CN109554946A - The method that ionic liquid collaboration ultrasonic treatment ECF bleached kraft pulp prepares paper base material - Google Patents
The method that ionic liquid collaboration ultrasonic treatment ECF bleached kraft pulp prepares paper base material Download PDFInfo
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- 239000000123 paper Substances 0.000 title claims abstract description 83
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000002655 kraft paper Substances 0.000 title claims abstract description 27
- 238000009210 therapy by ultrasound Methods 0.000 title claims abstract description 10
- 238000004061 bleaching Methods 0.000 claims abstract description 74
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 64
- 230000008569 process Effects 0.000 claims abstract description 46
- 230000002195 synergetic effect Effects 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 229920005610 lignin Polymers 0.000 claims abstract description 8
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 51
- 239000002585 base Substances 0.000 claims description 37
- 238000009835 boiling Methods 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 229920002472 Starch Polymers 0.000 claims description 12
- 235000019698 starch Nutrition 0.000 claims description 12
- 239000008107 starch Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 238000009897 hydrogen peroxide bleaching Methods 0.000 claims description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000010411 cooking Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 claims description 7
- -1 2- ethoxy trimethylammonium ion Chemical class 0.000 claims description 6
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000004155 Chlorine dioxide Substances 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229930002839 ionone Natural products 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 40
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002023 wood Substances 0.000 abstract description 3
- 230000004792 oxidative damage Effects 0.000 abstract 1
- 241000219927 Eucalyptus Species 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000011002 quantification Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- DFGWJCZWKBGVOX-UHFFFAOYSA-N [Cl+].[O-2].[O-2].[Ti+4] Chemical compound [Cl+].[O-2].[O-2].[Ti+4] DFGWJCZWKBGVOX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- KVQVSHRZOYESHB-UHFFFAOYSA-N ethoxy(trimethyl)azanium Chemical compound CCO[N+](C)(C)C KVQVSHRZOYESHB-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1005—Pretreatment of the pulp, e.g. degassing the pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
- D21H11/04—Kraft or sulfate pulp
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
Abstract
The invention discloses the methods that ionic liquid cooperates with ultrasonic treatment ECF bleached kraft pulp to prepare paper base material, cooperate with ultrasound to pre-process unbleached kraft pulp using ionic liquid, pretreated kraft pulp is then carried out ECF bleaching.The present invention causes fiber seriously to be degraded the problem for causing bleached pulp physical strength low for oxygen delignification poor selectivity in bleaching process, the present invention proposes to use the pretreated method of ionic liquid synergistic supersonic wave, utilize the physics cavitation of ultrasonic wave and the chemical treatment effect of ionic liquid, make paper pulp fiber short texture in bleaching process and improves the swollen and fibrillating degree of paper pulp fiber, keep lignin readily removed, to avoid the oxidative damage of fiber in bleaching process, the physical strength performance of leaf wood paper base material can not only be improved, the whiteness of paper base material can also be improved.
Description
Technical field
The present invention relates to belong to pulp technology for making paper, and in particular to a kind of ionic liquid synergistic supersonic wave pretreatment Eucalyptus
The method that ECF bleached kraft pulp prepares paper base material.
Background technique
Here statement only provides background information related to the present invention, without necessarily constituting the prior art.
Pulp and paper industry is one of national economy important foundation raw material industry, is accounted for always in global industry manufacturing industry
According to critical role.The productive consumption level of paper and cardboard, which has become, measures a national economic development level and social progress
Important symbol.Since 2012, the total output of China's paper and cardboard has been more than a quarter of global yield, is sure to occupy the world
One.Mainly based on timber resources, ratio of the wood fiber raw material in paper making raw material reaches world's paper industry at present
94%, wherein the leaf woods such as poplar, Eucalyptus specific gravity shared in pulping and paper-making production continues to increase.As paper technology is to can
The attention of Sustainable cleaner production, papermaking enterprise mostly use cleaning delignification technology, such as float completely without chlorine (TCF), element-free chlorine (ECF)
White technology thus greatly reduces the content of Organic Pollutants in Wastewater.But ECF is mainly bleached by oxidation reaction, especially
It is the degradation that oxygen bleaching easily causes carbohydrate, makes that fibrous polymer degree reduces and to influence paper pulp strong at the physical property such as anti-tensile of paper
It spends more low.
