EP0925401B1 - Verfahren zum bleichen von papierzellstoff - Google Patents
Verfahren zum bleichen von papierzellstoff Download PDFInfo
- Publication number
- EP0925401B1 EP0925401B1 EP97919018A EP97919018A EP0925401B1 EP 0925401 B1 EP0925401 B1 EP 0925401B1 EP 97919018 A EP97919018 A EP 97919018A EP 97919018 A EP97919018 A EP 97919018A EP 0925401 B1 EP0925401 B1 EP 0925401B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pulp
- acid
- stage
- process according
- acids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000004061 bleaching Methods 0.000 title claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 60
- 238000011282 treatment Methods 0.000 claims abstract description 60
- 239000002738 chelating agent Substances 0.000 claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 44
- 238000010306 acid treatment Methods 0.000 claims abstract description 31
- 150000007513 acids Chemical class 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000010979 pH adjustment Methods 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 56
- 230000009920 chelation Effects 0.000 claims description 32
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 10
- 150000004965 peroxy acids Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004155 Chlorine dioxide Substances 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 7
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001420 alkaline earth metal ion Inorganic materials 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 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 4
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- AEMOLEFTQBMNLQ-YMDCURPLSA-N D-galactopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-YMDCURPLSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 claims description 2
- AEMOLEFTQBMNLQ-HNFCZKTMSA-N L-idopyranuronic acid Chemical compound OC1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-HNFCZKTMSA-N 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 150000001720 carbohydrates Chemical group 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 229920001277 pectin Polymers 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims 3
- IUKURYKOMRUDCY-UHFFFAOYSA-N 1-azabicyclo[2.2.0]hexane-4-carboxylic acid Chemical compound C1CN2CCC21C(=O)O IUKURYKOMRUDCY-UHFFFAOYSA-N 0.000 claims 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims 2
- ODAKQJVOEZMLOD-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)CN(CC(O)=O)CC(O)=O ODAKQJVOEZMLOD-UHFFFAOYSA-N 0.000 claims 1
- 239000004471 Glycine Substances 0.000 claims 1
- AEMOLEFTQBMNLQ-BKBMJHBISA-N alpha-D-galacturonic acid Chemical class O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-BKBMJHBISA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 description 20
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 150000002978 peroxides Chemical class 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 235000020094 liqueur Nutrition 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910001902 chlorine oxide Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FATUQANACHZLRT-KMRXSBRUSA-L calcium glucoheptonate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O FATUQANACHZLRT-KMRXSBRUSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- -1 ions metals Chemical class 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000726768 Carpinus Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 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 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1042—Use of chelating agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1005—Pretreatment of the pulp, e.g. degassing the pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- chemical pulp By chemical pulp is meant the pulp having undergone a minor treatment in the presence of chemical reagents such as sulfide of sodium in an alkaline medium (kraft or sulphate cooking) or by others alkaline processes.
- chemical reagents such as sulfide of sodium in an alkaline medium (kraft or sulphate cooking) or by others alkaline processes.
- metal ions having an effect harmful are transition metal ions including, inter alia, manganese, copper and iron which catalyze reactive decomposition reactions peroxides. They degrade the peroxidized reagents used for the delignification and bleaching via radical mechanisms and increase thus the consumption of these products while reducing the properties mechanical pulp.
- Removal of metal ions can be achieved by treatment with acid at room temperature from the pulp.
- these treatments in acid medium removes not only harmful metal ions but also alkaline earth metal ions such as magnesium and calcium which have a stabilizing effect on the peroxidized reagents used and a beneficial effect on the optical and mechanical qualities of paper pulp.
- WO-A-96/12063 proposes a method for destroying selectively 4-deoxy-b-L-threo-hex-4-enepyranosyluronic acid groups (hexeneuronic groups) by treating the paper pulp to a temperature between 85 ° C and 150 ° C and at a pH between 2 and 5.
- the destruction of hexeneuronic groups reduces the kappa number from 2 to 9 units and non-selectively reduces the adsorption of transition metal ions and of alkaline earth metals.
- EP-A-0 456 626 describes a process for bleaching paper pulp in which a chelation stage (stage Q) is carried out in a pH zone between 3.1 and 9.0 before treating the pulp with hydrogen peroxide (step P).
