CN102877346B - Totally chlorine-free bleaching process using coniferous and broadleaf mixed sulfate chemical pulp - Google Patents
Totally chlorine-free bleaching process using coniferous and broadleaf mixed sulfate chemical pulp Download PDFInfo
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- CN102877346B CN102877346B CN201210405720.7A CN201210405720A CN102877346B CN 102877346 B CN102877346 B CN 102877346B CN 201210405720 A CN201210405720 A CN 201210405720A CN 102877346 B CN102877346 B CN 102877346B
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Abstract
The invention discloses a novel totally chlorine-free bleaching process using coniferous and broadleaf mixed sulfate chemical pulp. The novel totally chlorine-free bleaching process includes mixing coniferous wood chemical pulp prepared by sulfate cooking with broadleaf wood chemical pulp prepared by sulfate cooking according to the mass ratio of 3:7-7:3; and performing high-whiteness bleaching by TCF (total chlorine-free) bleaching comprising an XO1PO2PQP1 or XO1O2PQP1P2 bleaching procedure after the coniferous wood chemical pulp and the broadleaf wood chemical pulp are uniformly mixed. Compared with a conventional process for respectively cooking and bleaching paper pulp, the totally chlorine-free bleaching process has the advantages that chemicals consumed in an integral technological procedure is reduced by 5-15%, and after pulp forming, under the condition that coniferous and broadleaf mixing ratios and pulping degrees are identical respectively, pulping energy consumption for the coniferous wood chemical pulp and the broadleaf wood chemical pulp which are cooked respectively and then are mixed for bleaching can be reduced by 10-25% as compared with that of coniferous wood chemical pulp and broadleaf wood chemical pulp which are respectively cooked and respectively used for bleaching. Besides, the whiteness stability of bleached paper pulp and various physical indexes, such as a burst index, a fracture length, a tearing index and folding resistance, of manufactured paper are high.
Description
Technical field
The technique that the present invention relates to the wealthy mixed sulfate chemical pulp of a kind of pin total chlorine free bleaching, belongs to pulp technology for making paper.
Background technology
Along with the fast development of Chinese national economy and the raising of living standards of the people, the pulp and paper industry of China is also in fast development.Along with the increasingly stringent of environmental requirement, pulping wood progressively becomes the main raw material(s) of China's pulp and paper industry, and wood raw material comprises two kinds of needlebush and leaf woods.At present, needlebush and leaf wood produce chemical pulp and mainly contain two kinds of methods, and a kind of is sulfate process, and a kind of is that NaOH is anthraquinone.Content of cellulose in chemical pulp is high, paper strength greatly, easily bleach, be difficult for the feature of brightness reversion, good endurance, be the requisite paper pulp of high-grade paper of manufacturing paper with pulp.
In the actual production process of paper, because different types of paper is to becoming the performance of paper different with physical strength index request, the ratio of copying of joining of the wealthy chemical pulp of pin of paper pulp is different.Present circumstances is that leaf wood and needlebush are distinguished boiling, bleaching, then this paper pulp is mixed to join to copy and produces various high-grade paper.
Applicant of the present invention has submitted the patent application about the wealthy mixed bleach of sulphate chemical pulp pin and the wealthy mixed bleach of NaOH anthraquinone chemical pulp pin on September 26th, 2011, the open stage at present, its publication number is respectively: CN 102345241A, CN 102337694A, these two patents are the wealthy mixed bleach of pin, the method for bleaching adopting is that element-free chlorine is ECF(Elemental Chlorine Free) method for bleaching, can be by the whiteness bleaching of the wealthy mixed pulp of pin to 85%ISO, even can reach 88%ISO, meet the needs of producing high-grade paper completely, and in the waste water after ECF bleaching except the undecomposed ClO of minute quantity
2in addition, waste water is containing other noxious material, and the waste water producing can recycle, meets the requirement of cleaner production.But the raising along with living standards of the people, has stricter requirement to high-grade wrapping papers such as luxury food, medicine.
