CN102926261A - Total-chlorine-free bleaching process of coniferous wood and broadleaf wood mixed sodium hydroxide anthraquinone chemical pulp - Google Patents
Total-chlorine-free bleaching process of coniferous wood and broadleaf wood mixed sodium hydroxide anthraquinone chemical pulp Download PDFInfo
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- CN102926261A CN102926261A CN2012104074965A CN201210407496A CN102926261A CN 102926261 A CN102926261 A CN 102926261A CN 2012104074965 A CN2012104074965 A CN 2012104074965A CN 201210407496 A CN201210407496 A CN 201210407496A CN 102926261 A CN102926261 A CN 102926261A
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Abstract
The invention discloses a novel total-chlorine-free bleaching process of coniferous wood and broadleaf wood mixed sodium hydroxide anthraquinone pulp. The novel process comprises the steps of: mixing coniferous wood chemical pulp steamed by using a sodium hydroxide anthraquinone way with broadleaf wood chemical pulp steamed by using the sodium hydroxide anthraquinone way according to a mass ratio of (3:7)-(7:3); and after the uniform mixing, performing the high-whiteness bleaching by adopting a TCF (Total Chlorine Free) bleaching process with the bleaching procedures of XO1PO2PQP1 or XO1O2PQP1P2. In comparison with conventional pulp which is steamed respectively and bleached respectively, the whole process disclosed by the invention has the advantages that the consumption of the consumed chemical products is reduced by 5-15%, and pulping energy consumption is reduced by 10-25%when the same pulping degree is realized, the mixed bleached finished pulp steamed respectively and the pulp steamed respectively and bleached respectively are mixed for pulping at the presence of the same mixing ratio of the coniferous wood and the broadleaf wood after the pulp is formed. Relatively good whiteness stability of the bleached pulp and various physic indexes of paper made of the pulp such as a breakage resistance index, a fracture length, a tearing index and folding endurance are achieved.
Description
Technical field
The present invention relates to the technique of the wealthy mixing NaOH of a kind of pin anthraquinone chemical pulp total chlorine free bleaching, belong 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 the chemical pulp is high, paper strength greatly, easily bleach, be difficult for the characteristics 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 different with the physical strength index request to the performance that becomes paper, 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 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 that adopts is that element-free chlorine is ECF(Elemental Chlorine Free) method for bleaching, can be with 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 fully, and in the waste water after the ECF bleaching except the undecomposed ClO of minute quantity
2In addition, waste water does not contain other noxious material, and the waste water that produces 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.NaOH anthraquinone slurry is compared with sulfate pulp, do not produce the waste gas of sulfur-bearing in the digestion process, therefore do not need to install waste gas recovering device, but same paper making raw material, the paper pulp that the intensity of the anthraquinone slurrying gained of NaOH paper pulp makes a little less than sulfate process, therefore, in the factory of actual production, which kind of pulping process different manufacturers often determines to adopt according to s own situation.
Summary of the invention
For above-mentioned prior art, the technique of the wealthy mixing NaOH of a kind of pin of the present invention anthraquinone chemical pulp total chlorine free bleaching, that needlebush and leaf wood are distinguished boiling according to conditions of cooking separately, then bleach after mixing according to the wealthy ratio of pin required in producing, can control preferably like this Kappa number hardness of needlebush magma and leaf wood magma, be conducive to follow-up bleaching, and environmental protection is pollution-free, is beneficial to energy-saving and emission-reduction.
The wealthy NaOH anthraquinone of the pin of this patent slurry mixed bleach 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 strict demand.
Specifically, the present invention is achieved by the following technical solutions:
The technique of the wealthy mixing NaOH of a kind of pin anthraquinone chemical pulp total chlorine free bleaching, step is as follows: mixing according to the ratio of mass ratio 3:7～7:3 with the anthraquinone well-done softwood pulp of NaOH and the anthraquinone well-done hardwood chemical pulp of NaOH, after mixing, the employing bleaching process is XO
1PO
2PQP
1Or XO
1O
2PQP
1P
2The TCF bleaching process carry out High brightenss bleach.
