EP2931968B1 - Utilisation de dithionite de sodium dans un processus de cuisson de cellulose - Google Patents
Utilisation de dithionite de sodium dans un processus de cuisson de cellulose Download PDFInfo
- Publication number
- EP2931968B1 EP2931968B1 EP13805310.3A EP13805310A EP2931968B1 EP 2931968 B1 EP2931968 B1 EP 2931968B1 EP 13805310 A EP13805310 A EP 13805310A EP 2931968 B1 EP2931968 B1 EP 2931968B1
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- EP
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- Prior art keywords
- digestion
- cooking
- wood
- phase
- acid
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- 238000000034 method Methods 0.000 title claims description 58
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 title claims description 31
- 239000001913 cellulose Substances 0.000 title claims description 20
- 229920002678 cellulose Polymers 0.000 title claims description 20
- 238000004537 pulping Methods 0.000 title description 14
- 238000010411 cooking Methods 0.000 claims description 73
- 230000029087 digestion Effects 0.000 claims description 57
- 239000002023 wood Substances 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 38
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 30
- 239000012978 lignocellulosic material Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 15
- CPMVCRMQKZREQQ-UHFFFAOYSA-L ctk4c8528 Chemical compound [Ca+2].[O-]S(=O)S([O-])=O CPMVCRMQKZREQQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PENRVBJTRIYHOA-UHFFFAOYSA-L zinc dithionite Chemical compound [Zn+2].[O-]S(=O)S([O-])=O PENRVBJTRIYHOA-UHFFFAOYSA-L 0.000 claims description 6
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 239000011734 sodium Substances 0.000 description 31
- 239000002253 acid Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- 229910021653 sulphate ion Inorganic materials 0.000 description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 14
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 14
- 241000218657 Picea Species 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 11
- 229920005610 lignin Polymers 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- GOYYUYNOGNSLTE-UHFFFAOYSA-N copper;2-azanidylethylazanide Chemical compound [Cu+2].[NH-]CC[NH-].[NH-]CC[NH-] GOYYUYNOGNSLTE-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000011122 softwood Substances 0.000 description 4
- 102100030386 Granzyme A Human genes 0.000 description 3
- 101001009599 Homo sapiens Granzyme A Proteins 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003638 chemical reducing agent 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
- 239000002904 solvent Substances 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 240000000731 Fagus sylvatica Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 206010017577 Gait disturbance Diseases 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004182 chemical digestion Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- LPHFLPKXBKBHRW-UHFFFAOYSA-L magnesium;hydrogen sulfite Chemical compound [Mg+2].OS([O-])=O.OS([O-])=O LPHFLPKXBKBHRW-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 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
- 241001148717 Lygeum spartum Species 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000013431 Pinus clausa Nutrition 0.000 description 1
- 235000000773 Pinus glabra Nutrition 0.000 description 1
- 241001502813 Pinus glabra Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 206010041662 Splinter Diseases 0.000 description 1
- 240000003021 Tsuga heterophylla Species 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- FCMYSEXCLRFWBP-UHFFFAOYSA-N [NH4+].[NH4+].[O-]S(=O)S([O-])=O Chemical compound [NH4+].[NH4+].[O-]S(=O)S([O-])=O FCMYSEXCLRFWBP-UHFFFAOYSA-N 0.000 description 1
- KJPJKTCATSVXHG-UHFFFAOYSA-N [dihydroxy(oxo)-$l^{6}-sulfanylidene]magnesium Chemical compound OS(O)(=O)=[Mg] KJPJKTCATSVXHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 238000005303 weighing Methods 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
- D21C3/00—Pulping cellulose-containing materials
-
- 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
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
- D21C11/08—Deodorisation ; Elimination of malodorous compounds, e.g. sulfur compounds such as hydrogen sulfide or mercaptans, from gas streams
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
- D21C3/022—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of S-containing compounds
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
-
- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
-
- 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
- D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
- D21C9/1089—Bleaching ; Apparatus therefor with reducing compounds with dithionites
Definitions
- the present invention relates to a process for producing cellulose from lignocellulosic material by means of sulfite digestion or sulfate digestion as defined in the claims.
