CN112796152A - Organically modified filler, preparation method thereof and papermaking process using filler - Google Patents
Organically modified filler, preparation method thereof and papermaking process using filler Download PDFInfo
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- CN112796152A CN112796152A CN202011605226.6A CN202011605226A CN112796152A CN 112796152 A CN112796152 A CN 112796152A CN 202011605226 A CN202011605226 A CN 202011605226A CN 112796152 A CN112796152 A CN 112796152A
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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
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Abstract
The invention relates to an organic modified filler, a preparation method thereof and a papermaking process using the filler. Polyvinyl alcohol or starch is added into the filler. The invention provides a novel modified filler and a papermaking process using the novel filler, which can realize the improvement of paper filler addition, can reduce the production cost of papermaking enterprises and has good application value.
Description
Technical Field
The invention relates to an organic modified filler, a preparation method thereof and a papermaking process using the filler, belonging to the technical field of papermaking.
Background
The fillers used in the paper making industry at present mainly comprise: inorganic mineral substances such as Ground Calcium Carbonate (GCC), light calcium carbonate (PCC), talcum powder, titanium dioxide, kaolin and the like. The application of the inorganic carbon substance can reduce the production cost of enterprises and endow paper with certain optical performance and printing performance. But inevitably has some negative effect on the strength of the paper, which is a key factor limiting the amount of filler added to the paper.
Experts in the paper industry and related fields have conducted various studies to improve the strength of fillers for paper making, such as: heavy calcium carbonate modifier, heavy calcium carbonate modification method, modified heavy calcium carbonate and application patent thereof, which are applied to China mining university, the patent numbers: 201910548186.7, the activation index of calcium carbonate can be increased to nearly 100% by modifying with alkyl diphosphonic acid. The following steps are repeated: patent of modification method of stone paper modified calcium carbonate applied by yunan Kun Steel stone paper environmental protection materials Co., Ltd, patent number: 201811528600.X, a cationic starch modifier is added for modification, and the cationic starch modifier is used for improving the product quality of the stone paper.
At present, no traditional filler modification method for papermaking exists, and the mechanical property of the filler can be improved.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a novel modified filler and a papermaking process using the novel filler, so that the filler is added into paper, and the production cost of a papermaking enterprise can be reduced.
The technical scheme adopted by the invention is as follows: an organically modified filler, to which polyvinyl alcohol or starch is added.
Further, the modified filler comprises the following components: GCC (ground calcium carbonate), PCC (light calcium carbonate), china clay, talc, titanium dioxide, polyvinyl alcohol or starch.
Further, the polymerization degree of PVA (polyvinyl alcohol) is: 500-2600, and the alcoholysis degree is: 75% -99%; dissolution temperature of PVA in water: 45-95 ℃, melting point of PVA: 95 to 150 ℃.
Further, based on 100 parts of oven-dried calcium carbonate, the PVA dosage is as follows: 1-50 parts.
Further, the starch is cationic starch, pregelatinized starch and native starch; is one or the combination of a plurality of cassava starch, corn starch, wheat starch and the like;
if cationic starch is selected, the substitution degree is as follows: 0.01 to 0.06.
Further, based on 100 parts of absolute dry calcium carbonate, the using amount of the starch is as follows: 1-50 parts.
A preparation method of a modified filler comprises the following steps: after the preparation of the traditional papermaking filler is finished, adding PVA (polyvinyl alcohol) or a starch reinforcing agent into the filler, stirring at high temperature, keeping the temperature for a certain time under the condition of stirring, and cooling to room temperature; and transferring the cooled mixture to a Raymond mill or other grinding equipment for secondary grinding, and controlling the proper grinding temperature and the size of the ground particles to obtain the organic modified filler.
Further, stirring at a high temperature in the following temperature range: and (3) stirring at 90-180 ℃, wherein the stirring time is as follows: 10-180 min, stirring speed: 10-1200 rpm;
the heat preservation temperature range is as follows: and (3) stirring at 90-180 ℃, wherein the stirring time is as follows: 10-180 min, stirring speed: 10 to 1200 rpm.
Further, the temperature range to be controlled in the Raymond mill or other grinding equipment is as follows: the temperature is 20-130 ℃, and the highest temperature cannot exceed the melting point temperature of PVA;
the particle size control range after grinding is as follows: C30-C99, or can pass through a 100-2000 mesh screen.