Summary of the invention
For above-mentioned prior art, the invention provides the technique of the wealthy mixed sulfate chemical pulp of a kind of pin total chlorine free bleaching, that needlebush and leaf wood are distinguished to boiling according to conditions of cooking separately, then after mixing according to the wealthy ratio of pin required in producing, bleach, can control preferably the Kappa number hardness of needlebush magma and leaf wood magma like this, be conducive to follow-up bleaching, and environmental protection is pollution-free, is beneficial to energy-saving and emission-reduction.
The wealthy sulfate pulp mixed bleach of pin of the present invention adopts is biotechnology and is TCF(Totally Chlorine Free completely without chlorine) method for bleaching, paper pulp after this TCF bleaching, the cleaner paper of more environmental protection of can manufacturing paper with pulp, the extra package that the paper pulp after this TCF bleaching is mainly used in food, medicine and the composition of wrapping paper is had to strict demand.
Specifically, the present invention is achieved by the following technical solutions:
The technique of the wealthy mixed sulfate chemical pulp of a kind of pin total chlorine free bleaching, step is as follows: mixing according to the ratio of mass ratio 3:7～7:3 with the good softwood pulp of kraft cooking and the good hardwood chemical pulp of kraft cooking, after mixing, employing bleaching process is XO
1Po
2PqP
1or XO
1o
2PqP
1p
2tCF bleaching process carry out High brightenss bleach.
Preferably, described processing step is specific as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 3:7～7:3 in mass ratio, after washing and mixing, the wealthy mixed pulp of this pin is put into polyethylene plastic bag, then regulate and starch dense and pH value, add zytase simultaneously, then polyethylene plastic bag is put in thermostat water bath, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, this bleaching section is X section;
(2) after X section finishes, paper pulp is washed, the paper pulp having washed is put into oxygen delignification reactor and is carried out O
1section oxygen delignification or O
1Pduan Qianghua oxygen delignification;
(3) at O1 section oxygen delignification or O
1Pstrengthening after oxygen delignification finishes, is washed paper pulp, and the paper pulp having washed again enters in the reactor of oxygen delignification and carries out O
2Pduan Qianghua oxygen delignification;
(4) at O
2Pafter Duan Qianghua oxygen delignification finishes, paper pulp is washed, the paper pulp having washed carries out the processing of Q section, with remove with chelating paper pulp in transition metal ions, for bleachery is below prepared;
(5) after Q section chelation treatment finishes, paper pulp is washed, the paper pulp having washed carries out P
1section or P
1p
2two sections of hydrogen peroxide bleachings.
Preferably, described step (1) is specific as follows: by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 3:7～7:3 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution (to adjust pH value used, for NaOH weak solution, for one of ordinary skill in the art, be conventional) concentration to 10% of adjusting paper pulp, pH value to 8～10, the zytase that adds 6～12IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, reaction time is 90～120min.
Preferably, in described step (2), carry out O
1the concrete steps of section oxygen delignification are as follows: the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2～3% NaOH and 0.3～0.8% MgSO
4, with running water, regulate slurry dense to 10%, then pass into oxygen, under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
1section oxygen delignification, time 15～30min.
Preferably, in described step (2), carry out O
1the concrete steps of Duan Qianghua oxygen delignification are as follows: the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3, and 0.3～0.7% EDTA or DTPA(MgSO
4, Na
2siO
3, and EDTA(or DTPA) as protective agent and the chelating agent of paper pulp), add 1.5%～3% H
2o
2(as the agent of strengthening oxygen delignification), regulates pulp density to 10% with running water, passes into oxygen, under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition, carries out O
1Pduan Qianghua oxygen delignification, time 15～30min.
Preferably, described step (3) is specific as follows: in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3, and 0.3～0.7% EDTA or DTPA(MgSO
4, Na
2siO
3, and EDTA(or DTPA) as protective agent and the chelating agent of paper pulp), add 1.5%～4% H
2o
2(as the agent of strengthening oxygen delignification), regulates pulp density to 10% with running water, passes into oxygen, under 90～105 ℃ of temperature, pressure 0.5～0.8MPa condition, carries out O
2Pduan Qianghua oxygen delignification, time 60min～90min.
