WO2010018301A2 - Gypsum product - Google Patents
Gypsum product Download PDFInfo
- Publication number
- WO2010018301A2 WO2010018301A2 PCT/FI2009/050287 FI2009050287W WO2010018301A2 WO 2010018301 A2 WO2010018301 A2 WO 2010018301A2 FI 2009050287 W FI2009050287 W FI 2009050287W WO 2010018301 A2 WO2010018301 A2 WO 2010018301A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fibre
- gypsum
- calcium sulphate
- process according
- crystallization
- Prior art date
Links
- 239000010440 gypsum Substances 0.000 title claims abstract description 92
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 92
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 116
- 239000000835 fiber Substances 0.000 claims abstract description 89
- 239000002131 composite material Substances 0.000 claims abstract description 79
- 239000013078 crystal Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 31
- 239000000945 filler Substances 0.000 claims abstract description 31
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims abstract description 24
- 239000000049 pigment Substances 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000011575 calcium Substances 0.000 claims abstract 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract 3
- 239000000123 paper Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 229920001131 Pulp (paper) Polymers 0.000 claims description 27
- 235000011132 calcium sulphate Nutrition 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 239000001175 calcium sulphate Substances 0.000 claims description 17
- 239000002655 kraft paper Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229960001484 edetic acid Drugs 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000834 fixative Substances 0.000 claims description 6
- VUGTZIIFNRVACY-UHFFFAOYSA-N 2,3,4,5-tetraamino-6-(1,2-diamino-2-phenylethenyl)benzenesulfonic acid Chemical class NC(=C(C=1C(=C(C(=C(C1N)N)N)N)S(=O)(=O)O)N)C1=CC=CC=C1 VUGTZIIFNRVACY-UHFFFAOYSA-N 0.000 claims description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 4
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000002491 polymer binding agent Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims 2
- 229960005069 calcium Drugs 0.000 claims 2
- 235000001465 calcium Nutrition 0.000 claims 2
- 229960003330 pentetic acid Drugs 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 44
- 238000001878 scanning electron micrograph Methods 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 12
- -1 alkyl ketene dimer Chemical compound 0.000 description 11
- 235000019592 roughness Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000003115 biocidal effect Effects 0.000 description 8
- 239000003139 biocide Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003490 calendering Methods 0.000 description 7
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000000149 argon plasma sintering Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 244000166124 Eucalyptus globulus Species 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
- 230000035699 permeability Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- ULUIMLJNTCECJU-UHFFFAOYSA-N 3-amino-4-hydroxybenzenesulfonate;hydron Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1O ULUIMLJNTCECJU-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 241001325941 Calyptus Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 239000012861 aquazol Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- ZNEWHQLOPFWXOF-UHFFFAOYSA-N coenzyme M Chemical compound OS(=O)(=O)CCS ZNEWHQLOPFWXOF-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/466—Conversion of one form of calcium sulfate to another
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/025—Calcium sulfates
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- 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
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
-
- 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
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
- D21H15/10—Composite fibres
- D21H15/12—Composite fibres partly organic, partly inorganic
-
- 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
- D21H17/66—Salts, e.g. alums
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Definitions
- the invention relates to a gypsum -fibre composite product.
- the gypsum -fibre composite product can be used as a coating pigment or a filler pigment in the pro- duction of paper.
- the invention also relates to a process for the preparation of the gypsum -fibre composite product. In the production of paper improved retention of the filler pigment and homogenous filler distribution can be obtained.
- a papermaking process starts with stock preparation where cellulosic fibers are mixed with water and mineral filler (usually clay or calcium carbonate or also gypsum).
- the obtained slurry is delivered by means of a head box on a forming fabric or press fabric or wire to form a fibrous web of cellulosic fibers at the forming section of the paper machine.
- water is drained in the draining section and the formed web is conducted to the press section including a series of roll presses where additional water is removed.
- the web is then conducted to the drying section of the paper machine where most of the remaining water is evaporated typically by means of steam-heated dryer drums.
- Post drying operations include calendering where the dry paper product passes between rolls under pressure, thereby improving the surface smoothness and gloss and making the cali- per/thickness profile more uniform.
- calenders such as machine calenders where the rolls usually are steel rolls and include a heated roll (thermo roll).
- Gypsum or calcium sulphate dihydrate CaSO 4 -2H 2 O is suitable as material for both coating pigment and filler, especially in paper products. Especially good coat- ing pigment and filler is obtained if the particular gypsum has high brightness, gloss and opacity.
- the gloss is high when the particles are sufficiently small, flat and broad (platy).
- the opacity is high when the particles are refractive, small and of equal size (narrow particle size distribution).
- the morphology of the gypsum product particles can be established by examining scanning electron micrographs. Useful micrographs are obtained e.g. with a scanning electron microscope of the type Philips FEI XL 30 FEG.
- the size of the gypsum product particles is expressed as the weight average diameter D 50 of the particles contained therein. More precisely, D 50 is the diameter of the presumably round particle, smaller than which particles constitute 50 % of the total particle weight. D 50 can be measured with an appropriate particle size analyzer, such as Sedigraph 5100.
- the flatness of a crystal means that it is thin.
- the form of flat crystals is suitably expressed by means of the shape ratio SR.
- the SR is the ratio of the crystal length (the longest measure) to the crystal thickness (the shortest transverse measure).
- the SR of the claimed gypsum product is meant the average SR of its individual crystals.
- the platyness of a crystal means that it is broad. Platyness is suitable expressed by means of the aspect ratio AR.
- the AR is the ratio between the crystal length (the longest measure) and the crystal width (the longest transverse measure).
- the AR of the claimed gypsum product is meant the average AR of its individual crystals.
- Both the SR and the AR of the gypsum product can be estimated by examining its scanning electron micrographs.
- a suitable scanning electron microscope is the above mentioned Philips FEI XL 30 FEG.
- Equal crystal particle size means that the crystal particle size distribution is narrow.
- the width is expressed as the gravimetric weight distribution WPSD and it is expressed as (D 75 -D 2 SyD 50 wherein D 75 , D 25 and D 50 are the diameters of the pre- sumably round particles, smaller than which particles constitute 75, 25 and 50 %, respectively, of the total weight of the particles.
- the width of the particle distribution is obtained with a suitable particle size analyzer such as the above mentioned type Sedigraph 5100.
- Gypsum occurs as a natural mineral or it is formed as a by-product of chemical processes, e.g. as phosphogypsum or flue gas gypsum.
- phosphogypsum or flue gas gypsum In order to refine the gypsum further by crystallising it into coating pigment or filler, it must first be calcined into calcium sulphate hemihydrate (CaSO 4 - 1 /4H 2 O), after which it may be hydrated back by dissolving the hemihydrate in water and precipitating to give pure gypsum. Calcium sulphate may also occur in the form of anhydrite lacking crystalline water (CaSO 4 ).
- the calcium sulphate hemihydrate may occur in two forms; as ⁇ - and ⁇ -hemihydrate.
- the ⁇ - form is obtained by heat-treating the gypsum raw material at atmospheric pressure while the ⁇ -form is obtained by treating the gypsum raw material at a steam pres- sure which is higher than atmospheric pressure or by means of chemical wet calcination from salt or acid solutions at e.g. about 45 ° C.
- WO 88/05423 discloses a process for the preparation of gypsum by hydrating calcium sulphate hemihydrate in an aqueous slurry thereof, the dry matter content of which is between 20 and 25 % by weight. Gypsum is obtained, the largest measure of which is from 100 to 450 ⁇ m and the second larges measure of which is from 10 to 40 ⁇ m.
- AU 620857 discloses a process for the preparation of gypsum from a slurry containing not more than 33,33 % by weight of ground hemihydrate, thereby yielding needle-like crystals having an average size of between 2 and 200 ⁇ m and an aspect ratio between 5 and 50. See page 15, lines 5 to 11 , and the examples of this document.
- US 2004/0241082 describes a process for the preparation of small needle-like gypsum crystals (length from 5 to 35 ⁇ m, width from 1 to 5 ⁇ m) from an aqueous slurry of hemihydrate having a dry matter content of between 5 and 25 % by weight.
- the idea in this US document is to reduce the water solubility of the gypsum by means of an additive in order to prevent the crystals from dissolving during paper manufacture.
- DE 32 23 178 C1 discloses a process for producing organic fibres coated with one or more mineral substances.
- One embodiment comprises mixing cellulose fibres, gypsum and water. The mixture is compacted to give a plastic mass which subsequently is dried and mechanically comminuted to give fine particles.
- the obtained product can be used as an additive or filler e.g. in bitumen masses or putties.
- WO 2008/092990 discloses a gypsum product consisting of intact crystals having a size from 0.1 to 2.0 ⁇ m.
- the crystals have a shape ratio SR of at least 2.0, preferably between 2.0 and 50, and a aspect ratio AR between 1.0 and 10, preferably between 1.0 and below 5.0.
- WO 2008/092991 discloses a process for the preparation of a gypsum product wherein calcium sulphate hemihydrate and/or calcium sulphate anhydrite and wa- ter are contacted so that the calcium sulphate hemihydrate and/or calcium sulphate anhydrite and the water react with each other and form a crystalline gypsum product.
- the formed reaction mixture has a dry matter content of between 34 and 84 % by weight.
- the aim of the invention is to provide a gypsum -fibre composite product wherein the gypsum is crystallized on the surface of the fibre and attached fairly strongly to the fibre.
- the composite product can be used as a filler pigment or coating pig- ment in the production of paper. In the production of paper improved retention of the filler pigment and homogenous filler distribution can be obtained. Also higher filler load can be obtained.