- cellulose (herein and also referred to in the art as "pulp") from lignocellulosic material, such as wood, are known and, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 17, “Paper, Fiber Raw Materials", pp. 531-576, Verlag Chemie Weinheim, New York (1979 ).
- the cellulose is obtained by chemical digestion processes from the lignocellulosic material, such as wood.
- chemical digestion methods are, for example, the sulphite digestion used for this purpose or the likewise known sulfate digestion. Sulfite digestion and sulfate digestion are described, for example, in the Ullmann literature cited above.
- lignocellulosic material in both of the above processes is treated as follows to recover cellulose.
- lignocellulosic material usually wood
- an acidic or neutral medium in the presence of sulfites (salts of sulfuric acid H 2 SO 3 ) treated with a so-called cooking acid
- said Lignin is usually sulfonated and water soluble and thus can be removed from the fibers leaving the pulp.
- DE-C-912 169 describes the boiling of spruce wood chips with sulphate lye.
- the sulfate liquor may contain sodium dithionite (Na 2 S 2 O 4 ).
- the wood chips are mixed with the sulphate liquor and boiled. This means that the sodium dithionite is present in the cooking liquor from the beginning and is heated with this.
- US-A-2012/0168102 relates to the pretreatment of lignocellulosic material by water extraction and subsequent impregnation with oxidizing or reducing agents ("reducing agent") before the lignocellulosic material thus treated is fed into a "kraft pulping process", or sulphate digestion.
- reducing agent oxidizing or reducing agents
- An "alkali metal dithionite (hydrosulfite)" can be used as a "reducing agent”.
- magnesium in the form of magnesium oxide (MgO) is used as base which is then converted to dihydrogen sulphite.
- acidic bisulfite digestion can also use calcium (Ca), sodium (Na) or ammonium (NH 4 + ) as the base for the cooking solution, which are then used as corresponding oxides or hydroxides analogously to magnesium.
- these metals can usually be used analogously, except for calcium, also in bisulfite digestion.
- lignocellulosic material usually conifers such as spruce wood, also fir wood and the wood of Hemlocktanne in question.
- conifers such as spruce wood, also fir wood and the wood of Hemlocktanne in question.
- some hardwood species such as beech, poplar and birch are also suitable.
- Spruce wood is preferred in the sulfite process.
- the above-mentioned different types of processes of the sulfite process usually operate at pressures in the range of 0.1 to 10 bar and generally in certain ranges of pH.
- the acidic bisulfite digestion a) usually at a pH in the range from 2 to 3, the bisulfite digestion b) usually at a pH in the range from 3 to 5, the neutral sulfite digestion c) usually at a pH Value in the range of 6 to 9 and the alkali sulfite digestion d) usually at a pH around 11.
- the digestion temperatures differ in the sulfite process.
- the temperature range of the acidic bisulfite pulping a) is usually at 120 to 150 ° C
- the bisulfite pulping b) usually at 150 to 160 ° C
- the sodium sulfite pulping c) or also of the Alkalisulfite digestion d) usually at 160 to 180 ° C.
- the cooking acid of the sulfite process usually contains so-called free sulfur dioxide (SO 2 ), which is present as SO 2 and sulfurous acid (hereinafter also "H 2 SO 3 ”) and bound SO 2 , which is bound to a cation (base). Free SO 2 and bound SO 2 are usually given as total SO 2 .
- the cooking acid of the sulfite process is generally composed as follows: M 2 SO 3 + H 2 SO 3 + SO 2 + H 2 O, of these, the H 2 SO 3 and the SO 2 are assigned to the free SO 2 and the M 2 SO 3 to the bound SO 2 .
- M is the respective so-called base, example magnesium.
- the proportion of the base and the SO 2 in the cooking acid is given in percent by weight.
- a cooking acid with a total SO 2 content of 80 g per liter contains 8% total SO 2 .