Preferably, described step (4) is specific as follows: reacted paper pulp in step (3) is washed with running water, then put into polyethylene plastic bag, add 0.3%～0.7% chelating agent EDTA or DTPA, use H
2sO
4it is 5 in the most preferred pH value of 4～6(that weak solution regulates paper pulp pH value), with running water adjusting, starch densely to 8%, be then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
Preferably, in described step (5), the concrete steps of carrying out P1 section hydrogen peroxide bleaching are as follows: reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3with 3～6% H
2o
2, with running water, regulate slurry dense to 10%, be then put into bleaching (being P1 section) in the thermostat water bath of 90 ℃ of temperature, time 70～150min.
Preferably, described step (5) is specific as follows: carry out P
1p
2the concrete steps of two sections of hydrogen peroxide bleachings are as follows: reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3with 3～6% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 70～150min; Reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3with 2～4% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
2section), time 70～120min.
In described step (5), P
1after section hydrogen peroxide bleaching, whether carry out P
2section hydrogen peroxide bleaching, depends on following condition: P
1after section hydrogen peroxide bleaching, paper pulp washs with running water, if more than whiteness reaches 80%ISO, can not carry out P
2section bleaching, if whiteness not yet reaches 80%ISO, can carry out P
2section post-bleach.Generally speaking, if all add H when two sections of oxygen delignifications
2o
2strengthen oxygen delignification, so at P
1after section bleaching finishes, the whiteness of paper pulp generally reaches 82%ISO left and right, has substantially met the requirement of actual production; If do not add H during first paragraph oxygen delignification
2o
2, only have second segment to add H
2o
2strengthen oxygen delignification, P
1after section bleaching finishes, the whiteness of paper pulp, between 78～81%ISO, therefore needs P
2section bleaching, makes its final whiteness in 82%ISO left and right.
Slurry described above is dense, the consumption of zytase, NaOH consumption, MgSO
4consumption, Na
2siO
3consumption, H
2o
2consumption, DTPA and EDTA consumption etc. is for oven dry stock, related percentage is mass percent.
The technique of above-mentioned not detailed description is common process of the prior art, is that one of ordinary skill in the art understand thoroughly and know, and does not repeat them here.
The present invention mixes the good softwood pulp of kraft cooking with by the ratio that the good hardwood chemical pulp of kraft cooking mixes according to mass ratio 3:7～7:3, then adopts X, O
1(O
1P), O
2P, Q, P
1(P
2) bleaching process that newly floats order carries out TCF High brightenss bleach.The Kappa number scope of softwood kraft pulp is 16～23, the Kappa number scope of broad-leaved wood sulphate pulp is 16～22, show by experiment, the softwood kraft pulp that Kappa number is close or suitable and broad-leaved wood sulphate pulp have produced synergy bleaching collaborative discoloration in other words when mixed bleach, kept mixed chemical to starch good pulp property, the more excellent paper of the physical index of having manufactured paper with pulp out.Whole bleaching process of the present invention is compared with the paper pulp of boiling respectively of the prior art, bleaching respectively, and the chemicals usage consuming (mainly refers to bleaching agent H
2o
2consumption) reduce 5～15%, meet energy-saving and emission-reduction strategy.And due to the Kappa number of two kinds of paper pulp quite or close, its whole bleaching process process conditions are gentleer, whiteness and the stability of floating rear paper pulp are better, become every physical index of paper, as all better in burst index, fracture length, tear index, folding strength etc.
The technique of the wealthy mixed sulfate chemical pulp of pin of the present invention total chlorine free bleaching, needlebush and leaf wood adopt respectively kraft cooking, then according to different mixing proportion, carry out TCF bleaching, in whole bleaching process, only use zytase, oxygen, NaOH, hydrogen peroxide, EDTA(or DTPA), the free of contamination chemicals of nontoxic free from extraneous odour such as magnesium sulfate, sodium metasilicate.In prior art, needlebush and leaf wood respectively boiling are bleached respectively, need two bleaching production lines, but the present invention adopts needlebush and leaf wood mixed bleach technique after boiling respectively, has saved a bleaching production line.Simultaneously, owing to adopting biological pre-bleaching technology, following bleaching drug dosage reduces 5～15%, and the more soft more easily making beating of the pulping after mixed pulp bleaching, reducing energy consumption can find out by the required making beating revolution difference of identical beating degree from table 1 at 20%(), therefore the present invention is not only a kind of environmental protection production new technology, but also is a kind of energy-saving and emission-reduction production new technology.