- stage Q a chelation stage
- step P hydrogen peroxide
- Example 1 of this patent application shows that the whiteness maximum pulp after treatment with peroxide is ISO 66.1 ° and that it is reached when the pH of step Q is equal to 6.1. At higher pH, the whiteness of the paper pulp decreases rapidly, reaching only 61.9 ° ISO at pH 7.7 and 56.4 ° ISO at pH 9.1.
- step Q the amount of peroxide of hydrogen consumed increases as well as the cost of production.
- even a small change in pH during step Q has influences considerable on the quality and / or cost price of chemical paper pulp.
- it is difficult to precisely control the pH when this one is close to neutral because the buffering capacity of the pulp suspension is relatively weak.
- EP-A-0 456 626 describes a process for bleaching paper pulp in which a step of chelation (step Q) using aminocarboxylic chelating agents such as EDTA or DTPA is carried out in a pH zone between 3.1 and 9.0 before treating the pulp with hydrogen peroxide (step P).
- a disadvantage of this process is linked to the use of chelating agents very powerful aminocarboxylates such as ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA).
- EDTA ethylenediaminetetraacetic acid
- DTPA diethylenetriaminepentaacetic acid
- the purpose of the present invention is to provide a method of delignification and bleaching of chemical pulp which allows to expand the effective pH zone of the chelation (stage Q) prior to treatment with an oxidizer, without altering the whiteness of the paper pulp.
- the pH of the paper pulp it is no longer necessary to strictly control the pH of the paper pulp during treatment with a chelating agent. In other words, even if at during the chelation the pH of the pulp varies, the result, i.e. the whiteness of the paper pulp obtained after the treatment step with an oxidant, is not affected. During chelation the pH can even be higher than 9. In general, the pH is less than or equal to 12.
- the amount of oxidant consumed remains substantially constant in a wide pH range of chelation and is generally below that of known methods.
- the pulp thus treated retains good properties. optical and mechanical in a wide pH range of chelation.
- alkaline earth metal ions such as magnesium and calcium must be deposit or redeposit on the fibers to obtain a high ion ratio beneficial / harmful ions i.e. alkaline earth metal ions / metal ions of transition on the fibers. It is particularly important to be in the presence a high magnesium / manganese ratio on the fibers to avoid catalytic decomposition of the oxidant during the oxidant treatment step. This magnesium / manganese ratio on the fibers is preferably above of 30.
- alkaline earth metal ions can be added, if necessary to the pulp suspension in order to increase the ion ratio of alkaline earth metals / transition metal ions on the fibers. If we wish to increase the magnesium / manganese ratio on the fibers, we can add magnesium to the pulp and preferably before adjusting the pH or in any case before the washing step (c).
- Another advantage of this process is that it can avoid pH jumps when processing the pulp and thereby reducing the amount of reagents put in action. Indeed, after the acid treatment step aimed at reducing the amount of hexeneuronic acids, the pH of the paper pulp is adjusted by adding e.g. a base such as sodium hydroxide and paper pulp is then washed to to remove the chelated transition metal ions. The paper pulp therefore no longer has need to be acidified before chelation. Therefore, the amount of reagent implementation in the oxidizing treatment step in an alkaline medium is less.
- a base such as sodium hydroxide
- the acid treatment step (a) pulp is made at a pH above about 2.
- the pH does not exceed 6.5.
- the temperature of the acid treatment step (a) of the paper pulp is preferably above 85 ° C. It is advantageously less than 150 ° C.
- acids such as inorganic acids eg sulfuric acid, nitric acid, hydrochloric acid and organic acids such as acid formic acid and / or acetic acid can be used to adjust the pH of the pulp suspension during the acid treatment step.
- acids can be buffered eg with salts of acids such as formates to keep the pH as constant as possible throughout treatment.
- the duration of the acid treatment step (a) depends on the pH, the temperature and the paper pulp used.
- the acid treatment step (a) of the paper pulp is performed in the presence of an oxidant.
- the acid treatment step (a) of the dough paper in the presence of an oxidant is carried out at a pH above about 2. From preferably the pH does not exceed 6.5.
- the oxidant during the acid treatment step (a) with an oxidant can be chosen from chlorine, chlorine dioxide, ozone, peracids, peroxide of hydrogen and their mixtures.