Summary of the invention
In order to solve the deficiencies in the prior art, the object of the present invention is to provide ionic liquids to cooperate with ultrasonic treatment ECF bleaching
The method that kraft pulp prepares paper base material, can not only improve sulfate bleached pulp at paper physical strength performance, moreover it is possible to improve
The whiteness of sulfate bleached pulp.
To achieve the goals above, the technical solution of the present invention is as follows:
First aspect present invention is to provide ionic liquid collaboration ultrasonic treatment ECF bleached kraft pulp and prepares paper base material
Method cooperates with ultrasound to pre-process unbleached kraft pulp, then by pretreated sulfate using ionic liquid
Slurry carries out ECF bleaching.
Ionic liquid is that one kind is made of zwitterion completely, and the low temperature molten salt of liquid, tool are presented at room temperature
There is the features such as thermal stability is good, recyclable, non-volatile, dissolubility is good.Ionic liquid handles plant fiber can be to the knot of cellulose
Brilliant degree and crystal form have an impact, while energy swollen fiber, increase specific surface area, the binding force between reinforcing fiber.In addition, ion
Also the property of can choose separates wood fibre chemical constituent to liquid, promotes bleaching effect, reinforcing fiber physical strength.
Ultrasonication technology has the characteristics that low energy consumption, pollution-free, safe, cheap.Utilize the cavitation of ultrasonication
Effect generates the shock wave of high pressure and high pressure generation in fiber surface, generates Stress-strain concentration, causes fibrous inside knot
Structure changes, and crystallite is caused to misplace, and fiber is loose, and specific surface area increases, and crystallinity decline, unformed area increases, and enhancing is fine
Bond strength between dimension improves the physics and optical property of paper pulp；Meanwhile the fiber after ultrasonic treatment also has preferable water conservation
Value and accessibility；The processing of ultrasonic wave added ionic liquid can improve plant fibre surface charge density and pulp freeness, from
And improve anti-tensile, tearing and the damage resistibility energy of paper pulp.
Design concept of the invention are as follows: causing fiber seriously to be degraded for oxygen delignification poor selectivity in bleaching process causes
The low problem of bleached pulp physical strength, the present invention propose to use the pretreated method of ionic liquid synergistic supersonic wave, using super
The physics cavitation of sound wave and the chemical treatment effect of ionic liquid, make in bleaching process paper pulp fiber short texture and are mentioned
The swollen and fibrillating degree of high paper pulp fiber, keep lignin readily removed, so that the oxidation of fiber in bleaching process be avoided to damage
Wound, can not only improve the physical strength performance of leaf wood paper base material, moreover it is possible to improve the whiteness of paper base material.
The second aspect of the present invention is to provide a kind of paper base material of above method preparation.The paper base material not only has more
Good physical strength performance, and there is higher whiteness.
The invention has the benefit that
(1) present invention is pre-processed by ionic liquid synergistic supersonic wave, keeps the paper base material being prepared with higher
The advantages that folding strength, tensile strength, bursting strength, tearability, is suitble to prepare a plurality of types of paper base materials.
(2) ionic liquid pretreatment in the present invention, plays protective effect to fiber, alleviates it in following bleaching mistake
Alkaline bleach liquor degradation in journey, improves paper pulp fiber quality, and ionic liquid stable structure used, and benefit can be recycled in zero vapour pressure
With environmentally protective.
(3) preprocess method of the present invention improves broadleaf paper pulp bleaching property, can reduce bleached chemical medicament use
Amount improves bleaching efficiency, reduces pollutional load.
(4) processing method of the present invention is simple, practical, easy to spread.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Can be bleached by oxidation reaction in view of the presence of ECF makes the reduction of fibrous polymer degree influence paper pulp into the physical of paper
Can be insufficient, in order to solve technical problem as above, the present disclosure proposes ionic liquids to cooperate with ultrasonic treatment ECF bleached kraft pulp
The method for preparing paper base material.
A kind of exemplary embodiment of the disclosure provides ionic liquid collaboration ultrasonic treatment ECF bleached kraft pulp system
The method of standby paper base material cooperates with ultrasound to pre-process unbleached kraft pulp, then will locate in advance using ionic liquid
Kraft pulp after reason carries out ECF bleaching.
