CN105332308A - Method for preparing nanocellulose papermaking auxiliary agent with waste newspaper or waste electrostatic copy paper as raw material - Google Patents
Method for preparing nanocellulose papermaking auxiliary agent with waste newspaper or waste electrostatic copy paper as raw material Download PDFInfo
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- CN105332308A CN105332308A CN201510617219.0A CN201510617219A CN105332308A CN 105332308 A CN105332308 A CN 105332308A CN 201510617219 A CN201510617219 A CN 201510617219A CN 105332308 A CN105332308 A CN 105332308A
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- paper
- slurry
- deinking
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- cellulose
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002994 raw material Substances 0.000 title claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 title abstract description 5
- 239000002699 waste material Substances 0.000 title abstract 7
- 229920001046 Nanocellulose Polymers 0.000 title abstract 6
- 239000002761 deinking Substances 0.000 claims abstract description 76
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 22
- 239000010893 paper waste Substances 0.000 claims abstract description 15
- 244000166124 Eucalyptus globulus Species 0.000 claims abstract description 10
- 239000002023 wood Substances 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims description 63
- 239000001913 cellulose Substances 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000002002 slurry Substances 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 21
- 229920001131 Pulp (paper) Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- -1 acid hydrolysis Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000013022 venting Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 30
- 235000010980 cellulose Nutrition 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
-
- 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F13/00—Making discontinuous sheets of paper, pulpboard or cardboard, or of wet web, for fibreboard production
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Landscapes
- Paper (AREA)
Abstract
The invention discloses a method for preparing a nanocellulose papermaking auxiliary agent with waste newspaper or waste electrostatic copy paper as raw material, and is characterized in that nanocellulose is prepared by deinking and acid hydrolysis of the waste newspaper and the waste electrostatic copy paper as the raw material, then the prepared nanocellulose as the auxiliary agent is added to a pulp prepared with domestic eucalyptus wood as raw material according to a certain proportion to prepare paper. The prepared paper has the main performance that the tensile index is 90-95 N*m*g<-1>, the tearing index is 25-30 mN*m<2>*g<-1>, and the folding strength is 35-40 times. The method has the advantages that with the waste paper as the raw material for preparation of the nanocellulose, not only can the waste paper be used again, but also the utilization value and economic benefits are effectively improved, and a positive way is provided for utilization of the waste newspaper. With the prepared nanocellulose as the papermaking auxiliary agent, not only can the performance of the paper be improved, but also pollution brought by paper preparation and use is reduced.
Description
Technical field
The present invention relates to pulping and paper-making field, be specifically related to be a kind of with old newsprint or useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material.
Background technology
All be faced with severe environmental problem and the Sustainable Utilization of resource within the scope of world today, utilize discarded object to prepare new material and its reprocessing and recycle are come into one's own day by day.Paper regeneration has that reduced investment, energy consumption are low, the consumption of the chemicals that economizes in raw materials, reduces, the advantage such as protect forest resources, and therefore, waste paper recycling is subject to the attention of paper industry day by day.To reach 53,598 ten thousand tons according to the discarded amount of prediction 2011-2020 China of Chinese papermaking association paper product, and be only 43.8% for the state of the regenerated resources papermaking rate of recovery of giving up, there is great potential in the recycling of waste paper.Along with the progress of society and the raising of people's living standard, the paper grades that there is specific function to various and the requirement of consumption increasing, modern industrial technology and the performance of life style to paper propose many new requirements, and these requirements nearly all will be realized by the paper making additive adding various function.The exploitation of China's paper making additive is started late, although China's paper industry grows continuously and fast in recent years, general status is that quantity is few, kind few, can not meet the requirement of paper industry technological progress and model change.Because the problem that paper making additive kind is single, unstable product quality makes the performance of the paper obtained not meet the need of market becomes increasingly conspicuous.At present, environment-friendly and green and the exploitation that effectively can improve the paper making additive of paper performance receive the concern of people day by day.
