CN104099802A - Papermaking technology - Google Patents
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- CN104099802A CN104099802A CN201310129274.6A CN201310129274A CN104099802A CN 104099802 A CN104099802 A CN 104099802A CN 201310129274 A CN201310129274 A CN 201310129274A CN 104099802 A CN104099802 A CN 104099802A
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Abstract
A papermaking technology comprises the following steps: providing nanometer cellulose with the carboxyl content of 0.2-1.5 mmol/g and the average diameter of 100 nm or less, taking the nanometer cellulose as retention-assisting filtering-assisting agent and adding into paper pulp to form a mixed pulp, wherein the addition amount of the nanometer cellulose is 100-10000 ppm based on the bone dry pulp of the paper pulp; and utilizing the mixed pulp to make paper. Compared with a conventionally employed inorganic particle retention assisting technology, the provided papermaking technology is capable of improving the retention-assisting filtering-assisting performances, and also is capable of enabling the strength performance of the made paper to keep or exceed the strength performance of paper prepared by employing the conventional technology.
Description
Technical field
The present invention relates to a kind of paper technology, relate in particular to a kind of paper technology of the retention aid and filtering aid performance that can effectively improve paper pulp.
Background technology
In modern paper technique, in the process of slurrying and making beating, can produce a large amount of fiber fines, in order to reduce paper production cost and to improve printing performance, a large amount of inorganic fillers are added in paste system simultaneously.
On the one hand, due to the fiber fines in slurry and filler size less, in dehydration, be difficult to keep on paper, on the other hand, in slurry, contained a large amount of fiber fines and filler can reduce again the water filtering performance of slurry.But, fiber fines in paper pulp and filler are again in modern paper technique, to keep the requisite component of paper performance, therefore, in order to reduce the loss of fiber fines and filler, promote the speed of service of paper machine, paper plant is used retention aid and filtering aid system with in improving the retention of fiber fines and filler at wet end conventionally, can improve again the water filtering performance of slurry, thereby promotes the runnability of paper machine.
Retention is by fiber fines and filler are combined into larger wadding polymers, and adhesion and fiber surface, improves keeping of filler and fiber fines, drainage is to improve water filtering performance, improve dewatering speed, in most cases drainage and retention are carried out simultaneously, are called retention aid and filtering aid effect.In the development and application of high-speed paper machine technology, some combine use containing the aqueous dispersion of solia particle during with cationic polymer, their existing Retentions, can mix wadding again with the floc sedimentation of the high-strength shearing of process again gathers, improve the drainability of paper, these are called as " Retention-drainage system ", and the aqueous dispersion that wherein contains the inorganic particles such as modified alta-mud and Ludox is the most common " Retention-drainage system ".
Why the particulate aqueous dispersion that contains the inorganic particles such as modified alta-mud and Ludox has effect of retention, drainage, its reason is, the particle diameter of the inorganic particles in these particulate aqueous dispersions is less and surperficial with certain negative electrical charge, conventionally particle diameter is less, and the particulate that surface negative charge density is higher has better retention and drainage effect.But inorganic particles surface negative charge density is conventionally not high, to limited through the floc sedimentation compressed capability of wadding a quilt with cotton again after gathering, in floc sedimentation, still contain more water, simultaneously due to inorganic particles surface carboxyl and hydroxy functional group few, the intensity of adhesion between fiber and paper is had to adverse effect.
Summary of the invention
In view of this, provide a kind of paper technology of the retention aid and filtering aid performance that can effectively improve paper pulp real in necessary.
A kind of paper technology, it comprises the steps: to provide carboxyl-content is the nano-cellulose that 0.2～1.5mmol/g, average diameter are less than or equal to 100nm; Join using described nano-cellulose as retention and drainage aid agent in paper pulp and mix slurry to form, wherein, the addition of described nano-cellulose is 100～10000ppm of paper pulp oven dry stock; And utilize described mixing to starch the paper of manufacturing paper with pulp.
Preferably, the carboxyl-content of described nano-cellulose is 1.0-1.5mmol/g.
Preferably, the average diameter of described nano-cellulose is less than or equal to 10nm.