- the gypsum -fibre composite product of the invention is especially well suited for the production of fine paper.
- a gypsum -fibre composite product wherein the gypsum appears as crystals on the surface of the fibre and wherein the gypsum crystals are obtained by contacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and an aqueous fibre suspension.
- the gypsum is attached to the fibre and consequently the gypsum -fibre composite is shown by most measurement methods as a single piece.
- the shape and size of the gypsum can roughly be estimated by means of microscopic images.
- the gypsum crystals attached to the fibre can have the shapes and sizes described in WO 2008/092990 and WO 2008/092991. However, according to the invention the crystallized gypsum can also be needle-like.
- the size of the gypsum crystals is preferably from 0.1 to 5.0 ⁇ m, more preferably from 0.1 to 4.0 ⁇ m, and most preferably from 0.2 to 4.0 ⁇ m.
- the size of the gypsum crystals may also be from 0.1 to 2.0 ⁇ m or from 0.2 to 2.0 ⁇ m.
- the fibre of the gypsum -fibre composite product comprises a cellulosic fibre such as a chemical, mechanical, chemi-mechanical or deinked pulp fibre or a synthetic fibre, such as a polyolefine, e.g. polypropene.
- Chemical pulps include kraft pulp and sulphite pulp.
- Mechanical pulps include stone groundwood pulp (SGW), refiner mechanical pulp (RMP), pressure groundwood (PGW), thermome- chanical pulp (TMP), and also chemically treated high-yield pulps such as chemi- thermomechanical pulp (CTMP).
- Deinked pulp can be made using mixed office waste (MOW), newsprint (ONP), magazines (OMG) etc. Also mixtures of different pulps can be used.
- the weight ratio of gypsum to fibre on dry basis is in the range from 95:5 to 50:50, preferably from 75:25 to 50:50.
- the gypsum -fibre composite product may additionally comprise additional substances such as a natural or synthetic polymer binder and/or an optical bhghtener and/or a rheology modifier and/or sizing agents.
- the sizing agent may be a rosin size or a reactive size such as alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA).
- the gypsum product of the invention is typically a coating or filler pigment.
- the composite product is a coating pigment and comprises gypsum crystals preferably having a size of between 0.1 and 1.0 ⁇ m, more preferably between 0.5 and 1.0 ⁇ m.
- it is a filler and comprises gypsum crystals preferably having a size of between 1 .0 and 5.0 ⁇ m, more preferably between 1 .0 and 4.0 ⁇ m.
- the gypsum crystals in the filler composite may also have a size of between 1.0 and below 2.0 ⁇ m.
- a process for the preparation of a gypsum -fibre composite product comprising contacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and an aqueous fibre suspension to form gypsum crystals on the surface of the fibre.
- the weigh ratio of calcium sulphate hemihydrate and/or calcium sulphate anhydrite to water in the crystallization is in the range from 0.03 to 0.6:1 , more preferably from 0.05 to 0.5:1.
- the dry fiber content in the crystallization is from 3 to 30 % by weight.
- the content of calcium sulphate hemihydrate and/or calcium sulphate anhydrite in the crystallization is from 10 to 57 % by weight.
- the process of the invention may additionally comprise the steps of drying and comminuting the obtained product to form a gypsum -fibre composite product in the form of particles.
- a fixative can be introduced into the crystallization.
- the fixative can be selected from the group consisting of poly aluminum chloride, poly diallyldimethylammonium chloride (poly DADMAC), anionic and cationic poly- acrylates.
- the crystallization can be carried out in the absence of crystallization habit modifiers.
- the crystallization can also be carried out in the presence of a crystallization habit modifier.
- the crystallization habit modifier can be added to water or aqueous fibre suspension before the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
- the temperature of the water in the reaction mixture can be anything between 0 and 100 ° C.
- the temperature is between 0 and 80 ° C, more preferably between 0 and 50 ° C, even more preferably between 0 and 40 ° C, most preferably between 0 and 25 ° C.
- the crystallization habit modifier is an inorganic acid, oxide, base or salt.
- useful inorganic oxides, bases and salts are AIF 3 , AI 2 (SO 4 ) 3 , CaCI 2 , Ca(OH) 2 , H 3 BO 4 , NaCI , Na 2 SO 4 , NaOH, NH 4 OH, (NH 4 ) 2 SO 4 , MgCI 2 , MgSO 4 and MgO.
- the crystallization habit modifier is an organic compound, which is an alcohol, an acid or a salt.
- Suitable alcohols are methanol, ethanol, 1 -butanol, 2-butanol, 1 -hexanol, 2-octanol, glycerol, i-propanol and alkyl polyglucoside based Cs-Cio-fatty alcohols.
- the crystallization habit modifier is preferably a compound having in its molecule one or several carboxylic or sulphonic acidic groups, or a salt of such a compound.
- organic acids may be mentioned carboxylic acids such as acetic acid, propionic acid, succinic acid, citric acid, tartaric acid, ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene thamine pentaacetic acid (DTPA), nithlotriacetic acid (NTA), N-bis-(2- (1 ,2-dicarboxyethoxy)ethyl aspartic acid (AES), and sulphonic acids such as amino-1 -naphthol-3,6-disulphonic acid, 8-amino-1 -naphthol-3,6-disulphonic acid, 2-aminophenol-4-sulphonic acid, anthrachinone-2,6-disulphonic
- organic salt may be mentioned the salts of carboxylic acids such as Mg formiate, N a- and NH 4 -acetate, Na2-maleate, NH 4 -citrate, Na2-succinate, K- oleate, K-stearate, Na2-ethylenediamine tetraacetic acid (Na2-EDTA), Na ⁇ - aspartamic acid ethoxy succinate (Na ⁇ -AES) and Na ⁇ -aminotriethoxy succinate (Na 6 -TCA).
- carboxylic acids such as Mg formiate, N a- and NH 4 -acetate, Na2-maleate, NH 4 -citrate, Na2-succinate, K- oleate, K-stearate, Na2-ethylenediamine tetraacetic acid (Na2-EDTA), Na ⁇ - aspartamic acid ethoxy succinate (Na ⁇ -AES) and Na ⁇ -aminotriethoxy succinate (Na 6 -TCA).
- salt of sulphonic acids are useful, such as Na-n-(Ci O -Ci 3 )-alkylbenzene sulphonate, Cio-Ci6-alkylbenzene sulphonate, Na-1 -octyl sul phonate, Na-1- dodecane sulphonate, Na-1 -hexadecane sulphonate, the K-fatty acid sulphonates, the Na-Ci 4 -Ci6-olefin sulphonate, the Na-alkylnaphthalene sulphonates with ani- onic or non-ionic surfactants, di-K-oleic acid sulphonates, as well as the salts of di- , tetra-, and hexaaminostilbene sulphonic acids.
- organic salts containing sulphur should also be mentioned the sulphates such as the Ci2-Ci 4 -fatty alcohol ether sulphates, Na-2-ethyl hexyl sulphate, Na-n-dodecyl sulphate and Na-lauryl sulphate, and the sulphosuccinates such as the monoalkyl polyglycol ether of Na- sulphosuccinate, Na-dioctyl sulphosuccinate and Na-dialkyl sulphosuccinate.
- the sulphates such as the Ci2-Ci 4 -fatty alcohol ether sulphates, Na-2-ethyl hexyl sulphate, Na-n-dodecyl sulphate and Na-lauryl sulphate
- the sulphosuccinates such as the monoalkyl polyglycol ether of Na- sulphosuccinate, Na-dioctyl
- Phosphates may also be used, such as the Na-nonylphenyl- and Na-dinonyl phenylethoxylated phosphate esters, the K-aryl ether phosphates, as well as the triethanolamine salts of polyaryl polyetherphosphate.
- crystallization habit modifier may also be used cationic surfactants such as oc- tyl amine, triethanol amine, di(hydrogenated animal fat alkyl) dimethyl ammonium chloride, and non-ionic surfactants such as a variety of modified fatty alcohol eth- oxylates.
- cationic surfactants such as oc- tyl amine, triethanol amine, di(hydrogenated animal fat alkyl) dimethyl ammonium chloride, and non-ionic surfactants such as a variety of modified fatty alcohol eth- oxylates.
- polyacrylic acids and polyacrylates examples include the polyacrylic acids and polyacrylates, the acrylate-maleate copolymers, polyacrylamide, poly(2-ethyl-2-oxazoline), polyvinyl phosphonic acid, the copoly- mer of acrylic acid and allylhydroxypropyl sulphonate (AA-AHPS), poly- ⁇ - hydroxyacrylic acid (PHAS), polyvinyl alcohol, and poly(methyl vinyl ether - alt.- maleic acid).
- AA-AHPS allylhydroxypropyl sulphonate
- PHAS poly- ⁇ - hydroxyacrylic acid
- polyvinyl alcohol examples include poly(methyl vinyl ether - alt.- maleic acid).
- Especially preferable crystallization habit modifiers are ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene thamine pentaacetic acid (DTPA), nithlotriacetic acid (NTA), N-bis-(2- (1 ,2-dicarboxyethoxy)ethyl aspartic acid (AES), the di-, tetra- and hexa- aminostilbenesulfonic acids and their salts such as Na-aminothethoxy succinate (Na ⁇ -TCA), as well as the alkylbenzenesulphonat.es.