Preferably, described processing step is specific as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 3:7～7:3, after washing and mixing, the wealthy mixed pulp of this pin is put into polyethylene plastic bag, then regulate the dense and pH value of slurry, add simultaneously zytase, then polyethylene plastic bag is put in the thermostat water bath, the wealthy mixed pulp of pin is carried out Biological Pretreatment, this bleaching section is the X section;
(2) after the X section finishes, paper pulp is washed, the paper pulp that washing is good is put into the oxygen delignification reactor and is carried out O
1Section oxygen delignification or O
1PThe Duan Qianghua oxygen delignification;
(3) at O
1Section oxygen delignification or O
1PAfter strengthening oxygen delignification and finishing, paper pulp is washed, the paper pulp that washing is good again enters in the reactor of oxygen delignification and carries out O
2PThe Duan Qianghua oxygen delignification;
(4) at O
2PAfter the Duan Qianghua oxygen delignification finishes, paper pulp is washed, the paper pulp that washing is good carries out the Q section to be processed, with remove with chelating paper pulp in transition metal ions, for the bleachery of back is prepared;
(5) after Q section chelation treatment finishes, paper pulp is washed, the paper pulp that washing is good carries out P
1Section or P
1P
2Two sections hydrogen peroxide bleachings.
Preferably, described step (1) is specific as follows: well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 3:7～7:3, wash with running water, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, (it is used to adjust the pH value to add running water and NaOH solution, be the NaOH weak solution, conventional for one of ordinary skill in the art) concentration to 10% of adjusting paper pulp, pH value to 8～10, the zytase that adds 6～12IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out Biological Pretreatment, and the reaction time is 90～120min.
Preferably, in the 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, the NaOH of adding 2～3% and 0.3～0.8% MgSO
4, it is dense to 10% to regulate slurry with running water, then passes into oxygen, carries out O under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition
1The section oxygen delignification, time 15～30min.
Preferably, in the 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 strengthening the oxygen delignification agent), regulate pulp density to 10% with running water, pass into oxygen, under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
1PThe Duan Qianghua oxygen delignification, time 15～30min.
Preferably, described step (3) is specific as follows: reacted paper pulp washs with running water in the step (2), 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 strengthening the oxygen delignification agent), regulate pulp density to 10% with running water, pass into oxygen, under 90～105 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 60min～90min.
Preferably, described step (4) is specific as follows: reacted paper pulp in the 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 is regulated paper pulp pH value), starch densely to 8% with the running water adjusting, then be put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
Preferably, in the described step (5), carry out P
1The concrete steps of section hydrogen peroxide bleaching are as follows: reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
1Section), time 70～150min.
Preferably, described step (5) is specific as follows: carry out P
1P
2The concrete steps of two sections hydrogen peroxide bleachings are as follows: reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
2Section), time 70～120min.
In the described step (5), P
1Whether carry out P behind the section hydrogen peroxide bleaching
2The section hydrogen peroxide bleaching depends on following condition: P
1Behind the section hydrogen peroxide bleaching, paper pulp washs with running water, if whiteness reaches more than the 80%ISO, can not carry out P
2The section bleaching if whiteness not yet reaches 80%ISO, can be carried out P
2The section post-bleach.Generally speaking, if when two sections oxygen delignifications, all add H
2O
2Strengthen oxygen delignification, so at P
1After the section bleaching finished, the whiteness of paper pulp generally reached 82%ISO, has basically satisfied the requirement of actual production; If do not add H during the first paragraph oxygen delignification
2O
2, only have second segment to add H
2O
2Strengthen oxygen delignification, P
1After the section bleaching finished, therefore the whiteness of paper pulp needed P between 75～80%ISO
2The section bleaching makes its final whiteness about 82%ISO.
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 according to the ratio that mass ratio 3:7 to 7:3 mixes the anthraquinone well-done softwood pulp of NaOH with the anthraquinone well-done hardwood chemical pulp of NaOH, then adopts X, O
1(O
1P), O
2P, Q, P
1(P
2) bleaching process that newly floats order carries out the TCF High brightenss bleach.The Kappa number scope of needlebush NaOH anthraquinone slurry is 16～23, the Kappa number scope of leaf wood NaOH anthraquinone slurry is 16～22, show by experiment, the needlebush NaOH anthraquinone slurry that Kappa number is close or suitable and leaf wood NaOH anthraquinone slurry have produced in other words collaborative discoloration of synergy bleaching when mixed bleach, kept the good pulp property of mixed chemical slurry, the more excellent paper of the physical index of having manufactured paper with pulp out.The whole bleaching process of the present invention is compared with the paper pulp of respectively boiling of the prior art, respectively bleaching, and the chemicals usage that consumes (mainly refers to bleaching agent H
2O
2Consumption) reduces 5～15%, meet the energy-saving and emission-reduction strategy.Because the Kappa number of two kinds of paper pulp quite or close, its whole bleaching process process conditions are relatively gentleer, float the whiteness of rear paper pulp and stability better, become every physical index of paper, and are all better such as burst index, fracture length, tear index, folding strength etc.