Summary of the invention
The object of this invention is to provide a kind of with old newsprint or useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material, can not only solve and cause because current paper making additive kind is single, quality is unstable the problem that obtained paper performance is unsatisfactory, and better can utilize waste paper, improve value and the economic benefit of waste paper.
In order to achieve the above object, the present invention adopts following technical scheme:
Taking old newsprint as the method that nano-cellulose paper making additive prepared by raw material, it is characterized in that, take old newsprint as raw material, and obtain through deinking, acid hydrolysis, concrete steps are as follows:
A, deinking
Waste paper fragment is put into the pulp density of the hot water furnishing mass fraction 5-8% of 70-80 DEG C, then add the H of NaOH, the 10-12% accounting for waste paper chip mass 4-6%
2o
2, 8-10% Na
2siO
3; Carry out after abundant mixing discongesting process; Slurry isothermal reaction 50-60min under 70-80 DEG C of condition of gained will be discongested again; Reacted slurry is washed till neutrality, for subsequent use.
B, acid hydrolysis
By the slurry after steps A deinking process under the ice bath of-2-0 DEG C, mix by the mass ratio of 1:8 with the concentrated sulfuric acid of mass concentration 55-65%, the described concentrated sulfuric acid is added dropwise to lentamente among slurry by the speed of 1-2ml/s, ice bath stirs 5-10min, then hydrolysis 50-60min is stirred 40-50 DEG C of hot bath, centrifugal after hydrolysis, collecting precipitation, and by washing of precipitate to neutral, process to obtain nano-cellulose suspension finally by ultrasonic; Described nano-cellulose suspension is through concentrating, being drying to obtain nano-cellulose.
As preferably, in described deinking step, to be 5%, NaOH consumption be slurry concentration 5%, H
2o
2consumption is 10%, Na
2siO
3consumption is 10%, and reaction temperature is 80 DEG C, and the reaction time is 60min.
As preferably, in described deinking step, the rotating speed of fluffer is 1500r/min, and the time of discongesting is 45min.
As preferably, in described acid hydrolysis step, the concentration of the concentrated sulfuric acid is 61%, and ice bath mixing time is 10min, and heating bath temperature is 40 DEG C, and the pyrohydrolysis time is 60min.
The present invention ask to protect simultaneously a kind of with useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material, it is characterized in that, with useless electro-photographic paper for raw material, obtain through deinking, acid hydrolysis, concrete steps are as follows:
A, deinking
(1) after being shattered by useless electro-photographic paper, in normal-temperature water, soak 20-24h, adding water after immersion is adjusted to 12-15% by pulp density;
(2) carried out pulling an oar, discongesting by the paper pulp of step (1), it is stand-by to have discongested rear gained slurry;
(3) in the slurry of step (2), add the Na of NaOH, the 2-4% accounting for useless xerography paper quality 1-2%
2siO
3, 0.5-1.5% H
2o
2, 0.4-0.6% EDTA, adjustment slurry dense be 2-4%, then at the water bath with thermostatic control stirring reaction 50-60min of 60-70 DEG C;
(4) paper pulp after step (3) reaction is poured into washing in pulp washing bag extremely neutral, stand-by;
B, acid hydrolysis
By the slurry after steps A deinking process under the ice bath of-2-0 DEG C, mix by the mass ratio of 1:8 with the concentrated sulfuric acid of mass concentration 55-65%, the described concentrated sulfuric acid is added dropwise to lentamente among slurry by the speed of 1-2ml/s, ice bath stirs 5-10min, then hydrolysis 50-60min is stirred 40-50 DEG C of hot bath, centrifugal after hydrolysis, collecting precipitation, and by washing of precipitate to neutral, process to obtain nano-cellulose suspension finally by ultrasonic, described nano-cellulose suspension is through concentrating, being drying to obtain nano-cellulose.
As preferably, in the step (3) of described deinking, pulp density is the consumption of 2.5%, NaOH is 1%, Na
2siO
3consumption be 3%, H
2o
2consumption be 1%, the consumption of EDTA is 0.4%, water bath with thermostatic control temperature is 70 DEG C, reaction time 60min.