A papermaking process of an organic modified filler comprises the following steps: the method comprises the following steps of brewing and diluting an organic modified filler according to a traditional papermaking filler mode, adding the organic modified filler into a paper machine system, wherein an adding point can be one or more of traditional adding points of the paper machine filler such as a mixed pulp tank, a paper machine pulp tank, a pulp forming tank, a fan pump, a pressure screen and the like, adding the organic modified filler into a pulp material, and obtaining paper containing the modified filler through a head box, a forming net, a squeezing part, a drying part and reeling;
the drying cylinder temperature of the drying part and the temperature range of the first section of drying cylinder are as follows: 20-35 ℃, and the temperature range of the second section drying cylinder is as follows: and the temperature of the third section of drying cylinder is 30-45 ℃, and the temperature range of the third section of drying cylinder is as follows: 40-65 ℃, and the temperature range of the fourth section of drying cylinder is as follows: 55-70 ℃.
The invention has the advantages that: the invention provides a novel modified filler and a papermaking process using the novel filler, which can realize the improvement of paper filler addition, can reduce the production cost of papermaking enterprises and has good application value.
Detailed Description
The main technical route of the organic modified filler and the application thereof is as follows: after the preparation of the traditional papermaking filler, adding reinforcing agents such as PVA (polyvinyl alcohol) or starch and the like into the filler, stirring at high temperature, keeping under stirring, preserving heat for a certain time, and cooling to room temperature. And transferring the cooled mixture to a Raymond mill or other grinding equipment for secondary grinding, and controlling the proper grinding temperature and the size of the ground particles to obtain the organic modified filler.
The method comprises the steps of brewing and diluting the organic modified filler according to the traditional papermaking filler mode, adding the organic modified filler into a paper machine system, wherein the adding point can be one or more of the traditional adding points of the paper machine filler such as a mixed pulp tank, a paper machine pulp tank, a pulp forming tank, a fan pump, a pressure screen and the like, adding the organic modified filler into the pulp, and obtaining the paper containing the modified filler through a head box, a forming net, a squeezing part, a drying part and reeling. It should be noted that the drying cylinder temperature profile of the drying section may be adjusted to some extent when conventional fillers are used. That is, except for the first section of drying cylinder which adopts low temperature or cold cylinder, the temperature of the second section of drying cylinder is increased by 2-5 ℃ compared with the traditional filler, the temperature of the third section of drying cylinder is increased by 5-10 ℃ compared with the traditional filler, and the temperature of the fourth section of drying cylinder at least needs to reach more than 65 ℃. The subsequent drying cylinder temperature keeps the same increasing curve as when the traditional filler is used.
The water-soluble PVA, starch and the like on the surface of the filler after organic modification are dissolved by utilizing the temperature of a drying cylinder and are bonded on paper fibers, so that the strength of paper is greatly improved, especially the key strength indexes of paper such as internal bonding force, tensile strength, folding strength and the like are realized, the aim of adding the filler into the paper, not influencing the strength of finished paper and even increasing the strength of the paper is fulfilled, the production cost of enterprises is further reduced, and the quality of the paper is improved.
The papermaking filler mainly comprises: GCC (ground calcium carbonate), PCC (light calcium carbonate), china clay, talcum powder, titanium dioxide and other conventional inorganic fillers for papermaking. Wherein, the GCC particle size is controlled between C30-C99, preferably C60-C90, (C60 means that the proportion of calcium carbonate particles below 2um reaches 60%, C90 means that the proportion of calcium carbonate particles below 2um reaches 90%, and the like). The particle size of the talcum powder and the porcelain clay is controlled to be between 100 meshes and 2000 meshes of screen, and preferably between 200 meshes and 1000 meshes of screen. The filler can be brewed and has a concentration of 10% to 70%, preferably below 50%, and most preferably is a dry powder filler.
The polymerization degree of PVA (polyvinyl alcohol) is as follows: 500-2600, preferably 1300-1700, and the alcoholysis degree is as follows: 75% to 99%, preferably 95% to 99%. Dissolution temperature of PVA in water: 45-95 ℃, preferably 55-65 ℃, and the melting point of PVA: 95-150 ℃, preferably 120-140 DEG C
The PVA dosage is as follows: 1-50 parts (calculated by 100 parts of absolute dry calcium carbonate), preferably 3-10 parts, and the amount of PVA depends on the cost to be controlled and the strength of the modified filler, and if the strength of the modified filler needs to be improved, the amount of PVA can be increased, but the cost is increased correspondingly. Preferably 3-10 parts, simply means a relative balance of cost and calcium carbonate strength, and even more than 100 parts PVA may be used in certain specific cases.