The technique of the wealthy mixing NaOH of pin of the present invention anthraquinone chemical pulp total chlorine free bleaching, needlebush and leaf wood are adopted respectively the anthraquinone boiling of NaOH, then carry out the TCF bleaching according to different mixing proportion, in the 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 the prior art, needlebush and leaf wood respectively boiling are bleached respectively, need two bleaching production lines, but the present invention adopts respectively mixed bleach technique after the boiling of needlebush and leaf wood, has saved a bleaching production line.Simultaneously, owing to adopt biological pre-bleaching technology, the following bleaching drug dosage reduces 5～15%, and the more soft easier making beating of pulping after the mixed pulp bleaching, reducing energy consumption (can find out by the required making beating revolution difference of identical beating degree from table 1) about 20%, therefore this patent 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, finish from bleaching beginning to bleaching, only use zytase, NaOH, oxygen, magnesium sulfate, sodium metasilicate, EDTA(or DTPA), hydrogen peroxide etc., the avirulence of these chemicalss own, in the bleached pulp process, do not produce any poisonous material yet, belong to the free of contamination environmental protection production technology of high cleaning, although the pulp brightness of process total chlorine free bleaching is generally about 82%ISO, than the pulp brightness after the ECF bleaching gap is arranged, but can satisfying, the paper pulp of this whiteness produces high-grade food, medicine, and the paper that the composition of paper pulp is had specific (special) requirements.Simultaneously, CN100412267C compares with patent of invention, in the present invention, having adopted biological pre-bleaching technology is the X section, and in this section, the reaction condition of zytase pre-bleaching is: temperature 50 C, and the pH value is 8～10, processing time 120min, the xylan consumption is at 6～12IU/g, starches densely 10%, and the process conditions in this step are relatively gentleer, in actual production, operate than being easier to, and through the paper pulp behind the biological pre-bleaching in follow-up bleaching, with boiling respectively with bleach respectively and compare, can reduce the consumption of following bleaching chemicals about 10%, more be conducive to reduce production costs, meet the production requirement of energy-saving and emission-reduction.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
The technique of 1 one kinds of wealthy mixing NaOH of pin of embodiment anthraquinone chemical pulp total chlorine free bleaching
Step is as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 3:7, with running water washing, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate concentration to 10%, the pH value to 8 of paper pulp, the zytase that adds 8IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out 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, the NaOH of adding 2% and 0.5% MgSO
4, it is dense to 10% to regulate slurry with running water, then passes into oxygen, carries out O under 90 ℃ of temperature, pressure 0.5MPa condition
1The section oxygen delignification, time 30min.
(3) reacted paper pulp washs with running water in the step (2), 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, the H of adding 2%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 90min.
(4) reacted paper pulp washs with running water in the step (3), then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2SO
4Solution is regulated paper pulp pH value 5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
2Section), time 120min.
The whiteness of paper pulp reaches 83.3%ISO.
The technique of 2 one kinds of wealthy mixing NaOH of pin of embodiment anthraquinone chemical pulp total chlorine free bleaching
Step is as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 3:7, with running water washing, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate concentration to 10%, the pH value to 8 of paper pulp, the zytase that adds 6IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out 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, 0.7% Na
2SiO
3, and 0.5% EDTA, the H of adding 1.5%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
1PThe Duan Qianghua oxygen delignification, time 30min.
(3) reacted paper pulp washs with running water in the step (2), and then puts into the reactor of oxygen delignification, adds 2% NaOH, 0.8% MgSO
4, 0.7% Na
2SiO
3, and 0.5% EDTA, the H of adding 2.5%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 90 ℃ of temperature, pressure 0.5MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 90min.
(4) reacted paper pulp washs with running water in the step (3), then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2SO
4Solution is regulated paper pulp pH value 5.5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
1Section), time 90min.
The whiteness of paper pulp reaches 82.5%ISO.
The technique of 3 one kinds of wealthy mixing NaOH of pin of embodiment anthraquinone chemical pulp total chlorine free bleaching
Step is as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 1:1, with running water washing, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate concentration to 10%, the pH value to 9 of paper pulp, the zytase that adds 9IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out 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, the NaOH of adding 2.5% and 0.5% MgSO
4, it is dense to 10% to regulate slurry with running water, then passes into oxygen, carries out O under 95 ℃ of temperature, pressure 0.6MPa condition
1The section oxygen delignification, time 20min.