The design concept of the disclosure are as follows: causing fiber seriously to be degraded for oxygen delignification poor selectivity in bleaching process causes
The low problem of bleached pulp physical strength, the present invention propose to use the pretreated method of ionic liquid synergistic supersonic wave, using super
The physics cavitation of sound wave and the chemical treatment effect of ionic liquid, make in bleaching process paper pulp fiber short texture and are mentioned
The swollen and fibrillating degree of high paper pulp fiber, keep lignin readily removed, so that the oxidation of fiber in bleaching process be avoided to damage
Wound, can not only improve the physical strength performance of leaf wood paper base material, moreover it is possible to improve the whiteness of paper base material.
Inventive concept according to the present invention is located particular for Eucalyptus Kraft Pulp using ionic liquid synergistic supersonic wave in advance
Then reason is bleached in bleaching process with ECF method, available physical strength performance and the preferable paper pulp of whiteness.
In one or more embodiments of the embodiment, unbleached kraft pulp is that Eucalyptus is obtained through kraft cooking
Slurry.
In one or more embodiments of the embodiment, the time of the ultrasound is 40~80min.
In one or more embodiments of the embodiment, the dosage of ionic liquid is 5~15wt%.
By lot of experiment validation and analysis, in order to obtain optimal pretreating effect, the ultrasonic time is 60min, from
The dosage of sub- liquid is 10wt%.
In one or more embodiments of the embodiment, the anion of ionic liquid include hydrogen sulfate ion or chlorine from
The mixing of one or more of son.The cation of the ionic liquid includes 1- butyl 3- methyl-imidazolium ionic, 2- ethoxy
The mixing of one or more of trimethylammonium ion, triethyl ammonium ion.
The structural formula of 1- butyl 3- methyl-imidazolium ionic are as follows:
The structural formula of 2- ethoxy trimethylammonium ion are as follows:
Structural formula in triethyl ammonium ion are as follows:
In one or more embodiments of the embodiment, the program of the ECF bleaching is OAD1ED2, the steps include: head
First, O sections of oxygen deoxidation lignins are carried out to pretreated paper pulp, paper pulp is washed after O sections；Then it carries out at A sections of acid
It manages, paper pulp is washed after A sections；Then D is carried out1Section ClO 2 bleaching, D1Paper pulp is washed after section；
Then E sections of hydrogen peroxide bleachings are carried out, paper pulp is washed after E sections；Then D is carried out2Section ClO 2 bleaching, D2Section
Bleaching terminates, and washing pulp obtains bleached pulp.
OAD1ED2The concrete mode of bleaching schedule are as follows: O sections of Oxygen Delignification of Fast-Growing conditions are to starch dense 10%, NaOH dosage
3wt%, oxygen press 0.5MPa, 100 DEG C of temperature, time 60min and MgSO4Dosage 0.6wt%；A sections of acid treatment process conditions are pH
Value 3.5~4.5 and time 120min；D1Section ClO 2 bleaching process conditions are as follows: Chlorine 0.7wt%, pH value 2~
3, temperature 70 C, dense 10% and time 30min of slurry；E sections of hydrogen peroxide bleaching process conditions are hydrogen peroxide use 1wt%, starch
Dense 10wt%, pH value 11~12,90 DEG C of temperature and oxygen press 0.4MPa；D2Section ClO 2 bleaching process conditions are chlorine dioxide use
Measure 0.8wt%, pH value 2-3,75 DEG C of temperature, the dense 10wt% and time 120min of slurry.
In one or more embodiments of the embodiment, provide at a kind of better ionic liquid collaboration ultrasound of effect
The method that reason ECF bleached kraft pulp prepares paper base material, steps are as follows:
(1) boiling: taking Eucalyptus piece, is put into boiling in digester, and boiling terminates sufficiently to be washed and screened, and obtains Eucalyptus sulphur
Hydrochlorate slurry；The Kappa number of slurry is 12~16；
(2) ionic liquid synergistic supersonic wave pre-processes；
(3) ECF is bleached: carrying out ECF bleaching to by the pretreated slurry of ionic liquid synergistic supersonic wave, bleaching schedule is
OAD1ED2: firstly, to process ionic liquid synergistic supersonic wave O sections of oxygen deoxidation lignins of pretreated paper pulp progress, after O sections
Paper pulp is washed；Then A sections of acid processing are carried out, paper pulp is washed after A sections；Then D is carried out1Section chlorine dioxide
Bleaching, D1Paper pulp is washed after section；Then E sections of hydrogen peroxide bleachings are carried out, paper pulp is washed after E sections
It washs；Then D is carried out2Section ClO 2 bleaching, D2Section bleaching terminates, and washing pulp obtains bleached pulp；
(4) with by OAD1ED2The paper pulp of bleaching carries out copy paper.
