US20130199745A1 - Process for manufacturing paper and board - Google Patents
Process for manufacturing paper and board Download PDFInfo
- Publication number
- US20130199745A1 US20130199745A1 US13/822,777 US201113822777A US2013199745A1 US 20130199745 A1 US20130199745 A1 US 20130199745A1 US 201113822777 A US201113822777 A US 201113822777A US 2013199745 A1 US2013199745 A1 US 2013199745A1
- Authority
- US
- United States
- Prior art keywords
- kaolin
- fibre
- particles
- pulp
- structured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 129
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 128
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 119
- 239000000945 filler Substances 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000000835 fiber Substances 0.000 claims abstract description 53
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 13
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 8
- 239000000123 paper Substances 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 150000003839 salts Chemical class 0.000 claims description 41
- 239000002002 slurry Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 20
- 230000014759 maintenance of location Effects 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 17
- 229920001131 Pulp (paper) Polymers 0.000 claims description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- -1 optical brighteners Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000011859 microparticle Substances 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 229920005615 natural polymer Polymers 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920001059 synthetic polymer Polymers 0.000 claims description 5
- 239000004150 EU approved colour Substances 0.000 claims description 4
- 150000001399 aluminium compounds Chemical class 0.000 claims description 4
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 230000003311 flocculating effect Effects 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 26
- 230000002378 acidificating effect Effects 0.000 description 15
- 230000001965 increasing effect Effects 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 235000018185 Betula X alpestris Nutrition 0.000 description 4
- 235000018212 Betula X uliginosa Nutrition 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 230000003313 weakening effect Effects 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/73—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of inorganic material
-
- 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
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
-
- 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
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
Definitions
- the present invention relates to a fibre product that contains pulp or wood fibre, and to the manufacturing method of this product, wherein filler particles are attached between the pulp fibres or wood fibres as well as to fibrils, after which paper or board is produced from the fibre pulp.
- the fillers or pigments that are used in the manufacture of paper and board have an average particle size of less than 5 ⁇ m and a light colour.
- the most typical fillers include kaolins, talcs, ground calcium carbonate, and precipitated calcium carbonate.
- special pigments such as precipitated aluminium silicates, satin white, and titanium dioxide. Drawing an exact line between fillers and coating pigments is difficult; however, roughly speaking, fillers have a larger size than the pigments that are used in coating. From the point of view of a maximum light scattering, an optimal particle size for the most common fillers and coating pigments would be 0.4-0.5 ⁇ m.
- the average particle size of the coating pigments is 0.5-1 ⁇ m and that of the fillers 1.5-4 ⁇ m.
- the most common clay mineral that is used as filler in the manufacture of paper and board is kaolin that mainly consists of kaolinite.
- the kaolin mineral has a two-layer, laminar structure that comprises a tetrahedral layer of silicon dioxide and an octahedral layer of aluminium oxide. The layers are interconnected by oxygen atoms. Because of the silanol groups of the surface of kaolin, the surfaces of the kaolin mineral are negatively charged and its edges are positively charged, when suspended in water.
- Kaolin can be manufactured by dry or wet processes; however, in the wet process, it is possible to have a greater chemical effect on the final brightness of kaolin at the various process stages.
- the most common commercial kaolin grades include water-washed, delaminated, calcined, and chemically structured kaolins.
- the water-washed grade often contains several kaolin sheets that are attached to each other at their surfaces.
- kaolin surfaces are separated by grinding them into smaller groups and single kaolin sheets.
- the calcined kaolins are made by allowing kaolin sheets, which have a conveniently small particle size distribution, to partly melt to each other at a temperature of about 1000° C. At a temperature of over 450° C., the structure of kaolin crystals begins to change. Kaolin crystals that are heated at a temperature of about 500-800° C. are called metakaolin.
- metakaolin and calcined kaolin are particularly visible as an improvement in brightness and opacity compared with water-washed and delaminated kaolins. This is based on the fact that, between the kaolin sheets in the calcined kaolin, there are interfaces of air and kaolin which are effective in scattering light. The pores formed in the structure of the structured kaolins further help in the setting of ink.