As preferably, in described acid hydrolysis step, the concentration of the concentrated sulfuric acid is 60%, and ice bath mixing time is 10min, and heating bath temperature is 40 DEG C, and the pyrohydrolysis time is 60min.
The present invention also asks to protect a kind of papermaking process, it is characterized in that, comprises the steps:
(1) with the domestic Eucalyptus of match stick size for raw material, added in cooker, in absolute dry wood 100g for, in cooker, add the NaOH102.7ml of 150g/L, the Na of 70g/L
2s82.7ml, adding water move to liquor ratio is 1: 4-5, after mixing, start heating, when temperature rises to 118-122 DEG C, open vent valve, venting 4-5min, then closes vent valve and continues be heated to 140-145 DEG C and be incubated 50-60min, be finally warming up to 155-160 DEG C and be incubated 1.5-2h;
(2) the slurry taking-up in cooker is washed with water to neutrality, and be adjusted to 8-10% by dense for slurry, treat further bleaching;
(3) slurry of step (2) is placed in pressure reaction still, add and account for the domestic magnesium sulfate of Eucalyptus material quality 0.5-1%, the NaOH of 3-4%, under the Oxygen Condition protection of 0.6-0.8MPa, reactor be warming up to 80-85 DEG C and be incubated 80-90min, by stand-by for reacted slurry gained paper pulp after pulling an oar, discongesting;
(4) get to add in the slurry after discongesting while paper pulp mixer prepared by step (3) constantly stirs and account for domestic Eucalyptus material quality 3-5% nano-cellulose, 10min discongested by fluffer, and terminating that rear PK-3A handshcet former is copied into is quantitatively 60g/m
2page, and at 90-98 DEG C vacuumize 8-9min, obtain dry page.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1) the invention provides a kind of paper adding the excellent performance that nano-cellulose is prepared as auxiliary agent in paper making pulp, its main performance is: tensile index is at 82-95Nmg
-1between, tear index is at 21-24mNm
2g
-1between, folding strength is 35-40 time.
2) nano-cellulose of the present invention is a kind of natural free of contamination organic material, and with it as paper making additive, can reduce the pollution that the preparation of paper and use bring, be a kind of paper making additive of environmental protection.
3) the present invention prepares nano-cellulose raw material used is waste paper, not only makes waste paper again to utilize, and effectively improves its value and economic benefit, and the utilization for old newsprint provides a kind of positive preparation method.
Accompanying drawing explanation
Fig. 1 is the design sketch of old newsprint before deinking under ESEM.
Fig. 2 is the design sketch of old newsprint after deinking under ESEM.
Fig. 3 is nano-cellulose AFM Fig. 1.
Fig. 4 is nano-cellulose AFM Fig. 2.
Fig. 5 is the useless electro-photographic paper scanning electron microscope (SEM) photograph before deinking.
Fig. 6 is the useless electro-photographic paper scanning electron microscope (SEM) photograph after deinking.
Fig. 7 is X diffraction analysis figure.
In Fig. 7, J: be useless electro-photographic paper JT: the useless electro-photographic paper after deinking.
Fig. 8 is infrared spectrogram.
In Fig. 8, J: useless electro-photographic paper JT: the useless electro-photographic paper X after deinking: pure cellulose.
Fig. 9 is afm scan figure.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
Being the method that nano-cellulose paper making additive prepared by raw material with old newsprint, take old newsprint as raw material, and obtain through deinking, acid hydrolysis, concrete steps are as follows:
A, deinking
1) experimental principle: be itself and fiber separation by effects such as chemicals, mechanical external force and heating by the ink particle sticking to fiber surface, and from the process that paper pulp is separated.
