CN1510212A - Modified pulp material, high-ash pulp board prepared from modified pulp material and preparation method - Google Patents
Modified pulp material, high-ash pulp board prepared from modified pulp material and preparation method Download PDFInfo
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- CN1510212A CN1510212A CNA021597715A CN02159771A CN1510212A CN 1510212 A CN1510212 A CN 1510212A CN A021597715 A CNA021597715 A CN A021597715A CN 02159771 A CN02159771 A CN 02159771A CN 1510212 A CN1510212 A CN 1510212A
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000835 fiber Substances 0.000 claims abstract description 117
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 73
- 239000011707 mineral Substances 0.000 claims abstract description 72
- 239000003607 modifier Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000010902 straw Substances 0.000 claims abstract description 8
- 239000011121 hardwood Substances 0.000 claims abstract description 7
- 239000011122 softwood Substances 0.000 claims abstract description 7
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 6
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 6
- 235000010755 mineral Nutrition 0.000 claims description 64
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 43
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 229920001131 Pulp (paper) Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000395 magnesium oxide Substances 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 18
- 235000012255 calcium oxide Nutrition 0.000 claims description 18
- 235000012241 calcium silicate Nutrition 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 15
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 15
- 229920002472 Starch Polymers 0.000 claims description 14
- 229910000278 bentonite Inorganic materials 0.000 claims description 14
- 239000008107 starch Substances 0.000 claims description 14
- 235000019698 starch Nutrition 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000000440 bentonite Substances 0.000 claims description 13
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002401 polyacrylamide Polymers 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000010434 nepheline Substances 0.000 claims description 8
- 229910052664 nepheline Inorganic materials 0.000 claims description 8
- 239000010435 syenite Substances 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 7
- 238000010009 beating Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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 description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 3
- 239000011505 plaster Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 210000004209 hair Anatomy 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229920001410 Microfiber Polymers 0.000 abstract 4
- 239000003658 microfiber Substances 0.000 abstract 4
- 239000011882 ultra-fine particle Substances 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract 1
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 229910001653 ettringite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- 235000005205 Pinus Nutrition 0.000 description 5
- 241000218602 Pinus <genus> Species 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
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- 238000004061 bleaching Methods 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- 239000011087 paperboard Substances 0.000 description 4
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
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- JHXCINJSAAFBDH-UHFFFAOYSA-N [Ca].O[Si](O)(O)O Chemical compound [Ca].O[Si](O)(O)O JHXCINJSAAFBDH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
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- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
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Abstract
Disclosed is a high-ash pulp sheet, which comprises softwood pulp as long fiber, hardwood pulp or straw pulp or recycled pulp as medium long fiber, mineral microfiber, artificial mineral microfiber as short fiber and mineral ultrafine particle, wherein the various fibers are interwoven into a net structure, and the artificial mineral microfiber and the mineral ultrafine particle are adhered to the surfaces of the long fiber, the medium long fiber and the mineral microfiber. The high ash pulp board is made of a modified pulp material, which comprises softwood pulp as long fiber, hardwood pulp or straw pulp or recycled pulp as medium long fiber, mineral superfine fiber and modifier. The chemical composition of the modifier is as follows: 9-13 weight portionsSiO powder26-9 weight of Al2O31-3 parts of MgO, 12-16 parts of CaO and 27-34 parts of SO4 2－10-14 parts by weight of H2O+11-21 parts by weight of H2O－Wherein the composition further contains Na2O，K2O and Fe2O3The total amount of the modifier is less than 3.5 percent of the total weight of the modifier, and the main crystal phases of the modifier are fibrous ettringite, xonotlite, magnesium silicate and magnesium aluminum silicate.
Description
Technical field
The present invention relates to the paper pulp material through modification, the ash-rich pulpboard that makes with this material, and the preparation method of this ash-rich pulpboard.
Background technology
It is resource scarcity and environmental protection day by day that the mankind face the biggest problem in 21 century.The required wood pulp of tradition pulpboard is from timber, through peeling, chip, operations such as boiling, washing, bleaching, making beating, consume a large amount of timber on the one hand, can produce a large amount of pollutants such as black liquor on the other hand in pulping process, both all produce heavy damage to ecological, environment.Along with the wood pulp price goes up and under-supply gradually significantly, handle these pulping waste liquors and government to the requirement of ecological aspect especially increase cost again.As a result, paper industry and consumer are faced with two alternatives: or pay expensively, or reduce the quality and quantity of fiber in the pulpboard and cardboard quality that final production is gone out descends.
Paper-making industry has been carried out many trials and has been reduced production costs.A kind of method that has adopted is to add talcum, calcium carbonate, kaolinite and other mineral-filled things to replace fiber in paper-making process, but have been found that these charges volume of holding in pulpboard surpasses at 15% o'clock and the characteristics such as intensity of cardboard can be reduced to the degree that the people can not be satisfied with, and the confining force of this mineral-filled thing in pulpboard is very poor, its actual retention only 30～40%, 60～70% mineral-filled thing runs off with plain boiled water, and deposition is got up in plain boiled water, and the result makes the treatment and purification of white water and waste disposal become serious problems.
Adopted multiple flocculating agent, develop according to Kano Bel's paper chemistry company as Sweden, use cationic starch and colloid silicon to be called the Compozil system, allied colloid is developed the microparticle retention aid of being made up of polyacrylamide and clay, be called the Hydrocol system and solve the confining force problem, but the result of use of these reagent can not allow the people satisfied fully.In the heavu weights plate, solve the confining force of filler, it is not difficult matter, difficult point is that height adds the amount of filling out and not only high confining force (75～85%) arranged but also can satisfy and make every index of the pulpboard of producing reach related standards, especially the tensile strength of pulpboard, next is that height adds the filler of the amount of filling out and the lamination problem of paper pulp, drainability and technical barrier such as repeatedly multiplexing when pulpboard evenness problem, last net forming.
Summary of the invention
An object of the present invention is to provide a kind of ash-rich pulpboard, this pulpboard has the microstructure of improvement, and its every index satisfies related standards, and some indexs also obtain optimizing.
Another object of the present invention provides a kind of method of making the ash-rich pulpboard.
A further object of the invention provides a kind of paper pulp material through modification, and this paper pulp material can be improved the microstructure of pulpboard, can use less fiber to obtain required intensity.This paper pulp material can be added in the paper pulp and keep 75～85% retention with 30～70% the amount of filling out that adds in paper-making process, and the every index that makes pulpboard satisfies related standards, and some indexs also obtain optimizing.
Further object of the present invention provides the application of paper pulp material in manufacturing ash-rich pulpboard through modification.