- the manufacture of chemically structured kaolins is based on the formation of the same interfaces, but in this case, the interfaces can be chemically bound to each other—not by means of high temperatures.
- the light scattering efficiency of the chemically structured kaolins is normally between that of the delaminated and calcined kaolins.
- filler particles are obtained, which have a suitable size category to fill the openings between the pulp fibres.
- the required strength is thus achieved for the fibre product, and at the same time, part of the pulp can be replaced.
- achieving the strength has been sufficient.
- Another purpose of fillers and additives, however, is the retention which is very difficult to improve in connection with improving the strength of the product.
- the various fillers also bind less water than fibres do, contributing to the financial advantage of their use due to the accelerated dewatering.
- the lower water retention capacity is visible as a quicker dewatering and, thus, lower energy costs in drying, when the filler is used.
- the fillers and fibres have an anionic charge. Therefore, to improve the filler retention, a cationic charge in the form of ions or polymers should generally be supplied to the pulp to bind the filler to the fibre network. In printing papers, the filler contents are about 30%, calculated from dry fibre.
- the retention can be divided into a mechanical and chemical one, of which the chemical retention definitely has more significance. The mechanical retention has more meaning for boards of a high basis weight.
- the decrease in strength and stiffness of the paper or board product when replacing the fibre with filler is mainly caused by the fact that the fillers weaken the formation of hydrogen bonds between the fibres, since the surfaces of the fillers do not form hydrogen bonds.
- the filler is added directly to the pulp. In the wire section, only part of the added filler is attached to the finished paper or board web. The rest of the filler travels through the white water system to finally constitute part of the finished paper or board structure, but then the risks of various runnability problems have increased mainly due to the attachment of various hydrophobic substances to the fillers of the white water system. In the paper or board machine, the runnability problems caused by this usually appear as contamination, breaks, of the wires and felts, for example. Part of the filler of the white water system also finally burdens the sewage treatment plant, because it is never entirely carried out of the process along with the finished paper or board.
- An object of the present invention is to provide a new paper or board product that has good strength and high opacity.
- An object of the present invention is to provide a new paper or board product that contains, as filler, granules that attach between the fibres and carbonates that attach to the fibrils.
- the object of the present invention is to utilize an aqueous, carbonate-bearing salt composition to suspend structured kaolin in the manufacture of the paper and board products.
- an aqueous, carbonate-bearing salt composition to suspend structured kaolin in the manufacture of the paper and board products.
- the kaolin sheets among others, latexes can be used as binders, by means of which the kaolin sheets and stacks can be attached to each other to form granules or agglomerates from the kaolin slurry by means of a mixing technique or spray drying.
- the purpose is to provide structured kaolin with an average particle size of over 5 micrometres.
- the structured kaolin thus dried can then be converted into calcined kaolin or metakaolin by heating it in a furnace.
- an improvement is achieved by using the structured kaolin that is suspended in the aqueous solution, according to the invention, whereby quicker dewatering and higher retention are utilized in the wire section.
- carbonate filler is precipitated to the fibre structure by means of an increase in the pH, pressure or temperature, preferably at the tail of the wire section and/or after the press section.
- the goal is to introduce a desired amount and distribution of precipitated carbonate filler into the lumen and fibrils of the fibre structure, whereby the effect of structured kaolin that weakens the stiffness can be prevented.
- the carbonate filler thus created increases the brightness, opacity, and printability that are achieved by using structured kaolin alone.
- the carbonate filler thus created would be contained in the fibrils of the fibres, increasing the stiffness, among others, and the structured kaolin would be contained in the holes of the fibre network, whereby the weakening of the strength and stiffness of the fibre network caused by the prevention of the formation of hydrogen bonds between the fibres of the filler would be lesser than when using fillers or pigments with an average particle size of less than 5 micrometres.
- the present invention thus relates to a fibre product that contains pulp fibre or wood fibre, the product preferably being paper or board, and to the manufacturing method of this product, wherein filler particles are attached between the pulp or wood fibres and to the fibrils, after which the said paper or board is produced from the pulp.
- the fibre product that contains pulp fibre or wood fibre is such that filler particles are attached between the fibres and to the fibrils, part of them having chemically structured kaolin agglomerates or granules, and part having carbonate.