The starch is generally cationic starch, pregelatinized starch, native starch and the like, and can be one or a combination of more of tapioca starch, corn starch, wheat starch and the like according to the difference of starch raw materials, if cationic starch is selected, the substitution degree is as follows: 0.01 to 0.06, preferably 0.02 to 0.04.
The dosage of the starch is as follows: 1-50 parts (calculated by 100 parts of absolute dry calcium carbonate), preferably 5-10 parts, wherein the amount of the starch is determined by the cost which is required to be controlled and the strength of the modified filler, and if the strength of the modified filler is required to be improved, the amount of the starch can be increased. Preferably 5-10 parts, simply means a relative balance of cost and calcium carbonate strength, and even more than 100 parts of starch in certain specific cases.
Stirring at a high temperature, wherein the temperature range is as follows: and (3) 90-180 ℃, preferably 120-140 ℃, and stirring time is as follows: preferably, the mixing time is 10-180 min, and is 20-60 min, wherein the mixing speed is as follows: 10-1200 rpm, preferably 400-600 rpm (laboratory), 30-60 rpm (actual production).
The heat preservation temperature range is as follows: and (3) 90-180 ℃, preferably 110-130 ℃, and stirring time is as follows: 10-180 min, preferably 30-60 min, stirring speed: 10-1200 rpm, preferably 400-600 rpm (laboratory), 30-60 rpm (actual production).
The temperature range required to be controlled in the Raymond mill or other grinding equipment is as follows: the temperature is 20-130 ℃, namely the highest temperature cannot exceed the melting point temperature of PVA, and the lower the temperature is, the better the temperature is, so that the temperature of a Raymond mill or other grinding equipment can be controlled by a cooling system. The cooling method can be water cooling, oil cooling, air cooling or using cold coal.
The particle size control range after grinding is as follows: C30-C99, preferably: C60-C90 or a sieve with 100-2000 meshes, preferably 200-1000 meshes.
The temperature of the drying cylinder and the temperature range of the first section of drying cylinder are as follows: 20-35 ℃, and the temperature range of the second section drying cylinder is as follows: and the temperature of the third section of drying cylinder is 30-45 ℃, and the temperature range of the third section of drying cylinder is as follows: 40-65 ℃, and the temperature range of the fourth section of drying cylinder is as follows: 55-70 ℃, and the preferred scheme is as follows: in this range, the temperature of the second-stage oven is increased compared with the original set value: 2-5 ℃, and the temperature of the third section of the oven is improved compared with the original set value: 5-10 ℃, and the temperature of the fourth section of drying cylinder reaches more than 65 ℃.
Organically modified filler, example one:
filling: heavy calcium carbonate (GCC), particle size C60, dry powder are adopted
Step one of organic modification of the filler:
1. adding 100 parts of heavy dry powder calcium carbonate into a sealed stirring tank, adding 10 parts of PVA dry powder with the polymerization degree of 1700, the alcoholysis degree of 95 percent, the water solution temperature of 65 ℃ and the melting point of 105 DEG C
2. Heating the temperature of the stirring tank to 120 ℃, stirring for 60min, keeping the temperature at 100 ℃, stirring for 45min, and cooling to 30 ℃.
3. And transferring the cooled mixture into a Raymond mill, controlling the grinding temperature of the Raymond mill to be 45 ℃, and keeping the grain diameter after grinding to be C60 grade.
4. Obtaining the organic modified filler.
The application of the organic modified filler in the papermaking step:
1. diluting the organically modified filler to 20% concentration, adding the filler into a paper machine pulp pool to replace the originally used GCC, and using the following amount: 20%, 25%, 30% and 35%.
2. The paper containing the organic modified filler is obtained through a paper machine head line, a forming net, a pressing part, a drying part (the temperature of a drying cylinder is regulated and shown in the table I), gluing and reeling.
The physical properties of the paper are shown in the table I:
by contrast, it can be found that the organic modified filler prepared in the first step replaces the traditional papermaking filler GCC, and the tensile strength, the folding strength and the internal bonding force are obviously increased under the condition of the same ash content, namely the ash content is increased by nearly 12.5%, and the strength is still close to that of the traditional papermaking filler GCC.
