Method for production of paper mass

FIELD: textile, paper.

SUBSTANCE: method includes dissolution of cellulose and its grinding down to specified extent of grinding. Preparation of the first dispersion with application of return water, containing fibres of microcrystal cellulose, produced by its grinding in mixture with titanium dioxide and calcium hydroxide in specified amount. The second dispersion is prepared from cellulose fibres with application of return water. Then the first suspension is mixed with the second, and produced mixture is treated with carbon dioxide. In case of this treatment calcium hydroxide under action of carbon dioxide results in production of chemically deposited chalk and production of paper mass at specified ratio of components. Grinding of microcrystalline cellulose in mixture with titanium dioxide and calcium hydroxide is carried out in vibration mill with provision of impact and wear effect at mixture.

EFFECT: increased extent of fillers retention in paper, improvement of its printing properties, provision of possibility to vary bulk and porosity of paper, provision of possibility to use fully closed cycle of return water.

1 tbl, 8 ex

 

The invention relates to the production of paper for various purposes using nanofibrillated of cellulose modified with nanosized particles of pigments, and can be used in the pulp and paper industry.

A method of producing paper using as filler precipitated calcium carbonate particles which have an average diameter of 1.5 μm, whiteness 95,8-97,0% and a specific surface area of 20-30 m3/, Filler into the fibre mass is injected in the form of a dispersion 27-33%concentration (US, 6887351, IPC D21H 23/12, publ. 03.05.2005,). Introduction to a paper weight of precipitated calcium carbonate with these characteristics makes it possible to adjust the porosity of the paper increases its whiteness, improving printing properties, enhances light scattering. However, with the introduction of ready-made filler in the fiber with getting bumagoobrazuyuschie suspension not containing retaining substances, the degree of his retention in the sheet of paper during its formation on the grid paper machine (PM) is low. The accumulation of particles in the circulating water quantity formed in the fabric increases and at the same low level of retention. When the preset content of the filler, for example, in high-ash paper concentration in the circulating water reaches reproportion the real high level.

Also known vibratory mill (EN, application No. 2005129753, IPC VS 19/00 from 27.03.2007) and processing technology in it a mixture of TiO2and microcrystalline cellulose (MCC) in terms of the percussive and abrasive effects on the mixture. Discussed the possibility of using the obtained with the use of mill material as filler paper describes some characteristics of pilot castings paper (W-l "Bulletin National technical University, hut, Kharkov, No. 38, p.7-11, 2008), but information about the ash content of the paper, the degree of retention in the casting filler particles MCC and TiO2- not given.

The closest in technical essence and purpose of the present invention is a method for preparing pigment preparations and their use for the preparation of paper pulp and, consequently, paper (US No. 6579410, IPC D21C 9/00, D21H 17/64, publ. 17.06.2003 year). This method comprises preparing a dispersion containing a combination of long and fine fibers at a ratio in parts by weight from 89:20 to 47:53, fine TiO2and calcium hydroxide, processing the dispersion of carbon dioxide with getting it chemically precipitated caso3. In the process of its preparation, you can use the circulating water. The result is a composite pigment consisting of cellulose fibers, TiO2and the ASO 3and TiO2according to the authors, evenly and firmly fixed in the matrix of caso3and fibers. The ratio of fiber/TiO2/CaCO3in parts by weight for examples of the use of the method can be 50/5/45 to 10/55/35. In these ranges, the formation of agglomerates of particles of TiO2and/or caso3was not observed in the dispersion even at high content of these components.

When using this material as a filler in paper pulp in a dry or wet mixed in the desired proportions with dispersion milled to the desired degree of grinding of the pulp fibers and from this mass using to hold the filler additives is formed into the paper web.

In one of the examples in the description of the way the prototype was made on paper using a composite filler ratio in mass fiber/TiO2/Caso3=50/5/45. The amount of filler added to the fiber dispersion, provided the ash content of the paper to 8.1%. Were determined the degree of "primary" hold TiO2in the manufacture of this paper (80%) and, for comparison, the degree of retention of TiO2in the manufacture of paper using as filler only TiO2(33%). The term "primary" we hold call hold, for example, expressed in grams order the body per gram of fiber, measured upon receipt paper casts listonline installation, that is without adding in the pulp circulating water contained in it dispergirovannykh and dissolved substances.