- EDDS ethylene diamine succinic acid
- ISA iminodisuccinic acid
- EDTA ethylene diamine tetraacetic acid
- DTPA diethylene thamine pentaacetic acid
- NTA nithlotriacetic acid
- AES N-bis-(
- the crystallization habit modifier can be used in an amount of 0.01 to 5.0 %, most preferably 0.02-1.78 %, based on the weight of the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
- ⁇ -calcium sulphate hemihydrate is typi- cally used. It may be prepared by heating gypsum raw-material to a temperature of between 140 and 300 ° C, preferably from 150 to 200 ° C. At lower temperatures, the gypsum raw-material is not sufficiently dehydrated and at higher temperatures it is over-dehydrated into anhydrite. Calcinated calcium sulphate hemihydrate usually contains impurities in the form of small amounts of calcium sulphate dihydrate and/or calcium sulphate anhydrite.
- ⁇ -calcium sulphate hemihydrate obtained by flash calcination e.g by fluid bed calcination, whereby the gypsum raw-material is heated to the required temperature as fast as possible.
- ⁇ -calcium sulphate hemihydrate in the crystallization.
- anhydrite It is also possible to use calcium sulphate anhydrite as starting material for the process of the invention.
- the anhydrite is obtained by calcination of gypsum raw material.
- the other forms, the so called Anhydrite III also known as soluble anhy- drite has three forms: ⁇ -anhydrite III, ⁇ -anhydrite III', and a-anhydrite III and Anhydrite ll-s form pure gypsum upon contact with water.
- aqueous fibre suspension and optionally crystallization habit modifier As the calcium sulphate hemihydrate and/or calcium sulphate anhydrite, aqueous fibre suspension and optionally crystallization habit modifier have been contacted, they are allowed to react into calcium sulphate dihydrate i.e. gypsum.
- the reaction takes e.g. place by mixing, preferably by mixing strongly, said substances together for a sufficient period of time, which can easily be determined experimentally. At high dry matter contents strong mixing is necessary because, the slurry is thick and the reagents do not easily come into contact with each other.
- the hemihydrate and/or anhydrite, the aqueous fibre suspension and optionally the crystallization habit modifier are mixed at the above mentioned temperature given for the water.
- the initial pH is typically between 3.5 and 9.0, most preferably between 4.0 and 7.5. It is preferred that the initial pH is acidic, preferably between 3 and 7, more preferably between 3 and 6. If necessary, the pH is regulated by means of an aqueous solution of NaOH and/or H 2 SO 4 , typically a 10 % solution of NaOH and/or H 2 SO 4 . Because gypsum has a lower solubility in water than hemihydrate and soluble anhydrite, the gypsum formed by the reaction of hemihydrate and/or anhydrite with water immediately tends to crystallize from the water medium.
- the crystallization according to the invention can be regulated by means of the above mentioned crystallization habit modifier so that a useful product according to the invention is obtained.
- the gypsum -fibre composite product of the present invention can also be treated with other additives.
- a typical additive is a biocide which prevents the activity of microorganisms when storing and using the product.
- a paper product comprising the gypsum -fibre composite product of the invention as a filler pigment or coating pigment.
- An especially preferred paper product is fine paper which typically is uncoated and preferably woodfree (prepared from chemical pulp).
- fine papers are writing and printing grade papers including offset, bond, duplicating and photocopying papers.
- the amount of the gypsum -fibre composite product in the paper product is from 20 to 100 % by weight on dry basis.
- Other preferred ranges are from 20 to 90 % and 20 to 80 % and 20 to 70 % and 20 to 60 % and 20 to 50% by weight on dry basis.
- Additional preferred ranges are from 30 to 100 % and from 40 to 100 % and from 50 to 100 % and 60 to 100 % by weight on dry basis.
- the paper product of the present invention preferably comprises in addition to the gypsum -fibre composite product cellulosic fibres.
- the cellulosic fibres comprise conventional papermaking pulp fibres in- eluding chemical, mechanical, chemi-mechanical or deinked pulp fibres.
- Chemical pulps include kraft pulp and sulphite pulp.
- Mechanical pulps include stone groundwood pulp (SGW), refiner mechanical pulp (RMP), pressure groundwood
- PGW thermomechanical pulp
- CMP chemically treated high-yield pulps
- MOW mixed office waste
- OOG newsprint
- OMG magazines
- Said cellulosic fibres can be similar as or different from the fiber in the gypsum - fibre composite product, and preferably the fibres are similar.
- the cellulosic fibres are preferably kraft pulp fibres.
- the amount of the gypsum -fibre composite product in the paper product is preferably from 10 to 60 %, more preferably from 20 to 50 % by weight on dry basis.
- the amount of said cellulosic fibres in the paper product is pref- erably from 40 to 90 %, more preferably from 50 to 80 % by weight on dry basis.
- the invention relates to the use of the gypsum -fibre composite product of the invention as a filler pigment or coating pigment in the production of paper.
- Figures 1-8 show electron microscope micrographs of calcium sulfate dihydrate - fiber composite products of examples 1-8, figure 9 shows electron microscope micrographs of paper samples, and figures 10-16 show various properties of paper samples.
- Figure 1 a shows SEM micrograph of calcium sulfate dihydrate/ TMP composite at hemihydrate solids content of 18% (HH/(HH+water)).
- Figure 1 b shows SEM micrograph of the same composite as in Figure 1 a washed in saturated calcium sulfate solution.
- Figure 2a shows SEM micrograph of calcium sulfate dihydrate/ TMP composite at hemihydrate solids content of 42% (HH/(HH+water)).
- Figure 2b shows SEM micrograph of the same composite as in Figure 2a washed in saturated calcium sulfate solution.
- Figure 3 shows SEM micrograph of calcium sulfate dihydrate/ eucalyptus kraft pulp composite at hemihydrate solids content of 6.25% (HH/(HH+water)).
- Figure 4 shows SEM micrograph of the fibers from calcium sulfate dihydrate/ eu- calyptus kraft pulp composite at hemihydrate solid s content of 7.5% (HH/(HH+water)).
- Figure 5a shows SEM micrograph of calcium sulfate dihydrate/ pine kraft pulp composite using poly aluminum chloride as fixative, composite being washed with saturated calcium sulfate solution.
- Figure 5b shows SEM micrograph of the same composite as in Figure 5a being stirred with Heidolph laboratory mixer at 350 rpm for a couple of minutes.
- Figure 6a shows SEM micrograph of calcium sulfate dihydrate/ pine kraft pulp composite using poly-DADMAC as fixative, composite being washed with satu- rated calcium sulfate solution.
- Figure 6b shows SEM micrograph of the same composite as in Figure 6a being stirred with Heidolph laboratory mixer at 350 rpm for a couple of minutes.
- Figure 7 shows SEM micrograph of calcium sulfate dihydrate/ birch kraft pulp composite washed with saturated calcium sulfate solution.
- Figure 8 shows SEM micrograph of calcium sulfate dihydrate/ plastic fiber composite washed with saturated calcium sulfate solution.
- Figures 9a, 9b and 9c show cross sectional SEM images of uncalendered paper samples.
- Figure 10 shows Yellowness of paper samples.
- Figure 11 shows Light scattering and opacity of paper samples.
- Figure 12 shows ISO Brightness, CIE Whiteness and CIE L * of paper samples.
- Figure 13 shows PPS Roughness of both sides of uncalendered paper samples.
- Figure 14 shows PPS Roughness of uncalendered and calendered paper samples.
- Figure 15 shows air permeability (Bendtsen porosity) of paper samples.
- Figure 16 shows light scattering vs. tensile index of paper samples.
- HH initial hemihydrate, w-%) 5-57 Fiber concentration (w-%) 3-30
- the reaction was carried out at system pH.
- the amount of habit modifier chemical is calculated as per cent of the precipitated calcium sulfate dihydrate (w-% of DH)
- the reactor was of Hobart type N50CE.
- the hemihydrate and the chemicals are added batchwise to the aqueous fiber suspension phase and a hemihydrate slurry with an initial solids of 5 - 57 w-% is obtained.
- Mixing speed is about 250 - 500 rpm. Reaction is carried out at system pH.
- Morphology of calcium sulfate dihydrate was studied by using FEI XL 30 FEG scanning electron microscope. Conversion of hemihydrate to dihydrate was analyzed using Mettler Toledo TGA/SDTA85 1/1100-thermogravimetric analyzer (TG). Crystal structure was determined with Philips X'pert x-ray powder diffractometer (XRD).
- TMP Thermomechanical pulp
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 200 g (giving 18 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes. 4. Wait for the formation of calcium sulfate dihydrate for one hour.
- the obtained pigment-fiber composite is shown in figure 1 a, after washing with calcium sulfate saturated water in figure 1 b.
- TMP Thermomechanical pulp
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 570 g (giving 42 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes.
- the obtained pigment-fiber composite is shown in figure 2a, after washing with calcium sulfate saturated water in figure 2b.
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 25 g (giving 6.25 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes. 3. Wait for the formation of calcium sulfate dihydrate for one hour.
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 25 g (giving 7.5 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes.
- the obtained fiber product is shown in figure 4.
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 160 g (giving 20 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes.
- the obtained pigment-fiber composite after washing with calcium sulfate saturated water is shown in figure 5.
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 200 g (giving 20 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes.
- Fluidized bed calcined ⁇ -calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1.
- the total amount of hemihydrate added is 300 g (giving 34 % by weight of HH/(HH+water)).
- the operation speed of the stirrer is raised to position 2.
- Composite is stirred for five minutes. 4. Wait for the formation of calcium sulfate dihydrate for one hour.
- Calcium sulphate was precipitated on eucalyptus kraft pulp refined to SR 32. Fiber solids content was 8% and hemihydrates solids 20% in the precipitation. Filler levels of the hand sheets were adjusted to 20, 30 and 40% by changing the composite/ untreated pulp ratio. Composite was disintegrated using valley Hollander re- finer without weights for 30 minutes. Hand sheets were prepared using Haage Rapid Koethen Sheet Former. Basis weight was 60 g/m 2 .