2) instrument and equipment: fluffer, thermostat water bath, analytical balance, glass bar
3) chemicals: NaOH, Na
2siO
39H
2o, deinking agent, hydrogen peroxide
4) concrete steps are: pulp density waste paper fragment being put into the hot water furnishing mass fraction 5-8% of 70-80 DEG C, then adds the H of NaOH, the 10-12% accounting for waste paper chip mass 4-6%
2o
2, 8-10% Na
2siO
3; Carry out after abundant mixing discongesting process; Slurry isothermal reaction 50-60min under 70-80 DEG C of condition of gained will be discongested again; Reacted slurry is washed till neutrality, for subsequent use
B, acid hydrolysis
1) experimental principle: cellulose, with acid, hydrolysis occurs, removes the amorphous region in cellulose, while minimizing microcrystalline cellulose size, prepares the cellulose of high-crystallinity.
2) laboratory apparatus: analytical balance, agitator, cryogenic thermostat reactive bath technique, thermostat water bath, Ultrasound Instrument, ultrasonic washer, controllable temperature baking oven, AFM
3) chemicals: the concentrated sulfuric acid
4) concrete steps are: by the slurry after steps A deinking process under the ice bath of-2-0 DEG C, mix by the mass ratio of 1:8 with the concentrated sulfuric acid of mass concentration 55-65%, the described concentrated sulfuric acid is added dropwise to lentamente among slurry by the speed of 1-2ml/s, ice bath stirs 5-10min, then stir hydrolysis 50-60min 40-50 DEG C of hot bath, centrifugal after hydrolysis, collecting precipitation, and by washing of precipitate to neutral, process to obtain nano-cellulose suspension finally by ultrasonic; Described nano-cellulose suspension is through concentrating, being drying to obtain nano-cellulose.
In deinking step, the rotating speed of fluffer is 1500r/min, and the time of discongesting is 45min.
As preferably, ice bath mixing time is 10min, and heating bath temperature is 40 DEG C, and the pyrohydrolysis time is 60min.Chemical constituent test before and after old and useless newspaper process
The mensuration (see GB/T2677.6-1994) of benzene-ol extract, the mensuration (see GB2677.10-81) of holocellulose, cellulosic mensuration (see GB2677.10-81), the assay method of pentosan: (see GB/T2677.9-1994), the mensuration (see GB2677.8-81) of Klason lignin, the mensuration (see GB/T10337-1989) of acid soluble lignin content.
The determination of old newsprint deinking process
According to table 1, measure the more all schemes of whiteness by whiteness instrument, deinking efficiency is preferably experimental program 8, its deinking conditions: starch dense 5%, NaOH consumption 5%, H
2o
2consumption 10%, Na
2siO
3consumption 10%.
The deinking process experimental program of table 1 old newsprint
(in table 1, deinking reaction temperature is 80 DEG C, and the reaction time is 60min.)
The effect of old newsprint under deinking traversing of probe Electronic Speculum
As seen from Figure 1, old newsprint fiber adheres to a lot of ink particle, and waste paper pulp fiber in Fig. 2,3 exists ink particle hardly.Comparison diagram 1,2,3 known, the fiber after deinking is comparatively smooth, and its length and width do not see change.Preparing the factor of influence of nano-cellulose technique in order to reduce later stage sulphuric acid hydrolysis, will accomplish that deinking is complete, to reduce the experiment effect in the impurity effect later stages such as ink particle as far as possible.
The comparative analysis of chemical constituent before and after old newsprint process
Before and after the process of table 2 old newsprint, chemical composition compares
As shown in Table 2, after deinking process, alcohol benzene extractive declines comparatively obvious, and undressed old newsprint alcohol benzene extractive is up to 0.85%, and this wherein may includes the composition of ink in old newsprint; Content of cellulose after deinking process increases, this is because lignin destroyed removing in experimentation, causes cellulosic content to increase.
The comparative analysis of the degree of polymerization before and after old newsprint process
As shown in Table 3, old newsprint is after deinking process, and in paper pulp, cellulosic average degree of polymerization obviously increases.This is because old newsprint all can have this program of pulp washing after each step chemical treatment, washed off at washing process fubril, the large fiber stayed is improve overall average degree of polymerization.
