US3725194A - Treatment of alkaline pulp with an acidic medium followed by oxygen bleaching and delignification - Google Patents
Treatment of alkaline pulp with an acidic medium followed by oxygen bleaching and delignification Download PDFInfo
- Publication number
- US3725194A US3725194A US00161954A US3725194DA US3725194A US 3725194 A US3725194 A US 3725194A US 00161954 A US00161954 A US 00161954A US 3725194D A US3725194D A US 3725194DA US 3725194 A US3725194 A US 3725194A
- Authority
- US
- United States
- Prior art keywords
- pulp
- alkaline
- bleaching
- oxygen gas
- protector
- 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
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- 238000004061 bleaching Methods 0.000 title claims abstract description 61
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 36
- 238000011282 treatment Methods 0.000 title claims description 97
- 239000001301 oxygen Substances 0.000 title description 30
- 229910052760 oxygen Inorganic materials 0.000 title description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 91
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 81
- 239000002253 acid Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000001012 protector Effects 0.000 claims abstract description 48
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000009471 action Effects 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 12
- 239000011707 mineral Substances 0.000 claims abstract description 12
- 239000004291 sulphur dioxide Substances 0.000 claims abstract description 12
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 8
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 25
- 238000005660 chlorination reaction Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 13
- 235000010755 mineral Nutrition 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal borates Chemical class 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229940037003 alum Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000004115 Sodium Silicate Substances 0.000 abstract description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 24
- 235000011121 sodium hydroxide Nutrition 0.000 description 23
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 16
- 239000002655 kraft paper Substances 0.000 description 14
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 11
- 235000011613 Pinus brutia Nutrition 0.000 description 11
- 241000018646 Pinus brutia Species 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- 239000011122 softwood Substances 0.000 description 10
- 239000004155 Chlorine dioxide Substances 0.000 description 8
- 235000019398 chlorine dioxide Nutrition 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000002939 deleterious effect Effects 0.000 description 4
- 239000000391 magnesium silicate Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 150000002927 oxygen compounds Chemical class 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 108010023321 Factor VII Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- BBBFJLBPOGFECG-VJVYQDLKSA-N calcitonin Chemical compound N([C@H](C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC=1NC=NC=1)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H]([C@@H](C)O)C(=O)NCC(=O)N[C@@H](CO)C(=O)NCC(=O)N[C@@H]([C@@H](C)O)C(=O)N1[C@@H](CCC1)C(N)=O)C(C)C)C(=O)[C@@H]1CSSC[C@H](N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)O)C(=O)N1 BBBFJLBPOGFECG-VJVYQDLKSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Inorganic materials ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910000386 magnesium trisilicate Inorganic materials 0.000 description 1
- 235000019793 magnesium trisilicate Nutrition 0.000 description 1
- 229940099273 magnesium trisilicate Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- D21C9/1005—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
- D21C9/1068—Bleaching ; Apparatus therefor with O2
Definitions
- a method of delignifying and bleaching alkaline pulp which comprises the steps of pretreating the pulp with an acidic medium having a pH from 1.2 to 4.8, such as an aqueous sulphur dioxide solution or a mineral acid, and thereafter subjecting the pulp in an alkaline medium, preferably sodium hydroxide, to the action of oxygen gas at elevated temperature and pressure.
- an alkaline medium preferably sodium hydroxide
- the pretreated pulp is subjected to the action of oxygen gas in the alkaline medium in the presence of a protector, such as magnesium carbonate or sodium silicate, which is operative to inhibit degradation of the physical strength properties of the pulp.
- This invention relates to the bleaching and delignification of alkaline pulps, such as soda, kraft and sulphate pulps, with oxygen gas.
- cellulose chemical pulp may be produced by an alkaline process, such as the conventional soda, kraft, counter-current kraft, or sulphate process, from suitable starting material which may, for example, be derived from conifers, such as pine; from deciduous woods, such as eucalyptus, or from fibrous non-woody plants, such as bagasse.
- an alkaline process such as the conventional soda, kraft, counter-current kraft, or sulphate process
- suitable starting material which may, for example, be derived from conifers, such as pine; from deciduous woods, such as eucalyptus, or from fibrous non-woody plants, such as bagasse.
- a cellulose chemical pulp produced by an alkaline process will simply be referred to as an alkaline pump.
- untreated alkaline pump normally contains impurities, such as lignins, and has a dark brown color and is generally bleached to some degree before use in all but the roughest of papers.