Being used as with the aqueous dispersion that uses inorganic particles such as containing modified alta-mud and Ludox in existing paper technology the mode that retention and drainage aid agent uses compares, above-mentioned paper technology provided by the present invention, it utilizes carboxyl-content is 0.2～1.5mmol/g, the nanofiber that average diameter is less than or equal to 100nm usually substitutes the aqueous dispersion that contains the inorganic particles such as modified alta-mud and Ludox, to use as retention and drainage aid agent, like this: on the one hand, because the carboxyl-content on adopted nano-cellulose surface is 0.2～1.5mmol/g, preferred carboxyl-content is 1.0-1.5mmol/g, when by after joining in paper making pulp with the nano-cellulose of a large amount of carboxyls, a large amount of carboxyls with negative electrical charge can greatly improve the adhesion between paper pulp fiber and filler grain, thereby can effectively promote the filler retention of paper pulp, on the other hand, because the average diameter of used nano-cellulose is less than or equal to 100nm, the preferred 10nm that is less than or equal to, thereby, have under high-carboxyl-content, undersized double action, make nano-cellulose used in the present invention there is higher surface negative charge density, the surface negative charge density of height not only can better be compressed the floc sedimentation after wadding gathers again, improve the drainage capacity of slurry, also shortened interfibrous distance, be conducive to maintenance or the raising of paper strength simultaneously.
Detailed description of the invention
The paper technology that embodiment of the present invention provides, it comprises the steps: to provide carboxyl-content is the nano-cellulose that 0.2～1.5mmol/g, average diameter are less than or equal to 100nm; Join using described nano-cellulose as retention and drainage aid agent in paper pulp and mix slurry to form, wherein, the addition of described nano-cellulose is 100～10000ppm of paper pulp oven dry stock; Utilize described mixing to starch the paper of manufacturing paper with pulp.
Preferably, the carboxyl-content of described nano-cellulose is 1.0-1.5mmol/g.
Preferably, the average diameter of described nano-cellulose is less than or equal to 10nm.
Preferably, the addition of described nano-cellulose is 2000～4000ppm of paper pulp oven dry stock.
In the present embodiment, described nano-cellulose makes in the following way:
(1) string is carried out to carboxylated modification, to obtain the modified fibre of carboxyl-content at 0.2～1.5mmol/g;
In the present invention, described string mainly refers to softwood, broadleaf, grass and other plant fiber material.In the present embodiment, preferred softwood and broadleaf fibrous raw material are used as the string of carboxylated modification.
In the present embodiment, adopt TEMPO oxidation system to carry out carboxylated modification to string, concrete, in described TEMPO oxidation system, mainly comprise catalyst, oxidant and three kinds of materials of cocatalyst, wherein, catalyst is TEMPO or derivatives thereof, oxidant can be selected one or more in hypochlorite, chlorite, perchlorate, hydrogen peroxide, chlorine dioxide, and cocatalyst can be selected iodide, bromide or their mixture.
In present embodiment, by utilizing TEMPO oxidation system the primary hydroxyl of cellulosic molecule C6 position to be there is to the characteristic of high selectivity oxidation, the primary hydroxyl of cellulosic molecule C6 position can be oxidized to carboxyl, thereby form a large amount of carboxyls at the cellulose surface of string.
It should be noted that, because cellulose is polyol, in its macromolecular chain, on each glucose basic ring, have three active hydroxyls (being respectively a primary hydroxyl that is positioned at two secondary hydroxyls of C2, C3 position and is positioned at C6 position).In the ordinary course of things, the various multi-form oxidation reactions of cellulose mostly occur on these three hydroxyls, can there is different oxidation reactions in different hydroxyls, the reaction that oxidation generation carboxyl wherein may occur mainly comprises: the primary hydroxyl of (1) C6 position is oxidized to aldehyde radical, and continues to be oxidized to carboxyl; (2) the reducibility radical oxidation in chain end link becomes carboxyl; (3) two secondary hydroxy oxidations of C2, C3 position become aldehyde radical, and continue to be oxidized to carboxyl.
Due to, in this step, its main purpose is that string is carried out to carboxylated modification, to obtain having the modified fibre of high-carboxyl-content, (carboxyl-content reaches 0.2～1.5mmol/g, preferably, reach 1.0-1.5mmol/g), therefore, in the present invention, described string is carried out in the process of carboxylated modification, be not limited in the primary hydroxyl of cellulosic molecule C6 position is carried out to carboxylated modification, according to the difference of the reaction principle of used oxidation system, C2 in cellulosic molecule, the secondary hydroxyl of C3 position, other position that can oxidizedly be modified as carboxyl in the primary hydroxyl of C6 position and cellulosic molecule all can be used as the position of carrying out carboxylated modification that can select in this step.