The table 3 old newsprint process forward backward averaging degree of polymerization
Fibre morphology analysis before and after old newsprint process
Before and after the process of table 4 old newsprint, fibre length and width compares
As shown in Table 4, old newsprint after deinking process Fiber length and width comparatively old newsprint there is no significant change, illustrating that deinking in this experiment, method for bleaching are little to fibre damage, is reasonable treatment process.
Sulphuric acid hydrolysis prepares nano-cellulose process conditions
Table 5 sulphuric acid hydrolysis prepares nano-cellulose scheme
Prepare nano-cellulose according to scheme in table 5, adopt the nano-cellulose morphology and distribution that atomic force microscope observation has been prepared, optimization optimum process condition.Wherein the nano-cellulose image that obtains of scheme 13 as shown in Figure 3, can find out that the draw ratio of nano-cellulose is larger and dispersion is more even.And the particle of the nano-cellulose of other scheme is comparatively large, disperse uneven, as shown in Figure 4, as can be seen here, it is H that sulphuric acid hydrolysis prepares nano-cellulose optimum process condition
2sO
4concentration 61%, ice bath stirs 10min, 40 DEG C of centrifugal 10min of hydrolysis 1h, 8000rpm, ultrasonic 25min under 360kW.
Embodiment 2
With useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material, with useless electro-photographic paper for raw material, obtain through deinking, acid hydrolysis, concrete steps are as follows:
A, deinking
(1) after being shattered by useless electro-photographic paper, in normal-temperature water, soak 20-24h, adding water after immersion is adjusted to 12-15% by pulp density;
(2) carried out pulling an oar, discongesting by the paper pulp of step (1), it is stand-by to have discongested rear gained slurry;
(3) in the slurry of step (2), add the Na of NaOH, the 2-4% accounting for useless xerography paper quality 1-2%
2siO
3, 0.5-1.5% H
2o
2, 0.4-0.6% EDTA, adjustment slurry dense be 2-4%, then at the water bath with thermostatic control stirring reaction 50-60min of 60-70 DEG C;
(4) paper pulp after step (3) reaction is poured into washing in pulp washing bag extremely neutral, stand-by;
B, acid hydrolysis
By the slurry after steps A deinking process under the ice bath of-2-0 DEG C, mix by the mass ratio of 1:8 with the concentrated sulfuric acid of mass concentration 55-65%, the described concentrated sulfuric acid is added dropwise to lentamente among slurry by the speed of 1-2ml/s, ice bath stirs 5-10min, then hydrolysis 50-60min is stirred 40-50 DEG C of hot bath, centrifugal after hydrolysis, collecting precipitation, and by washing of precipitate to neutral, process to obtain nano-cellulose suspension finally by ultrasonic, described nano-cellulose suspension is through concentrating, being drying to obtain nano-cellulose.
As preferably, in the step (3) of described deinking, pulp density is the consumption of 2.5%, NaOH is 1%, Na
2siO
3consumption be 3%, H
2o
2consumption be 1%, the consumption of EDTA is 0.4%, water bath with thermostatic control temperature is 70 DEG C, and the reaction time is 60min.
As preferably, in described acid hydrolysis step, the concentration of the concentrated sulfuric acid is 60%, and ice bath mixing time is 10min, and heating bath temperature is 40 DEG C, and the pyrohydrolysis time is 60min.
The determination of the deinking technological conditions of useless electro-photographic paper
Table 6 gives up the deinking process condition of electro-photographic paper
According to late detection with continue experiment, find that deinking process is in all schemes used: through 10min making beating process, starch dense 2.5%, 1%NaOH, 3%NaSiO
3, 1%H
2o
2, 0.4%EDTA, 70 DEG C of water bath processing 1h time, observe pulp surface attachment ink minimum.
The chemical composition of useless electro-photographic paper
Chemical composition before and after electro-photographic paper deinking of giving up table 7 compares
As shown in Table 7, after deinking, the cellulose of useless electro-photographic paper and pentosan content proportion improve, and the ratio shared by alcohol benzene extractive, lignin reduces, illustrate that in deinking process, cellulose and pentosan have been retained while deinking, other materials are then partially removed.Like this, improve cellulose yield and also reduce the interference of other materials to later experiments, therefore both to have met deinking requirement also helpful to subsequent experimental for this deinking process.