- the manufacturing method of the fibre product includes adding an oxide or hydroxide to an aqueous solution to form a hydroxide slurry, and reducing the pH of the solution to a range of 6.0-8.3 by conveying carbon dioxide to the solution so that the content of the salts of carbonic acid formed from the carbon dioxide and the hydroxide slurry is at least 0.01%, calculated from the total weight of the solid matter of the solution, whereby a salt composition is formed; suspending kaolin sheets or stacks or both in water together with a binder, whereby a kaolin composition is formed; producing kaolin drops in a spray drier from the kaolin composition, which is formed from the kaolin sheets or stacks or both and contains the binder, whereby excess water also evaporates, whereby structured kaolin particles are formed, or forming these structured kaolin particles by means of a mixing technique from the kaolin sheets or stacks or both, which are in the form of the slurry in the salt composition described above or its dissolved portion, with the bin
- the present invention is multifunctional and it improves various properties: the quality properties of paper and board and the economic activity of the manufacturing process.
- the invention makes it possible, among others, to improve the brightness, opacity, and printability; at the same time, the dewatering can be accelerated and the retention improved in the wire section.
- An additional advantage of the use of kaolin also comprises the effect of further improving the stiffness, opacity, brightness, and printability that are given to the fibre structure by the precipitated carbonate filler. At the same time, part of the fibre of the end product is now replaced with the filler without weakening the strength properties.
- the present invention relates to a fibre product that contains pulp fibre or wood fibre, wherein filler particles are attached between the fibres and to the fibrils, part of the particles consisting of structured agglomerates or granules of kaolin, metakaolin or calcined kaolin, and part consisting of the salts or esters of carbonic acid or a combination thereof, preferably the various states of carbonate.
- This invention proves that when the aqueous salt composition is used in the manufacture of structured kaolin slurry and when the pH of the paper or board pulp that is diluted with this composition is increased with an alkali and/or the temperature is increased, possibly simultaneously with increasing the solid matter content of the pulp, a carbonate filler can be precipitated to the paper or board structure.
- This precipitated carbonate filler has a positive effect on the brightness, opacity, printability (the absorption properties of the ink), thickness, and stiffness of the paper or board product.
- the product can contain as much as 25% by weight of structured kaolin particles from the dry matter, at least 5% by weight from the fibre. They are essentially spherical in shape and have a size of >5 ⁇ m, preferably 10-40 ⁇ m, more preferably 20-40 ⁇ m. They consist of chemically structured kaolin agglomerates or granules, which are optionally processed so that a part thereof, preferably the surface, is calcined or changed into metakaolin.
- the kaolin of the filler is preferably delaminated, water-washed, dry-classified, or treated by means of two or more of the said treating methods.
- the amount of carbonate in the product is at least 0.01% by weight from the dry matter, for example 0.01-5% by weight, particularly 0.01-3% by weight.
- the salts of carbonic acid comprise carbonate or bicarbonate salts, preferably bicarbonate and colloidal carbonate. They may have an average particle size of ⁇ 0.3 nm, most suitably ⁇ 0.1 nm.
- Colloidal carbonate particles in the present application refer to carbonates that have a small average particle size of less than 300 nm, preferably less than 100 nm.
- the salts or esters of carbonic acid are preferably made of a corresponding oxide or hydroxide and they consist of an inorganic or organic salt or a composite or mixture of several salts, most preferably calcium salt or magnesium salt or a mixture thereof
- the filler particles are attached to each other and to the fibres by a binder, which is preferably latex, silicon dioxide, alum or aldehyde or a mixture thereof, most preferably in an amount of 0.5-50% by weight.
- a binder which is preferably latex, silicon dioxide, alum or aldehyde or a mixture thereof, most preferably in an amount of 0.5-50% by weight.
- the product can further contain other retention agents or flocculating or coagulating microparticles or a mixture thereof, preferably at least microparticles, most preferably together with conventional retention agents.
- Natural polymers are generally called polysaccharides. Examples of these include starch, which is the most commonly used natural polymer in the manufacture of paper and board, if fibres are not taken into account.