The authors of the difference in the values of the degree of retention of TiO2bind with durable its fixation in the matrix of the composite filler. In this regard, the following should be noted. It is necessary to distinguish the retention of the filler particles, due to the strength of its fastening on the cellulose fibers with some forces, such as intermolecular interaction forces (dispersion forces shrinkage), which are called by the van der Waltz hold, due to the presence of dense filter layer formed during forced dehydration of the mass on the grid, BM, hold, due to the action of substances introduced into the pulp specially to hold the filler, and, finally, retention, caused by two factors or more of the above. However, if it is to increase the degree of restraint at the expense of increasing the strength of fixing of the particles of the filler or fillers on the surface of the cellulose fibers due to some technical methods, it is necessary to measure the degree of retention, to the maximum extent eliminating the influence of all other factors. Therefore, the conclusion of the authors of the method according to the prototype, not is all correct, since bumagoobrazuyuschie mass was used cationic substance, designed specifically to hold the filler. As shown by the following results of our tests of composite filler obtained by the prototype, the degree of initial retention of mineral components of the pigment and the fine fibers is not high enough.

New technical result of the invention is to increase the degree of retention of fillers in paper, improving its print properties, providing the possibility to vary the bulk and porosity of paper, enabling the use of fully closed-loop circulating water.

This result is achieved in that in a method of producing paper pulp, comprising dissolving pulp, grinding to the desired degree of grinding, cooking with the use of recycled water first dispersion containing fine cellulose fibers, pigment titanium dioxide and calcium hydroxide, subsequent processing of calcium hydroxide with carbon dioxide with the formation of chemically precipitated chalk, preparing a second aqueous dispersion of cellulose fibers, mixing the dispersions according to the invention, as the fine cellulose fibers in the first dispersion using fiber microcrystalline cellulose, obtained its breakage of smese with titanium dioxide and calcium hydroxide in a given number this second dispersion is prepared with the use of recycled water, the first dispersion is mixed with the second, the processing of calcium hydroxide with carbon dioxide is carried out in a mixture of dispersions and receive a paper weight with the following ratio of components, in parts by weight:

boyhoodparadise cellulose fibers100
microcrystalline cellulose5-10
titanium dioxide3-6
precipitated calcium carbonate6-12

Milling of microcrystalline cellulose (MCC) in a mixture with titanium dioxide (TiO2) and calcium hydroxide (CA(Oh)2) it is reasonable to implement in the vibratory mill with providing percussion and abrasive effects on the mixture.

The proposed method is as follows. In vibratory mill, providing a combination of impact and abrasive effects on the material being processed, served in predetermined quantities MCC, TiO2and CA(Oh)2. In the mill ICC and CA(Oh)2milled particles and fibrils MCC due to various forces of interaction, in particular the dispersion forces shrinkage, electrostat the economic forces of attraction, 'm entwined with several layers of a mixture of TiO2and CA(Oh)2. At the exit of the mill get a lot, almost not containing free particles and fibrils MCC. She served in the mixer together with the circulating water in a given mass ratio, mix and get the first dispersion with a concentration of dry substances of 10-30%. When mixing with water, the particles of titanium dioxide for the most part and all the particles of calcium hydroxide washed and are in the aqueous phase in the free state. However, some of the particles of titanium dioxide remains associated with the surface of the particles MCC and kept them in all subsequent operations of the receiving paper. Such particles can be called modified.

In steady-state continuous production process of paper when the first dispersion using recycled water from the paper machine.

Prepare a second dispersion. Cellulose dissolving, grind to a predetermined degree of grinding, bring consistency to 4-5% of the fibers. In these operations in a steady process of making paper also uses recycled water.

Next, this dispersion are mixed in a given proportion with the first dispersion, the mixture is treated with carbon dioxide by ozonation in mass until complete conversion of CA(Oh)2in caso3.

Form is iesa in this process, the nanoparticles of caso 3have a high ability to interact with particles of TiO2, MCC and cellulose fibers associated with them. Fiber MCC and natural cellulose associated with them in the result of any processing particles of TiO2and caso3you can also call the modified fibers. As a result of such interaction may occur the formation of spatial structures such as clusters containing particles of fillers and modified cellulose fibers and therefore highly bumagoobrazuyuschie ability with a high degree of retention of the components of the mass.