The whiteness of useless electro-photographic paper and the degree of polymerization
Table 8 gives up whiteness before and after electro-photographic paper deinking and the degree of polymerization
As shown in Table 8, the useless electro-photographic paper whiteness after deinking and the degree of polymerization significantly improve, and illustrate that deinking process effectively removes the ink in useless electro-photographic paper, and therefore whiteness improves; And fiber fines is removed when deinking, therefore the degree of polymerization observed also is improved.
Fibre morphology before and after useless electro-photographic paper deinking
Table 9 gives up the fibre morphology before and after electro-photographic paper deinking
As shown in Table 9, useless electro-photographic paper fibre length and fiber width after deinking all decrease, and illustrate when deinking, and the fiber of useless electro-photographic paper itself also receives impact, create certain loss, ink particle and fiber fines are just separated from slurry Just because of this.
Design sketch before and after useless electro-photographic paper deinking under ESEM
From Fig. 5 and Fig. 6, clearly can find out that the useless electro-photographic paper fiber distribution before deinking is disorderly and unsystematic, fiber surface is attached with much ink, and the coarse injustice of fiber surface, has many fiber fines especially.And useless electro-photographic paper fiber sequence after deinking is neat, fiber surface totally smooth, fiber fines all disappear.Therefore can know, be removed by the give up ink particle of electro-photographic paper and fiber fines of deinking, the form of fiber is further optimized, and these are all conducive to dissolving step below.
X-ray diffraction analysis
As shown in Figure 7, the position of the useless electro-photographic paper diffraction maximum after the useless electro-photographic paper before deinking and deinking is consistent substantially, therefore can think that the fiber type of useless electro-photographic paper is not changed before and after deinking.
Degree of crystallinity before and after electro-photographic paper deinking of giving up table 10. compares
And as shown in Table 10, the change that before and after deinking, the fibre crystallinity of useless electro-photographic paper is too not large, therefore can know that deinking process does not cause anything to affect on the fibre structure of useless electro-photographic paper.
Infrared spectrum analysis
As shown in Figure 8, useless electro-photographic paper before and after deinking is compared with pure cellulose, characteristic peak on spectrogram does not all significantly change, and illustrate that the content of cellulose of useless electro-photographic paper is very high, and deinking does not damage to the chemical constitution of useless electro-photographic paper fiber.
Prepare the determination of nano-cellulose technique
Experiment employing method is: attempt different sulfuric acid concentrations, heat treatment temperature and heat treatment time respectively, wherein sulfuric acid concentration has: 55%, 60%, 65%; Heat treatment temperature has: 35 DEG C, 40 DEG C, 45 DEG C; Heat treatment time has: 1h, 2h, 3h.Condition fixing in experiment has: 6g paper pulp, K cryogenic treatment (-2 DEG C, 10min), ultrasonic process (360kW, 10min).
Nano-cellulose technique prepared by table 11.
By afm scan map analysis, nano-cellulose technique the best is scheme 6, and as shown in Figure 9, the cellulose grain prepared under these process conditions is less, is uniformly dispersed.