Organically modified filler, example two:
filling: light calcium carbonate (PCC) with the average grain diameter of 4.5um is adopted as dry powder
Step one of organic modification of the filler:
1. adding 100 parts of light dry powder calcium carbonate into a sealed stirring tank, adding 3 parts of PVA dry powder with the polymerization degree of 1300, the alcoholysis degree of 99 percent, the water solution temperature of 55 ℃ and the melting point of 100 DEG C
2. Heating the temperature of the stirring tank to 110 ℃, stirring for 45min, controlling the heat preservation temperature at 95 ℃, stirring for 60min, and cooling to 30 ℃.
3. And transferring the cooled mixture into a Raymond mill, controlling the grinding temperature of the Raymond mill to be 35 ℃, and controlling the average grain diameter after grinding to be about 5 um.
4. Obtaining the organic modified filler.
The application of the organic modified filler in the papermaking step:
1. diluting the organically modified filler to 28% concentration, adding the filler to a paper machine pulp pool to replace the PCC used originally, and using the following components in percentage by weight: 20%, 22%, 24% and 26%.
2. The paper containing the organic modified filler is obtained through a paper machine head line, a forming net, a pressing part, a drying part (the temperature of a drying cylinder is regulated according to the table II), gluing and reeling.
3. The physical properties of the paper are shown in the second table:
by comparison, the organic modified filler prepared in the step two is used for replacing the traditional paper making PCC, so that the tensile strength, the folding strength and the internal bonding force are obviously increased under the condition of the same ash content, even if the ash content is increased by nearly 3.9 percent, the strength is still slightly superior to the traditional paper making PCC.
An organic modified filler is added into the mixture,
example three:
filling: sieving talcum powder with a 1000-mesh sieve, wherein the brewing concentration is as follows: 30 percent of
Step one of organic modification of the filler:
100 parts of talcum powder dry powder is added into a sealed stirring tank, clear water is added, the concentration is controlled to be 30%, 50 parts of PVA dry powder with the polymerization degree of 700 and the alcoholysis degree of 85%, the water solubility temperature is 70 ℃, the melting point is 125 ℃, and 30 parts of cationic starch with the substitution degree of 0.04 are added.
1. The temperature of the stirring tank is raised to 140 ℃, the stirring is carried out for 70min, and the rotating speed: 30 r/min, keeping the temperature at 100 ℃, stirring for 180min at the rotating speed of 30 r/min to obtain a dry substance, and cooling to room temperature.
2. Transferring the cooled mixture into a Raymond mill, controlling the grinding temperature of the Raymond mill to be below 50 ℃, and sieving the ground organic modified filler through a 1000-mesh sieve
3. Obtaining the organic modified filler.
The application of the organic modified filler in the papermaking step:
1. diluting the organically modified filler to 20% concentration, adding the filler into a paper machine pulp tank to replace originally used talcum powder, wherein the dosage is as follows: 40%, 50% and 60%.
2. The paper containing the organic modified filler is obtained through a paper machine head line, a forming net, a pressing part, a drying part (the temperature of a drying cylinder is regulated to be shown in the table III), gluing and reeling.
The physical properties of the paper are shown in the table III:
by comparison, the organic modified filler prepared in the third step is used for replacing the traditional filler talcum powder for papermaking, and due to the fact that the PVA and the starch are higher in dosage, ash content is reduced, but strength is greatly increased under the condition of the same dosage. Under the condition of adjusting to be similar to ash content, tensile strength, folding strength and internal binding force are all obviously increased, even if the ash content is increased by nearly 10 percent, the strength is still slightly superior to that of the traditional filler talcum powder for papermaking.
Claims (10)
1. An organically modified filler, characterized in that polyvinyl alcohol or starch is added to the filler.
2. An organically modified filler according to claim 1, characterised in that it comprises the following components: GCC (ground calcium carbonate), PCC (light calcium carbonate), china clay, talc, titanium dioxide, polyvinyl alcohol or starch.
3. Organically modified filler according to claim 2, characterized in that the degree of polymerization of PVA (polyvinyl alcohol) is: 500-2600, and the alcoholysis degree is: 75% -99%; dissolution temperature of PVA in water: 45-95 ℃, melting point of PVA: 95 to 150 ℃.
4. The organically modified filler according to claim 2, wherein the PVA is used in an amount of, based on 100 parts by weight of absolute amount of calcium carbonate: 1-50 parts.