- the base portion is represented as its respective oxide form, such as MgO, CaO, Na 2 O.
- the preparation of a cooking acid is usually carried out by absorption of SO 2 to water and base carrier.
- the following equation is intended to serve as an example of the principle of cooking acid production of bisulfite digestion with magnesium as base (magnesium bisulfite).
- sulphate process also referred to as "power digestion” or “sulphate digestion” in the art
- lignocellulosic material for example, the wood of trees or from annuals, such as reeds, cereals (straw), Sugarcane (bagasse), corn won.
- wood chips of the lignocellulose-containing material for example wood or comminuted plant stems
- wood chips of the lignocellulose-containing material are usually heated in pressure vessels for several hours, for example 3 to 6 hours, at elevated pressure, for example in the range from 7 to 10 bar, usually in a mixture of sodium hydroxide solution ( aqueous NaOH), sodium sulfide (Na 2 S), and sodium sulfate (hereinafter also "Na 2 SO 4 ”) and optionally sodium carbonate (hereinafter also "Na 2 CO 3 ").
- sodium hydroxide solution aqueous NaOH
- Na 2 S sodium sulfide
- Na 2 SO 4 sodium sulfate
- optionally sodium carbonate hereinafter also "Na 2 CO 3 "
- black liquor soluble alkali lignin
- Cellulose can be separated from lignin with the abovementioned sulfite and sulfate processes, although it is still desirable to increase the pulp yield, in particular with a simultaneous low lignin content of the pulp.
- the kappa number is a measure of the lignin content of the pulp.
- pulp components
- pulp mainly hemicelluloses
- a disadvantage of the pulping by the sulfate process is the formation of malodorous substances such as mercaptans, in particular methylmercaptan.
- Na 2 S 2 O 4 sodium dithionite
- G. Jayme and G. Wörner describe an alkaline sulfite digestion of spruce at 170 ° C, 24 hours, wherein in 100 cm 3 of the digestion solution 3 g of NaOH, 1.56 g of sodium dithionite (Na 2 S 2 O 4 ) and 4, 69 g Na 2 SO 3 were included. ( G. Jayme, G. Wörner, paper, 6th year, Issue 11, pp. 220-222 (1952 )). In it, relatively large amounts of sodium dithionite, based on the wood to be treated, are described indirectly by means of the quantity of chemicals and the "lye ratio" (p. 221, left-hand column "Zahlentafel" and the subsequent paragraph).
- Object of the present invention was to obtain a high pulp yield with low lignin content of the pulp in the digestion of lignocellulosic material, in particular in the sulfate process, the formation of malodorous emissions should be reduced.
- Lignocellulosic material herein is any material, preferably from nature, containing lignin and cellulose.
- Preferred lignocellulose-containing material are woods, including shredded wood, such as wood sections from sawmills.
- Suitable woods are softwoods, preferably spruce or pine or hardwoods such as beech.
- lignocellulose-containing material is understood here to mean grasses and annual plants, for example straw, reed, esparto grass, bamboo and bagasse, which are usually not digested by the sulfite process but are preferably digested with alkaline digestion or neutral sulfite. Method.
- Salts of the dithionic acid herein are all metal salts or substituted (NR 4 + ) or unsubstituted (NH 4 + ) ammonium salts of this acid.
- Highly suitable salts of the dithionic acid are the alkali metal salts, alkaline earth metal salts, salts of the metals of group 12 of the Periodic Table of the Elements, and ammonium (NH 4 + ) salts.
- Preferred salts of dithionic acid are sodium dithionite (Na 2 S 2 O 4 ), potassium dithionite (K 2 S 2 O 4 ), calcium dithionite (CaS 2 O 4 ), zinc dithionite (ZnS 2 O 4 ), ammonium dithionite ((NH 4 ) 2 S 2 O 4 ).
- Salts of dithionic acid including those preferred above, of course also include those individuals containing water of crystallization and / or additives, the latter for example for stabilization.
