulation amount is 60g/m 2The l Water Paper page or leaf then with l Water Paper page or leaf in vacuum drier dry 48 hours, after metal spraying is processed, is that the ESEM of QUANTA200 is observed and taken pictures in model, and accelerating potential is 10kV.
2.1.9 atomic force microscope observation
Getting slurry sample 0.1g to be measured is distributed in the distilled water of 200mL, break up with dispersing device, fiber is evenly distributed in the water, then getting a droplet with pipette is put on the mica sheet, so that single fiber is distributed on the mica sheet, then air-dry 24h under the room temperature uses MultiMode SPM model AFM (AFM) produced in USA to carry out scanning and photograph, and the model of probe is NP-20.
2.1.10 xylanase activity is measured
Adopt the DNS method to measure (being conventional determining method of the prior art).
2.1.11 enzyme preparation characteristic is determined
Zytase X 1, X 2, X 3Enzyme activity determination measure according to the DNS method, it the results are shown in Table 13 and table 14.
The characteristic of table 13 liquid xylanase preparation
2.2 result and the effect of discussion xylanase treatment to fast-growing poplar NaOH-AQ slurry TCF bleached pulp
Want thoroughly to eliminate the pollution of organic chloride, must adopt and bleach completely without chlorine (TCF).The TCF bleaching is mainly with O 2, O 3And H 2O 2For mainly floating agent, the order of floating commonly used has OQP, O 1O 2QP, O PQP etc.In the present embodiment, adopted (X) O PQP, (X) O 1O 2PQP and (X) O 1PO 2PThree kinds of QP etc. float ordered pair fast-growing poplar NaOH-AQ slurry and carry out the TCF bleaching experiment, inquire into the effect of novel commercial xylanase in fast-growing poplar NaOH-AQ slurry TCF bleaching.
All bleaching process of the oxygen delignification section bleaching that contains in this experiment all carry out before oxygen delignification during xylanase treatment paper pulp, and its process conditions are the xylanase treatment process conditions of optimizing among the embodiment 1.
2.2.2.1 three kinds of xylanase pretr eatments are to fast-growing poplar NaOH-AQ slurry O PThe impact of QP bleaching results
Adopt zytase X 1, X 2And X 3At fast-growing poplar NaOH-AQ slurry O PQP carries out preliminary treatment before floating the order bleaching, inquires into xylanase treatment to the impact of fast-growing poplar NaOH-AQ slurry bleachability.
The process conditions of three kinds of xylanase treatment fast-growing poplar NaOH-AQ slurry oxygen delignification best results optimizing according to embodiment 1 are in conjunction with reinforcement oxygen delignification and H 2O 2Bleaching conditions carry out this experiment.Concrete process conditions are as follows: X 1The process conditions of processing: enzyme dosage 10IU/L, 55 ℃ of temperature, pH8-9, time 120min; X 2The process conditions of processing: enzyme dosage 8IU/g, temperature 60 C, pH value 9, time 120min; X 3The process conditions of processing: enzyme dosage 10IU/g, 55 ℃ of temperature, pH8-9, time 120min.
O PQP floats the bleaching conditions of order: strengthen oxygen delignification O PThe process conditions of section are seen 2.1.4.The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
Fast-growing poplar NaOH-AQ slurry through xylanase treatment is carried out O with untreated paper pulp under above-mentioned identical bleaching process PQP bleaches, and guarantees the comparativity of bleaching results.Xylanase pretr eatment is to fast-growing poplar NaOH-AQ slurry O PThe QP bleaching results sees Table 15.Paper pulp after the bleaching is pulled an oar with PFI mill, and control is different floats the making beating revolution that order floats rear slurry its beating degree is controlled at about 45 ° of SR, then copies and makes quantitative 60g/m 2About paper, then the physical properties such as its folding strength, bursting strength, tear index, fracture length are detected its result such as table 16.
As can be seen from Table 15, fast-growing poplar NaOH-AQ slurry is through XO PQP floats the bleaching results that order finishes and is better than O PQP floats order.X wherein 2O PThe final bleaching whiteness that QP floats order is the highest, reaches 83.5%ISO, than O PThe final whiteness that QP floats order exceeds 2.5%ISO, and is these four kinds of maximum 720mL/g that float pulp viscosity in the order; Next is X 1O PQP and X 3O PThe final whiteness that QP floats order all reaches 83.2%ISO, than O PThe final whiteness that QP floats order exceeds 1.9%ISO, and has kept respectively higher pulp viscosity 713mL/g and 715mL/g.