Term used herein " microstructure " means between observed fibre morphology under light microscope or the electron microscope, surface characteristics, fiber and fiber between connecting relation, fiber and the charges and connects etc.
The invention provides a kind of ash-rich and the pulpboard of higher-strength is arranged, its microstructure is that softwood pulp (comprising not bleached pulp) is made long fiber, and hardwood pulp or straw pulp or recycled pulp are done medium-length fibre, mineral superfine fibre and man-made mineral fiber and made staple fibre and the common network structure of forming of the sticking connection of superfine powder agent.
Described mineral superfine fibre can be selected from natural calcium metasilicate, the draw ratio of fiber＞10.
Described man-made mineral fiber can select entringite, its draw ratio＞15, particle diameter＜1.0 μ m.
Described fine mineral particulate is meant and is selected from bentonite one magnesia colloidal sol, organic silicon sol, and organobentonite and magnesium silicate, fine mineral particulates such as eakleite, its diameter of particle is in the nano material of 1.0nm-1000nm.
Described man-made mineral fiber's entringite, eakleite, magnesium silicate, bentonite one magnesia colloidal sol, organic silicon sol etc. are the modifier materials of paper fiber and mineral superfine fibre.
In the ash-rich pulpboard, also at least a mineral that are selected from fibrous plaster, eakleite, diatomite and the serpentine can be used for replacing fiber.
The invention provides the nano modifier of a kind of paper fiber and mineral superfine fibre, the main chemical composition of described nano modifier is: 9-13 weight portion SiO
2, 6-9 weight Al
2O
3, 1-3 weight portion MgO, 12-16 weight portion CaO, 27-34 weight portion SO
4 2-, 10-14 weight portion H
2O
+, 11-21 weight portion H
2O
-
Described modifier also contains Na
2O, K
2O and Fe
2O
3Its gross weight is less than 3.5% of the modifier total amount.
The invention provides a kind of raw material of making paper fiber and mineral superfine fibre modifier, this raw material comprises (i) aluminium hydroxide or calcined kaolin or nepheline syenite powder, (ii) sulfuric acid, (iii) quick lime, (iv) light calcined magnesia, (the v) heavy powder of CATION, (vi) bentonite, (vii) polyacrylamide, (viii) water etc.
The invention provides a kind of manufacture method of modifier material, it is characterized in that in turn including the following steps:
(1), adds in the sulfuric acid solution and carry out acidolysis, filter cleaner to aluminium hydroxide or calcined kaolin or nepheline syenite powder;
(2) slowly add the ultra-fine emulsion that quick lime is made in the acidolysis solution after removing residue, carry out metathesis reaction, impel the generation of fibrous entringite and eakleite;
(3) the light calcined magnesia emulsion is added in the reactant of step (2), impel the generation of ultra micro magnesium silicate;
(4) emulsion after the slaking of adding cationic starch in step (3) is impelled the formation of organic silicon sol.Described slaking is cationic starch to be added water to make concentration be 3% emulsion, is boiled into pasty state in 80～95 ℃, and then thin up to concentration is 1%.
(5) in step (4), add the bentonite emulsion, impel the generation of bentonite-magnesia colloidal sol body;
(6) in step (5), add the polyacrylamide weak solution, impel bentonite to generate.
(7) with the formation thing of step 2～6, stirred 0.5 hour on 60～70 ℃, be incubated 0.5 hour the liquid modifying agent material, or with its concentrate, dry, be broken to 300 orders, get the Powdered modifier material of white solid.
The invention provides pulp modifying material, mainly by (i) natural calcium metasilicate, artificial fibre minerals calcium aluminite and (iii) (iv) cationic starch-silicon dioxide gel body (v) composition of forming such as bentonite-magnesia colloidal sol and polyacrylamide of eakleite.The chemical composition of said composition: 44-47 weight portion SiO
2, 1-2 weight portion Al
2O
3, 40-42 weight portion CaO, 0.6-0.8 weight portion MgO, 4-7.5 weight portion SO
4 2-, 1.5-2.5 weight portion H
2O
+, 4-6 weight portion H
2O
-Said composition also contains Na
2O, K
2O, Fe
2O
3Its gross weight is less than 2.5% of whole composition total weight, wherein Fe
2O
3Be the impurity that raw material brings.
The invention provides a kind of method of mineral superfine fibre modification, this method comprises:
Superfine fibre shape mineral are broken to the 100-325 order in advance;
Nano modifier is broken to the 100-325 order in advance;
Above-mentioned powder is mixed and further be crushed to 5-15 μ m, adds 4 times to the water of the suitable paper grade (stock) of powder, 20% white slurry is made concentration and is in sufficient stirring under 40-50 ℃ of temperature.
The present invention also provides the application of paper pulp material in papermaking through modification.
The present invention also provides and has comprised the paper products of the present invention through the modified pulp material, sole paperboard for example, ash end ivory board, the extraordinary pulpboard that filters, ash-rich true qualities pulpboard and bleaching pulpboard etc.
Pulp modifying material of the present invention can add the amount of filling out with the height of 40-70% and be added in the paper and remain on that the actual volume of holding reaches 75-85% in the paper fiber, makes every index of cardboard satisfy related standards simultaneously, and some indexs are optimized.This pulp modifying super-fine fiber material has certain purifying water effect, adds under the condition of filling out the still good drainability of tool at height, and helps the dehydration drying, saves the energy.This material is suitable for various paper kinds, especially is particularly suitable for the extraordinary pulpboard that filters of ash-rich packing board, and its application need not existing paper making equipment and technology are made big adjustment.The cost of pulp modifying material of the present invention is lower in addition, repeatedly still can make during regeneration the modified mineral superfine fibre in the sole plales can be among the paper product that utilizes again with the 75-85% retention, and easily discongest the making beating and be dispersed in the paper fiber, do not still have retention more than 70%, and have no side effect with retention agent.Preparation pulp modifying material method is simple, and does not have the three wastes (waste residue, waste water, waste gas), and production and safe in utilization is reliable.
Description of drawings
Below in conjunction with several embodiment and relevant accompanying drawing, describe the present invention in detail.
Fig. 1 shows the production procedure of pulpboard.
Fig. 2 a is the electron micrograph of inferior nanometer of the present invention, nano modifier;
Fig. 2 b is the electron micrograph after modifier dehydration of the present invention is solidified;
Fig. 2 c is the electron micrograph of the present invention through the natural calcium metasilicate superfine fibre of modification;
Fig. 2 d be of the present invention through modified pulp with combine through modified natural calcium metasilicate superfine fibre after, become the electron micrograph of paper ash part;
The electron micrograph of Fig. 2 e show of the present invention through modified pulp with combine feature through modified natural calcium metasilicate superfine fibre;
The electron micrograph of Fig. 2 f show the present invention through modified pulp with combine feature through modified natural calcium metasilicate, talcum, calcium carbonate.