- Figure 9a shows cross sectional SEM images of uncalendered paper sheets comprising gypsum -fiber composite of the present invention
- figure 9b shows cross sectional SEM images of uncalendered paper sheets comprising PCS (precipi- tated calcium sulphate) representing the prior art
- figure 9c shows cross sectional SEM images of uncalendered paper sheets comprising PCC (precipitated calcium carbonate) filler representing the prior art.
- Kompo and “Composite” refer to the gypsum -fiber composite of the present invention
- PCC stands for precipitated calcium carbonate
- PCS for precipitated calcium sulphate.
- the figure 30 in e.g. Kompo30 refers to the filler level of 30%.
- Grammage was measured according to standard ISO 536, thickness, density and bulk using ISO 534, PPS roughness using ISO 8791 -4, gloss Tappi 75° with ISO 8254-1 , air permeability with ISO 5636-3, ash content was determined using ISO 1762 standard by heating the samples at 850 0 C for three hours, tensile strength index was measured using L&W tensile tester and ISO standard
- the results in figure 11 show that Kompo improved light scattering with about 15 units compared to PCS and with about 3 units compared to PCC.
- the results in figure 11 also show that the opacity was improved for Kompo by about 2 units compared to PCC and PCS.
- the PPS Roughness results in figure 14 show that the Kompo had lowest roughness for uncalendered paper samples and for calendered paper samples at all tested calendering loads (10 kN, 30 kN and 50 kN).
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a gypsum -fibre composite product, wherein the gypsum appears as crystals on the surface of the fibre and wherein the gypsum crystals are obtained by contacting calcium sulphate hemihydrate and/or calcium anhydrite and an aqueous fibre suspension. The invention also relates to a process for the preparation of the gypsum -fibre composite product. The composite product can be used as a filler pigment or coating pigment in the production of paper.
Description
GYPSUM PRODUCT
OBJECTS OF THE INVENTION
The invention relates to a gypsum -fibre composite product. The gypsum -fibre composite product can be used as a coating pigment or a filler pigment in the pro- duction of paper. The invention also relates to a process for the preparation of the gypsum -fibre composite product. In the production of paper improved retention of the filler pigment and homogenous filler distribution can be obtained.
BACKGROUND OF THE INVENTION
A papermaking process starts with stock preparation where cellulosic fibers are mixed with water and mineral filler (usually clay or calcium carbonate or also gypsum). The obtained slurry is delivered by means of a head box on a forming fabric or press fabric or wire to form a fibrous web of cellulosic fibers at the forming section of the paper machine. Then water is drained in the draining section and the formed web is conducted to the press section including a series of roll presses where additional water is removed. The web is then conducted to the drying section of the paper machine where most of the remaining water is evaporated typically by means of steam-heated dryer drums. Post drying operations include calendering where the dry paper product passes between rolls under pressure, thereby improving the surface smoothness and gloss and making the cali- per/thickness profile more uniform. There are various calenders such as machine calenders where the rolls usually are steel rolls and include a heated roll (thermo roll).
Gypsum or calcium sulphate dihydrate CaSO4-2H2O is suitable as material for both coating pigment and filler, especially in paper products. Especially good coat- ing pigment and filler is obtained if the particular gypsum has high brightness, gloss and opacity. The gloss is high when the particles are sufficiently small, flat and broad (platy). The opacity is high when the particles are refractive, small and of equal size (narrow particle size distribution).
The morphology of the gypsum product particles can be established by examining scanning electron micrographs. Useful micrographs are obtained e.g. with a scanning electron microscope of the type Philips FEI XL 30 FEG.
The size of the gypsum product particles is expressed as the weight average diameter D50 of the particles contained therein. More precisely, D50 is the diameter of
the presumably round particle, smaller than which particles constitute 50 % of the total particle weight. D50 can be measured with an appropriate particle size analyzer, such as Sedigraph 5100.
The flatness of a crystal means that it is thin. The form of flat crystals is suitably expressed by means of the shape ratio SR. The SR is the ratio of the crystal length (the longest measure) to the crystal thickness (the shortest transverse measure). By the SR of the claimed gypsum product is meant the average SR of its individual crystals.
The platyness of a crystal means that it is broad. Platyness is suitable expressed by means of the aspect ratio AR. The AR is the ratio between the crystal length (the longest measure) and the crystal width (the longest transverse measure). By the AR of the claimed gypsum product is meant the average AR of its individual crystals.
Both the SR and the AR of the gypsum product can be estimated by examining its scanning electron micrographs. A suitable scanning electron microscope is the above mentioned Philips FEI XL 30 FEG.
Equal crystal particle size means that the crystal particle size distribution is narrow. The width is expressed as the gravimetric weight distribution WPSD and it is expressed as (D75-D2SyD50 wherein D75, D25 and D50 are the diameters of the pre- sumably round particles, smaller than which particles constitute 75, 25 and 50 %, respectively, of the total weight of the particles. The width of the particle distribution is obtained with a suitable particle size analyzer such as the above mentioned type Sedigraph 5100.
Gypsum occurs as a natural mineral or it is formed as a by-product of chemical processes, e.g. as phosphogypsum or flue gas gypsum. In order to refine the gypsum further by crystallising it into coating pigment or filler, it must first be calcined into calcium sulphate hemihydrate (CaSO4-1/4H2O), after which it may be hydrated back by dissolving the hemihydrate in water and precipitating to give pure gypsum. Calcium sulphate may also occur in the form of anhydrite lacking crystalline water (CaSO4).
Depending on the calcination conditions of the gypsum raw material, the calcium sulphate hemihydrate may occur in two forms; as α- and β-hemihydrate. The β- form is obtained by heat-treating the gypsum raw material at atmospheric pressure while the α-form is obtained by treating the gypsum raw material at a steam pres-
sure which is higher than atmospheric pressure or by means of chemical wet calcination from salt or acid solutions at e.g. about 45 °C.
WO 88/05423 discloses a process for the preparation of gypsum by hydrating calcium sulphate hemihydrate in an aqueous slurry thereof, the dry matter content of which is between 20 and 25 % by weight. Gypsum is obtained, the largest measure of which is from 100 to 450 μm and the second larges measure of which is from 10 to 40 μm.
AU 620857 (EP 0334292 A1 ) discloses a process for the preparation of gypsum from a slurry containing not more than 33,33 % by weight of ground hemihydrate, thereby yielding needle-like crystals having an average size of between 2 and 200 μm and an aspect ratio between 5 and 50. See page 15, lines 5 to 11 , and the examples of this document.
US 2004/0241082 describes a process for the preparation of small needle-like gypsum crystals (length from 5 to 35 μm, width from 1 to 5 μm) from an aqueous slurry of hemihydrate having a dry matter content of between 5 and 25 % by weight. The idea in this US document is to reduce the water solubility of the gypsum by means of an additive in order to prevent the crystals from dissolving during paper manufacture.
DE 32 23 178 C1 discloses a process for producing organic fibres coated with one or more mineral substances. One embodiment comprises mixing cellulose fibres, gypsum and water. The mixture is compacted to give a plastic mass which subsequently is dried and mechanically comminuted to give fine particles. The obtained product can be used as an additive or filler e.g. in bitumen masses or putties.
WO 2008/092990 discloses a gypsum product consisting of intact crystals having a size from 0.1 to 2.0 μm. The crystals have a shape ratio SR of at least 2.0, preferably between 2.0 and 50, and a aspect ratio AR between 1.0 and 10, preferably between 1.0 and below 5.0.
WO 2008/092991 discloses a process for the preparation of a gypsum product wherein calcium sulphate hemihydrate and/or calcium sulphate anhydrite and wa- ter are contacted so that the calcium sulphate hemihydrate and/or calcium sulphate anhydrite and the water react with each other and form a crystalline gypsum product. The formed reaction mixture has a dry matter content of between 34 and 84 % by weight.
DESCRIPTION OF THE INVENTION
The aim of the invention is to provide a gypsum -fibre composite product wherein the gypsum is crystallized on the surface of the fibre and attached fairly strongly to the fibre. The composite product can be used as a filler pigment or coating pig- ment in the production of paper. In the production of paper improved retention of the filler pigment and homogenous filler distribution can be obtained. Also higher filler load can be obtained. The gypsum -fibre composite product of the invention is especially well suited for the production of fine paper.
Thus, according to a first aspect of the invention there is provided a gypsum -fibre composite product, wherein the gypsum appears as crystals on the surface of the fibre and wherein the gypsum crystals are obtained by contacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and an aqueous fibre suspension.
The gypsum is attached to the fibre and consequently the gypsum -fibre composite is shown by most measurement methods as a single piece. The shape and size of the gypsum can roughly be estimated by means of microscopic images. The gypsum crystals attached to the fibre can have the shapes and sizes described in WO 2008/092990 and WO 2008/092991. However, according to the invention the crystallized gypsum can also be needle-like.
The size of the gypsum crystals is preferably from 0.1 to 5.0 μm, more preferably from 0.1 to 4.0 μm, and most preferably from 0.2 to 4.0 μm. The size of the gypsum crystals may also be from 0.1 to 2.0 μm or from 0.2 to 2.0 μm.