Table 15 xylanase pretr eatment is to fast-growing poplar NaOH-AQ slurry O PThe impact of QP bleaching results
Figure BDA00003525545500111
As can be seen from Table 15, through xylanase treatment and not through the fast-growing poplar NaOH-AQ of xylanase treatment slurry, through O PAfter QP floated order bleaching, the final Kappa number of paper pulp was not identical yet, X 2O PIt is minimum 1.8 that QP floats the Kappa number of order, than O PQP floats low 0.5 unit of Kappa number of order, secondly is X 3O PThe Kappa number that QP floats order is 1.9, than O PQP floats low 0.4 unit of Kappa number of order, is X at last 1O PThe Kappa number that QP floats order is 2.0, than O PQP floats low 0.3 unit of Kappa number of order.These experimental results show, process fast-growing poplar NaOH-AQ slurry through different enzymes, at O PQP floats in the order bleaching process, all is conducive to removing of lignin, further reduces the Kappa number of paper pulp, improves the whiteness of paper pulp, has kept than the conventional higher pulp viscosity of order bleaching that floats.
Can find out also that from table 15 fast-growing poplar NaOH-AQ slurry is through O PQP and XO PAfter the QP bleaching, copy the quantitative 60g/m of being that makes through making beating 2Paper, the whiteness of paper has decline in various degree.Wherein, do not pass through the O of xylanase treatment PThe whiteness reduction that QP floats order is at most 1.8%ISO, through the X of enzyme processing 2O PQP floats the minimum 1.6%ISO of being of whiteness reduction value of order, through X 1O PQP and X 3O PThe whiteness reduction value that QP floats order all is 1.7%ISO.These experimental datas show that the whiteness through the bleached pulp of xylanase treatment paper pulp after making beating reduces still less, and this may be because lower, the lignin content reason still less of Kappa number of slurry after the floating after processing through enzyme.
As can be seen from Table 16, fast-growing poplar NaOH-AQ slurry is through XO PPaper pulp after the QP bleaching compares O PThe easier making beating of paper pulp after the QP bleaching.When 45 ° of SR of close beating degree, required making beating revolution few 2500 turns, save beating energy consumption about 17.8%, this may be because the processing of paper pulp process zytase, in the easier gap that is impregnated into cellulose and hemicellulose of bleaching liquid, when impelling more lignin strippings, so that the more soft easier making beating of fiber.
Table 16 O PQP/XO PThe comparison of QP bleached pulp physical properties of paper
Figure BDA00003525545500112
Figure BDA00003525545500121
As can be seen from Table 16, fast-growing poplar NaOH-AQ slurry is through XO PPaper pulp after the QP bleaching compares O PThe physical indexs such as the folding strength of the paper pulp after the QP bleaching, bursting strength, fracture length are more better.XO PQP and O PThe bleached pulp that QP floats order is all copied and is made quantitative 60g/m 2About paper, through X 2O PPhysical property of pulp after the QP bleaching is best, and with exceeding 49 times that enzyme is processed, fracture length has not improved 0.35Km to the folding strength ratio, and burst index exceeds 0.5Nmg -1, several slurry tear indexes are very approaching, but X 2O PIt also is that this severally floats rear slurry and copy the maximum 5.23mNm that makes paper that QP floats rear slurry 2G -1Through X 1O PQP and X 3O PQP floats the rear slurry of floating of order, has shown equally good physical property: these two kinds of bleached pulps are than O PThe QP bleached pulp is copied the paper folding strength of making and has been improved respectively 37 and 35 times, and fracture length has improved respectively 0.19 and 0.21Km, and burst index has all improved 0.2Nmg -1Through X 1O PQP and X 3O PQP floats the tear index slight reduction of rear slurry but differs very little.
In sum, fast-growing poplar NaOH-AQ slurry is through XO PAfter QP floated the TCF bleaching of order, the whiteness maximum of paper pulp reached 83.5%ISO, and keeps relatively high viscosity, than O PThe paper pulp of QP bleaching can improve the final whiteness 2.2-2.5%ISO of paper pulp, XO in the situation that consumes identical chemicals PQP floats rear slurry than O PQP floats rear slurry and has kept higher pulp viscosity, has also kept better bleaching selectivity, has improved more significantly the physical property of floating rear slurry.