Fig. 3 be pulp modifying material of the present invention add the amount of filling out and the dynamic characteristic that becomes paper ash part, paper strength
Fig. 4 a is the x x ray diffraction collection of illustrative plates of modifier of the present invention;
Fig. 4 b is the x x ray diffraction collection of illustrative plates of the present invention through the natural calcium metasilicate superfine fibre of modification;
Fig. 4 c is a modified pulp of the present invention and x x ray diffraction collection of illustrative plates after modified natural calcium metasilicate superfine fibre combines.
The specific embodiment
General pulpboard mainly is made up of wood pulp fibre, its mechanical strength, as fracture length and tearability etc., the physical property (tensile strength of single fiber) that depends on the fiber that constitutes paper, chemical property is the geometry grating (mode of taking of long and short fiber of surface chemical property (adhesion between fiber and the fiber) and fiber especially, the length of fiber, diameter, draw ratio, fiber surface form, straight and branch brooming etc.) and the uniformity of surfing the Net into paper.In general, paper basis weight is big more, when copying paper, the online concentration also big, the online concentration big, paper-forming evenness is poor, its mechanical strength variation, in addition between paper fiber and the paper fiber because of electric exclusion, its adhesion is very little, is difficult to bring into play the inherent strength characteristic of paper fiber.Therefore in pulpboard, add and fill out unmodified common papermaking filler such as talcum, kaolin, calcium carbonate ... wait and replace fiber, height to add the amount of filling out and pulpboard ash＞30% and every index satisfies related standards is difficult.
The present invention starts with from the microstructure of improving pulpboard just, has solved all difficulties of making the ash-rich pulpboard.Fig. 2 e and Fig. 2 f have shown the microstructure of pulpboard of the present invention respectively.The microstructure of tradition pulpboard, the normally network structure that constitutes by the whole wood pulp fiber.Can clearly find out by Fig. 2 e and Fig. 2 f, pulpboard of the present invention is to make long fiber by the needle slurry, broad-leaved slurry or straw pulp or orchid make medium-length fibre and mineral superfine fibre and synthetic paper dimension by slurry and make the common network structure of forming rational paper or cardboard of staple fibre, so cardboard or paper product have higher-strength.From photo, can also know the bentonite one magnesia colloidal sol of seeing in material modified, silica one sun forms strong bonded from starch colloidal sol with paper fiber and fine mineral fiber, when dehydration is solidified, they are bonded together, and spontaneously grow the network structure that fluffy elongated fibrous whisker is further optimized pulpboard or paper product, make the pulpboard produced or paper product that high ash (＞30%) be arranged and the pulpboard or the paper product of higher-strength are arranged.Can also see from Fig. 2 c and 2d and Fig. 2 e and 2f that again the mineral superfine fibre of modification is evenly distributed on the paper fiber or in the space between the fiber very much, and the network structure of an even structure of mutual bonding formation further improves the tensile property of slurry.
Can also know from Fig. 2 a and 2b and to find out that the modifier of paper making raw material (comprising paper fiber and fine mineral fiber) is a kind of nano material, particle diameter is between 1～100nm.As everyone knows, the principal character of nano material, be that its diameter of particle is minimum, surface area is very big, adsorptivity is strong, and cation exchange capacity (CEC) is big, and electrically charged, charge property changes with the type and the condition of exchangeable cations in the system, as long as some ion of increase and decrease can make all substances in the participation system (paper fiber and fine mineral fiber and secondary mineral) realize the charge balance under this condition in prescription.Keep stable chemical bond combination, give full play to the durability of its strength characteristics and pulpboard.
The x x ray diffraction analysis x figure of Fig. 4 a-4c shows that modifier of the present invention is the cryptocrystalline mineral microparticle that can make X ray generation diffraction.
According to the complete chemical analysis of modifier, in conjunction with the x ray analysis, described cryptocrystalline mineral microparticle mainly is by (i) entringite, (ii) eakleite, (iii) Magnesiumaluminumsilicate (SM gel) MgAl
2SiO
6Deng mineral composition.
Fig. 3 shows: when adopting this pulp modifying material in paper-making process, the paper of being produced is compared than the paper that adopts other flocculating agents to produce, and has the characteristic of obvious raising intensity, can maximize the confining force of mineral charges in the paper simultaneously.Make ash＞30% of the pulpboard of producing, and higher-strength is arranged and satisfy the relevant standard of pulp board.Paper of producing by pulp modifying material provided by the invention or cardboard can add the amount of filling out with 30～60%, keep the retention more than 80% and keep the characteristic of higher intensity.
Below describe the manufacture method of ash-rich pulpboard of the present invention in detail.The pulpboard technological process of production is as follows:
Slurry → interpolation modified mineral superfine fibre → copy paper of pulling an oar → join
At first according to containing long stapled softwood pulp and containing the hardwood pulp of medium-length fibre or straw pulp or recycled pulp are joined slurry.In this embodiment, adopt 60～70% softwood pulp, the hardwood pulp of 30～40% medium-length fibres and waste stuff make it the reasonably rational gradation composition of long and short fiber.
Manufacture method according to ash-rich pulpboard of the present invention, the distinguishing feature of above-mentioned embodiment is after slurry is joined in making beating, copy before the paper step, in paper pulp, add and contain the material modified of fine mineral fiber and nano modifier making, this paper pulp material modified has this material of following characteristics (i) and is made up of mineral superfine fibre and nanoparticle, wherein＜10 μ m person accounts for 80～90%,＜1.0 μ m persons account for 10～20%, average whiteness 〉=85%, pulpboard or the paper product made after a large amount of (30% or more) joins in the paper pulp still have sufficiently high mechanical strength and 75～85% retentions; (ii) the draw ratio of mineral superfine fibre＞10 can substitute the key material (rather than the filler between the fiber) that the short wood pulp fibre of part becomes cardboard, so the paper product or the pulpboard intensity decreases that form are little; (iii) this material generates a spot of fibrous inorganic mineral entringite (claiming that again thin,tough silk is white), [3CaO, Al in the pulpboard drying course
2O
3Ca (SO
4, CO
3, Cl
2) 32H
2O], and a spot of bentonite one magnesia, the intensity of further increase of the submissive linear molecule of polyacrylamide organobentonite or paper product pulpboard; (iv) this material is mixing with paper pulp and is becoming in the paper process, and nano-mineral is bonded together the unified integral body of formation with paper fiber and mineral superfine fibre, makes pulpboard or the paper product produced that a higher anti-anti-folding and the anti-wear performance (Fig. 2 and Fig. 3) opened be arranged.