5. The organically modified filler according to claim 2, wherein the starch is a cationic starch, a pregelatinized starch, an original starch; is one or the combination of a plurality of cassava starch, corn starch, wheat starch and the like;
if cationic starch is selected, the substitution degree is as follows: 0.01 to 0.06.
6. An organically modified filler according to claim 2, characterised in that the amount of starch is such that, based on 100 parts of calcium carbonate absolute dry matter: 1-50 parts.
7. The preparation method of the modified filler is characterized by comprising the following steps of: after the preparation of the traditional papermaking filler is finished, adding PVA (polyvinyl alcohol) or a starch reinforcing agent into the filler, stirring at high temperature, keeping the temperature for a certain time under the condition of stirring, and cooling to room temperature; and transferring the cooled mixture to a Raymond mill or other grinding equipment for secondary grinding, and controlling the proper grinding temperature and the size of the ground particles to obtain the organic modified filler.
8. The method of claim 7, wherein the stirring is performed at an elevated temperature in the range of: and (3) stirring at 90-180 ℃, wherein the stirring time is as follows: 10-180 min, stirring speed: 10-1200 rpm;
the heat preservation temperature range is as follows: and (3) stirring at 90-180 ℃, wherein the stirring time is as follows: 10-180 min, stirring speed: 10 to 1200 rpm.
9. A method of producing a modified filler according to claim 7, wherein the temperature range to be controlled in the Raymond mill or other milling apparatus is: the temperature is 20-130 ℃, and the highest temperature cannot exceed the melting point temperature of PVA;
the particle size control range after grinding is as follows: C30-C99, or can pass through a 100-2000 mesh screen.
10. A papermaking process of an organic modified filler is characterized by comprising the following steps: the method comprises the following steps of brewing and diluting an organic modified filler according to a traditional papermaking filler mode, adding the organic modified filler into a paper machine system, wherein an adding point can be one or more of traditional adding points of the paper machine filler such as a mixed pulp tank, a paper machine pulp tank, a pulp forming tank, a fan pump, a pressure screen and the like, adding the organic modified filler into a pulp material, and obtaining paper containing the modified filler through a head box, a forming net, a squeezing part, a drying part and reeling;
the drying cylinder temperature of the drying part and the temperature range of the first section of drying cylinder are as follows: 20-35 ℃, and the temperature range of the second section drying cylinder is as follows: and the temperature of the third section of drying cylinder is 30-45 ℃, and the temperature range of the third section of drying cylinder is as follows: 40-65 ℃, and the temperature range of the fourth section of drying cylinder is as follows: 55-70 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103343480A (en) * | 2013-07-02 | 2013-10-09 | 金东纸业（江苏）股份有限公司 | Modified packing and preparation method thereof as well as papermaking technology adopting modified packing and paper |
| CN103397567A (en) * | 2013-08-05 | 2013-11-20 | 金东纸业（江苏）股份有限公司 | papermaking technology |
| CN103614944A (en) * | 2013-11-07 | 2014-03-05 | 金红叶纸业集团有限公司 | Preparation method of modified filler, papermaking process and prepared paper |
| CN104781469A (en) * | 2012-10-05 | 2015-07-15 | 特种矿物（密歇根）有限公司 | Filler suspension and its use in the manufacture of paper |
| CN106149459A (en) * | 2015-03-31 | 2016-11-23 | 上海东升新材料有限公司 | A kind of paper grade (stock) height retains filler and preparation method thereof |
-
2020
- 2020-12-30 CN CN202011605226.6A patent/CN112796152A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781469A (en) * | 2012-10-05 | 2015-07-15 | 特种矿物（密歇根）有限公司 | Filler suspension and its use in the manufacture of paper |
| CN103343480A (en) * | 2013-07-02 | 2013-10-09 | 金东纸业（江苏）股份有限公司 | Modified packing and preparation method thereof as well as papermaking technology adopting modified packing and paper |
| CN103397567A (en) * | 2013-08-05 | 2013-11-20 | 金东纸业（江苏）股份有限公司 | papermaking technology |
| CN103614944A (en) * | 2013-11-07 | 2014-03-05 | 金红叶纸业集团有限公司 | Preparation method of modified filler, papermaking process and prepared paper |
| CN106149459A (en) * | 2015-03-31 | 2016-11-23 | 上海东升新材料有限公司 | A kind of paper grade (stock) height retains filler and preparation method thereof |
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Application publication date: 20210514 |