In the series embodiment, the concrete mode of boiling in the step (1) are as follows: take 15~25mm of length, width 10~
20mm, 3~5mm of thickness relatively uniform Australian Eucalyptus piece carry out boiling after natural air drying, broadleaf Eucalyptus sulfuric acid are made
Salt magma, cooking schedule are alkali charge 21wt% (Na2O meter, relative to over dry raw material), sulphidity 25%, liquor ratio 1:5,
170 DEG C of boiling maximum temperature；It deflates at 105 DEG C, deflation 15min, heating-up time 90min, soaking time 90min；It steams
It boils rear slurry sufficiently to be washed and screened, is not floated Eucalyptus Kraft Pulp.
The another embodiment of the disclosure provides a kind of paper base material of above method preparation.The paper base material is not
Only there is physically better strength character, and there is higher whiteness.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool
The technical solution of the disclosure is described in detail in the embodiment of body.
Analysis method employed in embodiment is as follows:
The measurement of whiteness: paper pulp is copied into paper on the kayser method handshcet former of Austria's production after defiberizing machine is discongested
, it is measured afterwards with YQ-Z-48B whiteness instrument；
Folding number: domestic MIT folding tester is measured in.
Burst index: it is measured with the burst tester that swedish company L&W is produced.
Tensile index: domestic XLWA (B) Intelligent electronic tensil testing machine is measured in.
Tear index: domestic MIT tearability tester is measured in.
Remaining experimental method not elaborated is the conventional methods of this field.
The principle of the present invention are as follows: destroy fiber hydrogen bond network structure using ionic liquid, dissolved lignin dredges fibre structure
Pine improves fibre swelling degree, improves fiber fines composition features, the felt power between reinforcing fiber.At ultrasonic wave
The cavitation of reason improves the accessibility of paper pulp fiber.Meanwhile ionic liquid synergistic supersonic wave pre-processes, it is broken to glycan structures
It is bad small, promote the infiltration of subsequent drift agent, the destruction of chromophoric group and the diffusion dissolution of bleaching action product in paper pulp, Jin Erti
The performance of high bleached pulp web-forming material.
Embodiment 1:
Steps are as follows:
(1) conditions of cooking is alkali charge 21wt% (Na2O meter), sulphidity 25%, liquor ratio 1:5, boiling maximum temperature 170
DEG C, it deflates at 105 DEG C, heating-up time 90min, soaking time 90min；Paper pulp is sufficiently washed, is screened after boiling,
It obtains and does not float paper pulp.
(2) ionic liquid synergistic supersonic wave pre-processes: accurately weighing 3 bags of 25g slurries (oven dry stock meter), 10wt% (is pressed
According to slurry weight meter) dosage sulfuric acid hydrogenation triethyl ammonium ionic liquid (TEA-HSO4) be added separately in 3 bags of slurries, in poly- second
Adjustment slurry concentration is 10% in alkene bag, is rubbed to uniformly mixed.It is put into ultrasonic device and is ultrasonically treated, pretreating process item
Part is ionic liquid dosage 10wt%, ultrasonic time 40min, 50min, 80min and ultrasonic power 250W.
(3) ECF is bleached: carrying out OAD by the pretreated paper pulp of ionic liquid synergistic supersonic wave to above-mentioned1ED2Bleaching schedule
Bleaching.O sections of oxygen delignifications are carried out to Eucalyptus Kraft Pulp first, process conditions are to starch dense 10wt%, NaOH dosage 3wt%, oxygen
Press 0.5MPa, 100 DEG C of temperature, time 60min and MgSO4Dosage 0.6wt%, after slurry is washed.Then A is carried out
Section acid processing, process conditions are that pH value 3.5-4.5 and time 120min, after treatment wash slurry.D1Section dioxy
Change chlorine bleaching process conditions are Chlorine 0.7wt%, pH value 2-3, temperature 70 C, the dense 10wt% and time 30min of slurry,
Slurry is washed after bleaching.The E section hydrogen peroxide bleaching process conditions then carried out are hydrogen peroxide use
1wt%, dense 10%, pH value 11-12,90 DEG C of temperature and oxygen pressure 0.4MPa are starched, slurry is washed after processing.Then carry out
D2Section ClO 2 bleaching process conditions are Chlorine 0.8wt%, pH value 2-3,75 DEG C of temperature, the dense 10wt% of slurry and when
Between 120min, slurry is washed after bleaching.