Obtaining the present invention, to become paper ash part be the ash-rich pulpboard of 15-60%, just must carry out modification to paper pulp and mineral superfine fibre, and this material that is used for modification is known as modifier.The chemical composition of this modifier is: 9-13 weight portion SiO
2, 6-9 weight Al
2O
3, 1-3 weight portion MgO, 12-16 weight portion CaO, 27-34 weight portion SO
4 2-, 10-14 weight portion H
2O
+, 11-21 weight portion H
2O
-, wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than whole modifier weight 3.5%.
In a kind of preferred embodiment, the material modified chemical composition of mineral superfine fibre is: 44-47 weight portion SiO
2, 1-2 weight portion Al
2O
3, 40-42 weight portion CaO, 0.6-0.8 weight portion MgO, 4-7.5 weight portion SO
4 2-, 1.5～2.5 weight portion H
2O
+, 4-6 weight portion H
2O
-
Also contain Na in the described pulp modifying material
2O, K
2O and Fe
2O
3, its gross weight is less than 2.5% of whole pulp modifying material, wherein Fe
2O
3Be by the impurity that brings in the raw material.
Describe preparation method of pulp modifying material of the present invention and uses thereof below in detail.
At first relevant raw material, selectable content (percentage by weight is represented) and the effect of this raw material in material modified of explanation use.Also exemplified the place of production and the supply and marketing company of these raw materials, but be not limited thereto.
(1) natural calcium metasilicate, 65～80%, whiteness＞85% is in order to make fine mineral fiber, instead of part staple fibre paper pulp.For example there is the Jilin pear tree in the place of production, and is long white, the big wide old man in Jiangxi, Daye, Hubei, ground such as Yunnan Tengchong.For example can be available from the non-gold mine industry in Yunnan company, quality is Q/YNF J SO1-2000 for amount.
(2) diatomite, 2～10%, whiteness＞85% is based on the diatom of straight chain shape, in order to make fine mineral fiber instead of part paper fiber and anti-heavy agent and absorbing heavy metal ions in water.For example there is the Changbai in the place of production, Yunnan pioneer in the middle ten days, Tengchong.For example can be available from Chengdu painted sculptures glue Co., Ltd product.
(3) hair zeolite, 1～5%, whiteness＞80% is in order to make fine mineral fiber and ultrafine dust instead of part paper fiber and Adsorption of Heavy Metal Ions.For example there is the Changbai in the place of production, Jinyun county, Zhejiang province, or for example can be available from Chengdu painted sculptures glue Co., Ltd product.
(4) fibrous plaster, 1～5%, whiteness＞85% is in order to make fine mineral fiber, instead of part paper fiber and the effect of entringite crystallization nucleation.For example there is Yingcheng City, Hubei in the place of production, and the high eyebrow in Sichuan greatly or for example can be available from Hubei yingcheng gypsum Co., Ltd product.
(5) entringite, 5～30% or more, whiteness 〉=90%, mineral fibres is as modifier and the instead of part staple fibre and the absorption Cl of natural fabric shape mineral
-With oxygen acid group, CO
3 2-With heavy metal ion etc.
(6) aluminium hydroxide, 2～5%, whiteness＞90%, the effect of entringite crystallization nucleation.
(7) nepheline syenite, 2～5%, whiteness＞70% is made nano modifier.For example there is the Lin County, Shanxi in the main place of production, Fengcheng City, Liaoning, and Geju City, Yunnan, Yongping, Yangyuan County, Hubei, the Ningnan, Sichuan, areas such as Nan Jiang also are commercially available, for example can be available from Sichuan Chuan Bei silicon stone flour factory.
(8) sulfuric acid, technical grade (98% concentration) 2～5% is in order to decompose nepheline syenite and activation mineral powder surface.For example can be available from chemical plant, bluish white river, Sichuan.
(9) bentonite 1～5%, technical grade, and whiteness 70% in order to make nano modifier, is made inorganic binder.For example can win enlightening bentonite Co., Ltd available from Chengdu.
(10) light calcined magnesia 1～5%, technical grade, whiteness＞80%, bentonitic emulsifying agent, the effect of magnesium silicate crystallization nucleation, the dispersant of filler, retention agent.For example can be available from Dashiqiao, Liaoning rapid development refractory Company.
(11) cationic starch 4～7%, and technical grade is made organic binder bond, reinforcing agent, retention agent.For example can be available from Peng Lai, Sichuan starch additive factory.
(12) polyacrylamide 0.1～0.15%, and technical grade is made flocculant.For example can be available from auxiliary reagent factory, Pengxi, Sichuan.
(13) quick lime 14～17%, technical grade, whiteness＞85%, CaO＞95%, entringite, the effect of eakleite crystallization nucleation.For example can be available from Dujiangyan City, Sichuan magnetic hill Lime Factory.
The preparation method of modifier
The sulfuric acid of adding 1 82 gram concentration 2% or 248 gram concentration are 2% sulfuric acid solution in 1.93 gram aluminium hydroxides or 3.76 gram nepheline syenite powder, stirred 0.5 hour on 80-90 ℃, behind the filter cleaner, adding 29.9 gram concentration is 10% milk of lime, 10 gram concentration are 10% light calcined magnesia emulsion, 2.0 gram bentonite 16.6 gram concentration are 3% cationic starch, on 60-70 ℃ of stirring 20-30 minute, making solid content was the modifier 1 of 17 grams.As be dried, be crushed to 300 orders, get solid modifier.Recording No. 1 modifier chemical composition with international chemical analysis method is: 9.0 weight portion SiO
2, 6.1 weight portion Al
2O
3, 1.0 weight portion MgO, 11.8 weight portion CaO, 26.9 weight portion SO
4 2-, the 10.1 weight portion crystallizations water and 11.0 weight portion adsorbed water (H
2O
-), wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than whole modifier weight 2.8%.
In 2.14 gram aluminium hydroxides or 4.16 gram nepheline syenite powder, add 200 gram concentration and be 2% sulfuric acid solution or 275 gram concentration and be 2% sulfuric acid solution, stirred 0.5 hour on 80-90 ℃, behind the filter cleaner, adding 33 gram concentration is that 10% lime slurry, 15 gram concentration are 10% milk of magnesia, 3.0 gram bentonite, 20 gram concentration are 3% cationic starch emulsion, stirred 20-30 minute on 60-70 ℃, making solid content is No. 2 modifier of 18.8 grams, as be dried, be crushed to 300 orders and promptly get solid modifier.Record the chemical composition of No. 2 modifier with international complete chemical analysis method: 11.1 weight portion SiO
2, 7.4 weight portion Al
2O
3, 2.1 weight portion MgO, 14.1 weight portion CaO, 30.2 weight portion SO
4 2-, the 11.7 weight portion crystallizations water and 21.0 weight portion H
2O
-(adsorbed water) wherein also contains Na
2O, K
2O and Fe
2O
3, its total amount is less than whole modifier weight 3.2%.