(3) reacted paper pulp washs with running water in the step (2), 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, the H of adding 3%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 70min.
(4) reacted paper pulp washs with running water in the step (3), then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2SO
4Solution is regulated paper pulp pH value 5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
2Section), time 90min.
The whiteness of paper pulp reaches 82.5%ISO.
The technique of 4 one kinds of wealthy mixing NaOH of pin of embodiment anthraquinone chemical pulp total chlorine free bleaching
Step is as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 1:1, with running water washing, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate concentration to 10%, the pH value to 9 of paper pulp, the zytase that adds 8IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out 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, 0.8% Na
2SiO
3, and 0.5% EDTA, the H of adding 2%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 95 ℃ of temperature, pressure 0.6MPa condition, carry out O
1PThe Duan Qianghua oxygen delignification, time 25min.
(3) reacted paper pulp washs with running water in the step (2), 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, the H of adding 3%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 70min.
(4) reacted paper pulp washs with running water in the step (3), then puts into polyethylene plastic bag, adds 0.5% chelating agent EDTA, uses H
2SO
4Solution is regulated paper pulp pH value 5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
1Section), time 120min.
The whiteness of paper pulp reaches 82.9%ISO.
The technique of 5 one kinds of wealthy mixing NaOH of pin of embodiment anthraquinone chemical pulp total chlorine free bleaching
Step is as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 7:3, with running water washing, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate concentration to 10%, the pH value to 10 of paper pulp, the zytase that adds 10IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out 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, the NaOH of adding 2.5% and 0.5% MgSO
4, it is dense to 10% to regulate slurry with running water, then passes into oxygen, carries out O under 95 ℃ of temperature, pressure 0.6MPa condition
1The section oxygen delignification, time 15min.
(3) reacted paper pulp washs with running water in the step (2), 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, the H of adding 4%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 60min.
(4) reacted paper pulp washs with running water in the step (3), then puts into polyethylene plastic bag, adds 0.5% chelating agent DTPA, uses H
2SO
4Solution is regulated paper pulp pH value 5.5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
2Section), time 90min.
The whiteness of paper pulp reaches 82.4%ISO.
The technique of 6 one kinds of wealthy mixing NaOH of pin of embodiment anthraquinone chemical pulp total chlorine free bleaching
Step is as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 7:3, with running water washing, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate concentration to 10%, the pH value to 10 of paper pulp, the zytase that adds 10IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out 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, the H of adding 2%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 95 ℃ of temperature, pressure 0.6MPa condition, carry out O
1PThe Duan Qianghua oxygen delignification, time 15min.
(3) reacted paper pulp washs with running water in the step (2), 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, the H of adding 3%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 100 ℃ of temperature, pressure 0.6MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 60min.
(4) reacted paper pulp washs with running water in the step (3), then puts into polyethylene plastic bag, adds 0.5% chelating agent DTPA, uses H
2SO
4Solution is regulated paper pulp pH value 5.5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
(5) reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, is put into then that bleaching (is P in the thermostat water bath of 90 ℃ of temperature
1Section), time 120min.
The whiteness of paper pulp reaches 82.2%ISO.
Every physical index of experiment paper relatively
Adopt the paper pulp of above-described embodiment 1,3,6 technique preparation, making beating is copied and is made 60g/m
2Paper mixes making beating and copies and make 60g/m with paper pulp that preparation is bleached respectively in the respectively boiling of conventional method
2Paper carries out every physical index relatively, and is as shown in table 1.
Table 1
The physical property of pulp index of NaOH anthraquinone slurry mixed bleach and respectively bleaching is list relatively
Claims (10)
1. the technique of the wealthy mixing NaOH of a pin anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: step is as follows: mixing according to the ratio of mass ratio 3:7～7:3 with the anthraquinone well-done softwood pulp of NaOH and the anthraquinone well-done hardwood chemical pulp of NaOH, after mixing, the employing bleaching process is XO
1PO
2PQP
1Or XO
1O
2PQP
1P
2The TCF bleaching process carry out High brightenss bleach.