2.2.2.2 three kinds of xylanase pretr eatments are to fast-growing poplar NaOH-AQ slurry O 1O 2PThe impact of QP bleaching results
Adopt zytase X 1, X 2And X 3At fast-growing poplar NaOH-AQ slurry O 1O 2PQP carries out preliminary treatment before floating the order bleaching, inquires into xylanase treatment to the impact of fast-growing poplar NaOH-AQ slurry bleachability.
The process conditions of three kinds of xylanase treatment fast-growing poplar NaOH-AQ slurry oxygen delignification best results optimizing according to embodiment 1 are in conjunction with reinforcement oxygen delignification and H 2O 2Bleaching conditions carry out this experiment.Concrete process conditions are as follows: X 1The process conditions of processing: enzyme dosage 10IU/L, 55 ℃ of temperature, pH8-9, time 120min; X 2The process conditions of processing: enzyme dosage 8IU/g, temperature 60 C, pH9, time 120min; X 3The process conditions of processing: enzyme dosage 10IU/g, 55 ℃ of temperature, pH8-9, time 120min.
Fast-growing poplar NaOH-AQ starches O 1O 2PQP floats the bleaching conditions of order: oxygen delignification O 1With reinforcement oxygen delignification O 2PThe process conditions of section are seen 2.1.4.The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
Fast-growing poplar NaOH-AQ slurry through xylanase treatment is carried out O with untreated paper pulp under above-mentioned identical bleaching process 1O 2PQP bleaches, and guarantees the comparativity of bleaching results.Xylanase pretr eatment is to fast-growing poplar NaOH-AQ slurry O 1O 2PThe QP bleaching results sees Table 17.Paper pulp after the bleaching is pulled an oar with the PFI mill, and the making beating revolution of controlling different paper pulp is controlled at about 44.4 ° of SR its beating degree, then copies and makes quantitative 60g/m 2About paper, then the physical properties such as its folding strength, bursting strength, tear index, fracture length are detected its result such as table 18.
Table 17 xylanase pretr eatment is to fast-growing poplar NaOH-AQ slurry O 1O 2PThe impact of QP bleaching results
Figure BDA00003525545500122
As can be seen from Table 17, fast-growing poplar NaOH-AQ slurry is through XO 1O 2PQP floats the bleaching results that order finishes and obviously is better than O 1O 2PQP floats order.X wherein 2O 1O 2PThe final bleaching whiteness of QP is the highest to be 83.3%ISO, compares O 1O 2PThe final whiteness that QP floats order exceeds 2.5%ISO, and is these four kinds of maximum 742mL/g that float pulp viscosity in the order; Next is X 3O 1O 2PThe final whiteness of QP reaches 83.1%ISO, than O 1O 2PThe final whiteness that QP floats order exceeds 2.3%ISO, and its viscosity of floating rear slurry is 736mL/g, and the rear slurry that floats of more not processing with enzyme exceeds 15mL/g; X 1O 1O 2PThe final whiteness that QP floats order is 83.0%ISO, than O 1O 2PThe final whiteness that QP floats order exceeds 2.2%ISO, and the viscosity of floating rear slurry is 734mL/g, than O 1O 2PThe pulp viscosity of QP exceeds 13mL/g.Comparison sheet 15 and 17 can be found out O PQP and O 1O 2PQP floats order, XO PQP and XO 1O 2PQP floats order, at identical H 2O 2In the situation of consumption, O PQP and XO PQP floats the whiteness of rear slurry a little more than O 1O 2PQP and XO 1O 2PQP floats order, differs about 0.5%ISO, but the low 13-21mL/g of the viscosity of paper pulp.Can according to circumstances select required method for bleaching during actual production.
As can be seen from Table 17, fast-growing poplar NaOH-AQ slurry is through paper pulp xylanase treatment and that do not pass through xylanase treatment, at process O 1O 2PAfter QP floated order bleaching, the final Kappa number of paper pulp was also different, X 2O 1O 2PQP and X 3O 1O 2PIt all is 1.9 that QP floats the Kappa number of order minimum, than O 1O 2PQP floats low 0.5 unit of Kappa number of order, X 1O 1O 2PThe Kappa number that QP floats order is 2.0, than O 1O 2PQP floats low 0.4 unit of Kappa number of order.These experimental results show, XO 1O 2PQP compares O 1O 2PQP floats the order bleaching and more is conducive to removing of lignin, further reduces the Kappa number of paper pulp, improves the whiteness of paper pulp, and has kept higher pulp viscosity.Comparison sheet 15 and 17 can be found out, floats order O PQP compares O 1O 2PQP, XO PQP compares XO 1O 2PThe amplitude of the viscosity loss of the Kappa number Amplitude Ratio paper pulp that QP reduces more greatly.