To test the effectiveness of the proposed method is carried out without the use of retaining additives as follows. Cellulose dissolving, grind to the degree of fineness of the fibers 37°SR. Prepare boyhoodparadise dispersions with different composition and content components. From hanging the dispersions formed on the grid No. 28 of the casting. Concentration supplied to the casting mass in terms of dry substances 0,11-0,13%. The content of cellulose fibers in each sample 1,2, Mass on the grid to first dehydrate under the action of gravity, then under pressure to dryness casting 20-23%. Casting is dried at 95°C. the Filtrates defend until complete precipitation. Precipitation is used for simulating the return of the circulating water in the process of making paper is th mass or dried to determine the amount of ash components in the dehydration of castings.

Upon receipt of the casting of the dispersion of cellulose fibers (black) determine the mass loss (ablation in the filtrate) small fibers. Ash is 7.1% of the mass of fibers in the sample.

Upon receipt of the casting of the dispersion of a mixture of black and MCC (black/MCC=100/10) ash 8.0% by weight of the total dry substance.

When testing the dispersion of a mixture of black and TiO2(Black/TiO2=100/15) ablation of small fibers and TiO2is based on TiO2, 78%, the degree of retention are equal, respectively, 22%. Solids in the filtrate is a mixture of free particles of TiO2(87-90% of its amount in the filtrate) and small fibers, at least some of the modified particles of TiO2. For full clarification of the filtrate required 10-12 hours.

Upon receipt of the casting of the dispersion of a mixture of black, MCC and TiO2the composition in parts by weight (color/ICC/TiO2=100/10/15), common ash is 19,45 h, or 15,56% (based on the amount of dry matter in the sample, ablation of TiO2is 11.1 h or 74% by weight of TiO2. Hold the actual TiO2in the casting - 26%. The bulk of solids in the filtrate is free of particles of TiO2. For full clarification of the filtrate required 10-12 hours.

For testing paper pulp on the prototype, but without the use of retaining substances, preparing a dispersion composition color/TiO2/Ca(OH)2handle it with carbon dioxide and receive a variance from the ratio of the parts by weight of the group of and components black/TiO2/Caso3=100/50/50. This is one of the stages of the preparation of paper pulp. This dispersion is prepared casting. The degree of retention of TiO2and caso3(in amount) equal to 44%, fly ash, respectively, equal to 56%. In the filtrate the small number of modified fibers is not more than 30% of the weight of dry matter. The remaining loose particles of TiO2and caso3.

When the mixture of intermediate composition with a variance of color get the ratio of black/TiO2/CaCO3=100/8/8, that is the end product of the method of the prototype. In the manufacture of castings from a mass of the degree of retention of TiO2and caso3increases to 52% (Example 1). Ash, respectively, equal to 48%.

The table shows the test results of the dispersions according to examples. The values a, B, In - experienced, And settlement. Be calculated as follows: G=a-b; D=B; E=b/a·100; G=D/B·100;=A/D·100. In the calculations the values of D, W, And ignored the content in the ash of cellulose fibers and MCC. When it is given the value of D, W, And increase. In the tests, the actual mass of precipitation and the difference (a-b) differ by 2-4%. This difference can be neglected and therefore, as the value G is used, the value (a-b).

In the description of the way the prototype refers to the possibility of use in the preparation of paper pulp turnover is Noah water, for example, by adding CA(Oh)2processing a mixture of carbon dioxide and feed the resulting suspension in the process of preparation of intermediate composition. However, confirmation of the use of recycled water in description is omitted.

For testing dispersions according to the proposed method of preparing a suspension of the composition in parts: MCC/TiO2/Ca(OH)2=50/60/46, mix it in the desired ratio with the dispersion of cellulose fibers, the mixture is treated with carbon dioxide and receive a paper weight of the composition (Example 2): black/MCC/TiO2/CaCO3=100/5/6/6.

Example 3 preparing a suspension of the composition by mass: MCC/TiO2/CA(Oh)2=100/30/92, mix it with a dispersion of cellulose fibers, the mixture is treated with carbon dioxide and receive a paper weight of composition by mass: color/ICC/TiO2/CaCO3=100/10/3/12.

These dispersions are prepared casting, define the required parameters. As shown by these tables, the degree of retention of the amounts of fillers increases from 52 to 66-73%. Weight of dry matter of the leachate on PR and 3 are 90-93% of modified cellulose fibers and MCC, and accordingly, 7-10% free particles TiO2and caso3. The filtrate is asserted at 95-97% of the contained substances for 2.5-3 hours.