- the pulp is thus often lightly treated to remove only a portion of the color or it may be fully treated in a multiplicity of bleaching operations to obtain the highest white possible by present art, or it may be treated in any intermediate manner as needed. In all but special cases, care is taken to preserve as far as possible the physical strength properties of the fibers.
- This sequence is generally referred to as the C-E-I-I sequence.
- Chlorination converts lignins into waterand alkalisoluble chlorinated lignin compounds which are removed by water washing and by the alkali extraction step.
- the delignified pulp is bleached during the hypochlorite treatment to produce a so-called semibleached pulp.
- the semi-bleached pulp may be subjected to the following additional stages of treatment after the C-E-H sequence:
- the full bleaching sequence is generally referred to as the C-E-H-D-E-D sequence.
- Color reversion is relatively high at the semibleached stages as well as at the fully bleached stage.
- the capital outlay for chemical plant for the production of the chemicals is high, or alternatively, the cost of purchasing the chemicals is relatively high.
- the basic C-E-H sequence may be modified by using mixtures of chlorine and chlorine dioxide or even chlorine dioxide alone in the chlorination stage.
- Active oxygen compounds such as hydrogen peroxide have been used in the final bleaching of alkaline pulp as a substitute for, or an addition to, chlorine dioxide. It has been found that, for all practical purposes, active oxygen compounds are not effective for delignification and are, therefore, not suitable in the early delignification stages of purification. However, active oxygen compounds can be used to advantage in the later bleaching stages to give the sequence C-E-I-I-D-P-D or the sequence C-E-I-I-D-E-D- P, where P denotes the peroxide or other active oxygen stage.
- alkali pulps can be delignified and bleached by subjecting it in an alkaline medium to the action of oxygen gas or any other gas containing free oxygen, such as air. When this treatment is carried out at elevated temperature and pressure, good delignification and bleaching can be obtained but it has been found that the physical strength properties of the pulp are affected adversely.
- LAir Liquide S.A. discloses that by treating a chemical pulp with oxygen gas in an alkaline I medium in the presence of certain catalysts or protectors the physical and mechanical strength properties of the pump can be preserved, and in some cases even improved, while giving a very complete delignifi- I cation and a significant increase in brightness. More particularly, the pulp is treated with oxygen gas in an alkaline medium in the presence of a catalyst used at a concentration from 0.5 to about 3 percent by weight of the pulp and selected from the group consisting of barium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, alkali metal borates and titanium dioxide.
- the LAir Liquide method gives improved results, but still suffers from the disadvantage that if higher brightnesses are required, there is still a tendency for undesirable degradation in the physical strength properties to occur so that the limits of operation have to be carefully defined. Also, it is normally necessary to conduct the treatment over extended periods of time of up to 2 hours. On alkaline pulps, brightnesses over 45 percent are rarely obtained and then only with undesirable degradation in physical strength properties.
- a method of delignifying and bleaching an alkaline pulp includes the steps of pretreating the pulp with an acidic medium, and thereafter subjecting the pulp in an alkaline medium to the action of oxygen gas.
- the oxygen gas acts to delignify and bleach the pretreated pulp. if only a semi-bleached pulp is required, no further treatment need be effected. However, the oxygen gas treatment mayeasily be followed by any suitable bleaching stage or stages. Thus, if the semi-bleached pulp is bleached by the known D-E-D treatment, it can lead to full-bleached brightnesses with a saving in time and bleaching chemicals due to more efficient bleaching that can be achieved.
- the method according to our invention can replace the C-E-H or C-E stages of conventional semiand fullbleaching procedures to achieve a saving in expensive treating chemicals and to minimize the effluent problem and the color reversion problem, while still obtaining high brightnesses and maintaining the physical strength properties of the pulp.
- the pretreated pulp pretreated pulp to bewell washed, preferably with water, before being subjected to oxygen gas bleaching.
- the wash water should be substantially free from any deleterious or interfering elements, such as manganese.
- fresh pulp to be pretreated may be slurried in water recycled from the washing operation, without any deleterious results.
- the pretreating action is a function of the pH of the acidic medium and it has been found that for most pulps, the required duration of the pretreatment decreases with decreasing pH when all other conditions remain constant.
- the acidic medium may have-a pH from L2 to 4.8, and preferably from 2.5 to 4.8.
- the duration of the pretreatment may be from 5 to 60 minutes.