Can find out also that from table 17 fast-growing poplar NaOH-AQ slurry is through O 1O 2PQP and XO 1O 2PAfter the QP bleaching, copy the quantitative 60g/m of being that makes through making beating 2Paper, the whiteness of paper all descends to some extent.Wherein, do not pass through the O of xylanase treatment 1O 2PThe whiteness decline that QP floats order is at most 2.0%ISO, through the X of enzyme processing 2O 1O 2PQP and X 3O 1O 2PQP floats the minimum 1.7%ISO of being of whiteness decline of order, through X 1O 1O 2PThe whiteness reduction value that QP floats order is 1.8%ISO.These experimental results show, the loss of whiteness of bleached pulp paper pulp after making beating of fast-growing poplar NaOH-AQ slurry process xylanase treatment still less, this may be because the paper pulp after processing through enzyme in bleaching process, can remove more lignin, thereby lignin content still less in the pulping, the Kappa number of paper pulp is lower, and paper pulp more is difficult for brightness reversion.
As can be seen from Table 18, fast-growing poplar NaOH-AQ slurry is through XO 1O 2PPaper pulp after the QP bleaching compares O 1O 2PPulp beating after the QP bleaching is easier.When reaching close 44.4 ° of SR of beating degree, required making beating revolution few 2500 turns, save beating energy consumption about 17.8%, this may be because paper pulp process xylanase treatment before oxygen delignification, make in the easier gap that is impregnated into cellulose and hemicellulose of following bleaching liquid, when impelling the more strippings of lignin, fiber soak into liquid fully act on down more softening, easier making beating.
As can be seen from Table 18, fast-growing poplar NaOH-AQ slurry is through XO 1O 2PPaper pulp after the QP bleaching compares O 1O 2PPaper pulp after the QP bleaching becomes the physical index such as the folding strength, bursting strength, fracture length of paper more better.XO 1O 2PQP and O 1O 2PThe bleached pulp that QP floats order is all copied and is made quantitative 60g/m 2About paper, through X 2O 1O 2PPhysical property of pulp after the QP bleaching is best, and with exceeding 49 times that enzyme is processed, fracture length has not improved 0.36Km to the folding strength ratio, and burst index exceeds 0.5Nmg -1, several slurry tear indexes are very approaching, but X 2O 1O 2PIt also is that this severally floats rear slurry and copy the maximum 5.23mNm that makes paper that QP floats rear slurry 2G -1Through X 1O 1O 2PQP and X 3O 1O 2PQP floats the rear slurry of floating of order, has shown equally good physical property: these two kinds of bleached pulps are than O 1O 2PThe QP bleached pulp is copied the paper folding strength of making and is improved respectively 37 and 34 times, and fracture length improves respectively 0.19 and 0.14Km, and burst index improves respectively 0.4 and 0.3Nmg -1, but these two kinds of tear indexes that float rear slurry descend slightly.
Table 18 O 1O 2PQP/XO 1O 2PThe comparison of QP bleached pulp physical properties of paper
Figure BDA00003525545500131
In sum, through XO 1O 2PAfter QP floated the TCF bleaching of order, the whiteness maximum of paper pulp reached 83.3%ISO, and keeps relatively high viscosity, than O 1O 2PThe paper pulp of QP bleaching can improve the final whiteness 2.2-2.5%ISO of paper pulp, XO in the situation that consumes identical chemicals 1O 2PQP floats rear slurry than O 1O 2PQP floats rear slurry and has kept higher pulp viscosity, has also kept better bleaching selectivity, has improved preferably and has floated rear physical property of starching into paper.
2.2.2.3 three kinds of xylanase pretr eatments are to fast-growing poplar NaOH-AQ slurry O 1PO 2PThe impact of QP bleaching results
Adopt zytase X 1, X 2And X 3At fast-growing poplar NaOH-AQ slurry O 1PO 2PQP carries out preliminary treatment before floating the order bleaching, inquires into xylanase treatment to the impact of fast-growing poplar NaOH-AQ slurry bleachability.
The process conditions of three kinds of xylanase treatment fast-growing poplar NaOH-AQ slurry oxygen delignification best results optimizing according to embodiment 1 are in conjunction with reinforcement oxygen delignification and H 2O 2Bleaching conditions carry out this experiment.Concrete process conditions are as follows: X 1The process conditions of processing: enzyme dosage 10IU/L, 55 ℃ of temperature, pH8-9, time 120min; X 2The process conditions of processing: enzyme dosage 8IU/g, temperature 60 C, pH value 9, time 120min; X 3The process conditions of processing: enzyme dosage 10IU/g, 55 ℃ of temperature, pH value 8-9, time 120min.