Therefore, in the present invention, string is carried out to the oxidation system that carboxylated modification uses and be not limited in the TEMPO oxidation system that present embodiment is used, according to different oxidation mechanisms, in the present invention, string is carried out to the oxidation system that carboxylated modification uses can be: non-selective oxidation system, and it comprises at least one in the oxidant that clorox, hydrogen peroxide, persulfate etc. can be oxidized the primary hydroxyl on cellulose and secondary hydroxyl simultaneously; Or can carry out to cellulosic secondary hydroxyl the oxidizer system of selective oxidation, it comprises at least one in periodic acid, periodates; It can also be the oxidizer system that can carry out to cellulosic primary hydroxyl selective oxidation, it,, except TEMPO series nitrogen oxygen base class oxidation system, also comprises the nitrogen oxide type oxidation system of hypochlorite oxidation system, NO2 and N2O4 series, the oxidation system that comprises sodium bromate, sodium chlorate and sodium chlorite.As long as can make the carboxyl-content of the fiber after modification reach 0.2～1.5mmol/g, preferred, reach 1.0-1.5mmol/g.
(2) described modified fibre is carried out to mechanical treatment, be less than or equal to the nano-cellulose of 100nm to obtain carboxyl-content in 0.2～1.5mmol/g, average diameter.
The mode of in this step, described modified fibre being carried out to mechanical treatment comprises that high pressure homogenizer processing, microfluidization device process or mill processing.
In the present embodiment, preferably adopt high pressure homogenizer processing to prepare nano-cellulose, the operating pressure of described high pressure homogenizer is 10～300MPa, preferably 90～150MPa; Number of processes is 2～30 times, preferably 5～10 times.
Understandable, in the present invention, be that the mode that 0.2～1.5mmol/g, average diameter are less than or equal to the nano-cellulose of 100nm is not limited to aforesaid way for the preparation of described carboxyl-content, in the art, be that the preparation method of 0.2～1.5mmol/g, the average diameter nano-cellulose that is less than or equal to 100nm all can be applied in the present invention to prepare described carboxyl-content and is less than or equal to the nano-cellulose of 100nm as 0.2～1.5mmol/g, average diameter as long as can obtain carboxyl-content.
It should be noted that, the present invention utilizes carboxyl-content usually to replace the inorganic retention and drainage aid agent using in traditional paper technology for the nanofiber that 0.2～1.5mmol/g, average diameter are less than or equal to 100nm, therefore, in paper technology provided by the present invention, mode from the traditional aqueous dispersion that contains the inorganic particles such as modified alta-mud and Ludox to paper pulp, opportunity that described nano-cellulose adds in to the mode adding in paper pulp, opportunity and are similar.
In the present embodiment, described nano-cellulose is to join in described paper pulp system with 0.5% form of suspension.
Being used as with the aqueous dispersion that uses inorganic particles such as containing modified alta-mud and Ludox in existing paper technology the mode that retention and drainage aid agent uses compares, above-mentioned paper technology provided by the present invention, it utilizes carboxyl-content is 0.2～1.5mmol/g, the nanofiber that average diameter is less than or equal to 100nm usually substitutes the aqueous dispersion that contains the inorganic particles such as modified alta-mud and Ludox, to use as retention and drainage aid agent, like this: on the one hand, because adopted nano-cellulose surface is formed with a large amount of carboxyls, when by after joining in paper making pulp with the nano-cellulose of a large amount of carboxyls, a large amount of carboxyls with negative electrical charge can greatly improve the adhesion between paper pulp fiber and filler grain, thereby can effectively promote the filler retention of paper pulp, on the other hand, because the average diameter of used nano-cellulose is less than or equal to 100nm, the preferred 10nm that is less than or equal to, thereby, have under high-carboxyl-content, undersized double action, make nano-cellulose used in the present invention there is higher surface negative charge density, the surface negative charge density of height not only can better be compressed the floc sedimentation after wadding gathers again, improve the drainage capacity of slurry, also shortened interfibrous distance, be conducive to the maintenance of paper strength simultaneously.
Below, further illustrate the advantage place of the paper technology that embodiment of the present invention provides by specific embodiment, wherein, comparative example 1 is in paper pulp, to add CPAM(cationic polyacrylamide), APAM(anionic polyacrylamide) the copy paper experiment carried out after binary retention aid and filtering aid system, comparative example 2 is in paper pulp, to add CPAM, silicon dioxide gel, the copy paper experiment of carrying out after APAM ternary retention aid and filtering aid system, embodiment 1～7th, according to paper technology provided by the present invention, taking carboxyl-content as 0.2～1.5mmol/g, the nano-cellulose replacement of silicon dioxide colloidal sol that average diameter is less than or equal to 100nm uses the copy paper experiment of carrying out as retention and drainage aid agent, what need to further illustrate is, the average diameter of the nano-cellulose using in following embodiment 1～5 is 3～10nm.