- synthetic polymers polyacrylamides should be mentioned. Polymer, in particular, is selected from a group of polyacrylamide, polyethyleneimine, starch, polydadmac, polyacrylamide, polyamine, starch-based coagulant, any copolymer of the above or a mixture of two or more such polymers or copolymers. The polymer is most preferably polydadmac, polyamine, polyacrylamide or the copolymer of two or more of these.
- microparticles are preferably used together with these polymeric retention agents to improve the dewatering, retention, and formation.
- colloidal silicon dioxide polysilicic acid, silicon dioxide sol, microgel, etc.
- bentonite are especially well-suited to this purpose.
- Other alternatives include other sols, gels, microgels, silicic acids, and polysilicic acids or mixtures thereof that contain bentonites or silicon dioxides.
- the product can also contain one or more chemicals known as such, which are selected from a group of aluminium compounds, stock sizes, surface sizes, antislime agents, colouring agents, starches, optical brighteners, dispersing agents, anti-foam agents, plastic pigments, and conventional fillers and coating materials.
- chemicals known as such are selected from a group of aluminium compounds, stock sizes, surface sizes, antislime agents, colouring agents, starches, optical brighteners, dispersing agents, anti-foam agents, plastic pigments, and conventional fillers and coating materials.
- the present invention also relates to the manufacturing method of such a fibre product, wherein
- the solid matter of the paper or board pulp is diluted with the kaolin composition that is suspended in the salt composition, according to the invention.
- the salt composition consists of the states of carbonate, i.e., carbonates and bicarbonates, and calcium or magnesium ions or a mixture thereof, which are added to and produced in the aqueous solution at a pH that remains below 8.3 throughout the production state.
- states of carbonate can include, among others, colloidal-size carbonate partices, bicarbonate ions, carbonate ions and carbonic acid, which are formed in the aqueous solution, when the pH is below 8.3.
- slurry of structured kaolin is added to a salt composition similar to the one described above, at the manufacturing stage of the paper or board product that is before the headbox of the paper machine, or the structured particles are formed in this salt composition.
- the slurry of structured kaolin is very useful, for example, in accelerating the dewatering and improving the retention in the wire section of the paper machine.
- carbonate in the drying of paper or board, carbonate can be precipitated to the fibre structure from the salt composition, the carbonate enhancing the light scattering efficiency of kaolin, whereby the opacity and brightness increase, while the total amount of filler remains the same.
- carbonate can be precipitated either by increasing the pH (e.g, by using an alkali) or by increasing the pressure in the wire, press, and dryer sections. It is essential, however, to try to keep the pH of the paper or board manufacture on the acidic side in the long and short cycles.
- Kaolin slurries in aqueous solutions are naturally acidic, whereas calcium carbonate and talc slurries are alkaline.
- pH of the circulation water is to be increased by increasing the temperature or pressure, or by increasing the pH by adding alkali, this is not carried out before the headbox or the wire section of the paper or board machine.
- Said “aqueous solution” can be any watery solution.
- this aqueous solution is raw water, chemically or mechanically purified water, wire water, filtered water that is purified to various degrees of purity, or another kind of water used in the paper factory, or a mixture thereof, preferably filtered water or process water, from which the solid matter is separated or has been separated.
- the said aqueous solution employed consists of chemical pulp (sulphate or sulphite pulp), mechanical or chemi-mechanical pulp, pulp manufactured by means of alkalis, recycled fibre, deinked pulp (purified by washing or flotation), nano-cellulose, coated reject, uncoated reject or a mixture thereof
- paper pulp is first manufactured from the aqueous solution, the solid matter of the paper pulp being mixed with the solution in the paper pulp, whereafter the stages of the method mentioned above are carried out.
- the “salt composition” thus contains salts of carbonic acid.
- the salt composition preferably consists of the carbonates or bicarbonates of magnesium or calcium or a mixture thereof, and it is preferably manufactured by adding the slurry of oxide or hydroxide to the aqueous solution and by conveying carbon dioxide to the solution, so that the pH in the aqueous solution remains essentially below 8.3 throughout this stage, whereby bicarbonate and colloidal carbonate are formed, their average particle size being ⁇ 0.3 nm, most preferably ⁇ 0.1 nm.