- peracids examples include peracetic acid, performic acid, permonosulfuric acid, their salts, in in particular the salt of permonosulfuric acid, and their mixtures.
- the pH of the paper pulp is adjusted to a pH greater than or equal to 3 during the pH adjustment step (b).
- the pH is preferably adjusted between 4 and 12 and particularly preferred between 7 and 12, respectively 10 and 12.
- the step is not added during the step for adjusting the pH (b), ions of alkaline earth metals, in particular magnesium and calcium ions.
- An additional washing step for the dough can be carried out after the pH adjustment step (b) and before adding the chelating agent, if necessary.
- additional dough processing step is meant alkaline extractions, possibly reinforced by oxygen or else chlorine, chlorine dioxide or mixtures thereof.
- the chelating agent can be chosen from aminocarboxylic acids, hydroxycarboxylic, phosphonic and their salts.
- EDTA ethylenediaminetetraacetic
- DTPA diethylenetriaminepentaacetic acid
- DTMPA diethylenetriaminepentamethylenephosphonic acid
- an aminocarboxylic chelating agent is used in a amount less than 0.4% compared to dry paper pulp.
- An advantage of this first embodiment lies in the fact that the quantity of chelating agents discharged with effluents into rivers is reduced compared to conventional methods. Indeed, these classic processes in practice require approximately twice as many chelating agents to achieve same results. The risk to the environment caused by the solubilization of heavy metals from riverbed sediments is therefore minimized because the amount of chelating agents used is reduced.
- step of acid treatment (a) aimed at reducing the quantity of hexeneuronic acids in the dough to a pH adjustment before washing the dough reduces significantly the amount of chelating agents used. She is advantageously less than or equal to 0.3%, in particular less than or equal to 0.2% compared to dry paper pulp.
- EDTA ethylenediaminetetraacetic acid
- DTPA acid diethylenetriaminepentacetic
- a biodegradable chelating agent In a second embodiment of the method according to the invention, it is uses a biodegradable chelating agent.
- This embodiment allows you to control the profile of metal ions in the pulp without having to use chelating agents which are difficult or non-biodegradable. She allows the use of biodegradable chelating agents which have properties weaker chelating agents which would have been ineffective in processes conventional for bleaching chemical pulp.
- agent biodegradable chelating agent means a chelating agent capable of being degraded by living organisms.
- the optimal pH during treatment with the chelator and more precisely the pH optimal pH adjustment step is towards the alkaline zone, where the capacity dough suspension buffer is higher, which greatly facilitates pH control in the conduct of this process compared to the processes known.
- a step of acid treatment (a) aimed at reducing the quantity of hexeneuronic acids in the dough to pH adjustment before washing the dough allows the use of agents weaker chelating agents which are therefore more easily biodegradable.
- the second embodiment allows the use of liqueurs from a bleaching and delignification step for paper pulp rich in fragments of oxidized carbohydrates either directly or indirectly as a source of biodegradable chelating agents.
- the second embodiment it is possible to recycle the liqueurs from the oxidation stage (d) and add them directly to the acid suspension to adjust the pH thereof.
- Residual oxidizing reagents such as ozone, hydrogen peroxide or peracids contained in this liquor can act on paper pulp. The effectiveness of the process is therefore improved.
- the pH adjustment step (b) can advantageously be combined with the application of oxidizing reagents such as oxygen and hydrogen peroxide, in an alkaline medium.
- a washing step additional dough can be made, if necessary after the step pH adjustment (b) and before adding the biodegradable chelating agent.
- the agents preferred chelating agents are polyhydroxycarboxylic acids containing only 1 carboxylic group.
- the oxidant of the treatment step with an oxidant (d) is advantageously chosen from hydrogen peroxide, the peracids and ozone.
- hydrogen peroxide is used in an alkaline medium, ie under conventional conditions either at high temperature and pressure.
- This oxygen pulp treatment step can be presented as a step O, Op, Eo, Eop in which O represents a step with pressurized oxygen, Op an oxygen step reinforced with pressurized hydrogen peroxide, Eo an alkaline extraction step reinforced with oxygen, Eop a step extraction reinforced with oxygen and hydrogen peroxide.