(4) OAD copy paper: will be passed through1ED2Then slurry pulping after bleaching discongests paper pulp in device in fiber to 60 ° of SR
Progress paper pulp fiber, which is discongested, makes it be uniformly dispersed, and will discongest rear slurry and be copied into quantification of 80g/m on sheet forming apparatus2Body paper
Paper base material.
(5) simultaneously, selection is without the pretreated OAD of ionic liquid synergistic supersonic wave1ED2Bleached pulp is beaten to 60 °
Then paper pulp is discongested in fiber and carries out paper pulp fiber in device and discongest it is made to be uniformly dispersed by SR, will discongest rear slurry page at
Quantification of 80g/m is copied on type device2Body paper paper base material.
(6) performance indicator of gained body paper paper base material is as shown in table 1, under identical paper pulp fiber raw material, by ion
The performance indexes of the pretreated body paper paper base material of liquid synergistic supersonic wave is superior to without pretreated normal condition
The body paper paper base material of lower bleaching.
Pass through under the different ultrasonic times of table 1 and without the pretreated Eucalyptus OAD of ionic liquid synergistic supersonic wave1ED2Bleaching
Starch the body paper paper base material performance indicator manufactured paper with pulp
As a result: after testing, without pretreated Eucalyptus bleached pulp performance indicator be whiteness 75.2%ISO, anti-tensile refers to
Number 4.35Nmg-1, tear index 6.75mNm2·g-1, burst index 4.06kPam2·g-1With folding number 115 times.
Compared with passing through the pretreated bleached pulp of ionic liquid synergistic supersonic wave under identical bleaching conditions, by dosage 10wt%
(opposite oven dry stock meter) ionic liquid TEA-HSO4It is improved with the performance indicator of the paper pulp of 40-80min ultrasonic pretreatment,
Folding strength improves 154.8-220.1%, and tensile index improves 7.3-17.0%, and tear index improves 6.2-19.4%,
Burst index improves 3.4-6.4%, and whiteness improves 0.5-1.1%；Wherein ultrasonication 60min and ionic liquid TEA-
Pretreating effect is more excellent under HSO4 dosage 10wt% pretreatment condition, and paper folding strength improves 220.1%, and tensile index improves
17.0%, tear index improves 19.4%, burst index improves 3.4%, and whiteness improves 1.1%.As it can be seen that by from
The bleachability and strength character of sub- liquid synergistic supersonic wave pretreatment paper pulp are improved.
Embodiment 2:
Steps are as follows:
(1) conditions of cooking is alkali charge 21wt% (Na2O meter), sulphidity 25%, liquor ratio 1:5, boiling maximum temperature 170
DEG C, it deflates at 105 DEG C, heating-up time 90min, soaking time 90min；Paper pulp is sufficiently washed, is screened after boiling,
It obtains and does not float paper pulp.
(2) ionic liquid synergistic supersonic wave pre-process: accurately weigh 3 bags of 25g slurries (oven dry stock meter), by 5wt%,
The sulfuric acid of 10wt%, 15wt% hydrogenate triethyl ammonium ionic liquid (TEAHSO4) be added separately in 3 bags of slurries, in polyethylene
Adjustment slurry concentration is 10% in bag, and rubbing is then placed in ultrasonic device and is ultrasonically treated to being uniformly mixed.Pretreating process
Condition is ionic liquid dosage 5wt%, 10wt%, 15wt%, ultrasonic time 60min and ultrasonic power 250W.
(3) ECF is bleached: carrying out OAD by the pretreated paper pulp of ionic liquid synergistic supersonic wave to above-mentioned1ED2Bleaching schedule
Bleaching.O sections of oxygen delignifications are carried out to Eucalyptus Kraft Pulp first, process conditions are to starch dense 10%, NaOH dosage 3wt%, oxygen pressure
0.5MPa, 100 DEG C of temperature, time 60min and MgSO4Dosage 0.6wt%, after slurry is washed.Then A sections are carried out
Acid processing, process conditions are that pH value 3.5-4.5 and time 120min, after treatment wash slurry.D1Section titanium dioxide
Chlorine bleaching process conditions are Chlorine 0.7wt%, pH value 2-3, temperature 70 C, starch dense 10wt% and time 30min, drift
Slurry is washed after white.The E section hydrogen peroxide bleaching process conditions then carried out be hydrogen peroxide use 1wt%,
Dense 10%, pH value 11-12,90 DEG C of temperature and oxygen pressure 0.4MPa are starched, slurry is washed after processing.The D then carried out2Section two
Chlorine monoxid bleaching conditions are Chlorine 0.8wt%, pH value 2-3,75 DEG C of temperature, starch dense 10wt% and time
120min washs slurry after bleaching.