- the pulp consistency during pretreatment may be about 5 percent, but there is nothing inherent in the pretreatment which restricts the consistency to this value if suitable equipment is used.
- Any suitable acidic medium may be used for the pretreatment.
- Sulphur dioxide or mineral acids, such as hydrochloric acid or sulphuric acid have been found to give good results. It is also possible to use an acidic material such as alum, or a mixture of acidic media. Sulphur dioxide is preferably used at a concentration from 0.5 to 1 percent by weight of the pulp on a dry ba- SIS.
- An alkaline pump may be pretreated by adding an aqueous sulphur dioxide solution to a pulp slurry, preferably at ambient temperatureflt has been found that no significant improvement in the bleaching or the protection of the physical strength properties against degradation is obtained if the S0 content is increased above 1% by weight on a dry pulp basis. On the other hand, if the S0 content is reduced below 0.5 percent by weight on a dry pulp basis, the results obtained are, although significant, not as satisfactory as in the preferred range of S0 concentration of 0.5 to l percent.
- the subsequent oxygen gas treatment may be carried out in any suitable alkaline medium, preferably sodium hydroxide.
- any suitable alkaline medium preferably sodium hydroxide.
- sodium hydroxide Generally speaking, about 6 percent by weight sodium hydroxide on a dry pulp basis is preferred for most pulps if maximum bleaching and delignification is required. However, with pulps with a low lignin content, the quantity of sodium hydroxide may be reduced.
- the sodium hydroxide content will generally vary from 2% to 12% by weight on a dry pulp basis.
- the oxygen gas treatment may be carried out at an operating temperature from C to 135C (although for most purposes a temperature of 130C will be preferred) and at an oxygen pressure from 70 to 400 p.s.i.
- the pulp consistency may be from 4 to 30 percent, preferably from 8 to 18 percent.
- the pulp may be subjected to the oxygen gas treatment for a period of time ranging from 10 to minutes depending on the results required or the nature of the pulp being treated.
- the acid pretreated pulp may be subjected to the action of oxygen gas in the alkaline medium in the presence of a protector operative to inhibit degradation of the physical strength properties of the pulp.
- a protector operative to inhibit degradation of the physical strength properties of the pulp.
- about 1 percent by weight of protector on a dry pulp basis is preferred, but the amount of protector may vary from 0.5 to 3.0 percent by weight on a dry pulp basis.
- the protector may be selected from the group consisting of barium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, alkali metal borates and titanium dioxide, which is disclosed in French patent specification No. 1,387,853.
- magnesium carbonate is the preferred protector.
- the protector may also be selected from the group consisting of silica; an alkali metal silicate, such as sodium silicate; an alkali earth silicate, such as magnesium silicate; an alkali earth oxide, such as magnesium oxide; an alkali earth hydroxide, such as magnesium hydroxide; and an alkali earth salt, preferably a magnesium salt, such as magnesium phosphate, magnesium acetate, or magnesium chloride.
- an alkali metal silicate such as sodium silicate
- an alkali earth silicate such as magnesium silicate
- an alkali earth oxide such as magnesium oxide
- an alkali earth hydroxide such as magnesium hydroxide
- an alkali earth salt preferably a magnesium salt, such as magnesium phosphate, magnesium acetate, or magnesium chloride.
- sodium silicate, magnesium oxide and magnesium silicate are particularly advantageous, sodium silicate being preferred because of its solubility.
- the acid pretreatment according to the invention may be used without a protector being employed in the subsequent oxygen treatment. It has been found that without a protector, the acid treatment can result in a higher brightness after the oxygen treatment than is possible also be used with compressed air or any other gas containing free oxygen, provided no detrimental materials are present.
- the oxygen gas treatment is best carried out in any suitable pressure apparatus which will ensure intimate contact or adequate exposure of the pulp mass with or to oxygen in the gas phase, thus to ensure adequate resaturation of the liquid medium with oxygen.
- solubility of the oxygen gas used By increasing the solubility of the oxygen gas used, faster and improved bleaching and delignification can be obtained. Since such solubility of oxygen at any selected temperature is a function of the partial pressure of the oxygen, it is advantageous to carry out the oxygen treatment at as high an oxygen concentration and/or as high a total gas pressure as is practically feasible. In order to protect the pulp against degradation of its physical strength properties when it is subjected to severe conditions of time, temperature and pressure to obtain higher brightnesses and improved delignification, it is advantageous to use a protector during the oxygen gas treatment.