- the acid treatment step to reduce the amount of acids hexeneuronics present in the paper pulp must make it possible to remove a large fraction of hexeneuronic groups, i.e. at least 10% of them.
- the amount of hexeneuronic acids is generally reduced by at least minus 15%, especially at least 20%. Reduced quantities of at least 25%, and more particularly at least 30% are preferred. Results particularly favorable are obtained with quantities reduced by at least 35%, especially 40%. Quantities reduced by at least 50% are all particularly preferred.
- the pulp is treated in the presence of water to a consistency of 0.1 to 50% by weight and preferably from 1 to 20% by weight.
- the process according to the invention can be used in sequences of delignification and bleaching aimed at reducing the amount of elemental chlorine, elemental chlorine-free (ECF) bleaching sequences or totally chlorine-free sequences (TCF) or in sequences aimed at minimizing water consumption, eg by recycling effluents. he allows, in these types of sequences, to more easily achieve the objective of reducing the amount of chlorine or chlorine dioxide to achieve a same level of whiteness.
- ECF elemental chlorine-free
- TCF totally chlorine-free sequences
- a method of delignification and bleaching of chemical paper pulp including the steps : A (Q) N (Q) W P in which step A represents a step for processing the acid paper pulp to reduce the amount of hexeneuronic acids, N represents a step of adjusting the pH in order to deposit or redeposit the ions of alkaline earth metals on the dough, (Q) represents the addition of a chelating agent which is done before or during step A and / or before, during or after step N for pH adjustment, W represents a step for washing the paper pulp and P represents an oxidation step.
- oxidants sensitive to transition metals is meant reagents that decompose on contact with transition metals such as hydrogen peroxide, peracids and ozone.
- the present delignification and laundering process pulp can be combined with any other conventional bleaching step y included in steps using enzymes or chlorinated reagents such than chlorine and chlorine dioxide.
- wood used for the production of chemical pulp are suitable for the implementation of the present process and in particular those used for kraft pulp, namely softwoods such as p. ex. the various pine and fir species and hardwoods such as birch, beech, oak, hornbeam and eucalyptus.
- Figure 1 shows the whiteness expressed in ISO degree of a paper subjected to an A N Q W P treatment and that of a paper pulp having undergone conventional Q W P treatment i.e. without acid treatment or neutralization.
- Figure 2 shows the consumption of hydrogen peroxide as a function of the pH during the chelation of a paper pulp subjected to an A N Q W treatment P or a Q W P treatment.
- Q W P treatment the consumption of hydrogen peroxide is higher and goes through a minimum which is between pH 4 and 6.
- a N Q W P treatment the consumption of hydrogen peroxide is lower.
- the consumption of hydrogen peroxide remains at a lower value for pH between 4 and 10 during chelation.
- the treatment of paper pulp according to the present process therefore allows obtain paper pulps with better optical properties and mechanical and this with a reduced consumption of hydrogen peroxide.
- Figure 3 shows the whiteness expressed in ISO degree of a paper pulp subjected to an A N Q W P treatment and that of a pulp that has undergone conventional Q W P treatment i.e. without acid treatment or neutralization depending on the amount of EDTA.
- a hardwood pulp with a starting pH of 10.5 and a consistency of 37.6% by weight was subjected to a delignification treatment and bleaching A N Q W P.
- a paper pulp with a starting pH of 10.5 and a consistency of 37.6% by weight, a whiteness of 48.2 ° ISO and a Kappa Index of 11.2 was subject to delignification and bleaching treatment A N Q W P.
- a paper pulp with a starting pH of 8.5 and a consistency of 24.6% by weight, a whiteness of 60.3 ° ISO and a Kappa Index of 5.4 was subjected to a conventional delignification and bleaching treatment Q W P and to comparison to treatment A N Q W P.
- the first four tests were carried out using a delignification and conventional bleaching comprising a chelation step and an oxidation step using hydrogen peroxide in an alkaline medium (Q W P).
- the chelation was carried out at room temperature for 30 minutes at pH values between pH 3 and pH 11. 1% by weight of glucoheptonate was used as a chelating agent.
- the hydrogen peroxide oxidation of the paper pulp was carried out in alkaline medium at 90 ° C for 120 minutes.