Adding 232 gram concentration in 2.48 gram aluminium hydroxides or 4.82 gram nepheline syenite powder is that 2% sulfuric acid solution or 318 gram concentration are 2% sulfuric acid solution, stirred 0.5 hour on 80-90 ℃, behind the filter cleaner, adding 38 gram concentration are 10% lime slurry, 20 gram concentration are 10% milk of magnesia, 4.0 gram bentonite 23.3 gram concentration are 3% cationic starch emulsion, stirred 20-30 minute on 60-70 ℃, making solid content is No. 3 modifier of 21.78 grams, as be dried and be crushed to 300 orders, promptly get solid product.Record the chemical composition of No. 3 modifier with international complete chemical analysis method: 13.0 weight portion SiO
2, 9.1 weight portion Al
2O
3, 2.9 weight portion MgO, 16.2 weight portion CaO, 34.0 weight portion SO
4 2-, 14.1 weight portion H
2O
+With 14.3 weight portion H
2O
-Wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than whole modifier weight 3.5%.
Above-mentioned modifier 1,2 and 3, its principal crystalline phase is an entringite, eakleite, Magnesiumaluminumsilicate etc.
The preparation of pulp modifying material
Solid content to undried is to add the natural calcium metasilicate of 83 grams (available from the Nonmetallic Minerals in Yunnan Province research department, quality is Q/YNF J SO1-2000 for amount) in 17 modifier 1 that restrain, and on 30-40 ℃ of stirring 20-30 minute, adds 0.01 gram polyacrylamide.
Gained modified mineral super-fine fiber material is a white, whiteness＞85%, record with international complete chemical analysis method, the weight percentage of fibrous particle is 90%, with draw ratio＞10 that the S-130 of HIT type Electronic Speculum records fiber, record the chemical composition of this modified mineral superfine fibre with international complete chemical analysis method: 44.1 weight portion SiO
2, 1.0 weight portion Al
2O
3, 39.8 weight portion CaO, 0.6 weight portion MgO, 3.9 weight portion SO
4 2-, 1.5 weight portion H
2O
+, 6.1 weight portion H
2O
-Wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than 2.0% of whole modified mineral superfine fibre weight.Fe
2O
3Be the impurity that raw material brings.
In plastics mixer, mix the natural calcium metasilicate of 76 grams (available from the Nonmetallic Minerals in Yunnan Province research department, the quality code name is Q/YNF J SO1-2000), 2 the gram diatomite (company being arranged) available from Chengdu painted sculptures glue, add 18.8 gram powder modifying agents 2, mix, further further be crushed to 10～15 μ m with CX-130 type ultrafine crusher.
This modified fiber materials of gained is a white, whiteness＞85%, record with international complete chemical analysis method, the weight percentage of fibrous particle is 90%, with draw ratio＞10 that the S-130 of HIT type Electronic Speculum records fiber, record the chemical composition of this modified mineral fiber with international complete chemical analysis method: 45.7 weight portion SiO
2, 1.5 weight portion Al
2O
3, 41.1 weight portion CaO, 0.7 weight portion MgO, 5.5 weight portion SO
4 2-, 2.1 weight portion H
2O
+, 4.8 weight portion H
2O
-Wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than 2.2% of whole modified mineral fibre weight.Fe
2O
3Be the impurity that raw material brings.
Solid content to undried is to add the natural calcium metasilicate of 73 grams in 21.78 modifier 3 that restrain (available from the Nonmetallic Minerals in Yunnan Province research department, the quality code name is Q/YNFJ SO1-2000), 5 the gram diatomite (company being arranged) available from Chengdu painted sculptures glue, stirred adding 0.02 gram polyacrylamide 20～30 minutes on 30～40 ℃.
This modified fiber materials of gained, be white, whiteness＞85%, record with international complete chemical analysis method, the weight percentage of fibrous particle is 90%, with draw ratio＞10 that the S-130 of HIT type Electronic Speculum records fiber, record the chemical composition of this modified mineral fiber with international complete chemical analysis method: 47.1 weight portion SiO
2, 2.1 weight portion Al
2O
3, 42.0 weight portion CaO, 0.8 weight portion MgO, 7.5 weight portion SO
4 2-, 2.5 weight portion H
2O
+, 3.9 weight portion H
2O
-Wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than 2.5% of whole modified mineral superfine fibre weight.Fe
2O
3Be the impurity that raw material brings.
The principal crystalline phase that outstanding feature is a modifier among above-mentioned three embodiment is fibrous entringite (accounting for 70%) and fibrous eakleite (accounting for 10%), the natural calcium metasilicate that is modified etc. also is a superfine fibre, when practical application, formula rate according to modifier, adjust arbitrarily modifier and be the ratio with natural calcium metasilicate etc., better result of use is all arranged.
Papermaking and test
Obtain pulp modifying material by the described identical method of above embodiment, make pulpboard with this material, and the gained pulpboard is tested.
Want earlier slurrying when carrying out papermaking at the pulp modifying material (as embodiment 2) that uses solid modifier to make, promptly meet to material modified that to add mineral superfine fibre in the clean water that papermaking requires material modified with 4 times, stirred maintenance pH6.5～7.5 20～30 minutes on 40～50 ℃.
The technological process of conventional pulping plate be pulp beating-join starch → dilute → copy paper, after joining slurry, online is copied and is added the above-mentioned pulp modifying material that makes before the paper, makes pulpboard flow process manufacture paper with pulp cardboard or paper more routinely, and measures the pulpboard produced or the key technical indexes of paper.
Production Example 1 is made pulpboard ash＞50%
Method by embodiment 1 prepares liquid pulp modifying material, and it is 880 kilograms liquid modified dose 1 and 0.2 kg polypropylene acid amides that the ratio of each component in material modified is extended to 4300 kilograms of natural calcium metasilicates, solid content).It is 20% slip that this liquid state pulp modifying material is mixed with concentration, joins 100m
3In the secondary paper pulp (concentration is 2.8%, and oven dry stock is 2.8 tons, and the ash content of coal that is detained in the slurry is 21%), 2W21 * ly1760 fourdrinier wire multi-cylinder culture paper of producing with Shanghai paper plant carries out papermaking, and the basal ration of predetermined paper is 200 gram/m
2
In the process of manufacturing paper with pulp continuously, the physical index of monitoring stuff box ash and finished product cardboard, testing result is listed as following table 1.