(4) OAD copy paper: will be passed through1ED2Then slurry pulping after bleaching discongests paper pulp in device in fiber to 60 ° of SR
Progress paper pulp fiber, which is discongested, makes it be uniformly dispersed, and will discongest rear slurry and be copied into quantification of 80g/m on sheet forming apparatus2Body paper
Paper base material.
(5) simultaneously, selection is without the pretreated OAD of ionic liquid synergistic supersonic wave1ED2Bleached pulp is beaten to 60 °
Then paper pulp is discongested in fiber and carries out paper pulp fiber in device and discongest it is made to be uniformly dispersed by SR, will discongest rear slurry page at
Quantification of 80g/m is copied on type device2Body paper paper base material.
(6) performance indicator of gained body paper paper base material is as shown in table 2, under identical paper pulp fiber raw material, by ion
The performance indexes of the pretreated body paper paper base material of liquid synergistic supersonic wave is superior to without pretreated normal condition
The body paper paper base material of lower bleaching.
Pass through under 2 different ionic liquid dosage of table and without the pretreated Eucalyptus OAD of ionic liquid synergistic supersonic wave1ED2
The body paper paper base material performance indicator that bleached pulp is manufactured paper with pulp
As a result: after testing, being folding number 115 times without pretreated Eucalyptus bleached pulp performance indicator, anti-tensile refers to
Number 4.35Nmg-1, tear index 6.75mNm2·g-1, burst index 4.06kPam2G-1 and whiteness 75.2%
ISO.Compared with passing through the pretreated bleached pulp of ionic liquid synergistic supersonic wave under identical bleaching conditions, by dosage 5-
15wt% (opposite oven dry stock meter) ionic liquid TEA-HSO4It is mentioned with the performance indicator of the paper pulp of 60min ultrasonic pretreatment
Height, folding strength improve 154.8-220.1%, and tensile index improves 12.9-17.0%, and tear index improves 6.5-
19.4%, burst index improves 2.6-8.1%, and whiteness improves 0.5-1.1%；Wherein dosage 10wt% ionic liquid TEA-
The effect of HSO4 and 60min ultrasonic pretreatment is more excellent, and paper folding strength improves 220.1% under this pretreatment condition, anti-tensile
Index improves 17.0%, and tear index improves 19.4%, and burst index improves 3.4%, and whiteness improves 1.1%.It can
See, is improved by the bleachability and strength character of ionic liquid synergistic supersonic wave pretreatment paper pulp.
Embodiment 3:
Steps are as follows:
(1) conditions of cooking is alkali charge 21wt% (Na2O meter), sulphidity 25%, liquor ratio 1:5, boiling maximum temperature 170
DEG C, it deflates at 105 DEG C, heating-up time 90min, soaking time 90min；Paper pulp is sufficiently washed, is screened after boiling,
It obtains and does not float paper pulp.
(2) ionic liquid synergistic supersonic wave pre-processes: 4 bags of 25g slurries (oven dry stock meter) is accurately weighed, by 10wt% sulfuric acid
Hydrogenate triethyl ammonium ionic liquid (TEA-HSO4), 10wt% sulfuric acid hydrogenate 1- butyl 3- methyl-imidazolium ionic liquid (BMIM-
HSO4), 10wt% chlorination 1- butyl 3- methyl-imidazolium ionic liquid (BMIM-Cl), 10wt% chlorination 2- ethoxy trimethylammonium from
Sub- liquid (Ch-Cl) is added separately in 4 bags of slurries, and adjustment slurry concentration is 10wt% in Polythene Bag, and rubbing is equal to mixing
It is even.It is put into ultrasonic device and is handled, pretreating process condition is ionic liquid dosage 10wt%, ultrasonic treatment time
60min and ultrasonic power 250W.