- the density of the samples has been adjusted to 4% and an identical amount of glucoheptanoate was added to each sample and acted at 30 ° C for 30 minutes.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Claims (19)
- Verfahren zur Delignifizierung und zum Bleichen von Papierzellstoff, umfassend der Reihe nach:a) einen Schritt zur sauren Behandlung des Zellstoffs, um die Menge an in dem Zellstoff vorhandenen Hexenuronsäuren um wenigstens 10% zu vermindern,b) einen Schritt zum Einstellen des pH-Werts des Zellstoffs, um Erdalkalimetallionen auf dem Zellstoff abzuscheiden oder wieder abzuscheiden, durch Zugabe von alkalischer Flüssigkeit und ohne Zusatz von Erdalkaliionen,c) einen Schritt zum Waschen des Zellstoffs,d) einen Schritt zur Behandlung des Zellstoffs mit einem Oxidationsmittel,
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass der Schritt zur sauren Behandlung (a) des Zellstoffs bei einem pH von etwa 2 bis 6,5 und bei einer Temperatur zwischen 85°C und 150°C ausgeführt wird.
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass der Schritt zur sauren Behandlung (a) des Zellstoffs bei einem pH von etwa 2 bis 6,5 in Gegenwart eines Oxidationsmittels ausgeführt wird.
- Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, dass das Oxidationsmittel des Schritts zur sauren Behandlung (a) aus Chlor, Chlordioxid, Ozon, den Persäuren, Wasserstoffperoxid und ihren Gemischen ausgewählt ist.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der pH des Zellstoffs auf einen pH höher oder gleich 3 während des Schritts zum Einstellen des pH-Werts (b) eingestellt wird.
- Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass der pH des Zellstoffs auf einen pH zwischen 4 und 12 während des Schritts zum Einstellen des pH-Werts (b) eingestellt wird.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein zusätzlicher Schritt zum Waschen des Zellstoffs nach dem Schritt zum Einstellen des pH-Werts (b) und vor der Zugabe des Chelatbildners ausgeführt wird.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein oder mehrere zusätzliche Schritte zur Behandlung des Zellstoffs zwischen den Schritt zum Waschen (c) und den Schritt zur Behandlung mit einem Oxidationsmittel (d) eingeschoben werden.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Chelatbildner aus der Gruppe ausgewählt ist, die von den Amino-carbon-, Hydroxycarbon-, Phosphonsäuren und ihren Salzen gebildet wird.
- Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, dass man als Chelatbildner Ethylendiamintetraessigsäure (EDTA), Diethylentriaminpentaessigsäure (DTPA), Zitronensäure, Milchsäure, Weinsäure, Aldonsäuren, Uronsäuren, Diethylentriaminpentamethylenphosphonsäure (DTMPA), die Salze dieser Säuren und/oder ihre Gemische verwendet.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Oxidationsmittel des Schritts zur Behandlung mit einem Oxidationsmittel (d) aus Wasserstoffperoxid, den Persäuren und Ozon ausgewählt ist.
- Verfahren gemäß Anspruch 11, dadurch gekennzeichnet, dass das Oxidationsmittel des Schritts zur Behandlung mit einem Oxidationsmittel (d) Wasserstoffperoxid in basischem Medium ist.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass man die Zugabe des Chelatbildners nach dem Schritt zum Einstellen des pH-Werts (b) mit einer Behandlung des Zellstoffs mittels Sauerstoff kombiniert.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein Chelatbildner des Aminocarbonsäuretyps in einer Menge, die geringer als 0,4 Gew.-%, bezogen auf den trockenen Papierzellstoff, ist, verwendet wird.
- Verfahren gemäß Anspruch 14, dadurch gekennzeichnet, dass man als Chelatbildner Ethylendiamintetraessigsäure (EDTA) und Diethylentriaminpentaessigsäure (DTPA), die Salze dieser Säuren und/oder ihre Gemische verwendet.
- Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass ein biologisch abbaubarer Chelatbildner verwendet wird.
- Verfahren gemäß Anspruch 16, dadurch gekennzeichnet, dass der pH des Zellstoffs auf einen pH zwischen 7 und 12 während des Schritts zum Einstellen des pH-Werts (b) eingestellt wird.