O 1PO 2PQP floats the bleaching conditions of order: strengthen oxygen delignification O 1PO 2PThe process conditions of section are seen 2.1.4.The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
Poplar NaOH-AQ slurry through xylanase treatment is carried out O with untreated paper pulp under above-mentioned identical bleaching process 1PO 2PQP bleaches, and guarantees the comparativity of bleaching results.Xylanase pretr eatment is to fast-growing poplar NaOH-AQ slurry O 1PO 2PThe QP bleaching results sees Table 19.Paper pulp after the bleaching is pulled an oar with the PFI mill, and the making beating revolution of controlling various slurries is controlled at about 45.5 ° of SR its beating degree, then copies and makes quantitative 60g/m 2About paper, then the physical properties such as its folding strength, bursting strength, tear index, fracture length are detected its result such as table 20.
Table 19 xylanase pretr eatment is to fast-growing poplar NaOH-AQ slurry O 1PO 2PThe impact of QP bleaching results
Figure BDA00003525545500141
As can be seen from Table 19, fast-growing poplar NaOH-AQ slurry is through XO 1PO 2PQP floats the bleaching results that order finishes and is better than O 1PO 2PQP floats order.X wherein 2O 1PO 2PThe final bleaching whiteness that QP floats order is the highest, reaches 84.0%ISO, than O 1PO 2PThe final whiteness that QP floats order exceeds 2.2%ISO, and is these four kinds of maximum 732mL/g that float pulp viscosity in the order; X 1O 1PO 2PThe final whiteness of paper pulp that QP floats order is 83.7%ISO, and viscosity is 721mL/g, than O 1PO 2PThe whiteness that QP floats order exceeds 1.9%ISO, and viscosity exceeds 13mL/g; X 3O 1PO 2PThe final whiteness that QP floats order reaches 83.6%ISO, and viscosity is 726mL/g; Than O 1PO 2PThe final whiteness that QP floats order exceeds 1.5%ISO, and viscosity exceeds 18mL/g.
Comparison sheet 15 and 19 can find out that fast-growing poplar NaOH-AQ starches O 1PO 2PQP floats order and compares O PQP floats order at the H that strengthens oxygen delignification second segment multiplex 0.5% 2O 2Under the consumption, X 2O 1PO 2PThe pulp brightness that QP floats order is up to 84.0%ISO, although the whiteness value that improves is than X 2O PQP floats order and only has 0.5%ISO, but as the TCF bleaching, it is quite very difficult floating to 84.0%ISO; And O 1PO 2PQP floats the whiteness of order than O PQP floats order and has improved 0.8%ISO, but the viscosity of paper pulp is also than O PIt is high that QP floats the summary of order, and this shows two sections fast-growing poplar NaOH-AQ slurry reinforcement oxygen delignification O 1PO 2PStrengthen oxygen delignification O than one section PBetter effects if a little.
As can be seen from Table 19, fast-growing poplar NaOH-AQ slurry is through paper pulp xylanase treatment and that do not pass through xylanase treatment, at process O 1PO 2PAfter QP floated order bleaching, the final Kappa number of paper pulp was also different, X 2O 1PO 2PIt is 1.6 that QP floats the Kappa number of order minimum, than O 1PO 2PQP floats low 0.3 unit of Kappa number of order, secondly is X 1O 1PO 2PQP and X 3O 1PO 2PThe Kappa number that QP floats order is 1.7, than O 1PO 2PThe Kappa number that QP floats order all hangs down 0.2 unit.These experimental results show, through the paper pulp of enzyme processing, at O 1PO 2PQP floats in the order bleaching process, more is conducive to removing of lignin, further reduces the Kappa number of paper pulp, improves the whiteness of paper pulp, has kept than the conventional higher pulp viscosity of order bleaching that floats.Compare O 1PO 2PQP floats order and O PQP floats the bleaching results of order can find XO 1PO 2PQP floats order at the H that increases by 0.5% 2O 2In the situation of consumption, Kappa number and XO PQP floats the approaching or slightly reduction of order, but the whiteness of paper pulp and viscosity are higher.This shows that further two sections are strengthened oxygen delignification O 1PO 2PStrengthen oxygen delignification O than one section PBetter effects if a little.