- the acid pretreatment plus the use of a protector permits pressures up to 400 p.s.i. and even higher and temperatures as high as 130C to be used in order to obtain higher brightnesses substantially without increase in degradation of the physical strength properties of the pulp as compared with the same oxygen gas treatment but without the acid pretreatment and without the use of a protector.
- the operating temperature may range from 90C to 135C (although for most purposes a temperature of 130C will be preferred) and the operating pressure may be from 70 to 400 p.s.i. during the oxygen gas treatment in the presence of a protector after acid pretreatment.
- the effect of a protector will be apparent from the results shown in tables I and H below.
- the solubility of oxygen in the alkaline solution is a function of the partial pressure of the oxygen which can be increased by either increasing the total gas pressure or the oxygen content, or both, and since the method according to the invention permits the pressure to be increased considerably in relation to known methods, the method according to the invention is not limited to the use of relatively pure oxygen, but may consumed at a lower temperature. Also, the alkaline medium may be added stepwise during the treatment.
- the oxygen gas treated pulp may be washed in any suitable manner.
- the choice of the washing operation is largely governed by whether recovery of chemicals in the effluent or subsequent bleaching is contemplated. It is advantageous-for the washing operation to be done carefully and for the effluent to be treated in a chemical recovery process. Further economies in recovery of this filtrate can be achieved if portion of this filtrate is recirculated for dilution of pulp which is to be oxygen gas treated. This has been found to have no deleterious effects on the brightnesses obtained.
- Such filtrate, or recirculated filtrate may then, for example, be used as portion of the wash water used in the normal washing stages applied to the pulp as produced by the pulping process concerned, or may be added directly to the liquors at any stage in the recovery process concerned.
- the caustic soda in the filtrate may be recovered by any of the known methods of recovery. It is a big advantage of this process that despite the load of organic matter in these filtrates, they are substantially free of chlorides which are normally always present in bleach plant effluents. This enables the chemical recovery process to be conducted readily without the serious interferences caused by chlorides, and allows, if necessary, any recovered sodium carbonate to be converted to caustic soda for repeated re-use. The very heavy pollution load caused by normal multi-stage bleaching operations will in this way be very beneficially reduced.
- Higher brightness semi-bleached pulp may be produced by following the oxygen gas treatment with a second acidic treatment similar to the pretreatment.
- the oxygen gas treated pulp may be subjected to any of the conventional bleaching agents, such as hypochlorite, chlorine dioxide or peroxide, with a considerable saving in these agents as compared with conventional processes.
- the results achieved with a single additional bleaching stage after the oxygen gas treatment, are indicated in table IV below.
- the type of pulp which is conventionally subjected to the C.-E-H- D-E-D sequence may in accordance with our invention be subjected to the sequence SO -O -SO -D-E-D or to the sequence SO -O -H-D-E-D.
- the type of pulp which is conventionally subjected to the C-E-D-E-D sequence may be subjected to the sequence SO -O -D-E-D.
- caustic soda which can be recovered readily and re-used
- Pulp A a. untreated, unbleached, industrial softwood (pine) kraft pulp of KAPPA 23.9 (hereinafter referred to as Pulp A);
- Pulp B the pulp of (a) above after oxygen gas treatment in an alkaline medium without a protector and without an acid pretreatment
- Pulp C the pulp of (a) above after an acid pretreatment followed by the same oxygen gas treatment in an alkaline medium as in (b) above, but without a protector (hereinafter referred to as Pulp C);
- Pulp D the pulp of (a) above after the same acid pretreatment followed by the same oxygen gas treatment in an alkaline medium without a protector as in (c) above, but with the exception that the oxygen gas treatment was carried out for a shorter period of time (hereinafter referred to as Pulp D);
- Pulp E the pulp of (a) above after the same oxygen gas treatment in an alkaline medium as in (b) and (0) above, but with a protector and without an acid pretreatment
- Pulp F the pulp of (a) above after the same acid pretreatment as in (c) above followed by the same oxygen gas treatment in an alkaline medium and with a protector as in (e) above (hereinafter referred to as Pulp F).
- Pulps B, C and D show that the physical strength properties of the pulp are degraded by oxygen gas treatment without a protector.
- Pulps C and D which were subjected to acid pretreatment higher brightnesses were obtained as compared with Pulp B which did not have an acid pretreatment.
- a comparison of the results for Pulps C and D shows that the duration of the oxygen gas treatment affects the brightness and the physical strength properties that are obtained.