Preferably the fibre of the gypsum -fibre composite product comprises a cellulosic fibre such as a chemical, mechanical, chemi-mechanical or deinked pulp fibre or a synthetic fibre, such as a polyolefine, e.g. polypropene. Chemical pulps include kraft pulp and sulphite pulp. Mechanical pulps include stone groundwood pulp (SGW), refiner mechanical pulp (RMP), pressure groundwood (PGW), thermome- chanical pulp (TMP), and also chemically treated high-yield pulps such as chemi- thermomechanical pulp (CTMP). Deinked pulp can be made using mixed office waste (MOW), newsprint (ONP), magazines (OMG) etc. Also mixtures of different pulps can be used.
Preferably the weight ratio of gypsum to fibre on dry basis is in the range from 95:5 to 50:50, preferably from 75:25 to 50:50.
According to the invention the gypsum -fibre composite product may additionally comprise additional substances such as a natural or synthetic polymer binder and/or an optical bhghtener and/or a rheology modifier and/or sizing agents. The sizing agent may be a rosin size or a reactive size such as alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA).
As was stated before, the gypsum product of the invention is typically a coating or filler pigment. In addition to use as a paper additive, it can also be used as plastics filler, and as a raw material in glass industry, cosmetics, printing inks, building materials and paints. According to one embodiment of the invention, the composite product is a coating pigment and comprises gypsum crystals preferably having a size of between 0.1 and 1.0 μm, more preferably between 0.5 and 1.0 μm. According to another embodiment, it is a filler and comprises gypsum crystals preferably having a size of between 1 .0 and 5.0 μm, more preferably between 1 .0 and 4.0 μm. The gypsum crystals in the filler composite may also have a size of between 1.0 and below 2.0 μm.
According to a second aspect of the invention there is provided a process for the preparation of a gypsum -fibre composite product, comprising contacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and an aqueous fibre suspension to form gypsum crystals on the surface of the fibre.
Preferably the weigh ratio of calcium sulphate hemihydrate and/or calcium sulphate anhydrite to water in the crystallization is in the range from 0.03 to 0.6:1 , more preferably from 0.05 to 0.5:1.
Preferably the dry fiber content in the crystallization is from 3 to 30 % by weight.
Preferably the content of calcium sulphate hemihydrate and/or calcium sulphate anhydrite in the crystallization is from 10 to 57 % by weight.
The process of the invention may additionally comprise the steps of drying and comminuting the obtained product to form a gypsum -fibre composite product in the form of particles. According to the invention a fixative can be introduced into the crystallization.
The fixative can be selected from the group consisting of poly aluminum chloride, poly diallyldimethylammonium chloride (poly DADMAC), anionic and cationic poly- acrylates.
According to the invention the crystallization can be carried out in the absence of crystallization habit modifiers.
According to the invention the crystallization can also be carried out in the presence of a crystallization habit modifier.
The crystallization habit modifier can be added to water or aqueous fibre suspension before the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
The temperature of the water in the reaction mixture can be anything between 0 and 100 °C. Preferably, the temperature is between 0 and 80 °C, more preferably between 0 and 50 °C, even more preferably between 0 and 40 °C, most preferably between 0 and 25 °C.
According to one embodiment of the invention, the crystallization habit modifier is an inorganic acid, oxide, base or salt. Examples of useful inorganic oxides, bases and salts are AIF3, AI2(SO4)3, CaCI2, Ca(OH)2, H3BO4, NaCI , Na2SO4, NaOH, NH4OH, (NH4)2SO4, MgCI2, MgSO4 and MgO.
According to another embodiment, the crystallization habit modifier is an organic compound, which is an alcohol, an acid or a salt. Suitable alcohols are methanol, ethanol, 1 -butanol, 2-butanol, 1 -hexanol, 2-octanol, glycerol, i-propanol and alkyl polyglucoside based Cs-Cio-fatty alcohols.
The crystallization habit modifier is preferably a compound having in its molecule one or several carboxylic or sulphonic acidic groups, or a salt of such a compound. Among the organic acids may be mentioned carboxylic acids such as acetic acid, propionic acid, succinic acid, citric acid, tartaric acid, ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene thamine pentaacetic acid (DTPA), nithlotriacetic acid (NTA), N-bis-(2- (1 ,2-dicarboxyethoxy)ethyl aspartic acid (AES), and sulphonic acids such as amino-1 -naphthol-3,6-disulphonic acid, 8-amino-1 -naphthol-3,6-disulphonic acid, 2-aminophenol-4-sulphonic acid, anthrachinone-2,6-disulphonic acid, 2- mercaptoethanesulphonic acid, poly(styrene sulphonic acid), poly(vinylsulphonic acid), as well as the di-, tetra- and hexa-aminostilbenesulfonic acids.
Among the organic salt may be mentioned the salts of carboxylic acids such as Mg formiate, N a- and NH4 -acetate, Na2-maleate, NH4-citrate, Na2-succinate, K- oleate, K-stearate, Na2-ethylenediamine tetraacetic acid (Na2-EDTA), Naβ- aspartamic acid ethoxy succinate (Naβ-AES) and Naβ-aminotriethoxy succinate (Na6-TCA).
Also the salt of sulphonic acids are useful, such as Na-n-(CiO-Ci3)-alkylbenzene sulphonate, Cio-Ci6-alkylbenzene sulphonate, Na-1 -octyl sul phonate, Na-1- dodecane sulphonate, Na-1 -hexadecane sulphonate, the K-fatty acid sulphonates, the Na-Ci4-Ci6-olefin sulphonate, the Na-alkylnaphthalene sulphonates with ani- onic or non-ionic surfactants, di-K-oleic acid sulphonates, as well as the salts of di- , tetra-, and hexaaminostilbene sulphonic acids. Among organic salts containing sulphur should also be mentioned the sulphates such as the Ci2-Ci4-fatty alcohol ether sulphates, Na-2-ethyl hexyl sulphate, Na-n-dodecyl sulphate and Na-lauryl sulphate, and the sulphosuccinates such as the monoalkyl polyglycol ether of Na- sulphosuccinate, Na-dioctyl sulphosuccinate and Na-dialkyl sulphosuccinate.
Phosphates may also be used, such as the Na-nonylphenyl- and Na-dinonyl phenylethoxylated phosphate esters, the K-aryl ether phosphates, as well as the triethanolamine salts of polyaryl polyetherphosphate.
As crystallization habit modifier may also be used cationic surfactants such as oc- tyl amine, triethanol amine, di(hydrogenated animal fat alkyl) dimethyl ammonium chloride, and non-ionic surfactants such as a variety of modified fatty alcohol eth- oxylates. Among useful polymeric acids, salts, amides and alcohols may be mentioned the polyacrylic acids and polyacrylates, the acrylate-maleate copolymers, polyacrylamide, poly(2-ethyl-2-oxazoline), polyvinyl phosphonic acid, the copoly- mer of acrylic acid and allylhydroxypropyl sulphonate (AA-AHPS), poly-α- hydroxyacrylic acid (PHAS), polyvinyl alcohol, and poly(methyl vinyl ether - alt.- maleic acid).
Especially preferable crystallization habit modifiers are ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene thamine pentaacetic acid (DTPA), nithlotriacetic acid (NTA), N-bis-(2- (1 ,2-dicarboxyethoxy)ethyl aspartic acid (AES), the di-, tetra- and hexa- aminostilbenesulfonic acids and their salts such as Na-aminothethoxy succinate (Naβ-TCA), as well as the alkylbenzenesulphonat.es.
In the process of the invention, the crystallization habit modifier can be used in an amount of 0.01 to 5.0 %, most preferably 0.02-1.78 %, based on the weight of the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
In the process according to the invention, β-calcium sulphate hemihydrate is typi- cally used. It may be prepared by heating gypsum raw-material to a temperature of between 140 and 300 °C, preferably from 150 to 200 °C. At lower temperatures, the gypsum raw-material is not sufficiently dehydrated and at higher temperatures it is over-dehydrated into anhydrite. Calcinated calcium sulphate hemihydrate usually contains impurities in the form of small amounts of calcium sulphate dihydrate and/or calcium sulphate anhydrite. It is preferable to use β-calcium sulphate hemihydrate obtained by flash calcination, e.g by fluid bed calcination, whereby the gypsum raw-material is heated to the required temperature as fast as possible. However, it is also possible to use α-calcium sulphate hemihydrate in the crystallization.
It is also possible to use calcium sulphate anhydrite as starting material for the process of the invention. The anhydrite is obtained by calcination of gypsum raw material. There are three forms of anhydrite; the first one, the so called Anhydrite I, is unable to form gypsum by reaction with water like the insoluble Anhydrites ll-u and M-E. The other forms, the so called Anhydrite III, also known as soluble anhy- drite has three forms: β-anhydrite III, β-anhydrite III', and a-anhydrite III and Anhydrite ll-s form pure gypsum upon contact with water.
As the calcium sulphate hemihydrate and/or calcium sulphate anhydrite, aqueous fibre suspension and optionally crystallization habit modifier have been contacted, they are allowed to react into calcium sulphate dihydrate i.e. gypsum. The reaction takes e.g. place by mixing, preferably by mixing strongly, said substances together for a sufficient period of time, which can easily be determined experimentally. At high dry matter contents strong mixing is necessary because, the slurry is thick and the reagents do not easily come into contact with each other. Preferably the hemihydrate and/or anhydrite, the aqueous fibre suspension and optionally the crystallization habit modifier are mixed at the above mentioned temperature given for the water. The initial pH is typically between 3.5 and 9.0, most preferably between 4.0 and 7.5. It is preferred that the initial pH is acidic, preferably between 3 and 7, more preferably between 3 and 6. If necessary, the pH is regulated by means of an aqueous solution of NaOH and/or H2SO4, typically a 10 % solution of NaOH and/or H2SO4.