Embodiment 3
A kind of papermaking process, comprises the steps:
(1) with the domestic Eucalyptus of match stick size for raw material, added in cooker, in absolute dry wood 100g for, in cooker, add the NaOH102.7ml of 150g/L, the Na of 70g/L
2s82.7ml, adding water move to liquor ratio is 1: 4-5 (mass volume ratio), after mixing, start heating, when temperature rises to 118-122 DEG C, open vent valve, venting 4-5min, then close vent valve to continue be heated to 140-145 DEG C and be incubated 50-60min, be finally warming up to 155-160 DEG C and be incubated 1.5-2h;
(2) the slurry taking-up in cooker is washed with water to neutrality, and be adjusted to 8-10% by dense for slurry, treat further bleaching;
(3) slurry of step (2) is placed in pressure reaction still, add and account for the domestic magnesium sulfate of Eucalyptus material quality 0.5-1%, the NaOH of 3-4%, under the Oxygen Condition protection of 0.6-0.8MPa, reactor be warming up to 80-85 DEG C and be incubated 80-90min, by stand-by for reacted slurry gained paper pulp after pulling an oar, discongesting;
(4) get to add in the slurry after discongesting while paper pulp mixer prepared by step (3) constantly stirs and account for domestic Eucalyptus material quality 3-5% nano-cellulose, 10min discongested by fluffer, and terminating that rear PK-3A handshcet former is copied into is quantitatively 60g/m
2page, and at 90-98 DEG C vacuumize 8-9min, obtain dry page.
Paper performance prepared by this method is as shown in table 12.
Table 12 paper performance parameter
Claims (8)
1. be the method that nano-cellulose paper making additive prepared by raw material with old newsprint, it is characterized in that, take old newsprint as raw material, and obtain through deinking, acid hydrolysis, concrete steps are as follows:
A, deinking
Waste paper fragment is put into the pulp density of the hot water furnishing mass fraction 5 ~ 8% of 70 ~ 80 DEG C, then add and account for the NaOH of waste paper chip mass 4 ~ 6%, the H of 10 ~ 12%
2o
2, 8 ~ 10% Na
2siO
3; Carry out after abundant mixing discongesting process; Slurry isothermal reaction 50 ~ 60min under 70 ~ 80 DEG C of conditions of gained will be discongested again; Reacted slurry is washed till neutrality, for subsequent use;
B, acid hydrolysis
By the slurry after steps A deinking process under the ice bath of-2 ~ 0 DEG C, mix by the mass ratio of 1:8 with the concentrated sulfuric acid of mass concentration 55 ~ 65%, the described concentrated sulfuric acid is added dropwise to lentamente among slurry by the speed of 1 ~ 2ml/s, ice bath stirs 5 ~ 10min, then in 40 ~ 50 DEG C of hot baths, hydrolysis 50 ~ 60min is stirred, centrifugal after hydrolysis, collecting precipitation, and by washing of precipitate to neutral, process to obtain nano-cellulose suspension finally by ultrasonic; Described nano-cellulose suspension is through concentrating, being drying to obtain nano-cellulose.
2. according to claim 1 a kind of be the method that nano-cellulose paper making additive prepared by raw material with old newsprint, it is characterized in that, in described deinking step, to be 5%, NaOH consumption be slurry concentration 5%, H
2o
2consumption is 10%, Na
2siO
3consumption is 10%, and reaction temperature is 80 DEG C, and the reaction time is 60min.
3. according to claim 1 a kind of be the method that nano-cellulose paper making additive prepared by raw material with old newsprint, it is characterized in that, in described deinking step, the rotating speed of fluffer is 1500r/min, and the time of discongesting is 45min.
4. according to claim 1 a kind of be the method that nano-cellulose paper making additive prepared by raw material with old newsprint, it is characterized in that, in described acid hydrolysis step, the concentration of the concentrated sulfuric acid is 61%, ice bath mixing time is 10min, and heating bath temperature is 40 DEG C, and the pyrohydrolysis time is 60min.