- the aim is usually to keep the pH of the white water system within 6-8.
- the chemistry of carbonate ions and the buffering of pH provided by the same are then utilized.
- soluble carbon dioxide (CO 2 ) and, to a minor extent, carbonic acid (H 2 CO 3 ), are the main states of carbonate.
- bicarbonate or hydrocarbonate (HCO 3 ⁇ ) is the main state of carbonate all the way to a pH of 10. “Main” means that at least 50% by weight of the states comprise carbonate.
- carbonate (CO 3 2 ⁇ ) is the main state.
- the pH of 6-8, bicarbonate (HCO 3 ⁇ ) is thus the prevailing state.
- “Structured kaolin particles” are produced from the kaolin sheets or stacks of the kaolin composition, which are possible further processed, so that at least part of the kaolin, preferably of its surface, is converted into metakaolin or calcined kaolin.
- the granules or agglomerates of structured kaolin are manufactured by spray-drying the kaolin slurry by means of a binder.
- a rotating atomizer, discharge nozzles, a double-fluid nozzle, ultrasound or a combination of the foregoing can be used.
- Metakaolin or calcined kaolin can be manufactured from these granules or agglomerates by heating, in a furnace, the spray-dried kaolin granules or agglomerates or those that are manufactured by means of the binder using the mixing technique.
- “structured” kaolin i.e., spray-drying
- raw materials other than kaolin can also be used.
- the binder for example, calcium carbonate, titanium dioxide, talc or silicon dioxide or several substances, among others, can be added to the kaolin slurry that is manufactured in the aqueous solution, before manufacturing the granules or agglomerates.
- the “fibre dispersion” contains a source of fibre, binder, and the salt composition mentioned above.
- the fibres can consist of chemical pulp or mechanical pulp.
- CMP chemi-mechanical pulp
- TMP thermomechanical pulp
- PGW pressure groundwood
- the binder has settled on the surfaces of the formed kaolin particles, and it functions by binding the particles to each other and, particularly, by binding the particles to the fibres.
- Flocculants, coagulants or microparticles or a mixture or a copolymer thereof can be added, as a retention agent, to the aqueous solution or the fibre dispersion, in an amount of at least 0.01%, particularly about 0.01-3%, calculated from the total weight of the solid matter of the solution or dispersion, preferably at least microparticles, most preferably together with conventional flocculants or coagulants.
- One or more chemicals known as such can also be added to the fibre dispersion, the chemicals being selected from a group of aluminium compounds, stock sizes, surface sizes, colouring agents, starches, optical brighteners, plastic pigments, natural and synthetic polymers, and fillers and coating materials.
- the bicarbonate ions contained in the salt composition or mixed with the fibre dispersion can be converted into carbonate particles.
- carbon dioxide is released and the bicarbonate reacts with free calcium or magnesium ions according to the following reaction equation:
- the carbonate particles can be precipitated according to the following reaction equations:
- the carbonate particles thus formed fit between the fibrils and fibre, keeping the fibrils in their outward-oriented positions and giving the structure of the paper or board opacity, brightness, stiffness, and thickness (bulkiness).
- the carbonates on the surface of the paper or board improve the adsorption of the printing ink.
- Part of the precipitated carbonate is also inside the lumens and pores of the fibres.
- Structured kaolin in turn, fills the holes that remain between the fibres of the fibre network, whereby the strength and stiffness are reduced less than when using, e.g., pure fillers with an average particle size of 3 micrometres or less.
- the dispersion formed from these ingredients is then mixed to form the pulp, which at the last stage of the method according to the invention is filtered, pressed, and dried into the paper or board product.
- openings of about 10 micrometers remain between the fibres.
- the salt composition which hereinafter is called acidic water (below, also “AW”), was made in ion-exchanged water.
- AW acidic water
- 25 kg of ion-exchanged water were weighed into each one of closable plastic cans (of a volume of 30 litres).
- 170 g of burnt lime (CaO) were added thereto, having been slaked in 600 g of ion-exchanged water at 45° C. before the addition.