Because gypsum has a lower solubility in water than hemihydrate and soluble anhydrite, the gypsum formed by the reaction of hemihydrate and/or anhydrite with water immediately tends to crystallize from the water medium. The crystallization according to the invention can be regulated by means of the above mentioned crystallization habit modifier so that a useful product according to the invention is obtained.
The gypsum -fibre composite product of the present invention can also be treated with other additives. A typical additive is a biocide which prevents the activity of microorganisms when storing and using the product.
According to a third aspect of the invention there is provided a paper product comprising the gypsum -fibre composite product of the invention as a filler pigment or coating pigment.
An especially preferred paper product is fine paper which typically is uncoated and preferably woodfree (prepared from chemical pulp). Examples of fine papers are writing and printing grade papers including offset, bond, duplicating and photocopying papers.
Preferably the amount of the gypsum -fibre composite product in the paper product is from 20 to 100 % by weight on dry basis. Other preferred ranges are from 20 to 90 % and 20 to 80 % and 20 to 70 % and 20 to 60 % and 20 to 50% by weight on dry basis. Additional preferred ranges are from 30 to 100 % and from 40 to 100 % and from 50 to 100 % and 60 to 100 % by weight on dry basis.
The paper product of the present invention preferably comprises in addition to the gypsum -fibre composite product cellulosic fibres.
Preferably the cellulosic fibres comprise conventional papermaking pulp fibres in- eluding chemical, mechanical, chemi-mechanical or deinked pulp fibres. Chemical pulps include kraft pulp and sulphite pulp. Mechanical pulps include stone groundwood pulp (SGW), refiner mechanical pulp (RMP), pressure groundwood
(PGW), thermomechanical pulp (TMP), and also chemically treated high-yield pulps such as chemithermomechanical pulp (CTMP). Deinked pulp can be made using mixed office waste (MOW), newsprint (ONP), magazines (OMG) etc. Also mixtures of different pulps can be used.
Said cellulosic fibres can be similar as or different from the fiber in the gypsum - fibre composite product, and preferably the fibres are similar.
For fine papers the cellulosic fibres are preferably kraft pulp fibres.
The amount of the gypsum -fibre composite product in the paper product is preferably from 10 to 60 %, more preferably from 20 to 50 % by weight on dry basis. Correspondingly the amount of said cellulosic fibres in the paper product is pref- erably from 40 to 90 %, more preferably from 50 to 80 % by weight on dry basis.
Additionally the invention relates to the use of the gypsum -fibre composite product of the invention as a filler pigment or coating pigment in the production of paper.
SHORT DESCRIPTION OF THE DRAWINGS
Figures 1-8 show electron microscope micrographs of calcium sulfate dihydrate - fiber composite products of examples 1-8, figure 9 shows electron microscope micrographs of paper samples, and figures 10-16 show various properties of paper samples.
Figure 1 a shows SEM micrograph of calcium sulfate dihydrate/ TMP composite at hemihydrate solids content of 18% (HH/(HH+water)).
Figure 1 b shows SEM micrograph of the same composite as in Figure 1 a washed in saturated calcium sulfate solution.
Figure 2a shows SEM micrograph of calcium sulfate dihydrate/ TMP composite at hemihydrate solids content of 42% (HH/(HH+water)).
Figure 2b shows SEM micrograph of the same composite as in Figure 2a washed in saturated calcium sulfate solution.
Figure 3 shows SEM micrograph of calcium sulfate dihydrate/ eucalyptus kraft pulp composite at hemihydrate solids content of 6.25% (HH/(HH+water)).
Figure 4 shows SEM micrograph of the fibers from calcium sulfate dihydrate/ eu- calyptus kraft pulp composite at hemihydrate solid s content of 7.5% (HH/(HH+water)).
Figure 5a shows SEM micrograph of calcium sulfate dihydrate/ pine kraft pulp composite using poly aluminum chloride as fixative, composite being washed with saturated calcium sulfate solution.
Figure 5b shows SEM micrograph of the same composite as in Figure 5a being stirred with Heidolph laboratory mixer at 350 rpm for a couple of minutes.
Figure 6a shows SEM micrograph of calcium sulfate dihydrate/ pine kraft pulp composite using poly-DADMAC as fixative, composite being washed with satu- rated calcium sulfate solution.
Figure 6b shows SEM micrograph of the same composite as in Figure 6a being stirred with Heidolph laboratory mixer at 350 rpm for a couple of minutes.
Figure 7 shows SEM micrograph of calcium sulfate dihydrate/ birch kraft pulp composite washed with saturated calcium sulfate solution.
Figure 8 shows SEM micrograph of calcium sulfate dihydrate/ plastic fiber composite washed with saturated calcium sulfate solution.
Figures 9a, 9b and 9c show cross sectional SEM images of uncalendered paper samples.
Figure 10 shows Yellowness of paper samples.
Figure 11 shows Light scattering and opacity of paper samples.
Figure 12 shows ISO Brightness, CIE Whiteness and CIE L* of paper samples.
Figure 13 shows PPS Roughness of both sides of uncalendered paper samples.
Figure 14 shows PPS Roughness of uncalendered and calendered paper samples. Figure 15 shows air permeability (Bendtsen porosity) of paper samples.
Figure 16 shows light scattering vs. tensile index of paper samples.
EXAMPLES
In the following the invention will be illustrated in more detail by means of examples. The purpose of the examples is not to restrict the scope of the claims. In this specification the percentages refer to % by weight unless otherwise specified.
First, general information about the syntheses and product analyses is disclosed. Then, data about each example is presented.
Synthesis
General information is first presented. A method optimization for the paper pigments was carried out. The parameters were:
HH (initial hemihydrate, w-%) 5-57 Fiber concentration (w-%) 3-30
Additive concentration (w-% of DH(dihydrate) ) 0.100-1
The reaction was carried out at system pH. The amount of habit modifier chemical is calculated as per cent of the precipitated calcium sulfate dihydrate (w-% of DH)
The experiments were performed with the following equipment.
The reactor was of Hobart type N50CE. The hemihydrate and the chemicals are added batchwise to the aqueous fiber suspension phase and a hemihydrate slurry with an initial solids of 5 - 57 w-% is obtained. Mixing speed is about 250 - 500 rpm. Reaction is carried out at system pH.
Analysis
Morphology of calcium sulfate dihydrate was studied by using FEI XL 30 FEG scanning electron microscope. Conversion of hemihydrate to dihydrate was analyzed using Mettler Toledo TGA/SDTA85 1/1100-thermogravimetric analyzer (TG). Crystal structure was determined with Philips X'pert x-ray powder diffractometer (XRD).
Example 1
1. 800 g of water is placed into the Hobart N50 CE laboratory mixer. Couple of drops of biocide (Fennosan IT 21 ) is added.
2. 200 g of TMP (Thermomechanical pulp) with solids content of 36% is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 200 g (giving 18 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite is shown in figure 1 a, after washing with calcium sulfate saturated water in figure 1 b.
Example 2
1 . 430 g of water is placed into the Hobart N50 CE laboratory mixer. Couple of drops of biocide (Fennosan IT 21 ) is added.
2. 570 g of TMP (Thermomechanical pulp) with solids content of 36% is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 570 g (giving 42 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite is shown in figure 2a, after washing with calcium sulfate saturated water in figure 2b.
Example 3
1. 456.5 g of eucalyptus kraft pulp with solids content of 17.7% is placed into the Hobart N50 CE laboratory mixer.
2. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 25 g (giving 6.25 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes. 3. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite after washing with calcium sulfate saturated water is shown in figure 3.
Example 4
1. 47 g of water is placed into the Hobart N50 CE laboratory mixer. Couple of drops of biocide (Fennosan IT 21 ) is added.
2. 295.5 g of eucalyptus kraft pulp with solids content of 17.7% is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 25 g (giving 7.5 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained fiber product is shown in figure 4.
Example 5
1. 44.8 g of water is placed into the Hobart N50 CE laboratory mixer. 1.6 g of poly aluminum chloride and couple of drops of biocide (Fennosan IT 21 ) is added.
2. 640 g of pine kraft pulp with solids content of 7% is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 160 g (giving 20 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite after washing with calcium sulfate saturated water is shown in figure 5.
Example 6
1. 15.8 g of water is placed into the Hobart N50 CE laboratory mixer. 0.6 g of poly DADMAC and couple of drops of biocide (Fennosan IT 21 ) is added.
2. 226 g of pine kraft pulp with solids content of 7% is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 300 g (giving 57 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite after washing with calcium sulfate saturated water is shown in figure 6.
Example 7
1 . 1 16 g of water is placed into the Hobart N50 CE laboratory mixer. Couple of drops of biocide (Fennosan IT 21 ) is added.
2. 800 g of birch kraft pulp (solids content 14.5%) is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 200 g (giving 20 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite after washing with calcium sulfate saturated water is shown in figure 7.
Example 8
1. 600 g of water is placed into the Hobart N50 CE laboratory mixer. Couple of drops of biocide (Fennosan IT 21 ) is added.
2. 10 g of synthetic polypropene fiber is added to the reactor.
3. Fluidized bed calcined β-calcium sulphate hemihydrate is evenly added to the reactor with the operation speed of the stirrer set to position 1. The total amount of hemihydrate added is 300 g (giving 34 % by weight of HH/(HH+water)). After the addition the operation speed of the stirrer is raised to position 2. Composite is stirred for five minutes.
4. Wait for the formation of calcium sulfate dihydrate for one hour.
The obtained pigment-fiber composite after washing with calcium sulfate saturated water is shown in figure 8.
Example 9
Application tests were carried out with pigment -fiber composite as follows.