The present invention is a kind of method of total chlorine free bleaching, this bleaching process, from bleaching, start to finish to bleaching, only use zytase, NaOH, oxygen, magnesium sulfate, sodium metasilicate, EDTA(or DTPA), hydrogen peroxide etc., the avirulence of these chemicalss own, in bleached pulp process, do not produce any poisonous material yet, belong to high clean free of contamination environmental protection production technology, although the pulp brightness of process total chlorine free bleaching is generally in 82%ISO left and right, than the pulp brightness after ECF bleaching, there is gap, but can meeting, the paper pulp of this whiteness produces high-grade food, medicine, and the paper that the composition of paper pulp is had to specific (special) requirements.Simultaneously, CN100412267C compares with patent of invention, in the present invention, having adopted biological pre-bleaching technology is X section, and in this section, the reaction condition of zytase pre-bleaching is: temperature 50 C, pH value is 8～10, processing time 120min, xylan consumption is at 6～12IU/g, starch dense 10%, the process conditions of this step are gentleer, in actual production, than being easier to, operate, and the paper pulp after biological pre-bleaching is in follow-up bleaching, with boiling respectively and respectively bleaching compare, can reduce the consumption of following bleaching chemicals in 10% left and right, more be conducive to reduce production costs, meet the production requirement of energy-saving and emission-reduction.
The specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
The technique of the 1 one kinds of wealthy mixed sulfate chemical pulp of pin total chlorine free bleachings of embodiment
Step is as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 3:7 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, the pH value to 8 of paper pulp, the zytase that adds 8IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, the reaction time is 90min.
(2) the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2% NaOH and 0.5% MgSO
4, with running water, regulate slurry dense to 10%, then pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
1section oxygen delignification, time 30min.
(3) in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% EDTA, adds 2% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 90min.
(4) in step (3), reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2sO
4solution regulates paper pulp pH value 5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2% NaOH, 0.8% MgSO
4, 0.5% Na
2siO
3with 5% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 70min; Reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 2% NaOH, 0.8% MgSO
4, 0.5% Na
2siO
3with 2% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
2section), time 120min.
The whiteness of paper pulp reaches 83.1%ISO.
The technique of the 2 one kinds of wealthy mixed sulfate chemical pulp of pin total chlorine free bleachings of embodiment
Step is as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 3:7 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, the pH value to 8 of paper pulp, the zytase that adds 6IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, the reaction time is 90min.
(2) the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2% NaOH, 0.5% MgSO
4, 0.5% Na
2siO
3, and 0.5% EDTA, adds 1.5% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
1Pduan Qianghua oxygen delignification, time 30min.
(3) in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% EDTA, adds 2.5% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 90min.
(4) in step (3), reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2sO
4solution regulates paper pulp pH value 5.5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 5% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 90min.
The whiteness of paper pulp reaches 82.3%ISO.
The technique of the 3 one kinds of wealthy mixed sulfate chemical pulp of pin total chlorine free bleachings of embodiment
Step is as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 1:1 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, the pH value to 9 of paper pulp, the zytase that adds 9IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, the reaction time is 120min.
(2) the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2.5% NaOH and 0.5% MgSO
4, with running water, regulate slurry dense to 10%, then pass into oxygen, under 95 ℃ of temperature, pressure 0.6MPa condition, carry out O
1section oxygen delignification, time 20min.
(3) in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% EDTA, adds 3% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 70min.
(4) in step (3), reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2sO
4solution regulates paper pulp pH value 5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 4% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 120min; Reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 2% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
2section), time 90min.
The whiteness of paper pulp reaches 82.4%ISO.
The technique of the 4 one kinds of wealthy mixed sulfate chemical pulp of pin total chlorine free bleachings of embodiment
Step is as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 1:1 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, the pH value to 9 of paper pulp, the zytase that adds 8IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, the reaction time is 120min.