2. the technique of the wealthy mixing NaOH of a kind of pin according to claim 1 anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: described processing step is specific as follows:
(1) well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 3:7～7:3, after washing and mixing, the wealthy mixed pulp of this pin is put into polyethylene plastic bag, then regulate the dense and pH value of slurry, add simultaneously zytase, then polyethylene plastic bag is put in the thermostat water bath, the wealthy mixed pulp of pin is carried out Biological Pretreatment, this bleaching section is the X section;
(2) after the X section finishes, paper pulp is washed, the paper pulp that washing is good is put into the oxygen delignification reactor and is carried out O
1Section oxygen delignification or O
1PThe Duan Qianghua oxygen delignification;
(3) at O
1Section oxygen delignification or O
1PAfter strengthening oxygen delignification and finishing, paper pulp is washed, the paper pulp that washing is good again enters in the reactor of oxygen delignification and carries out O
2PThe Duan Qianghua oxygen delignification;
(4) at O
2PThe Duan Qianghua oxygen delignification washs paper pulp after finishing, and the paper pulp that washing is good carries out the Q section to be processed;
(5) after Q section chelation treatment finishes, paper pulp is washed, the paper pulp that washing is good carries out P
1Section or P
1P
2Two sections hydrogen peroxide bleachings.
3. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: described step (1) is specific as follows: well-done needlebush NaOH anthraquinone slurry and leaf wood NaOH anthraquinone are starched the in mass ratio ratio mixing of 3:7～7:3, wash with running water, mixing, then will wash the also even good wealthy mixed pulp of pin and put into polyethylene plastic bag, add running water and NaOH solution and regulate the concentration to 10% of paper pulp, pH value to 8～10, the zytase that adds 6～12IU/g, then place the thermostat water bath of temperature 50 C, the wealthy mixed pulp of pin is carried out Biological Pretreatment, and the reaction time is 90～120min.
4. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching is characterized in that: in the 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, the NaOH of adding 2～3% and 0.3～0.8% MgSO
4, it is dense to 10% to regulate slurry with running water, then passes into oxygen, carries out O under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition
1The section oxygen delignification, time 15～30min.
5. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching is characterized in that: in the 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, the H of adding 1.5%～3%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 90～95 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
1PThe Duan Qianghua oxygen delignification, time 15～30min.
6. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: described step (3) is specific as follows: reacted paper pulp washs with running water in the step (2), and then put into the reactor of oxygen delignification, the NaOH of adding 2～3%, 0.3～0.8% MgSO
4, 0.5～1% Na
2SiO
3, and 0.3～0.7% EDTA or DTPA, the H of adding 1.5%～4%
2O
2, regulate pulp density to 10% with running water, pass into oxygen, under 90～105 ℃ of temperature, pressure 0.5～0.8MPa condition, carry out O
2PThe Duan Qianghua oxygen delignification, time 60min～90min.
7. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: described step (4) is specific as follows: reacted paper pulp in the step (3) is washed with running water, then put into polyethylene plastic bag, chelating agent EDTA or the DTPA of adding 0.3%～0.7% use H
2SO
4Solution is regulated paper pulp pH value 3.5～5.5, regulates with running water and starches densely to 8%, then is put into chelation treatment Q section in the thermostat water bath of temperature 70 C, time 60min.
8. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: in the described step (5), the concrete steps of carrying out P1 section hydrogen peroxide bleaching are as follows: reacted paper pulp in the step (4) is washed with running water, then put into polyethylene plastic bag, the NaOH of adding 2～3%, 0.3～0.8% MgSO
4, 0.5～1% Na
2SiO
3With 3～6% H
2O
2, it is dense to 10% to regulate slurry with running water, then is put in the thermostat water bath of 90 ℃ of temperature and bleaches time 70～150min.
9. the technique of the wealthy mixing NaOH of a kind of pin according to claim 2 anthraquinone chemical pulp total chlorine free bleaching, it is characterized in that: described step (5) is specific as follows: carry out P
1P
2The concrete steps of two sections hydrogen peroxide bleachings are as follows: reacted paper pulp in the 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, it is dense to 10% to regulate slurry with running water, then is put in the thermostat water bath of 90 ℃ of temperature and bleaches 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, it is dense to 10% to regulate slurry with running water, then is put in the thermostat water bath of 90 ℃ of temperature and bleaches time 70～120min.
10. the paper pulp that the technique of the wealthy mixing NaOH of each described a kind of pin anthraquinone chemical pulp total chlorine free bleaching prepares in the claim 1～9.
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| CN107338670A (en) * | 2016-12-30 | 2017-11-10 | 齐鲁工业大学 | A kind of method that wealthy mixing sodium hydroxide anthraquinone total chlorine free bleaching chemical pulp of pin prepares paper base material |
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|---|---|
| CN102926261B (en) | 2014-05-07 |
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