Calcium sulphate was precipitated on eucalyptus kraft pulp refined to SR 32. Fiber solids content was 8% and hemihydrates solids 20% in the precipitation. Filler levels of the hand sheets were adjusted to 20, 30 and 40% by changing the composite/ untreated pulp ratio. Composite was disintegrated using valley Hollander re- finer without weights for 30 minutes. Hand sheets were prepared using Haage Rapid Koethen Sheet Former. Basis weight was 60 g/m2.
Figure 9a shows cross sectional SEM images of uncalendered paper sheets comprising gypsum -fiber composite of the present invention, figure 9b shows cross sectional SEM images of uncalendered paper sheets comprising PCS (precipi- tated calcium sulphate) representing the prior art, and figure 9c shows cross sectional SEM images of uncalendered paper sheets comprising PCC (precipitated calcium carbonate) filler representing the prior art. As can be seen in Figures 9a- 9c the paper obtained using calcium sulfate filler -fiber composite according to the present invention (Figure 9a) is smooth, dense and has homogeneous filler distri- bution, whereas the papers obtained using PCS and PCC fillers (Figures 9b and 9c) are less smooth and dense and have inhomogeneous filler distribution.
In the following "Kompo" and "Composite" refer to the gypsum -fiber composite of the present invention, PCC stands for precipitated calcium carbonate and PCS for precipitated calcium sulphate. The figure 30 in e.g. Kompo30 refers to the filler level of 30%.
Grammage was measured according to standard ISO 536, thickness, density and bulk using ISO 534, PPS roughness using ISO 8791 -4, gloss Tappi 75° with ISO 8254-1 , air permeability with ISO 5636-3, ash content was determined using ISO 1762 standard by heating the samples at 850 0C for three hours,
tensile strength index was measured using L&W tensile tester and ISO standard
1924-3, tear index was measured using ISO 1974, and
Scott Bond using T 569.
Following results were obtained.
The results in figure 10 show that the Yellowness (CIE yellow colour coordinate b*(C/2°)) was much lower for Kompo than for PCC and PCS.
The results in figure 11 show that Kompo improved light scattering with about 15 units compared to PCS and with about 3 units compared to PCC. The results in figure 11 also show that the opacity was improved for Kompo by about 2 units compared to PCC and PCS.
The results in figure 12 show that the ISO-Brightness (C/2° brightness measured at R457) for Kompo was increased compared to PCS and at the same level as for PCC. Furthermore the CIE Whiteness for Kompo was improved compared to both PCC and PCS. The CIE L* (C/2°) were equal for all three fillers. CIE L* is a measure of lightness and varies from 100 for perfect white to 0 for absolute black.
The PPS Roughness results in figure 13 show that smoother uncalendered paper surfaces, both top side (TS) and wire side (WS), were obtained using Composite at various filler levels as compared to PCC and PCS. Also the difference in rough- ness between top side (TS) and wire side (WS) was very low for Composite.
The PPS Roughness results in figure 14 show that the Kompo had lowest roughness for uncalendered paper samples and for calendered paper samples at all tested calendering loads (10 kN, 30 kN and 50 kN).
The results in figure 15 show that Air permeability, i.e. Brendtsen porosity, was lower for Kompo than for PCC and PCS for uncalendered paper samples and for calendered paper samples at all tested calendering loads (10 kN, 30 kN and 50 kN). Thus, a dense paper sheet with lower bulk was obtained using Kompo. The results also show that increasing filler content decreases the air permeability.
In figure 16 the light scattering is shown against tensile index. The results show that for the composite of the invention the scattering - tensile strength relationship is good.
Since composite samples were smoother than the other samples different calendering conditions can be used for same roughness values. Comparison at same roughness is shown in table 1 and at same bulk in table 2 for samples with filler content 30%.
In following Table 1 various paper properties are compiled.
Table 1
The results show that at the same roughness the Composite sample had highest bulk, light scattering and opacity.
In following Table 2 various paper properties are compiled.
Table 2
The results show that at the same bulk the Composite sample had highest smoothness and opacity.
Claims
1. A gypsum -fibre composite product, wherein the gypsum appears as crystals on the surface of the fibre and wherein the gypsum crystals are obtained by contacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and an aqueous fibre suspension.
2. The gypsum -fibre composite product according to claim 1 , wherein the gypsum crystals have a size from 0.1 to 5.0 μm.
3. The gypsum -fibre composite product according to claim 1 or 2, wherein the calcium sulphate hemihydrate comprises α-calcium sulphate hemihydrate or β- calcium sulphate hemihydrate.
4. The gypsum -fibre composite product according to any of claims 1 to 3, wherein the fibre comprises a cellulosic fibre such as kraft pulp fibre, mechanical pulp fibre, deinked pulp fibre or a synthetic fibre.
5. The gypsum -fibre composite product according to any of claims 1 to 4, wherein the weight ratio of gypsum to fibre on dry basis is in the range from 95:5 to 50:50, preferably from 75:25 to 50:50.
6. The gypsum -fibre composite product according to any of claims 1 to 5, wherein the composite additionally comprises a natural or synthetic polymer binder and/or an optical bhghtener and/or a rheology modifier and/or sizing agents.
7. A process for the preparation of a gypsum -fibre composite product comprising contacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and an aqueous fibre suspension to form gypsum crystals on the surface of the fibre.
8. The process according to claim 7, wherein the gypsum crystals have a size from 0.1 to 5.0 μm.
9. The process according to claim 7 or 8, wherein the calcium sulphate hemihydrate comprises α-calcium sulphate hemihydrate or β-calcium sulphate hemihydrate.
10. The process according to any of claim 7 to 9, wherein the fibre comprises a cellulosic fibre such as kraft pulp fibre, mechanical pulp fibre, deinked pulp fibre or a synthetic fibre.
11. The process according to any of claims 7 to 10, wherein the weight ratio of gypsum to fibre on dry basis is range from 95:5 to 50:50, preferably from 75:25 to 50:50.
12. The process according to any of claims 7 to 11 , wherein the weigh ratio of calcium sulphate hemihydrate and/or calcium anhydrite to water in the crystallization is in the range from 0.03 to 0.6:1 , preferably from 0.05 to 0.5:1.
13. The process according to any of claims 7 to 12, wherein the dry fiber content in the crystallization is from 3 to 30 % by weight.
14. The process according to any of claims 7 to 13, wherein the content of cal- cium sulphate hemihydrate and/or calcium anhydrite in the crystallization is from 5 to 57 % by weight.
15. The process according to any of claims 7 to 14, wherein the process additionally comprises drying and comminuting the obtained product to form a gypsum -fibre composite product in the form of particles.
16. The process according to any of claims 7 to 15, wherein the crystallization is carried out in the absence of crystallization habit modifiers.
17. The process according to any of claims 7 to 16, wherein the crystallization is carried out in the presence of crystallization habit modifiers.
18. The process according to claim 17 , wherein the crystallization habit modi- fier is added to water or aqueous fibre suspension before the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
19. The process according to claim 17 or 18, wherein the crystallization habit modifier is a compound the molecule of which has one or several carboxylic or sulphonic groups, or a salt thereof.
20. The process according to claim 19, wherein the crystallization habit modifier is selected from the group consisting of ethylene diamine succinic acid (EDDS), iminodisuccinic acid (ISA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), nithlotriacetic acid (NTA), N-bis-(2-(1 ,2- dicarboxyethoxy)ethyl aspartic acid (AES), the di- tetra-and hexa- aminostilbenesulfonic acids and their salts such as sodium aminothethoxy succinate (Naβ-TCA), as well as the alkylbenzenesulphonat.es.
21. The process according to any of claims 17 to 20, wherein the crystallization habit modifier is used in an amount of 0.01 to 5.0 %, based on the weight of the calcium sulphate hemihydrate and/or calcium sulphate anhydrite.
22. The process according to any of claims 7 to 21 , wherein a fixative is intro- duced into the crystallization.
23. The process according to claim 22, wherein the fixative is selected from the group consisting of poly aluminum chloride, poly DADMAC, anionic and cationic polyacrylates.
24. Use of a gypsum -fibre composite product as defined is any of claims 1 to 6 as a filler pigment or coating pigment in the production of paper, especially fine paper.
25. A paper product comprising a gypsum -fibre composite product as defined in any of claims 1 to 6 as a filler pigment or coating pigment.
26. The paper product according to claim 25, wherein the amount of the gypsum -fibre composite product is from 10 to 60 %, preferably from 20 to 50% by weight on dry basis.