Performance characterization parameter
Filter-aid performance: measure mixed slurry and filter the drainage amount after 10s, drainage amount is larger represents that filter-aid performance is better.
Retention performance: measure turbidity that mixed slurry filters the plain boiled water obtaining after 10s, utilize described mixed slurry to manufacture paper with pulp into the ash content of the paper after paper, wherein plain boiled water turbidity value is less, greyness of paper is higher represents that retention performance is better.
The physical strength of paper: tensile strength, pop strength and cohesive force.
Comparative example 1: the CPAM(cationic polyacrylamide that adds 300ppm in slurry) and the APAM(anionic polyacrylamide of 250ppm), obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Comparative example 2: add the nano silicon dioxide sol of CPAM, 3600ppm and the APAM of 250ppm of 300ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 1: add the CPAM of 300ppm, nano-cellulose that 1000ppm carboxyl-content is 1.5mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 2: add the CPAM of 300ppm, nano-cellulose that 2000ppm carboxyl-content is 1.5mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 3: add the CPAM of 300ppm, nano-cellulose that 3600ppm carboxyl-content is 1.5mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 4: add the CPAM of 300ppm, nano-cellulose that 4000ppm carboxyl-content is 1.5mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 5: add the CPAM of 300ppm, nano-cellulose that 6000ppm carboxyl-content is 1.5mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 6: add the CPAM of 300ppm, nano-cellulose that 3600ppm carboxyl-content is 0.3mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper;
Embodiment 7: add the CPAM of 300ppm, nano-cellulose that 3600ppm carboxyl-content is 0.8mmol/g and the APAM of 250ppm in slurry, obtain mixed slurry, utilize described mixed slurry to manufacture paper with pulp into paper.
Specific performance parameter is as shown in the table:
Can be found out by upper table data: aspect water filtering performance and filler retention, compared with prior art, within the specific limits, utilizing carboxyl-content is 0.2～1.5mmol/g, the slurry that the nano-cellulose that average diameter is less than or equal to 100nm is replaced after inorganic retention aid and filtering aid system to prepare out as retention and drainage aid agent has good retention and drainage effect equally, and, from comparative example 2, the comparing result of embodiment 3 can be seen, in the case of the consumption of retention aid and filtering aid system is identical, with use the prior art of inorganic retention aid and filtering aid particle in retention aid and filtering aid system compared with, include according to the present invention's employing the slurry obtaining after the retention aid and filtering aid system of the nano-cellulose that carboxyl-content is 1.5mmol/g and can show better retention and drainage effect, aspect paper strength, compared with prior art, adopt the manufacture paper with pulp tensile strength of the paper obtaining of paper technology provided by the present invention, the detected value of the paper that the detected value of pop strength and cohesive force and prior art obtain is suitable, this explanation is according in paper technology provided by the present invention, employing carboxyl-content is 0.2～1.5mmol/g, the nanofiber that average diameter is less than or equal to 100nm usually substitutes the mode of the aqueous dispersion that contains the inorganic particles such as modified alta-mud and Ludox to use as retention and drainage aid agent, in promoting retention aid and filtering aid performance, can also make the strength character of paper keep suitable with prior art, and can not have a negative impact to the intensity of paper.
In addition, those skilled in the art also can do other variation in spirit of the present invention.Therefore the variation that these do according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (10)
1. a paper technology, it comprises the steps:
It is the nano-cellulose that 0.2～1.5mmol/g, average diameter are less than or equal to 100nm that carboxyl-content is provided;
Join using described nano-cellulose as retention and drainage aid agent in paper pulp and mix slurry to form, wherein, the addition of described nano-cellulose is 100～10000ppm of paper pulp oven dry stock; And
Utilize described mixing to starch the paper of manufacturing paper with pulp.
2. paper technology as claimed in claim 1, is characterized in that: the carboxyl-content of described nano-cellulose is 1.0-1.5mmol/g.
3. paper technology as claimed in claim 1 or 2, is characterized in that: the average diameter of described nano-cellulose is less than or equal to 10nm.
4. paper technology as claimed in claim 1, is characterized in that: the addition of described nano-cellulose is 2000～4000ppm of paper pulp oven dry stock.
5. paper technology as claimed in claim 1, is characterized in that: described nano-cellulose is prepared from as follows: string is carried out to carboxylated modification, to obtain the modified fibre of carboxyl-content at 0.2～1.5mmol/g; Described modified fibre is carried out to mechanical treatment, be less than or equal to the nano-cellulose of 100nm to obtain carboxyl-content in 0.2～1.5mmol/g, average diameter.