Can find out also that from table 19 fast-growing poplar NaOH-AQ slurry is through O 1PO 2PQP and XO 1PO 2PAfter the QP bleaching, copy the quantitative 60g/m of being that makes through making beating 2Paper, the whiteness of paper has decline in various degree.Wherein, do not pass through the O of xylanase treatment 1PO 2PThe whiteness reduction that QP floats order is at most 1.8%ISO, through the X of enzyme processing 1O 1PO 2PQP and X 2O 1PO 2PIt all is 1.6%ISO that QP floats the whiteness reduction value of order minimum, through X 3O 1PO 2PThe whiteness reduction value that QP floats order is 1.7%ISO, these experimental datas show through the loss of whiteness of the bleached pulp of xylanase treatment paper pulp after making beating still less, this may be with process through enzyme after float after lower, the lignin in paper pulp content reason still less of slurry Kappa number.
As can be seen from Table 20, fast-growing poplar NaOH-AQ slurry is through XO 1PO 2PPaper pulp after the QP bleaching compares O 1PO 2PPulp beating after the QP bleaching is easier.When reaching close 44.8 ° of SR of beating degree, required making beating revolution few 2500 turns, save beating energy consumption about 17.8%, this may be because the processing of paper pulp process zytase, in the easier gap that is impregnated into cellulose and hemicellulose of bleaching liquid, when impelling more lignin strippings, so that fiber is further softening, it is easier to pull an oar.
Table 20 O 1PO 2PQP/XO 1PO 2PThe comparison of QP bleached pulp physical properties of paper
As can be seen from Table 20, fast-growing poplar NaOH-AQ slurry is through XO 1PO 2PPaper pulp after the QP bleaching compares O 1PO 2PThe physical indexs such as the folding strength of the paper pulp after the QP bleaching, bursting strength, fracture length are better.XO 1PO 2PQP and O 1PO 2PThe bleached pulp that QP floats order is all copied and is made quantitative 60g/m 2About paper, through X 2O 1PO 2PPhysical property of pulp after the QP bleaching is best, and with exceeding 49 times that enzyme is processed, fracture length has not improved 0.34Km to the folding strength ratio, and burst index exceeds 0.6Nm/g, the high 0.02mNm of tear index 2/ g.Fast-growing poplar NaOH-AQ slurry is through X 1O 1PO 2PQP and X 3O 1PO 2PQP floats the rear slurry of floating of order, has shown equally good physical property: these two kinds of bleached pulps are than O 1PO 2PThe QP bleached pulp is copied the paper folding strength of making and is improved respectively 33 and 30 times, and fracture length improves respectively 0.21 and 0.19Km, and bursting strength improves respectively 0.4 and 0.5Nm/g, and tear index all descends to some extent but amplitude is little.On the whole, the helping of three kinds of enzymes floats that effect is apparent in view, and whiteness and the viscosity of floating rear slurry are all higher, but the effect of different zytases there are differences, may be relevant with the performance of these three kinds of enzymes.
In sum, the paper pulp after fast-growing poplar NaOH-AQ slurry is processed through enzyme carries out O PQP, O 1O 2PQP, O 1PO 2PAfter the TCF bleaching of QP, the whiteness maximum of paper pulp reaches 84.0%ISO, and keeps relatively high viscosity.The more corresponding order bleached pulp that floats of not processing with enzyme is compared, in the situation that consumes identical chemicals, can improve the final whiteness 1.8-2.5%ISO of paper pulp, and kept higher pulp viscosity, and the physical indexs such as folding strength, bursting strength, fracture length that become paper all are better than the paper pulp do not processed with enzyme, this shows that these three kinds of enzymes have kept better bleaching selectivity, have improved the physical property of floating rear slurry more significantly.
2.2.3 scanning electron microscope analysis
Be further to understand before and after three kinds of xylanase treatment fast-growing poplar NaOH-AQ slurries and bleaching finish after the variation of fiber exterior appearance, magma, enzyme are processed slurry and corresponding bleached pulp is observed with environmental scanning electronic microscope.
2.2.3.1TCF bleached pulp scanning electron microscopic observation
Choose NaOH-AQ magma, process X 1The NaOH-AQ slurry of processing, process X 2The NaOH-AQ slurry of processing, process X 3The NaOH-AQ slurry, the O that process PQP bleached pulp, X 1O PQP bleached pulp, X 2O PQP bleached pulp, X 3O PThe QP bleached pulp, obtain Fig. 1～stereoscan photograph shown in Figure 8 according to the requirement of 2.1.8.