- Verfahren gemäß Anspruch 16 oder 17, dadurch gekennzeichnet, dass man Flüssigkeiten verwendet, die hervorgegangen sind aus einem Schritt zum Bleichen oder zur Delignifizierung von Papierzellstoffen, die reich an Fragmenten oxidierter Kohlenhydrate sind, entweder direkt oder indirekt als Quelle für biologisch abbaubare Chelatbildner.
- Verfahren gemäß einem der Ansprüche 16 bis 18, dadurch gekennzeichnet, dass man als biologisch abbaubaren Chelatbildner N,N-Bis-(carboxymethyl)-glycin (NTA), Zitronensäure, Milchsäure, Weinsäure, Polyhydroxyacrylsäuren, Aldonsäuren, Gluconsäure, Glucoheptonsäure, Uronsäuren, Iduronsäure, Galacturonsäure, Mannuronsäure, Pektine, Alginate und Gummis, Isoserindiessigsäure (ISDA), Diethanolglycin (DEG), die Salze dieser Säuren und/oder ihre Gemische verwendet.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9600764 | 1996-09-11 | ||
BE9600764A BE1010617A3 (fr) | 1996-09-11 | 1996-09-11 | Procede de blanchiment de pate a papier. |
BE9600858A BE1010678A3 (fr) | 1996-10-11 | 1996-10-11 | Procede de delignification et de blanchiment de pate a papier chimique. |
BE9600857 | 1996-10-11 | ||
BE9600857A BE1010677A3 (fr) | 1996-10-11 | 1996-10-11 | Procede de delignification et de blanchiment de pate a papier chimique. |
BE9600858 | 1996-10-11 | ||
PCT/EP1997/004758 WO1998011295A1 (fr) | 1996-09-11 | 1997-08-23 | Procede de blanchiment de pate a papier |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0925401A1 EP0925401A1 (de) | 1999-06-30 |
EP0925401B1 true EP0925401B1 (de) | 2002-01-16 |
Family
ID=27159855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97919018A Expired - Lifetime EP0925401B1 (de) | 1996-09-11 | 1997-08-23 | Verfahren zum bleichen von papierzellstoff |
Country Status (18)
Country | Link |
---|---|
US (1) | US6123809A (de) |
EP (1) | EP0925401B1 (de) |
JP (1) | JP2001503109A (de) |
AT (1) | ATE212087T1 (de) |
AU (1) | AU4300797A (de) |
BR (1) | BR9711743A (de) |
CA (1) | CA2265566A1 (de) |
CZ (1) | CZ86099A3 (de) |
DE (1) | DE69709656T2 (de) |
EE (1) | EE03881B1 (de) |
ES (1) | ES2171926T3 (de) |
ID (1) | ID19415A (de) |
MY (1) | MY132667A (de) |
NO (1) | NO991153L (de) |
PL (1) | PL332079A1 (de) |
PT (1) | PT925401E (de) |
RU (1) | RU2189412C2 (de) |
WO (1) | WO1998011295A1 (de) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1012675A6 (fr) * | 1999-05-11 | 2001-02-06 | Solvay | Procede de blanchiment de pate a papier. |
US6702921B2 (en) * | 2001-05-01 | 2004-03-09 | Ondeo Nalco Company | Methods to enhance pulp bleaching and delignification using an organic sulfide chelating agent |
WO2003016547A2 (en) * | 2001-08-13 | 2003-02-27 | Vanderbilt University | Distribution of solutions across a surface |
US7351764B2 (en) * | 2004-03-31 | 2008-04-01 | Nalco Company | Methods to enhance brightness of pulp and optimize use of bleaching chemicals |
EP1790771A4 (de) * | 2004-06-08 | 2012-10-03 | Jujo Paper Co Ltd | Zellstoffbleichverfahren |
US20060201642A1 (en) * | 2005-03-08 | 2006-09-14 | Andritz Inc. | Methods of treating chemical cellulose pulp |
US20070131364A1 (en) * | 2005-12-14 | 2007-06-14 | University Of Maine | Process for treating a cellulose-lignin pulp |
US20100224336A1 (en) * | 2005-12-14 | 2010-09-09 | University Of Maine System Board Of Trustees | Process of bleaching a wood pulp |
JP4893210B2 (ja) * | 2006-10-03 | 2012-03-07 | 三菱瓦斯化学株式会社 | 漂白パルプの製造方法 |
JP4973284B2 (ja) * | 2007-03-30 | 2012-07-11 | 栗田工業株式会社 | パルプ洗浄剤、パルプ製造方法、及びパルプ洗浄方法 |
PL2288752T3 (pl) | 2008-06-20 | 2014-07-31 | Int Paper Co | Kompozycja i arkusz drukowy o podwyższonej jakości optycznej |
FR3016359B1 (fr) * | 2014-01-10 | 2022-04-29 | Arkema France | Compositions de peroxyde d'hydrogene pour la delignification de matiere vegetale et leurs utilisations |