- a comparison of the results for Pulps B and D show that with an acid pretreatment according to the invention, a semi-bleached pulp with a higher brightness can be obtained substantially without loss in physical strength properties, than is possible with the oxygen gas treatment on its own.
- Pulps E and F show that where oxygen gas treatment is carried out in the presence of a protector, the physical strength properties of the pulp are preserved to a marked degree.
- Pulp F which was subjected to an acid pretreatment, the brightness was materially enhanced in relation to Pulp E which was not subjected to an acid pretreatment.
- EXAMPLE ll The lignin content, the brightness and the physical strength properties of an industrial softwood (pine) kraft pulp of KAPPA 23.1 after an acid pretreatment followed by oxygen gas treatment in the presence of an alkaline medium without a protector, are compared below in table II with those of the same pulp after the same acid pretreatment followed by the same oxygen gas treatment in an alkaline medium but in the presence of. different protectors, namely magnesium carbonate, sodium silicate and magnesium trisilicate.
- Table III compares the required duration of an oxygen gas treatment to bleach an industrial softwood .(pine) kraft pulp of KAPPA 32 to a brightness of 50 by the following treatments:
- Pulp G a. oxygen gas treatment in an alkaline medium with a protector at an oxygen pressure of 200 p.s.i.g., but without an acid pretreatment
- Pulp H the same oxygen gas treatment as in (a) above after an acid pretreatment in H 80 at pH 3.0 for minutes
- Pulp I the same oxygen gas treatment as in (a) above after an acid pretreatment in H 80 at pH 1.6 for 15 minutes
- Pulp J the same oxygen gas treatment as in (a) above after an acid pretreatment in S0 at pH 3.0 for 60 minutes (hereinafter referred to as Pulp J);
- Pulp K the same pretreatment and oxygen gas treatment as in (d) above with the exception that the oxygen gas treatment was carried out at 400 p.s.i.g. (hereinafter referred to as Pulp K).
- a comparison of the results for Pulps H, I and J with the results for Pulp G shows that with an acid pretreatment according to the invention, the required duration of the oxygen gas treatment at a given oxygen pressure to obtain a given brightness is reduced considerably as compared with oxygen gas treatment without an acid pretreatment.
- Pulps J and K show the marked reduction in the required duration of the oxygen gas treatment which is brought about by an increase in the oxygen pressure, when all other factors remain constant.
- EXAMPLE IV Table IV below given an indication of the potential of oxygen gas bleached pulps produced in accordance with the present invention, to further bleaching in a single additional bleaching stage after the oxygen gas treatment, by comparing the brightnesses and physical strength properties of an industrial softwood (pine) kraft pulp of KAPPA 20.0 after the following treatments:
- Pulp L a conventional C-E-I-I treatment (hereinafter referred to as Pulp L);
- Pulp M the same oxygen gas treatment in an alkaline medium with a protector but without an acid pretreatment as Pulp E in Example I above, followed by a hypochlorite treatment (hereinafter referred to as Pulp M);
- Pulp N the same acid pretreatment and the same oxygen gas treatment in an alkaline medium with a protector as Pulp F in Example I above, followed by a hypochlorite treatment (hereinafter referred to as Pulp N);
- Pulp 0 the same acid pretreatment and the same oxygen gas treatment in an alkaline medium with a protector as in (c) above, followed by a more concentrated hypochlorite treatment than in (c) above (hereinafter referred to as Pulp 0).
- Pulp N was subjected to a lower dosage of hypochlorite than Pulp M, a higher brightness was obtained as a result of the acid pretreatment.
- the brightness of 67.0 obtained with Pulp M after the hypochlorite treatment is the maximum obtainable for the pulp in question with a hypochlorite treatment after an oxygen gas treatment without an acid pretreatment.
- Pulp M was subjected to a higher dosage of hypochlorite than Pulp N, a higher brightness was obtained with the latter pulp which was subjected to an acid pretreatment.
- Pulp P the same oxygen gas treatment in an alkaline medium with a protector and without an acid pretreatment as applied to Pulp E .in Example I above, followed by a D-E-D sequence (hereinafter referred to as Pulp P);
- Pulp O the same treatment as in (a) above preceded by the same acid pretreatment as applied to Pulp F in Example I above (hereinafter referred to as Pulp O);
- Pulp R the same treatment as in (b) above, but with an acidic treatment similar to the acid pretreatment interposed between the oxygen gas and chlorine dioxide stages (hereinafter referred to as Pulp R);
- Pulp T a conventional C-E-I-I-D-E-D sequence (hereinafter referred to as Pulp T);
- Acceptable brightnesses are also obtained with the SO -O -D-E-D and SO -O -H-D-E-D sequences of pulps Q and S respectively, Pulp Q showing a better preservation of physical strength properties.