(3) ECF is bleached: carrying out OAD by the pretreated paper pulp of ionic liquid synergistic supersonic wave to above-mentioned1ED2Bleaching schedule
Bleaching.O sections of oxygen delignifications are carried out to Eucalyptus Kraft Pulp first, process conditions are to starch dense 10%, NaOH dosage 3wt%, oxygen pressure
0.5MPa, 100 DEG C of temperature, time 60min and MgSO4Dosage 0.6wt%, after slurry is washed.Then A sections are carried out
Acid processing, process conditions are that pH value 3.5-4.5 and time 120min, after treatment wash slurry.D1Section titanium dioxide
Chlorine bleaching process conditions are Chlorine 0.7wt%, pH value 2-3, temperature 70 C, starch dense 10% and time 30min, bleaching
After slurry is washed.The E section hydrogen peroxide bleaching process conditions then carried out are hydrogen peroxide use 1wt%, starch
Dense 10%, pH value 11-12,90 DEG C of temperature and oxygen press 0.4MPa, wash after processing to slurry.The D then carried out2Section dioxy
Change chlorine bleaching process conditions be Chlorine 0.8wt%, pH value 2-3,75 DEG C of temperature, slurry dense 10% and time 120min,
Slurry is washed after bleaching.
(4) OAD copy paper: will be passed through1ED2Then slurry pulping after bleaching discongests paper pulp in device in fiber to 60 ° of SR
Progress paper pulp fiber, which is discongested, makes it be uniformly dispersed, and will discongest rear slurry and be copied into quantification of 80g/m on sheet forming apparatus2Body paper
Paper base material.
(5) simultaneously, selection is without the pretreated OAD of ionic liquid synergistic supersonic wave1ED2Bleached pulp is beaten to 60 °
Then paper pulp is discongested in fiber and carries out paper pulp fiber in device and discongest it is made to be uniformly dispersed by SR, will discongest rear slurry page at
Quantification of 80g/m is copied on type device2Body paper paper base material.
(6) performance indicator of gained body paper paper base material is as shown in table 3, under identical paper pulp fiber raw material, by ion
The performance indexes of the pretreated body paper paper base material of liquid synergistic supersonic wave is superior to without pretreated normal condition
The body paper paper base material of lower bleaching.
Pass through under 3 different type ionic liquid of table and without the pretreated Eucalyptus OAD of ionic liquid synergistic supersonic wave1ED2
The body paper paper base material performance indicator that bleached pulp is manufactured paper with pulp
As a result: after testing, without pretreated Eucalyptus bleached pulp performance indicator be whiteness 75.2%ISO, anti-tensile refers to
Number 4.35Nmg-1, tear index 6.75mNm2·g-1, burst index 4.06kPam2·g-1With folding number 115 times.
Compared with passing through the pretreated bleached pulp of ionic liquid synergistic supersonic wave under identical bleaching conditions, pass through 10%wt respectively
Dosage (opposite oven dry stock meter) four seed type ionic liquid sulfuric acid hydrogenation triethyl ammonium ionic liquid (TEA-HSO4), sulfuric acid hydrogenation
1- butyl 3- methyl-imidazolium ionic liquid (BMIM-HSO4), chlorination 1- butyl 3- methyl-imidazolium ionic liquid (BMIM-Cl),
The pulp property index of chlorination 2- ethoxy trimethylammonium ion liquid (Ch-Cl) and 60min ultrasonic pretreatment is improved, resistance to
Folding degree improves 135.2-220.1%, and tensile index improves 6.2-17.0%, and tear index improves 5.9-19.4%, resistance to broken finger
Number improves 2.7-6.9%, and whiteness improves 0.1-1.1%；Wherein ionic liquid TEA-HSO4 synergistic supersonic wave pretreating effect
Optimal, paper folding strength improves 220.1%, and paper pulp tensile index improves 17.0%, and tear index improves 19.4%, resistance to
Broken index improves 3.4%, and whiteness improves 1.1%.As it can be seen that the bleaching of different type ionic liquid synergistic supersonic wave pretreatment paper pulp
Performance and strength character have obtained different degrees of improvement.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field
For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair
Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.
Claims (10)
1. the method that ionic liquid collaboration ultrasonic treatment ECF bleached kraft pulp prepares paper base material, characterized in that use ion
Liquid collaboration ultrasound pre-processes unbleached kraft pulp, and pretreated kraft pulp is then carried out ECF bleaching.