Under 3000 times environmental scanning electronic microscope, poplar NaOH-AQ magma is starched, X from Fig. 1,2,3,4 1The NaOH-AQ slurry, the X that process 2The NaOH-AQ slurry and the X that process 3The electromicroscopic photograph on the NaOH-AQ pulp fibres surface of processing can be found out significantly, does not pass through zytase X 1, X 2, X 3The fiber surface of the NaOH-AQ slurry of processing is smooth, and close structure exists without tiny or microfibre.Fiber surface through the NaOH-AQ of three kinds of xylanase treatments slurry seems loose, soft, and fiber surface fiber fines occurs like free state, and the surface area of fiber increases.
From Fig. 5,6,7,8 under 3000 times environmental scanning electronic microscope, O PQP bleached pulp, X 1O PQP bleached pulp, X 2O PQP bleached pulp, X 3O PThe electromicroscopic photograph of QP bleached pulp fiber surface can find out that the NaOH-AQ through xylanase treatment does not starch through O PThe pulp fiber surface of QP bleaching is smooth, and close structure is tiny or microfibre is considerably less.X through the enzyme processing 1O PQP, X 2O PQP and X 3O PThe specific area of the fiber of QP bleached pulp increases, and that fiber becomes is loose, microfibre increases, and it is more soft that fiber seems, this can explain the O through xylanase treatment to a certain extent PThe easier making beating of QP bleached pulp, more energy efficient.
2.3 the brief summary xylanase treatment is starched the result that affects of TCF bleaching on fast-growing poplar NaOH-AQ:
After bleaching through TCF with the paper pulp of not using xylanase treatment, the former whiteness and viscosity are higher, become the physical property of paper also to make moderate progress, and concrete outcome is as follows:
Fast-growing poplar NaOH-AQ starches XO PQP floats order at H 2O 2In the situation of total consumption 5%, the whiteness of floating rear slurry is up to 83.5%ISO, minimum 83.2%ISO; O PThe whiteness of QP bleached pulp is 81.0%ISO, through enzyme process than not with enzyme process float after the whiteness of slurry exceed 2.2-2.5%ISO, and kept higher pulp viscosity and lower Kappa number;
Fast-growing poplar NaOH-AQ starches XO 1O 2PQP floats order at H 2O 2In the situation of total consumption 5%, the whiteness of bleached pulp is up to 83.3%ISO, minimum 83.0%ISO; O 1O 2PThe whiteness of QP bleached pulp is 80.8%ISO, through enzyme process than not with enzyme process float after the whiteness of slurry exceed 2.2-2.5%ISO, and kept higher pulp viscosity and lower Kappa number;
Fast-growing poplar NaOH-AQ starches XO 1PO 2PQP floats order at H 2O 2In the situation of total consumption 5.5%, the whiteness of bleached pulp is up to 84.0%ISO, minimum 83.6%ISO; O 1PO 2PThe whiteness of QP bleached pulp is 81.8%ISO, through enzyme process than not with enzyme process float after the whiteness of slurry exceed 1.8-2.2%ISO, and kept higher pulp viscosity and lower Kappa number.
Top XO PQP and O PQP, XO 1O 2PQP and O 1O 2PQP, XO 1PO 2PQP and XO 1O 2PThe TCF bleached pulp of QP is copied through making beating and is made 60g/m 2Paper, the former making beating loss of whiteness value is than the latter still less; The former folding strength exceeds 30-49 time than the latter, and burst index exceeds 0.3-0.6Nmg -1, fracture length exceeds 0.15-0.36KM, and tear index changes little.When reaching identical or close beating degree, the former required making beating revolution still less can be saved beating energy consumption about 17.8%.
Paper pulp after fast-growing poplar NaOH-AQ slurry is processed through enzyme carries out O PQP, O 1O 2PQP, O 1PO 2PThe TCF bleaching of QP, in the situation that consumes identical chemicals, can improve the final whiteness 1.8-2.5%ISO of paper pulp, kept higher pulp viscosity, and the physical indexs such as folding strength, bursting strength, fracture length that become paper all are better than the paper pulp do not processed with enzyme, this shows that these three kinds of enzymes have kept better bleaching selectivity, has improved more significantly the physical property of floating rear slurry, wherein helps to float effect and it would be desirable X 2, X 1And X 3Effect suitable.