- By adding carbon dioxide to the weak calcium hydroxide slurry thus formed, Ca(OH) 2 the pH was dropped from about 12 to 6.3. This solution was allowed to sediment for 12 hours, after which the colloidal portion that had not sedimented was separated from the can. The precipitate that sedimented on the bottom was not used in the tests.
- Dry Covergloss (Kamin LLC) kaolin powder was suspended in ion-exchanged water to a dry matter content of 20%.
- 0.2% of the Dispex N40 (BASF) dispersing agent and 8% of latex (Acronal S505, BASF) were used, calculated from the weight of the kaolin.
- the suspension was spray-dried (Niro, mobile minor).
- the feed rate of the suspension was 50 ml/min
- the rotation speed of the atomizer was about 25 000 rotations per minute
- the temperature of the drying air was 250° C.
- the temperature of the output air was 110° C.
- the dried, structured kaolin (below, “struc”) was cooled to room temperature and suspended in acidic water into slurry of 20%.
- the average particle size of the structured kaolin thus manufactured (struc+AW) was 15 micrometres (Sedigraph 5120, Micromeritics).
- a Valley grinder was used to first grind a mixture of bleached pine pulp and bleached birch pulp to an SR number of 30.
- the amount of pine pulp from the weight of the pulp was 30% and that of birch pulp was 70%.
- the pulp was ground according to the standard method SCAN-C 25:76.
- This pulp was diluted with the ion-exchanged water according to the invention to a consistency of 0.2%, to which 0, 20 or 40%, calculated from dry pulp, of the 20% slurry of structured kaolin and acidic water (struc+AW) manufactured according to the previous example were added.
- struc+AW structured kaolin and acidic water
- pulps diluted to 0.2% with pure ion-exchanged water were manufactured, to which 0, 20 or 40% of precipitated calcium carbonate, calculated from dry pulp, (PCC, Precarb FS-240, Shaefer Finland Oy), Covergloss (Kamin LLC) or Alphatex (Imerys) were added. From all of these, a 20% slurry was made in ion-exchanged water before adding it to the pulp.
- the test points are called struc+AW, struc, PCC, Covergloss, and Alphatex.
- the basis weights of the sheets were at the target basis weight of 80 g/m 2 , with an accuracy of ⁇ 0.6 g/m 2 .
- the assessment of the printing properties of the sheets was made by measuring the optical density.
- the sheets were printed by a Universal Testprinter (Testprint B.V.) using a Cold set black (Sun Chemical, viscosity 7.3 Pas) with 10 milligrammes of ink on the wire side of the sheet.
- the optical densities were measured using a densitometer (Macbeth) from aerated and dried samples after 24 hours from the printing.
- the Universal testprinter employed a pressure of 630 N and a velocity of 1 m/s.
- the results are linearly normalized to the same filler content of 10%.
- a reliability of 95% means a confidence interval of 95%.
- dry Intrafil C (Imerys), which is conventional kaolin, is suspended in acidic water or ion-exchanged water to a dry matter content of 20%.
- the acidic water used is made as in example 1.
- the Valley grinder was used to first grind a mixture of bleached pine pulp and bleached birch pulp to an SR number of 35.
- the amount of pine pulp from the weight of the pulp was 30% and that of birch pulp was 70%.
- the pulp was ground according to the standard method SCAN-C 25:76. This pulp was diluted to a consistency of 0.2%, to which Intrafil C (Intra) that was suspended in 0, 20 or 40% of ion-exchanged water or Intrafil C (Intra+AW) that was suspended in acidic water was added.