5. with useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material, it is characterized in that, with useless electro-photographic paper for raw material, obtain through deinking, acid hydrolysis, concrete steps are as follows:
A, deinking
(1) after being shattered by useless useless electro-photographic paper, in normal-temperature water, soak 20 ~ 24h, adding water after immersion is adjusted to 12 ~ 15% by pulp density;
(2) carried out pulling an oar, discongesting by the paper pulp of step (1), it is stand-by to have discongested rear gained slurry;
(3) add in the slurry of step (2) and account for the useless useless NaOH of xerography paper quality 1 ~ 2%, the Na of 2 ~ 4%
2siO
3, 0.5 ~ 1.5% H
2o
2, 0.4 ~ 0.6% EDTA, adjustment slurry dense be 2 ~ 4%, then at the water bath with thermostatic control stirring reaction 50 ~ 60min of 60 ~ 70 DEG C;
(4) paper pulp after step (3) reaction is poured into washing in pulp washing bag extremely neutral, stand-by;
B, acid hydrolysis
By the slurry after steps A deinking process under the ice bath of-2 ~ 0 DEG C, mix by the mass ratio of 1:8 with the concentrated sulfuric acid of mass concentration 55 ~ 65%, the described concentrated sulfuric acid is added dropwise to lentamente among slurry by the speed of 1 ~ 2ml/s, ice bath stirs 5 ~ 10min, then hydrolysis 50 ~ 60min is stirred 40 ~ 50 DEG C of hot baths, centrifugal after hydrolysis, collecting precipitation, and by washing of precipitate to neutral, process to obtain nano-cellulose suspension finally by ultrasonic, described nano-cellulose suspension is through concentrating, being drying to obtain nano-cellulose.
6. according to claim 5 a kind of with useless useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material, it is characterized in that, in the step (3) of described deinking, pulp density is the consumption of 2.5%, NaOH is 1%, Na
2siO
3consumption be 3%, H
2o
2consumption be 1%, the consumption of EDTA is 0.4%, water bath with thermostatic control temperature is 70 DEG C, and the reaction time is 60min.
7. according to claim 5 a kind of with useless useless electro-photographic paper for the method for nano-cellulose paper making additive prepared by raw material, it is characterized in that, in described acid hydrolysis step, the concentration of the concentrated sulfuric acid is 60%, ice bath mixing time is 10min, and heating bath temperature is 40 DEG C, and the pyrohydrolysis time is 60min.
8. a papermaking process, is characterized in that, comprises the steps:
(1) with the domestic Eucalyptus of match stick size for raw material, added in cooker, in absolute dry wood 100g for, in cooker, add the NaOH102.7ml of 150g/L, the Na of 70g/L
2s82.7ml, adding water move to liquor ratio is 1: 4 ~ 5, after mixing, start heating, when temperature rises to 118 ~ 122 DEG C, open vent valve, venting 4 ~ 5min, then close vent valve to continue be heated to 140 ~ 145 DEG C and be incubated 50 ~ 60min, be finally warming up to 155 ~ 160 DEG C and be incubated 1.5 ~ 2h;
(2) the slurry taking-up in cooker is washed with water to neutrality, and be adjusted to 8 ~ 10% by dense for slurry, treat further bleaching;
(3) slurry of step (2) is placed in pressure reaction still, add and account for the domestic magnesium sulfate of Eucalyptus material quality 0.5 ~ 1%, the NaOH of 3 ~ 4%, under the Oxygen Condition protection of 0.6 ~ 0.8MPa, reactor be warming up to 80 ~ 85 DEG C and be incubated 80 ~ 90min, by stand-by for reacted slurry gained paper pulp after pulling an oar, discongesting;
(4) get to add in the slurry after discongesting while paper pulp mixer prepared by step (3) constantly stirs and account for domestic Eucalyptus material quality 3 ~ 5% nano-cellulose, 10min discongested by fluffer, and terminating that rear PK-3A handshcet former is copied into is quantitatively 60g/m
2page, and at 90 ~ 98 DEG C vacuumize 8 ~ 9min, obtain dry page.
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| CN106676927A (en) * | 2017-01-05 | 2017-05-17 | 广东工业大学 | Preparation method of nanocrystal cellulose |
| CN107287957A (en) * | 2017-07-20 | 2017-10-24 | 西安理工大学 | A kind of order nanometer waste paper fibre and preparation method thereof |
| CN108611900A (en) * | 2018-03-29 | 2018-10-02 | 句容市茂源织造厂 | A method of preparing paper making intensifier using waste paper |
| CN110590962A (en) * | 2019-09-23 | 2019-12-20 | 陕西科技大学 | Method for preparing cellulose acetate by using waste paper money as raw material |
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