- the acid pretreatment according to the invention results in improved color reversion properties as compared with the conventional C-E-I-I-D-E-D sequence of Pulp T.
- Pulp U a conventional C-E-H-D-E-D (hereinafter referred to as Pulp U);
- Pulp V the same acid pretreatment and oxygen gas treatment in an alkaline medium with a protector as applied to pulp F in Example I above, followed by an additional acidic treatment similar to the pretreatment and a D-E-D sequence (hereinafter referred to as Pulp V).
- the high brightness of 65.6 for Pulp V after the S0 0 sequence is typical of the brightness obtainable with that sequence on hardwood kraft pulps.
- Pulp consistency s Acidic medium (percent S02) 1 pH of acidic medium 3 3 Operating temperature A i t Duration (mins.) (30 Elrepho brightness 24. 1 26, 5 Oxygen gas treatment:
- i 1% MgCO *Pulps produced by a conventional C-E-H sequence normally have a colour reversion value of 4.3 for a brightness of 52 and a colour reversion value 01' 8.2 for a brightness of 60.
- Pulp G Pulp H Pulp I Pulp J Pulp K Pretreatmen! pulp consistency 5.0 5.0 5.0 5.0 acidic medium 0.8%H SO 5%H SO. 1%SO 1%SO pH of Acidic medium 3.0 1.6 3.0 3.0
- Pulps produced by a conventional C-E-H sequence normally have a color reversion value of4.1 for a brightness of 50.
- Pulp P Pulp Q Pulp R Pulp S Pulp T Bleaching Sequence O D-E- SOz-Oz" SO O1 SOz-Oz- C-E-H- D D-E-D SOz D-E-HD-E-D D-E-D Brightness: Untreated 25.5 25.5 25.5 25.5 502 27.0 27.0 27.0 Oz 53.0 58.0 58.0 58.0
- Double Folds (under 800 g) 40 35 Burst Factor 42 38 Tear Factor 72 75 Color Reversion 8.8 2.9
- a method of delignifying and bleaching an alkaline pulp without a chlorination stage comprising the steps of pretreating the alkaline pulp with an acidic medium having a pH from 1.2 to 4.8 for a time sufficient to enhance the ultimate brightness of the pulp after bleaching; washing the thus treated alkaline pulp; and thereafter subjecting same in an alkaline medium to the action of oxygen gas at a temperature of to C and a pressure in excess of 70 p.s.i.g.
- a method of delignifying and bleaching an alkaline pulp without a chlorination stage comprising the steps of pretreating the alkaline pulp with an acidic medium having a pH from 1.2 to 4.8 for a time sufficient to enhance the ultimate brightness of the pulp after bleaching and comprising at least one of the substances in the group consisting of sulphur-dioxide, a mineral acid and alum; washing the thus treated alkaline pulp; and thereafter subjecting same in an alkaline medium to the action of oxygen gas at a temperature of 90 to 135C. and a pressure in excess of 70 p.s.i.g.
- the acidic medium comprises sulphur-dioxide at a concentration of from 0.5 to 1 percent by weight of the pulp on a dry basis.
- a method of delignifying and bleaching an alkaline pulp without a chlorination stage comprising the steps of pretreating the alkaline pulp with a mineral acid at a pH from 1.2 to 4.8 for a time sufficient to enhance the ultimate brightness of the pulp after bleaching; washing the thus treated alkaline pulp; and thereafter subjecting same in the presence of 2 to 12 percent by weight of sodium hydroxide on a dry pulp basis to the action of oxygen gas at a temperature of 90 to 135C and a pressure in excess of 70 p.s.i.g.
- a method of delignifying and bleaching an alkaline pulp without a chlorination stage comprising the steps of pretreating the alkaline pulp with an acidic medium having a pH from 1.2 to 4.8 for a time sufficient to enhance the ultimate brightness of the pulp after bleaching; washing the thus treated alkaline pulp; and thereafter subjecting same in an alkaline medium to the action of oxygen gas at a temperature of 90 to 135C and a pressure in excess of 70 p.s.i.g. and in the presence of an inorganic or organic protector operative to inhibit degradation of the physical strength properties of the pulp, the alkaline medium being constituted by a substance other than the protector.