- the opacity and brightness in particular, do not improve as much with conventional kaolin as with structured kaolin.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FI20106168 | 2010-11-05 | ||
FI20106168A FI123224B (fi) | 2010-11-05 | 2010-11-05 | Kuitutuote ja menetelmä sen valmistamiseksi |
PCT/FI2011/050975 WO2012059650A2 (en) | 2010-11-05 | 2011-11-04 | Process for manufacturing paper and board |
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US20130199745A1 true US20130199745A1 (en) | 2013-08-08 |
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US13/822,777 Abandoned US20130199745A1 (en) | 2010-11-05 | 2011-11-04 | Process for manufacturing paper and board |
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US (1) | US20130199745A1 (fi) |
EP (1) | EP2635739A2 (fi) |
CN (1) | CN103221609A (fi) |
AU (1) | AU2011325010A1 (fi) |
CA (1) | CA2814025A1 (fi) |
FI (1) | FI123224B (fi) |
RU (1) | RU2013123906A (fi) |
WO (1) | WO2012059650A2 (fi) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130062028A1 (en) * | 2010-04-22 | 2013-03-14 | Nordkalk Oy Ab | Use of acidic water in the manufacture of paper |
US20130112360A1 (en) * | 2010-06-03 | 2013-05-09 | Nordkalk Oy Ab | Process for manufacturing paper or board |
US9718980B2 (en) | 2012-08-14 | 2017-08-01 | Goldeast Paper (Jiangsu) Co., Ltd | Coating composition and coated paper |
US10214859B2 (en) | 2016-04-05 | 2019-02-26 | Fiberlean Technologies Limited | Paper and paperboard products |
US11846072B2 (en) | 2016-04-05 | 2023-12-19 | Fiberlean Technologies Limited | Process of making paper and paperboard products |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FI123224B (fi) * | 2010-11-05 | 2012-12-31 | Nordkalk Oy Ab | Kuitutuote ja menetelmä sen valmistamiseksi |
CZ29098U1 (cs) * | 2014-12-17 | 2016-02-01 | Univerzita PalackĂ©ho v Olomouci | Kompozitní planární materiál na bázi celulózy |
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- 2011-11-04 CN CN2011800534446A patent/CN103221609A/zh active Pending
- 2011-11-04 EP EP11826171.8A patent/EP2635739A2/en not_active Withdrawn
- 2011-11-04 CA CA2814025A patent/CA2814025A1/en not_active Abandoned
- 2011-11-04 WO PCT/FI2011/050975 patent/WO2012059650A2/en active Application Filing
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US20130062028A1 (en) * | 2010-04-22 | 2013-03-14 | Nordkalk Oy Ab | Use of acidic water in the manufacture of paper |
US8906201B2 (en) * | 2010-04-22 | 2014-12-09 | Nordkalk Oy Ab | Use of acidic water in the manufacture of paper |
US20130112360A1 (en) * | 2010-06-03 | 2013-05-09 | Nordkalk Oy Ab | Process for manufacturing paper or board |
US8758566B2 (en) * | 2010-06-03 | 2014-06-24 | Nordkalk Oy Ab | Process for manufacturing paper or board |
US9718980B2 (en) | 2012-08-14 | 2017-08-01 | Goldeast Paper (Jiangsu) Co., Ltd | Coating composition and coated paper |
US10214859B2 (en) | 2016-04-05 | 2019-02-26 | Fiberlean Technologies Limited | Paper and paperboard products |
US11274399B2 (en) | 2016-04-05 | 2022-03-15 | Fiberlean Technologies Limited | Paper and paperboard products |
US11732421B2 (en) | 2016-04-05 | 2023-08-22 | Fiberlean Technologies Limited | Method of making paper or board products |
US11846072B2 (en) | 2016-04-05 | 2023-12-19 | Fiberlean Technologies Limited | Process of making paper and paperboard products |
US12203223B2 (en) | 2016-04-05 | 2025-01-21 | Fiberlean Technologies, Ltd. | Method of making paper or board products |
Also Published As
Publication number | Publication date |
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WO2012059650A2 (en) | 2012-05-10 |
WO2012059650A3 (en) | 2012-09-07 |
CA2814025A1 (en) | 2012-05-10 |
EP2635739A2 (en) | 2013-09-11 |
FI20106168A (fi) | 2012-05-06 |
CN103221609A (zh) | 2013-07-24 |
FI20106168L (fi) | 2012-05-06 |
FI20106168A0 (fi) | 2010-11-05 |
AU2011325010A1 (en) | 2013-05-09 |
RU2013123906A (ru) | 2014-12-10 |
FI123224B (fi) | 2012-12-31 |
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