(2) the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% EDTA, adds 2% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 95 ℃ of temperature, pressure 0.6MPa condition, carry out O
1Pduan Qianghua oxygen delignification, time 25min.
(3) in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% EDTA, adds 3% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 70min.
(4) in step (3), reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2sO
4solution regulates paper pulp pH value 5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 4% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 120min.
The whiteness of paper pulp reaches 82.6%ISO.
The technique of the 5 one kinds of wealthy mixed sulfate chemical pulp of pin total chlorine free bleachings of embodiment
Step is as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 7:3 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, the pH value to 10 of paper pulp, the zytase that adds 10IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, the reaction time is 120min.
(2) the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2.5% NaOH and 0.5% MgSO
4, with running water, regulate slurry dense to 10%, then pass into oxygen, under 95 ℃ of temperature, pressure 0.6MPa condition, carry out O
1section oxygen delignification, time 15min.
(3) in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% DTPA, adds 4% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 60min.
(4) in step (3), reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 0.5% chelating agent DTPA, uses H
2sO
4solution regulates paper pulp pH value 5.5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 3% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 120min; Reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 3% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
2section), time 90min.
The whiteness of paper pulp reaches 82.2%ISO.
The technique of the 6 one kinds of wealthy mixed sulfate chemical pulp of pin total chlorine free bleachings of embodiment
Step is as follows:
(1) by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 7:3 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, the pH value to 10 of paper pulp, the zytase that adds 10IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, the reaction time is 120min.
(2) the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% DTPA, adds 2% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 95 ℃ of temperature, pressure 0.6MPa condition, carry out O
1Pduan Qianghua oxygen delignification, time 15min.
(3) in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3, and 0.5% DTPA, adds 3% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 60min.
(4) in step (3), reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 0.5% chelating agent DTPA, uses H
2sO
4solution regulates paper pulp pH value 5.5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2.5% NaOH, 0.5% MgSO
4, 0.7% Na
2siO
3with 5% H
2o
2, with running water, regulate slurry dense to 10%, being then put into bleaching in the thermostat water bath of 90 ℃ of temperature (is P
1section), time 120min.
The whiteness of paper pulp reaches 82.1%ISO.
Every physical index comparison of experiment paper
Paper pulp prepared by the technique of employing above-described embodiment 1,3,6, making beating is copied and is made 60g/m
2paper, the paper pulp of bleaching respectively preparation with the boiling respectively of conventional method mixes making beating and copies and make 60g/m
2paper, carries out every physical index comparison, as shown in table 1.
The physical property of pulp index of table 1 sulfate pulp mixed bleach and bleaching is respectively list relatively
Claims (2)
1. a technique for the wealthy mixed sulfate chemical pulp of pin total chlorine free bleaching, is characterized in that: step is as follows:
(1) by well-done Kappa number scope, be 16～23 softwood kraft pulp and Kappa number scope be 16～22 broad-leaved wood sulphate pulp in mass ratio the ratio of 3:7～7:3 mix, after washing and mixing, the wealthy mixed pulp of this pin is put into polyethylene plastic bag, then regulate and starch dense and pH value, add zytase simultaneously, then polyethylene plastic bag is put in thermostat water bath, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, this bleaching section is X section;
(2) after X section finishes, paper pulp is washed, the paper pulp having washed is put into oxygen delignification reactor and is carried out O
1section oxygen delignification or O
1Pduan Qianghua oxygen delignification;
(3) at O
1section oxygen delignification or O
1Pstrengthening after oxygen delignification finishes, is washed paper pulp, and the paper pulp having washed again enters in the reactor of oxygen delignification and carries out O
2Pduan Qianghua oxygen delignification;
(4) at O
2Pafter Duan Qianghua oxygen delignification finishes, paper pulp is washed, the paper pulp having washed carries out the processing of Q section;