- a method of delignifying and bleaching an alkaline pulp without a chlorination stage comprising the steps of pretreating the alkaline pulp with an acidic medium having a pH of 1.2 to 4.8 for a time sufficient to enhance the ultimate brightness of the pulp after bleaching; washing the thus treated alkaline pulp; and thereafter subjecting same in an alkaline medium to the action of oxygen gas at a temperature of 90 to 135C and a pressure in excess of 70 p.s.i.g.
- a protector selected from the group consisting of barium carbonate, calcium carbonate, magnesium carbonate, magnesium acetate, zinc carbonate, alkali metal borates, titanium dioxide, silica, an alkali metal silicate, an alkali earth silicate, an alkali earth oxide, and an alkali earth hydroxide, the alkaline medium being constituted by a substance other than the protector.
- a method of delignifying and bleaching an alkaline pulp without a chlorination stage comprising the steps of pretreating the alkaline pulp with a mineral acid at a pH of 1.2 to 4.8 for a time sufficient to enhance the ultimate brightness of the pulp after bleaching; washing the thus treated alkaline pulp; and thereafter subjecting same in an alkaline medium comprising 2 to 12 percent by weight of sodium hydroxide on a dry pulp basis to the action of oxygen gas at a temperature of to C. and a pressure in excess of 70 p.s.i.g. and in the presence of up to 3 percent by weight on a dry pulp basis of a protector comprising a magnesium salt.
- a method as claimed in claim 12 wherein the magnesium salt is magnesium oxide or magnesium hydroxide.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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ZA673680 | 1967-06-20 | ||
ZA683772 | 1968-06-13 | ||
US16195471A | 1971-07-09 | 1971-07-09 |
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US3725194A true US3725194A (en) | 1973-04-03 |
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US00161954A Expired - Lifetime US3725194A (en) | 1967-06-20 | 1971-07-09 | Treatment of alkaline pulp with an acidic medium followed by oxygen bleaching and delignification |
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US (1) | US3725194A (en, 2012) |
FR (1) | FR1601408A (en, 2012) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4431480A (en) * | 1981-10-27 | 1984-02-14 | The Black Clawson Company | Method and apparatus for controlled addition of alkaline chemicals to an oxygen delignification reaction |
US4560437A (en) * | 1983-06-29 | 1985-12-24 | M. Peterson & Son A/S | Process for delignification of chemical wood pulp using sodium sulphite or bisulphite prior to oxygen-alkali treatment |
US4594130A (en) * | 1978-11-27 | 1986-06-10 | Chang Pei Ching | Pulping of lignocellulose with aqueous alcohol and alkaline earth metal salt catalyst |
EP0325731A1 (de) * | 1988-01-28 | 1989-08-02 | Degussa Aktiengesellschaft | Verfahren zur Herstellung von halbgebleichtem Kraftzellstoff |
US5073301A (en) * | 1989-07-18 | 1991-12-17 | Degussa Aktiengesellschaft | Process for stabilization of the viscosity of wood pulps |
WO1997017489A1 (en) * | 1994-05-10 | 1997-05-15 | Stora Kopparbergs Bergslags Ab | Process for oxygen delignification |
RU2126862C1 (ru) * | 1994-10-13 | 1999-02-27 | Альстрем Машинери Ой | Способ удаления групп гексенуроновых кислот из целлюлозы путем термообработки |
US6336994B1 (en) * | 1992-12-02 | 2002-01-08 | Kvaerner Pulping Aktiebolag | Totally chlorine free bleaching process using recovered filtrate |
US20020129911A1 (en) * | 2000-10-16 | 2002-09-19 | Marcoccia Bruno S. | Process and configuration for providing external upflow/internal downflow in a continuous digester |
EP1244840A4 (en) * | 1999-06-08 | 2003-04-16 | Eastern Pulp And Paper Corp | HIGH PRESSURE OXYGEN BLEACHING OF A PULP |
US6569284B1 (en) | 1996-09-24 | 2003-05-27 | International Paper Company | Elemental-chlorine-free bleaching process having an initial Eo or Eop stage |