Table 1 height adds to be filled out cardboard and becomes paper ash part, the on-the-spot testing result table of paper strength
| Time | Stuff box | The finished product pulpboard | Retention | Tensile index (Nm/g) | Annotate | |||||
| Ash (%) | Concentration (%) | Quantitative (g/m 2) | Ash (%) | Moisture (%) | ??(％) | Vertical | Horizontal | On average | Not having broken end manufactures paper with pulp continuously | |
| 6 minutes | 54.98 | ?4.93 | ??273 | ??38.00 | ??8.42 | The same | ||||
| 40 minutes | 54.98 | ?4.93 | ??265 | ??53.73 | ??7.86 | ??6.43 | ??4.53 | ??5.48 | The same | |
| 120 minutes | 54.98 | ?4.93 | ??285 | ??54.40 | ??8.43 | ??6.76 | ??3.59 | ??5.17 | The same | |
| 140 minutes | 54.98 | ?4.93 | ??106 | ??51.38 | ??4.36 | ??93.45 | The same | |||
| Cause 6.58 tons of pulpboards | ||||||||||
The manufacturing of Production Example 2 ash end blank paperboards
In addition, replace above-mentioned material modified slurry, make coated duplex board with grey back, measure the material modified and conventional talcous retention of the present invention in two kinds of paper, the results are shown in Table 2 by same procedure with conventional talcum powder.Measure the performance of producing the coated duplex board with grey back that obtains, the results are shown in Table 3.
Table 2
| Test item | Add the modified mineral fiber | Add talcum powder | ||
| Quantitatively | ????????240g/m 2～330g/m 2 | ???????????240g/m 2 | ||
| Add the amount of filling out | ?????????????30％ | ?????????????30％ | ||
| The starch adhesive ash | ????18.24％ | ????20.71％ | ????10.94％ | ????12.19 |
| Retention | ????60.8％ | ????69％ | ????36.46％ | ????40.63％ |
| Average retention | ?????????????64.9％ | ????????????38.54％ | ||
Table 3
| Test item | Unit | Sample 1 (it is material modified to add the present invention) | Sample 2 (it is material modified to add the present invention) | Conventional sample (adding talcum powder) | |
| Quantitatively | g/m 2 | ????328.6 | ????296.9 | ????233.8 | |
| Tightness | g/cm 3 | ????0.72 | ????0.66 | ????0.69 | |
| Degree of sizing | mm | ????＜0.5 | ????＜0.5 | ????＜0.5 | |
| Folding strength | Inferior | Horizontal 19 | | | |
| | S | Positive | 8 | | Positive 11 |
| Whiteness | ％ | Positive 77.2 | Positive 75.9 | Positive 78.5 | |
| Deflection | mN·m | Horizontal 5.28 | Horizontal 4.51 | Horizontal 2.33 | |
| Dirt count | (0.3～1.5)mm | ????28 | ????12 | ????24 | |
| (1.0～1.5) mm black wherein | ????20 | ????0 | ????8 | ||
| Greater than 1.5mm | ????8 | ????0 | ????0 | ||
| (1.5～2.5)mm | ????18 | ????0 | ????0 | ||
| Moisture content | ????7.1 | ????7.4 | ????8.2 | ||
| The starch adhesive ash | ????18.24 | ????20.71 | ????11.56 |
Production Example 3 is made the pulpboard of ash 30%
Method by embodiment 3 prepares liquid pulp modifying material, and it is 537 kilograms liquid modified dose 3 and 0.5 kg polypropylene acid amides that the ratio of each component in material modified is extended to 1800 kilograms of natural calcium metasilicates, 123 kilograms of diatomite, solid contents.It is 20% slip that this liquid state pulp modifying material is mixed with concentration.Quantitatively is 200 gram/m with material modified slurry (40 weight %), pinus khasys bleached pulp (50 weight %) and waste stuff (10 weight %) with the 2W21X1Y1760 fourdrinier wire multi-cylinder culture paper production that Shanghai paper plant produces
2The bleaching pulpboard.
In addition, using pinus khasys instead and do not float natural color pulp replacement pinus khasys bleached pulp, quantitatively is 200 gram/m with the same procedure preparation
2The true qualities pulpboard.Table 4 illustrate two kinds of pulpboards of gained quantitatively, become paper ash part and mechanical performance.
Table 4
| Pinus khasys bleaching pulpboard | Pinus khasys does not float the true qualities pulpboard | |
| Quantitative (g/m 2) | ??????250 | ??????222 |
| Tensile index (Nm/g) | ??????12.68 | ??????18.4 |
| Tear index | ??????13.66 | ??????14.10 |
| Become paper ash part % | ??????34.9 | ??????29.10 |
Production Example 4 is made the sole paperboard
Prescription by embodiment 2 provides 68 tons in modified superfine mineral fibres powder, produces reinforcement board, carries out industrial experiment continuously, and experimental result is shown in following table 5 and table 6.