2. the method as described in claim 1, characterized in that unbleached kraft pulp is that Eucalyptus must be starched through kraft cooking
Material.
3. the method as described in claim 1, characterized in that the time of the ultrasound is 40~80min；
Preferably, the ultrasonic time is 60min.
4. the method as described in claim 1, characterized in that the dosage of ionic liquid is 5~15wt%；
Preferably, the dosage of ionic liquid is 10wt%.
5. the method as described in claim 1, characterized in that the anion of ionic liquid includes hydrogen sulfate ion or chloride ion
One or more of mixing；
The cation of the ionic liquid includes 1- butyl 3- methyl-imidazolium ionic, 2- ethoxy trimethylammonium ion, triethyl ammonium
The mixing of one or more of ion.
6. the method as described in claim 1, characterized in that the program of the ECF bleaching is OAD1ED2, the steps include: firstly,
O sections of oxygen deoxidation lignins are carried out to pretreated paper pulp, paper pulp is washed after O sections；Then A sections of acid processing, A are carried out
Paper pulp is washed after section；Then D is carried out1Section ClO 2 bleaching, D1Paper pulp is washed after section；Then
E sections of hydrogen peroxide bleachings are carried out, paper pulp is washed after E sections；Then D is carried out2Section ClO 2 bleaching, D2Section bleaching
Terminate, washing pulp obtains bleached pulp.
7. method as claimed in claim 6, characterized in that OAD1ED2The concrete mode of bleaching schedule are as follows: O sections of oxygen delignification works
Skill condition is to starch dense 10%, NaOH dosage 3wt%, oxygen pressure 0.5MPa, 100 DEG C of temperature, time 60min and MgSO4Dosage
0.6%；A sections of acid treatment process conditions are pH value 3.5~4.5 and time 120min；D1Section ClO 2 bleaching process conditions are as follows:
Chlorine 0.7wt%, pH value 2~3, temperature 70 C, the dense 10wt% and time 30min of slurry；E sections of hydrogen peroxide bleaching works
Skill condition is hydrogen peroxide use 1wt%, the dense 10wt% of slurry, pH value 11~12,90 DEG C of temperature and oxygen press 0.4MPa；D2Section dioxy
Change chlorine bleaching process conditions are Chlorine 0.8wt%, pH value 2~3,75 DEG C of temperature, starch dense 10wt% and time
120min。
8. the method as described in claim 1, characterized in that steps are as follows:
(1) boiling: taking Eucalyptus piece, is put into boiling in digester, and boiling terminates sufficiently to be washed and screened, and obtains Eucalyptus sulfate
Slurry；The Kappa number of slurry is 12~16；
(2) ionic liquid synergistic supersonic wave pre-processes；
(3) ECF is bleached: carrying out ECF bleaching to by the pretreated slurry of ionic liquid synergistic supersonic wave, bleaching schedule is
OAD1ED2: firstly, to process ionic liquid synergistic supersonic wave O sections of oxygen deoxidation lignins of pretreated paper pulp progress, after O sections
Paper pulp is washed；Then A sections of acid processing are carried out, paper pulp is washed after A sections；Then D is carried out1Section chlorine dioxide
Bleaching, D1Paper pulp is washed after section；Then E sections of hydrogen peroxide bleachings are carried out, paper pulp is washed after E sections
It washs；Then D is carried out2Section ClO 2 bleaching, D2Section bleaching terminates, and washing pulp obtains bleached pulp；
(4) with by OAD1ED2The paper pulp of bleaching carries out copy paper.
9. the method as described in claim 1, characterized in that the concrete mode of boiling in the step (1) are as follows: take length 15~
25mm, 10~20mm of width, 3~5mm of thickness relatively uniform Australian Eucalyptus piece carry out boiling after natural air drying, are made
Broadleaf Eucalyptus sulfate magma, cooking schedule are alkali charge 21wt%, sulphidity 25%, liquor ratio 1:5, the boiling highest temperature
170 DEG C of degree；It deflates at 105 DEG C, deflation 15min, heating-up time 90min, soaking time 90min；After boiling slurry into
Row sufficiently washing and screening, is not floated Eucalyptus Kraft Pulp.
10. a kind of paper base material of any the method preparation of claim 1~9.
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| CN112048935A (en) * | 2020-08-14 | 2020-12-08 | 山鹰纸业(广东)有限公司 | Biological ultrasonic laser punched paper bag paper and preparation process thereof |
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