US20100269992A1 (en) * | 2009-04-24 | 2010-10-28 | International Paper Company | Sulfonation of pulp produced by alkali pulping process |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5510715B1 (en, 2012) * | 1971-06-24 | 1980-03-18 | ||
JPS4948902A (en, 2012) * | 1972-09-13 | 1974-05-11 | ||
GB1505529A (en) * | 1974-06-14 | 1978-03-30 | Mo Och Domsjoe Ab | Method for the oxygen-gas delignification of lignocellulosic material and apparatus for carrying out the method |
JPS5039161B2 (en, 2012) * | 1974-12-23 | 1975-12-15 | ||
US5211809A (en) * | 1991-05-21 | 1993-05-18 | Air Products And Chemicals, Inc,. | Dye removal in oxygen color stripping of secondary fibers |
US5302244A (en) * | 1992-02-18 | 1994-04-12 | Domtar Inc. | Oxygen delignification of waste cellulosic paper products |
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US2147618A (en) * | 1936-04-01 | 1939-02-14 | West Virginia Pulp & Paper Com | Method of bleaching pulp |
US2466633A (en) * | 1948-05-26 | 1949-04-05 | James M Daily | Method of bleaching cellulosic pulp |
US2878118A (en) * | 1953-02-18 | 1959-03-17 | Buckeye Cellulose Corp | Purified cellulose fiber and process for producing same |
US3024158A (en) * | 1958-07-02 | 1962-03-06 | Kimberly Clark Co | Manufacture of cellulosic products |
US3384533A (en) * | 1963-09-19 | 1968-05-21 | Air Liquide | Delignification and bleaching of chemical and semichemical cellulose pulps with oxygen and catalyst |
US3382149A (en) * | 1964-10-29 | 1968-05-07 | Du Pont | Bleaching of hardwood sulfite pulp with hydrogen peroxide, including pretreatment with alkali |
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4594130A (en) * | 1978-11-27 | 1986-06-10 | Chang Pei Ching | Pulping of lignocellulose with aqueous alcohol and alkaline earth metal salt catalyst |
US4431480A (en) * | 1981-10-27 | 1984-02-14 | The Black Clawson Company | Method and apparatus for controlled addition of alkaline chemicals to an oxygen delignification reaction |
US4560437A (en) * | 1983-06-29 | 1985-12-24 | M. Peterson & Son A/S | Process for delignification of chemical wood pulp using sodium sulphite or bisulphite prior to oxygen-alkali treatment |
AT386425B (de) * | 1983-06-29 | 1988-08-25 | Peterson & Son | Verfahren zur entlignifizierung von chemischer holzpulpe |
EP0325731A1 (de) * | 1988-01-28 | 1989-08-02 | Degussa Aktiengesellschaft | Verfahren zur Herstellung von halbgebleichtem Kraftzellstoff |
AU607026B2 (en) * | 1988-01-28 | 1991-02-21 | Degussa A.G. | Process for producing semibleached kraft pulp |
US5073301A (en) * | 1989-07-18 | 1991-12-17 | Degussa Aktiengesellschaft | Process for stabilization of the viscosity of wood pulps |
US6336994B1 (en) * | 1992-12-02 | 2002-01-08 | Kvaerner Pulping Aktiebolag | Totally chlorine free bleaching process using recovered filtrate |
WO1997017489A1 (en) * | 1994-05-10 | 1997-05-15 | Stora Kopparbergs Bergslags Ab | Process for oxygen delignification |
RU2126862C1 (ru) * | 1994-10-13 | 1999-02-27 | Альстрем Машинери Ой | Способ удаления групп гексенуроновых кислот из целлюлозы путем термообработки |
US6569284B1 (en) | 1996-09-24 | 2003-05-27 | International Paper Company | Elemental-chlorine-free bleaching process having an initial Eo or Eop stage |
EP1244840A4 (en) * | 1999-06-08 | 2003-04-16 | Eastern Pulp And Paper Corp | HIGH PRESSURE OXYGEN BLEACHING OF A PULP |
US20020129911A1 (en) * | 2000-10-16 | 2002-09-19 | Marcoccia Bruno S. | Process and configuration for providing external upflow/internal downflow in a continuous digester |
US20100269992A1 (en) * | 2009-04-24 | 2010-10-28 | International Paper Company | Sulfonation of pulp produced by alkali pulping process |
US8980051B2 (en) | 2009-04-24 | 2015-03-17 | International Paper Company | Sulfonation of pulp produced by alkali pulping process |
Also Published As
Publication number | Publication date |
---|---|
FR1601408A (en, 2012) | 1970-08-24 |
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