6. paper technology as claimed in claim 5, is characterized in that: adopt TEMPO series nitrogen oxygen base class oxidation system to carry out carboxylated modification to string.
7. paper technology as claimed in claim 5, is characterized in that: the non-selective oxidation system that employing can be oxidized the primary hydroxyl of string and secondary hydroxyl simultaneously carries out carboxylated modification to string.
8. paper technology as claimed in claim 7, is characterized in that: described non-selective oxidation system comprises at least one in clorox, hydrogen peroxide and persulfate.
9. paper technology as claimed in claim 5, it is characterized in that: adopt selective oxidation system to carry out carboxylated modification to string, described selective oxidation system comprises carries out the oxidizer system of selective oxidation and the primary hydroxyl of string is carried out to the oxidizer system of selective oxidation the secondary hydroxyl of described string.
10. paper technology as claimed in claim 9, it is characterized in that: the described oxidizer system that the secondary hydroxyl of described string is carried out to selective oxidation comprises at least one in periodic acid, periodates, the described oxidizer system that the primary hydroxyl of string is carried out to selective oxidation comprises TEMPO series nitrogen oxygen base class oxidation system, hypochlorite oxidation system, NO
2and N
2o
4the nitrogen oxide type oxidation system of series and the oxidation system that comprises sodium bromate, sodium chlorate and sodium chlorite.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310129274.6A CN104099802A (en) | 2013-04-15 | 2013-04-15 | Papermaking technology |
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| CN201310129274.6A CN104099802A (en) | 2013-04-15 | 2013-04-15 | Papermaking technology |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105463606A (en) * | 2015-12-31 | 2016-04-06 | 华南理工大学 | Nano-crystalline cellulose fiber high in carboxyl group content and preparation and application thereof |
| CN109844220A (en) * | 2016-09-16 | 2019-06-04 | 索理思科技公司 | The water filtering performance of paper manufacturing systems is improved using microfibrillated cellulose |
| CN110158348A (en) * | 2019-05-22 | 2019-08-23 | 济南圣泉集团股份有限公司 | A kind of modified composite fiber material and its preparation method and application |
| CN110685189A (en) * | 2018-07-04 | 2020-01-14 | 山东圣泉新材料股份有限公司 | Paper, preparation method and application thereof |
| CN111663361A (en) * | 2020-05-11 | 2020-09-15 | 济南圣泉集团股份有限公司 | Papermaking white water purifying agent, using method thereof, modified paper pulp containing papermaking white water purifying agent and modified paper |
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| CN102666987A (en) * | 2009-11-04 | 2012-09-12 | 凯米罗总公司 | Process for production of paper |
| CN102690358A (en) * | 2012-06-01 | 2012-09-26 | 南京信息工程大学 | Cellulose nanocrystal suspension and preparation method thereof |
| CN102947345A (en) * | 2009-12-15 | 2013-02-27 | 加拿大国家研究委员会 | Cellulose nanocrystals from renewable biomass |
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| CN101772517A (en) * | 2007-08-10 | 2010-07-07 | 陶氏环球技术公司 | The cellulosic nanoparticle of mild oxidation |
| JP2009263853A (en) * | 2008-03-31 | 2009-11-12 | Nippon Paper Industries Co Ltd | Coated paper for offset printing |
| CN102666987A (en) * | 2009-11-04 | 2012-09-12 | 凯米罗总公司 | Process for production of paper |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105463606A (en) * | 2015-12-31 | 2016-04-06 | 华南理工大学 | Nano-crystalline cellulose fiber high in carboxyl group content and preparation and application thereof |
| CN109844220A (en) * | 2016-09-16 | 2019-06-04 | 索理思科技公司 | The water filtering performance of paper manufacturing systems is improved using microfibrillated cellulose |
| CN110685189A (en) * | 2018-07-04 | 2020-01-14 | 山东圣泉新材料股份有限公司 | Paper, preparation method and application thereof |
| CN110158348A (en) * | 2019-05-22 | 2019-08-23 | 济南圣泉集团股份有限公司 | A kind of modified composite fiber material and its preparation method and application |
| CN111663361A (en) * | 2020-05-11 | 2020-09-15 | 济南圣泉集团股份有限公司 | Papermaking white water purifying agent, using method thereof, modified paper pulp containing papermaking white water purifying agent and modified paper |
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Application publication date: 20141015 |