27. The paper product according to claim 25 or 26 comprising fine paper.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09784146A EP2310319A2 (en) | 2008-08-11 | 2009-04-20 | Gypsum-fibre composite product and paper comprising such |
| CN2009801314624A CN102119126A (en) | 2008-08-11 | 2009-04-20 | Gypsum-fibre composite product and paper comprising such |
| CA2732169A CA2732169A1 (en) | 2008-08-11 | 2009-04-20 | Gypsum product |
| US13/058,646 US20110132560A1 (en) | 2008-08-11 | 2009-04-20 | Gypsum product |
| JP2011522526A JP2011530477A (en) | 2008-08-11 | 2009-04-20 | Gypsum products |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20085767A FI20085767L (en) | 2008-08-11 | 2008-08-11 | Gypsum product |
| FI20085767 | 2008-08-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2010018301A2 true WO2010018301A2 (en) | 2010-02-18 |
| WO2010018301A3 WO2010018301A3 (en) | 2010-09-02 |
Family
ID=39735634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FI2009/050287 WO2010018301A2 (en) | 2008-08-11 | 2009-04-20 | Gypsum product |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20110132560A1 (en) |
| EP (1) | EP2310319A2 (en) |
| JP (1) | JP2011530477A (en) |
| KR (1) | KR20110052618A (en) |
| CN (1) | CN102119126A (en) |
| CA (1) | CA2732169A1 (en) |
| FI (1) | FI20085767L (en) |
| RU (1) | RU2011108041A (en) |
| WO (1) | WO2010018301A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010122221A1 (en) * | 2009-04-20 | 2010-10-28 | Kemira Oyj | Paper product |
| WO2011098672A1 (en) * | 2010-02-10 | 2011-08-18 | Kemira Oyj | Process for the preparation of a pigment -fibre composite |
| WO2011141632A1 (en) | 2010-05-10 | 2011-11-17 | Kemira Oyj | Gypsum -fibre composite product |
| EP2460935A1 (en) | 2010-12-01 | 2012-06-06 | SAPPI Netherlands Services B.V. | Method for the production of calcium sulfate dihydrate based paper substrates and/or coating colours |
| EP3204342A4 (en) * | 2014-10-10 | 2018-03-14 | FPInnovations | Compositions, panels and sheets comprising cellulose filaments and gypsum and methods for producing the same |
| EP3783147A4 (en) * | 2018-04-20 | 2022-01-05 | Nippon Paper Industries Co., Ltd. | Composite fiber of cellulose fiber and inorganic particles, and manufacturing method for same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8343273B1 (en) * | 2012-03-30 | 2013-01-01 | United States Gypsum Company | Method of modifying beta stucco using diethylene-triamine-pentaacetic acid |
| EP2842921A1 (en) * | 2013-08-27 | 2015-03-04 | Construction Research & Technology GmbH | Novel fibers, methods for their preparation and use in the manufacture of reinforced elements |
| US10280288B2 (en) | 2013-12-06 | 2019-05-07 | Georgia-Pacific Gypsum Llc | Calcium sulfate crystals and methods for making the same |
| CN104312211A (en) * | 2014-09-28 | 2015-01-28 | 安徽盛佳彩印包装有限公司 | Multi-purpose ultrafine modified calcium carbonate and preparation method thereof |
| CN104651945A (en) * | 2015-01-26 | 2015-05-27 | 江苏一夫科技股份有限公司 | Method for modifying calcium sulphate whisker surface |
| CN111675521B (en) * | 2020-05-21 | 2022-02-11 | 贵州开磷磷石膏综合利用有限公司 | High-strength light keel and preparation method thereof |
| CN113637486B (en) * | 2021-09-07 | 2022-06-07 | 新洋丰农业科技股份有限公司 | Special soil conditioner for medium and light saline-alkali soil and preparation method thereof |
| CN114438597B (en) * | 2021-12-31 | 2024-09-20 | 佛山市中医院 | Calcium sulfate reinforced in-situ cured pore-forming tissue engineering polyester composite scaffold material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0056200A1 (en) * | 1981-01-02 | 1982-07-21 | S.A. Josep Maria Gussinyer | Process for preparing and using a crystalline product |
| DE3223178C1 (en) * | 1982-06-22 | 1984-03-22 | Fels-Werke Peine-Salzgitter Gmbh, 3380 Goslar | Process for producing organic fibres coated with mineral substances |
| WO2002092910A1 (en) * | 2001-04-24 | 2002-11-21 | M-Real Oyj | Multilayered fibrous product and a process for the production thereof |
| US20070227405A1 (en) * | 1997-08-21 | 2007-10-04 | United States Gypsum Company | Gypsum-containing board and tile, and method for producing same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970005867B1 (en) * | 1988-11-18 | 1997-04-21 | 유나이티드 스테이트 집섬 캄파니 | Composite material and method of producing it |
| DE4008084A1 (en) * | 1990-03-14 | 1991-09-19 | Pro Mineral Ges | METHOD FOR PRODUCING PLASTER PANELS, ESPECIALLY OF FLOOR PLATES |
| GB9310891D0 (en) * | 1993-05-26 | 1993-07-14 | Tran Ind Res Inc | Utilization of deinking sludge in building materials |
| US5558710A (en) * | 1994-08-08 | 1996-09-24 | Usg Interiors, Inc. | Gypsum/cellulosic fiber acoustical tile composition |
| CA2367593C (en) * | 2001-08-13 | 2003-02-18 | Kruger Inc. | Method of reducing the solubility of calcium sulfate dihydrate in an aqueous suspension and method of making the same |
| US20080160294A1 (en) * | 2006-12-27 | 2008-07-03 | United States Gypsum Company | Multiple layer gypsum cellulose fiber composite board and the method for the manufacture thereof |
-
2008
- 2008-08-11 FI FI20085767A patent/FI20085767L/en not_active IP Right Cessation
-
2009
- 2009-04-20 JP JP2011522526A patent/JP2011530477A/en not_active Withdrawn
- 2009-04-20 US US13/058,646 patent/US20110132560A1/en not_active Abandoned
- 2009-04-20 EP EP09784146A patent/EP2310319A2/en not_active Withdrawn
- 2009-04-20 RU RU2011108041/05A patent/RU2011108041A/en unknown
- 2009-04-20 KR KR1020117003192A patent/KR20110052618A/en not_active Application Discontinuation
- 2009-04-20 CA CA2732169A patent/CA2732169A1/en not_active Abandoned
- 2009-04-20 CN CN2009801314624A patent/CN102119126A/en active Pending
- 2009-04-20 WO PCT/FI2009/050287 patent/WO2010018301A2/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0056200A1 (en) * | 1981-01-02 | 1982-07-21 | S.A. Josep Maria Gussinyer | Process for preparing and using a crystalline product |
| DE3223178C1 (en) * | 1982-06-22 | 1984-03-22 | Fels-Werke Peine-Salzgitter Gmbh, 3380 Goslar | Process for producing organic fibres coated with mineral substances |
| US20070227405A1 (en) * | 1997-08-21 | 2007-10-04 | United States Gypsum Company | Gypsum-containing board and tile, and method for producing same |
| WO2002092910A1 (en) * | 2001-04-24 | 2002-11-21 | M-Real Oyj | Multilayered fibrous product and a process for the production thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010122221A1 (en) * | 2009-04-20 | 2010-10-28 | Kemira Oyj | Paper product |
| WO2011098672A1 (en) * | 2010-02-10 | 2011-08-18 | Kemira Oyj | Process for the preparation of a pigment -fibre composite |
| WO2011141632A1 (en) | 2010-05-10 | 2011-11-17 | Kemira Oyj | Gypsum -fibre composite product |
| EP2460935A1 (en) | 2010-12-01 | 2012-06-06 | SAPPI Netherlands Services B.V. | Method for the production of calcium sulfate dihydrate based paper substrates and/or coating colours |
| EP3204342A4 (en) * | 2014-10-10 | 2018-03-14 | FPInnovations | Compositions, panels and sheets comprising cellulose filaments and gypsum and methods for producing the same |
| EP3783147A4 (en) * | 2018-04-20 | 2022-01-05 | Nippon Paper Industries Co., Ltd. | Composite fiber of cellulose fiber and inorganic particles, and manufacturing method for same |
| US11447912B2 (en) | 2018-04-20 | 2022-09-20 | Nippon Paper Industries Co., Ltd. | Complex fibers of cellulose fibers with inorganic particles and processes for preparing them |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010018301A3 (en) | 2010-09-02 |
| CN102119126A (en) | 2011-07-06 |
| RU2011108041A (en) | 2012-09-20 |
| FI20085767A0 (en) | 2008-08-11 |
| FI20085767L (en) | 2010-02-12 |
| KR20110052618A (en) | 2011-05-18 |
| JP2011530477A (en) | 2011-12-22 |
| CA2732169A1 (en) | 2010-02-18 |
| EP2310319A2 (en) | 2011-04-20 |
| US20110132560A1 (en) | 2011-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20110132560A1 (en) | Gypsum product | |
| US10309060B2 (en) | Paper composition | |
| FI100729B (en) | Filler used in papermaking and method of making the filler | |
| RU2598447C2 (en) | Use of precipitated carbonate in manufacture of fibre product | |
| EP3221512B1 (en) | Method of producing a filler | |
| WO2003093577A1 (en) | Paper coating pigments | |
| CA2609411A1 (en) | Polymer-pigment hybrids for use in papermaking | |
| WO2012066308A2 (en) | Compositions | |
| WO2007031870A1 (en) | Process of manufacturing a co-ground calcium carbonate material of the gcc and pcc type with a specific steepness factor, obtained products and their uses | |
| US20120318471A1 (en) | Process for the preparation of a pigment-fibre composite | |
| US20120024488A1 (en) | Paper product | |
| Hu et al. | Synthesis of needle-like aragonite crystals in the presence of magnesium chloride and their application in papermaking | |
| WO2008125873A1 (en) | Grinding method | |
| EP2534102A1 (en) | Process for the preparation of a pigment -fibre composite | |
| Gullichsen et al. | Pigment Coating and Surface Sizing of Paper Series editors This word document was downloaded from/please remain this link information when you reproduce |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 200980131462.4 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09784146 Country of ref document: EP Kind code of ref document: A2 |
|
| DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2009784146 Country of ref document: EP |
|
| ENP | Entry into the national phase |
Ref document number: 2732169 Country of ref document: CA |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 909/CHENP/2011 Country of ref document: IN |
|
| ENP | Entry into the national phase |
Ref document number: 2011522526 Country of ref document: JP Kind code of ref document: A Ref document number: 20117003192 Country of ref document: KR Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 13058646 Country of ref document: US |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2011108041 Country of ref document: RU |