(5) after Q section chelation treatment finishes, paper pulp is washed, the paper pulp having washed carries out P
1section or P
1p
2two sections of hydrogen peroxide bleachings;
Described step (1) is specific as follows: by well-done softwood kraft pulp and the broad-leaved wood sulphate pulp ratio mixing of 3:7～7:3 in mass ratio, with running water, wash, mix, then washing the even good wealthy mixed pulp of pin are put into polyethylene plastic bag, add running water and NaOH solution to regulate concentration to 10%, pH value to 8～10 of paper pulp, the zytase that adds 6～12IU/g, then be placed in the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out to Biological Pretreatment, and the reaction time is 90～120min;
In described step (2), carry out O
1the concrete steps of section oxygen delignification are as follows: the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2～3% NaOH and 0.3～0.8% MgSO
4, with running water, regulate slurry dense to 10%, then pass into oxygen, under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
1section oxygen delignification, time 15～30min;
In described step (2), carry out O
1the concrete steps of Duan Qianghua oxygen delignification are as follows: the reacted paper pulp of step (1) is washed with running water, then put into the reactor of oxygen delignification, add 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3, and 0.3～0.7% EDTA or DTPA, add 1.5%～3% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
1Pduan Qianghua oxygen delignification, time 15～30min;
Described step (3) is specific as follows: in step (2), reacted paper pulp washs with running water, and then puts into the reactor of oxygen delignification, adds 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3, and 0.3～0.7% EDTA or DTPA, add 1.5%～4% H
2o
2, with running water, regulate pulp density to 10%, pass into oxygen, under 90～105 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
2Pduan Qianghua oxygen delignification, time 60min～90min;
Described step (4) is specific as follows: reacted paper pulp in step (3) is washed with running water, then put into polyethylene plastic bag, add 0.3%～0.7% chelating agent EDTA or DTPA, use H
2sO
4solution regulates paper pulp pH value 3.5～5.5, with running water, regulates and starches densely to 8%, is then put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min;
In described step (5), carry out P
1the concrete steps of section hydrogen peroxide bleaching are as follows: reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3with 3～6% H
2o
2, with running water, regulate slurry dense to 10%, be then put in the thermostat water bath of 90 ℃ of temperature and bleach, time 70～150min;
In described step (5), carry out P
1p
2the concrete steps of two sections of hydrogen peroxide bleachings are as follows: reacted paper pulp in step (4) is washed with running water, then put into polyethylene plastic bag, add 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3with 3～6% H
2o
2, with running water, regulate slurry dense to 10%, be then put in the thermostat water bath of 90 ℃ of temperature and bleach, time 70～150min; Reacted paper pulp washs with running water, then puts into polyethylene plastic bag, adds 2～3% NaOH, 0.3～0.8% MgSO
4, 0.5～1% Na
2siO
3with 2～4% H
2o
2, with running water, regulate slurry dense to 10%, be then put in the thermostat water bath of 90 ℃ of temperature and bleach, time 70～120min.
2. the paper pulp that the technique of the wealthy mixed sulfate chemical pulp of a kind of pin claimed in claim 1 total chlorine free bleaching prepares.
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| CN104611964B (en) * | 2015-01-15 | 2016-04-20 | 陕西科技大学 | A kind of pulping process of Acacia sulphite process high whiteness semi-chemical pulp |
| CN104611965B (en) * | 2015-01-15 | 2016-05-25 | 陕西科技大学 | The pulping process of the high whiteness semi-chemical pulp of a kind of Eucalyptus |
| CN106676928B (en) * | 2016-12-30 | 2018-07-03 | 齐鲁工业大学 | A kind of method that wealthy mixed sulfate element chlorine free bleaching chemical pulp of needle prepares paper substrate |
| CN106758486B (en) * | 2016-12-30 | 2018-05-08 | 齐鲁工业大学 | A kind of method that wealthy mixing sodium hydroxide anthraquinone element chlorine free bleaching chemical pulp of pin prepares paper base material |
| CN106758487B (en) * | 2016-12-30 | 2018-06-26 | 齐鲁工业大学 | A kind of method that wealthy mixed sulfate slurry total chlorine free bleaching chemical pulp of needle prepares paper base material |
| CN110670398A (en) * | 2019-10-28 | 2020-01-10 | 山东晨鸣纸业集团股份有限公司 | Method for pulping broad-leaved wood by totally chlorine-free bleaching |
| CN114921992B (en) * | 2022-06-01 | 2023-04-28 | 齐鲁工业大学 | Preparation method of bio-mechanical pulp treated by biological enzyme |
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