CN104313933A (zh) * | 2014-09-23 | 2015-01-28 | 华南理工大学 | 一种硫酸盐蔗渣浆绿色漂白方法 |
FR3062138B1 (fr) * | 2017-01-23 | 2019-06-07 | Centre Technique De L'industrie Des Papiers, Cartons Et Celluloses | Procede de blanchiment d'une pate a papier |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE500113C2 (sv) * | 1992-07-09 | 1994-04-18 | Kamyr Ab | Sätt vid blekning av massa för omhändertagande av utlösta metaller |
SE9301160L (sv) * | 1992-08-28 | 1994-03-01 | Sunds Defibrator Ind Ab | Förfarande för behandling av processvatten |
ATE184060T1 (de) * | 1993-04-20 | 1999-09-15 | Eka Chemicals Ab | Verfahren zum bleichen von lignozellulose- enthaltendem zellstoff |
US5571378A (en) * | 1993-11-23 | 1996-11-05 | Hampshire Chemical Ltd. | Process for high-pH metal ion chelation in pulps |
SE504826C2 (sv) * | 1994-10-07 | 1997-05-12 | Sunds Defibrator Ind Ab | Behandling av kemisk massa med komplexbildare i närvaro av ett oxidationsmedel |
US6736934B1 (en) * | 1995-02-17 | 2004-05-18 | Andritz Oy | Method of pretreating pulp in an acid tower prior to bleaching with peroxide |
-
1997
- 1997-08-23 PL PL97332079A patent/PL332079A1/xx unknown
- 1997-08-23 RU RU99107570/12A patent/RU2189412C2/ru not_active IP Right Cessation
- 1997-08-23 EP EP97919018A patent/EP0925401B1/de not_active Expired - Lifetime
- 1997-08-23 PT PT97919018T patent/PT925401E/pt unknown
- 1997-08-23 AU AU43007/97A patent/AU4300797A/en not_active Abandoned
- 1997-08-23 WO PCT/EP1997/004758 patent/WO1998011295A1/fr not_active Application Discontinuation
- 1997-08-23 AT AT97919018T patent/ATE212087T1/de not_active IP Right Cessation
- 1997-08-23 US US09/254,495 patent/US6123809A/en not_active Expired - Fee Related
- 1997-08-23 ES ES97919018T patent/ES2171926T3/es not_active Expired - Lifetime
- 1997-08-23 BR BR9711743A patent/BR9711743A/pt not_active Application Discontinuation
- 1997-08-23 DE DE69709656T patent/DE69709656T2/de not_active Expired - Fee Related
- 1997-08-23 CZ CZ99860A patent/CZ86099A3/cs unknown
- 1997-08-23 CA CA002265566A patent/CA2265566A1/fr not_active Abandoned
- 1997-08-23 EE EEP199900119A patent/EE03881B1/xx not_active IP Right Cessation
- 1997-08-23 JP JP10513208A patent/JP2001503109A/ja active Pending
- 1997-09-10 MY MYPI97004185A patent/MY132667A/en unknown
- 1997-09-11 ID IDP973169A patent/ID19415A/id unknown
-
1999
- 1999-03-10 NO NO991153A patent/NO991153L/no not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
WO1998011295A1 (fr) | 1998-03-19 |
EP0925401A1 (de) | 1999-06-30 |
AU4300797A (en) | 1998-04-02 |
EE9900119A (et) | 1999-10-15 |
PT925401E (pt) | 2002-07-31 |
PL332079A1 (en) | 1999-08-30 |
ATE212087T1 (de) | 2002-02-15 |
US6123809A (en) | 2000-09-26 |
ID19415A (id) | 1998-07-09 |
JP2001503109A (ja) | 2001-03-06 |
MY132667A (en) | 2007-10-31 |
EE03881B1 (et) | 2002-10-15 |
ES2171926T3 (es) | 2002-09-16 |
RU2189412C2 (ru) | 2002-09-20 |
NO991153L (no) | 1999-05-04 |
BR9711743A (pt) | 1999-08-24 |
CZ86099A3 (cs) | 1999-06-16 |
CA2265566A1 (fr) | 1998-03-19 |
DE69709656T2 (de) | 2002-10-17 |
DE69709656D1 (de) | 2002-02-21 |
NO991153D0 (no) | 1999-03-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0925401B1 (de) | Verfahren zum bleichen von papierzellstoff | |
EP2761081B1 (de) | Enzymatische vorbehandlung von holz in einem verfahren zur herstellung von mechanischem papierzellstoff | |
FR2467261A1 (fr) | Blanchiment de matiere lignocellulosique au moyen d'agents de blanchiment contenant du peroxyde | |
EP0496671B1 (de) | Enzymatische Behandlung von lignocellulosischem Zellstoff | |
BE1004674A3 (fr) | Procede pour le blanchiment d'une pate a papier chimique et application de ce procede au blanchiment d'une pate kraft. | |