Table 5
| Temperature: 20 ℃, humidity: 65% | Test specimen | |||
| Blank | Blank | Add the 50Kg calcium activated | Add the 200Kg calcium activated | |
| Actual (real) thickness (mm) | ??1.26 | ??1.26 | ????1.26 | ????1.22 |
| Basic weight (Kg/m 2) | ??0.62 | ??0.63 | ????0.65 | ????0.63 |
| Density (Kg/m 2) | ??0.49 | ??0.50 | ????0.51 | ????0.52 |
| TENSILE STRENGTH (MD does) Kg/m 2 | ??253 | ??256 | ????234 | ????268 |
| TENSILE STRENGTH (CD does) Kg/m 2 | ??169 | ??169 | ????164 | ????154 |
| Rigidity (MD) | ??960 | ??975 | ????960 | ????950 |
| Rigidity (CD) | ??480 | ??450 | ????496 | ????450 |
| Elmendorf is torn (MD) g | ??1400 | ??1500 | ????1600 | ????1400 |
| Elmendorf is torn (CD) g | ??1500 | ??1500 | ????1600 | ????1400 |
| Internal viscosity (doing) Kg/m 2 | ??4.04 | ??4.27 | ????2.74 | ????3.73 |
| SATRA flexing cycle (MD) | ??33.9 | ??22.94 | ????20.7 | ????15.02 |
| SATRA flexing cycle (CD) | ??1434 | ??1436 | ????712 | ????640 |
| Hot melt (Fsi) | ??105 | ??125 | ????109 | ????121 |
| Water absorption rate (%) | ??79.5 | ??71.96 | ????67.40/69.66 | ????57.82/58.57 |
| Dehydration rate (%) | ??97.96 | ??97.72 | ????97.8/97.70 | ????97.35/97.38 |
| Ash (%) | ????12.3 | ????18.7 | ||
Table 6
| Temperature: 20 ℃, humidity: 65% | Specimen sample | ||||
| Add 300Kg active silicic acid calcium | Add 400Kg active silicic acid calcium | ||||
| Actual (real) thickness (mm) | ??1.26 | ??1.25 | ??1.23 | ????1.26 | ????1.26 |
| Basic weight (Kg/m 2) | ??0.67 | ??0.67 | ??0.65 | ????0.67 | ????0.67 |
| Density (Kg/m 2) | ??0.53 | ??0.53 | ??0.53 | ????0.53 | ????0.53 |
| TENSILE STRENGTH (MD does) Kg/m 2 | ??232 | ??232 | ??248 | ????217 | ????197 |
| TENSILE STRENGTH (CD does) Kg/m 2 | ??133 | ??132 | ??136 | ????120 | ????120 |
| Rigidity (MD) | ??945 | ??930 | ??840 | ????900 | ????885 |
| Rigidity (CD) | ??450 | ??450 | ??390 | ????390 | ????390 |
| Elmendorf is torn (MD) g | ??1400 | ??1600 | ??1200 | ????1300 | ????1300 |
| Elmendorf is torn (CD) g | ??1500 | ??1500 | ??1500 | ????1200 | ????1300 |
| Internal viscosity (doing) Kg/m 2 | ??3.55 | ??3.84 | ??3.8 | ????3.43 | ????3.35 |
| SATRA flexing cycle (MD) | ??1027 | ??1195 | ??1621 | ????501 | ????518 |
| SATRA flexing cycle (CD) | ??525 | ??286 | ??307 | ????113 | ????194 |
| Hot melt (Fsi) | ??102 | ??105 | ??109 | ????88 | ????88 |
| Humidity (%) | ??5.56 | ??5.22 | ??5.69 | ????5.56 | ????5.60 |
| Water absorption rate (%) | ??54.20 | ??53.66 | ??52.03 | ????53.26 | ????49.3 |
| Dehydration rate (%) | ??97.39 | ??97.49 | ??97.28 | ????97.76 | ????97.78 |
Production Example 5Pinus khasys adds the material modified retention experiment of filling out pulpboard secondary beating and papermaking
The one-tenth paper ash part that to manufacture paper with pulp by Production Example 3 is that 15 tons of size degradation pulpings of pulpboard of 29.10% are discongested making beating with light cutter again, measures its ash, concentration, then enters the state of normally manufacturing paper with pulp, and true qualities add fills out the pulpboard secondary and copy experimental result again and be shown in table 7.
Table 7
| Condition is selected | Copy pulpboard ash (%) again | Moisture (%) | Retention (%) | Tensile index (Nm/g) |
| Not with retention agent | ?????22.91 | ????9.18 | ????78.74 | ????16.23 |
| Add retention agent *0.1%, 130m/ second | ?????28.92 | ????9.38 | ????99.38 | ????15.18 |
* retention agent is a polyacrylamide, available from auxiliary reagent factory, Pengxi, Sichuan.
By table 5 data as seen, the sole plales ash is 29.10%, when making beating is carried out manufacturing paper with pulp the second time, even not with retention agent, pulpboard ash and retention are all higher, add retention agent and then can obtain very high pulpboard ash and retention, and this shows that pulpboard of the present invention has good durability.
Claims (20)
1. ash-rich pulpboard, this pulpboard comprises that softwood pulp makes long fiber, hardwood pulp or straw pulp or recycled pulp and make medium-length fibre, mineral superfine fibre, artificial mineral superfine fibre and make staple fibre and mineral ultrafine dust, wherein, described various fiber is woven into a mesh structure jointly, is stained with described artificial mineral superfine fibre and described mineral ultrafine dust on the surface of described long fiber, medium-length fibre and mineral superfine fibre.
2. ash-rich pulpboard as claimed in claim 1 is characterized in that described mineral superfine fibre makes by being selected from natural calcium metasilicate, diatomite, fibrous plaster, choysotile and the hair zeolite at least a material.
3. ash-rich pulpboard as claimed in claim 1 is characterized in that described artificial mineral superfine fibre is artificial entringite fiber.
4. ash-rich pulpboard as claimed in claim 1 is characterized in that described mineral ultrafine dust is by being selected from bentonite, magnesia, aluminum sulfate, the nano material that two or more at least materials are made in active silica and the cationic starch.
5. as each described ash-rich pulpboard among the claim 1-4, the draw ratio that it is characterized in that described mineral superfine fibre is more than or equal to 10, and described artificial mineral superfine fibre draw ratio is more than or equal to 15, and the particle diameter of described mineral ultrafine dust is less than 1 μ m.
6. ash-rich pulpboard as claimed in claim 1, the ash that it is characterized in that pulpboard is in the scope of 15-60%.
7. ash-rich pulpboard as claimed in claim 1 is characterized in that the chemical composition of ash of described pulpboard is as follows: 44-47 weight portion SiO
2, 1-2 weight portion Al
2O
3, 40-42 weight portion CaO, 0.6-0.8 weight portion MgO, 4-7.5 weight portion SO
4 2-, 1.5～2.5 weight portion H
2O
+, 4-6 weight portion H
2O
-
8. ash-rich pulpboard as claimed in claim 7 is characterized in that also containing Na in the pulpboard ash
2O, K
2O and Fe
2O
3, its total weight parts is less than 2.5% of the total ash weight portion of the contained mineral matter of whole pulpboard.
9. ash-rich pulpboard as claimed in claim 1 is characterized in that it is quantitatively greater than 200g/m
2
10. the manufacture method of the described ash-rich pulpboard of claim 1, this method comprises and will contain long stapled needle slurry and contain the broad-leaved slurry of medium-length fibre or step that straw pulp or recycled pulp are discongested making beating, joined slurry, copy paper, before it is characterized in that after joining the slurry step, copying the paper step, in paper pulp, add mineral superfine fibre and modifier.
11. method as claimed in claim 10, it is characterized in that described join long fiber that proportioning that the slurry step adopts is 50-60% and 40-50% long in fibrous fiber grating.
12. method as claimed in claim 10, the manufacture method that it is characterized in that modifier comprises: add sulfuric acid solution and carry out acidolysis in aluminium hydroxide or calcined kaolin or nepheline syenite powder, add quick lime and light calcined magnesia emulsion, bentonite one milk of magnesia, cationic starch behind the filter cleaner again, fully stir, then, perhaps crystallisation by cooling and be dried and crushed into modifier powder perhaps adds polyacrylamide and obtains liquid modified dose.