Thus, one of the purposes of the proposed method is to increase the degree of retention of the fillers in the paper temperature is raised. Add in the pulp and, consequently, in the paper shredded MCC in a particular amount provides high printing qualities of the paper and gives the opportunity to vary its bulk and porosity. It is another objective of the method.

Fully closed-loop circulating water in a paper machine ensures a continuous supply of water in the process of making paper pulp prior to the processing of calcium hydroxide with carbon dioxide in the mixture of the first and second dispersions (see claims). You can put that in the course of performing such processing in accordance with the proposed method, the formed nanoparticles of caso3interact with contained in the circulating water particles. It's mostly small modified cellulose fibers. These fibers are modified more and able to participate in education volume structures that create dehydrating weight canvas paper (or casting). In the filtrate water carries less active "new" particles, mainly modified small fibers, and also a number of free particles of the fillers. Accordingly, in a streamlined continuous process in the circulating water constantly enters the filtrate with little changing composition and total mass of solids.

This mechanism is confirmed by the results of tests dispersions with the addition of the ECC preparation of each sample, but the first sludge filtrate from the previous casting and processing the mixture with carbon dioxide. Set in the testing goal is to get the paper (casting) with the composition and ratio of the components of the fiber/CMC/TiO2/Caso3=100/7/4/8 (filler concentration ~16%) when using for the first casting the dispersion of this composition is achieved already in the fourth casting (the proportion of fillers ~17,4%). In preparation for the next casting taken dispersion ratio color/ICC/TiO2/Ca(OH)2=100/3/2/8. It added to precipitate the filtrate from the previous casting in Example 7, the mixture is treated with carbon dioxide and prepared casting in Example 8.

The results are given in the table for all serial castings (PR-8). To maintain the parameters of the casting at a given level by reducing and/or increasing the supply MCC, TiO2and/or CA(Oh)2in the pulp in the process of its preparation with the use of recycled water.

Thus, the method provides the possibility of achieving all the goals.

When used in the preparation of the paper holding, hardening, water-repellent substances part of their fall in the circulating water. They also are held in the casting in accordance with the mechanism described above, and therefore the General laws are not violated.

1. The way to obtain paper pulp, comprising dissolving pulp, grinding to the desired degree of grinding, cooking with the use of recycled water is the first water dispersion containing fine cellulose fibers, pigment titanium dioxide and calcium hydroxide, subsequent processing of calcium hydroxide with carbon dioxide with the formation of chemically precipitated chalk, preparing a second aqueous dispersion of cellulose fibers, a mixture of dispersions, characterized in that as the fine cellulose fibers in the first dispersion using fiber microcrystalline cellulose, obtained it by grinding in a mixture with titanium dioxide and calcium hydroxide in a predetermined number, while the second dispersion is prepared using the reverse water, the first dispersion is mixed with the second, the processing of calcium hydroxide with carbon dioxide is carried out in a mixture of dispersions and receive a paper weight in the following ratio of components, parts by weight:

6-12
boyhoodparadise cellulose fibers100
microcrystalline cellulose5-10
titanium dioxide3-6
chemically precipitated chalk

2. The method according to claim 1, characterized in that the grinding microcrystalline cellulose in a mixture with titanium dioxide and calcium hydroxide is carried out in a vibratory mill with providing percussion and abrasive effects on the mixture.



 

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The invention relates to a rheology modifiers to achieve the thickening effect, regulating the expiry of water retention and other properties of aqueous systems

FIELD: textile, paper.

SUBSTANCE: according to one version, method includes provision of aqueous suspension that contains cellulose fibres. Addition of cation polysaccharide and polymer P2, which is an anion polymer, to produced suspension after all points of high polymer P1 shearing force, and P1 polymer is an anion polymer. Then water is removed from produced suspension to form paper. According to the other version, auxiliary agents are added for drainage and retention to produced suspension of cellulose fibres after all points of high shearing force. The latter are represented by a cation polysaccharide and polymer P2, being an anion polymer.

EFFECT: improved drainage without deterioration in retention and forming of paper, increased speed of paper-making machine and application of lower doses of polymer.

34 cl, 5 tbl, 5 ex

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