BE1012675A6 (fr) | Procede de blanchiment de pate a papier. | |
FR2910027A1 (fr) | Procede de blanchiment des pates papeteries chimiques par traitement final a l'ozone a haute temperature | |
EP3008240B1 (de) | Verfahren zur behandlung von chemischem zellstoff durch behandlung mit ozon in gegenwart von magnesiumionen | |
BE1010677A3 (fr) | Procede de delignification et de blanchiment de pate a papier chimique. | |
BE1010617A3 (fr) | Procede de blanchiment de pate a papier. | |
BE1010678A3 (fr) | Procede de delignification et de blanchiment de pate a papier chimique. | |
BE1010679A3 (fr) | Procede de delignification et de blanchiment de pate a papier chimique. | |
BE1011784A3 (fr) | Procede de blanchiment de pate a papier. | |
CA2157291A1 (fr) | Procede pour la delignification d'une pate a papier chimique | |
BE1007700A3 (fr) | Procede pour le blanchiment d'une pate a papier chimique. | |
BE1010880A3 (fr) | Procede de fabrication de pate a papier chimique. | |
BE1007757A3 (fr) | Procede pour le blanchiment d'une pate a papier chimique. | |
CA1128260A (fr) | Procede de fabrication de pates papetieres chimiques | |
WO1999046441A1 (fr) | Procede de blanchiment et/ou de delignification de pates a papier | |
BE1005800A3 (fr) | Procede pour la delignification et le blanchiment d'une pate a papier chimique. | |
EP0180529B2 (de) | Verfahren zur Bereitstellung von chemischen Holzpulpen hinsichtlich der Bleiche | |
FR2747406A1 (fr) | Procede de delignification a l'oxygene d'une pate a papier | |
FR2670513A1 (fr) | Procede de blanchiment des pates papetieres chimiques par traitement a l'oxygene en deux stades. | |
BE503145A (de) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19990412 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES FI FR PT SE |
|
AX | Request for extension of the european patent |
Free format text: LT PAYMENT 19990412;LV PAYMENT 19990412 |
|
17Q | First examination report despatched |
Effective date: 19990729 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE ES FI FR PT SE |
|
AX | Request for extension of the european patent |
Free format text: LT PAYMENT 19990412;LV PAYMENT 19990412 |
|
LTIE | Lt: invalidation of european patent or patent extension | ||
REF | Corresponds to: |
Ref document number: 212087 Country of ref document: AT Date of ref document: 20020215 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 69709656 Country of ref document: DE Date of ref document: 20020221 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20020416 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2171926 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030430 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20040806 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20040811 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20040812 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20040820 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20040825 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20040902 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20041021 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050823 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050823 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050824 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050824 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060223 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060301 |
|
EUG | Se: european patent has lapsed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20050824 |
|
BERE | Be: lapsed |
Owner name: S.A. *SOLVAY INTEROX Effective date: 20050831 |