13. method as claimed in claim 12 is characterized in that when modifier is powder type, the described step that adds mineral superfine fibre and modifier in paper pulp is as follows:
With mineral superfine fibre precomminution to the 100-325 order; With described modifier powder precomminution to the 100-325 order;
Above-mentioned two kinds of powder are even, and further be crushed to 5-15 μ m, add 4 times water, the sufficient stirring under 40-50 ℃ of temperature, keeping the pH value is 6.5-7.5, makes concentration and be 20% modified slurry.
14. method as claimed in claim 12 is characterized in that when modifier is liquid form, the described step that adds mineral superfine fibre and modifier in paper pulp further comprises the steps:
In liquid modified dose, add mineral superfine fibre, fully stir, add polyacrylamide then, be mixed with concentration and be 20% modified slurry.
15. the paper pulp material through modification, it comprises that softwood pulp is made long fiber, hardwood pulp or straw pulp or recycled pulp is made medium-length fibre, mineral superfine fibre and modifier.
16. the paper pulp material through modification as claimed in claim 15 is characterized in that the chemical composition of modifier is: 9-13 weight portion SiO
2, 6-9 weight Al
2O
3, 1-3 weight portion MgO, 12-16 weight portion CaO, 27-34 weight portion SO
4 2-, 10-14 weight portion H
2O
+, 11-21 weight portion H
2O
-, wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than whole modifier weight 3.5%, and its principal crystalline phase is fibrous entringite, eakleite, magnesium silicate and Magnesiumaluminumsilicate.
17. the paper pulp material through modification as claimed in claim 15 is characterized in that the chemical composition of mineral superfine fibre and modifier is: 44-47 weight portion SiO
2, 1-2 weight portion Al
2O
3, 40-42 weight portion CaO, 0.6-0.8 weight portion MgO, 4-7.5 weight portion SO
4 2-, 1.5～2.5 weight portion H
2O
+, 4-6 weight portion H
2O
-, wherein also contain Na
2O, K
2O and Fe
2O
3, its total amount is less than through 2.5% of modified pulp material gross weight, and its principal crystalline phase is natural meta-acid calcium.
18. the paper pulp material through modification as claimed in claim 15 is characterized in that whiteness 〉=85% of mineral superfine fibre and modifier.
19. the paper pulp material through modification as claimed in claim 15, the particle mean size that it is characterized in that mineral superfine fibre and modifier is 5-10 μ m, wherein the fibrous particle weight percentage is 80-90%, the draw ratio of described fibrous particle 〉=10, mineral ultrafine dust weight percentage is 10-20%, and granularity is between 1nm-1000nm.
20. the described paper pulp material through modification of claim 15 is being made the application in the ash-rich pulpboard.
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|---|---|---|---|
| CN 02159771 CN1238599C (en) | 2002-12-23 | 2002-12-23 | Modified pulp material, high-ash pulp board prepared from modified pulp material and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159771 CN1238599C (en) | 2002-12-23 | 2002-12-23 | Modified pulp material, high-ash pulp board prepared from modified pulp material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1510212A true CN1510212A (en) | 2004-07-07 |
| CN1238599C CN1238599C (en) | 2006-01-25 |
Family
ID=34237645
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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|---|---|
| CN (1) | CN1238599C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154937A (en) * | 2011-03-31 | 2011-08-17 | 广东理文造纸有限公司 | Preparation process of retention aid for papermaking |
| CN102433795A (en) * | 2011-10-20 | 2012-05-02 | 国能纸业有限公司 | Papermaking filler and pretreatment method thereof |
| CN103284647A (en) * | 2012-02-22 | 2013-09-11 | 金红叶纸业集团有限公司 | Paper for daily use |
| CN105336397A (en) * | 2015-11-04 | 2016-02-17 | 铜陵三佳变压器有限责任公司 | Non-deformable dimension high-stability insulation paper for transformer |
| CN105355267A (en) * | 2015-11-04 | 2016-02-24 | 铜陵三佳变压器有限责任公司 | Insulation paper containing glass fiber used for transformer |
| CN105355265A (en) * | 2015-11-04 | 2016-02-24 | 铜陵三佳变压器有限责任公司 | High-strength high-elasticity insulation paper used for transformer |
| CN106278080A (en) * | 2016-07-19 | 2017-01-04 | 昆山大乘环保科技有限公司 | A kind of kieselguhr breathes the preparation method of plate |
| CN106958166A (en) * | 2017-04-12 | 2017-07-18 | 明光市国星凹土有限公司 | One kind contains bentonitic paper and preparation method thereof |
| CN108193563A (en) * | 2017-12-29 | 2018-06-22 | 常德金德新材料科技股份有限公司 | A kind of method that paper surface is modified |
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2002
- 2002-12-23 CN CN 02159771 patent/CN1238599C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154937A (en) * | 2011-03-31 | 2011-08-17 | 广东理文造纸有限公司 | Preparation process of retention aid for papermaking |
| CN102433795A (en) * | 2011-10-20 | 2012-05-02 | 国能纸业有限公司 | Papermaking filler and pretreatment method thereof |
| CN102433795B (en) * | 2011-10-20 | 2013-09-11 | 国能纸业有限公司 | Papermaking filler and pretreatment method thereof |
| CN103284647A (en) * | 2012-02-22 | 2013-09-11 | 金红叶纸业集团有限公司 | Paper for daily use |
| CN105336397A (en) * | 2015-11-04 | 2016-02-17 | 铜陵三佳变压器有限责任公司 | Non-deformable dimension high-stability insulation paper for transformer |
| CN105355267A (en) * | 2015-11-04 | 2016-02-24 | 铜陵三佳变压器有限责任公司 | Insulation paper containing glass fiber used for transformer |
| CN105355265A (en) * | 2015-11-04 | 2016-02-24 | 铜陵三佳变压器有限责任公司 | High-strength high-elasticity insulation paper used for transformer |
| CN106278080A (en) * | 2016-07-19 | 2017-01-04 | 昆山大乘环保科技有限公司 | A kind of kieselguhr breathes the preparation method of plate |
| CN106958166A (en) * | 2017-04-12 | 2017-07-18 | 明光市国星凹土有限公司 | One kind contains bentonitic paper and preparation method thereof |
| CN108193563A (en) * | 2017-12-29 | 2018-06-22 | 常德金德新材料科技股份有限公司 | A kind of method that paper surface is modified |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1238599C (en) | 2006-01-25 |
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