Claims (7)

1. the NaOH anthraquinone of a fast-growing poplar is starched biochemical process TCF bleaching process, and it is characterized in that: step is as follows:
(1) boiling: get the quick growth poplar wood sheet, put into the digester boiling, get magma, then wash, screen, get paper pulp;
(2) xylanase pretr eatment;
(3) TCF bleaching: the above-mentioned paper pulp of processing through enzyme is bleached, and bleaching process is O P-Q-P, O 1-O 2P-Q-P or O 1P-O 2PThree kinds of-Q-P float one of order, and the step of bleaching process is: at first, the paper pulp of processing through enzyme is carried out the deoxidation lignin or strengthens the deoxidation lignin; Oxygen delignification washs paper pulp after finishing, and then carries out Q section chelation treatment; Q section chelation treatment is washed paper pulp after finishing, and then carries out P section H 2O 2Bleaching is finished.
2. the NaOH anthraquinone of fast-growing poplar according to claim 1 is starched biochemical process TCF bleaching process, it is characterized in that: the concrete mode of described boiling is: the quick growth poplar wood sheet of getting length 15～25mm, width 10～20mm, thickness 3～5mm, behind the natural air drying, carry out boiling, make fast-growing poplar NaOH anthraquinone magma, the condition of boiling is: alkali charge 22%, and to the over dry raw material, the NaOH meter; AQ consumption 0.05%, liquor ratio 1:4,165 ℃ of boiling maximum temperatures, the 10-15min that in the time of 105 ℃, exits, heating-up time 90min, temperature retention time 90min; The boiling disposed slurry gets paper pulp, the Kappa number 16～21 of paper pulp through fully washing, screening.
3. the NaOH anthraquinone of fast-growing poplar according to claim 1 is starched biochemical process TCF bleaching process, and it is characterized in that: the concrete mode of described xylanase pretr eatment is: adjusting pulp density is 10%, then uses zytase X 1, X 2Or X 3Process, in processing procedure, every interval 10～15min rubs once, takes out after processing, and puts into boiling water bath 10min, makes zytase inactivation cessation reaction, cleans paper pulp with running water.
4. the NaOH anthraquinone of fast-growing poplar according to claim 3 slurry biochemical process TCF bleaching process is characterized in that: described zytase X 1, X 2Or X 3The concrete technology condition of processing is as follows: dextranase X 1Process conditions be: enzyme dosage 10IU/L, temperature 50 C, pH8-9, time 90-120min; Zytase X 2Process conditions be: enzyme dosage 8IU/g, 55 ℃ of temperature, pH8-9, time 90-120min; Zytase X 3Process conditions be: enzyme dosage 10IU/g, temperature 50 C, pH8-9, time 120min.
5. the NaOH anthraquinone of fast-growing poplar according to claim 1 slurry biochemical process TCF bleaching process is characterized in that: described O PThe concrete mode of the white operation of-Q-P is: Oxygen Delignification of Fast-Growing is: starch dense 10%, NaOH consumption 2.5%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 80min, MgSO 4Consumption 0.5%; The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
6. the NaOH anthraquinone of fast-growing poplar according to claim 1 slurry biochemical process TCF bleaching process is characterized in that: described O 1-O 2PThe concrete mode of-Q-P bleaching process is: first paragraph oxygen delignification and second segment are strengthened the process conditions of oxygen delignification: first paragraph O 1: starch dense 10%, NaOH consumption 2%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, MgSO 4Consumption 0.5%; Second segment O 2P: replenish 0.5% NaOH, add 3% H 2O 2, Na 2SiO 3Consumption 0.7%, oxygen is pressed 0.5MPa, time 60min; The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
7. the NaOH anthraquinone of fast-growing poplar according to claim 1 slurry biochemical process TCF bleaching process is characterized in that: described O 1P-O 2PThe concrete mode of-Q-P bleaching process is: two sections process conditions of strengthening oxygen delignification: first paragraph O 1P: starch dense 10%, NaOH consumption 2%, H 2O 2Consumption 1%, oxygen is pressed 0.6MPa, 100 ℃ of temperature, time 20min, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%; Second segment O 2P: replenish 0.5% NaOH, add 2.5% H 2O 2, oxygen is pressed 0.5MPa, time 60min; The Q section: starch dense 8%, DTPA consumption 0.5%, temperature 70 C, time 60min, pH value 4-5; P section: H 2O 2Consumption is 2%, Na 2SiO 3Consumption 0.7%, MgSO 4Consumption 0.5%, original ph 12,90 ℃ of temperature, starch dense 10%, time 90min.
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