- a well-suited dithionic acid salt is the sodium dithionite product, which is marketed by BASF SE as Blankit® or Blankit®S.
- the digestion temperature during sulphite digestion is usually in the range from 100 to 160.degree.
- a well-suited for the process according to the invention sulfite pulping is the bisulfite process with Mg (HSO 3 ) 2 as a component of the cooking acid, which is described in more detail below.
- softwoods preferably spruce, preferably used as wood chips.
- the wood chips are usually fresh from the forest (ie with a dry content of about 50 wt .-%) used.
- the amount used is calculated as dry matter (otro), in order then to be able to determine, for example, the yield of pulp.
- the cooking acid can be prepared by slurrying magnesium carbonate (hereinafter also “MgCO 3 ”) in the water and then introducing SO 2 .
- MgCO 3 magnesium carbonate
- the introduction of SO 2 is usually carried out until a clear solution has formed, which has a pH of about 3.8, for example. Usually, approximately all the dissolved substance is present as Mg (HSO 3 ) 2 .
- the pH would continue to decrease as the proportion of sulphurous acid increases.
- the cooking of the so-called lignocellulose-containing material with the cooking acid takes place in the usual digesters, discontinuous or continuous.
- the total cooking time is in the range of 400 to 600 minutes.
- a temperature profile is used for the cooking in the bisulfite process mentioned herein, preferably the bisulfite process with Mg (HSO 3 ) 2 as the component of the cooking acid.
- a well-suited temperature profile is as follows. 1st phase: Heating from a temperature in the range of 15 to 30 ° C to a temperature in the range of 100 to 110 ° C, within 60 to 120 minutes. 2nd phase (impregnation phase): Stability for 60 to 90 minutes at a temperature in the range of 100 to 110 ° C. 3rd phase: Heating up from a temperature in the range of 100 to 110 ° C, to a temperature in the range of 150 to 160 ° C, within 45 to 90 minutes. 4th phase (final cooking time): 150 to 250 minutes remain at a temperature in the range of 150 to 160 ° C. 5th phase: Cooling to a temperature in the range of 100 to 90 ° C.
- the salt of the dithionic acid preferably sodium dithionite (Na 2 S 2 O 4 ), calcium dithionite (CaS 2 O 4 ), zinc dithionite (ZnS 2 O 4 ), more preferably sodium dithionite, is added to the mixture of lignocellulosic material, preferably the wood chips from spruce wood, and the cooking acid, as described above in an amount ranging from 0.1 to 4.0% by weight, preferably 1.0 to 2.0% by weight, based in each case on the oven-dried lignocellulose-containing material , preferably the oven-dry wood chips from spruce wood added.
- sodium dithionite Na 2 S 2 O 4
- CaS 2 O 4 calcium dithionite
- ZnS 2 O 4 zinc dithionite
- the salt of the dithionic acid is preferably added at the beginning of the second phase, ie the impregnation phase.
- lignocellulose-containing material are woods, such as deciduous or preferably coniferous wood, particularly preferably spruce wood, preferably used as wood chips.
- the cooking liquor known for the sulfate process mixture of sodium hydroxide solution (aqueous NaOH), sodium sulfide (Na 2 S) and sodium sulfate (hereinafter also “Na 2 SO 4 ”) and optionally sodium carbonate (hereinafter also “Na 2 CO 3 ”) may be used, to which the salt of dithionic acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, in an amount in the range of 0.1 to 4 wt .-% based on the amount of oven-dry lignocellulosic material was added ,
- the cooking liquor for sulphate digestion usually contains NaOH and sodium sulfide (Na 2 S) as effective cooking chemicals.
- NaOH sodium sulfide
- the necessary concentration of these substances in the cooking liquor is usually dependent on the so-called "alkali ratio".
- alkali ratio By this the expert understands mass proportions of cooking liquor in relation to mass fractions of lignocellulose-containing material, preferably wood (oven-dry (otro)).
- lignocellulose-containing material preferably wood (oven-dry (otro)
- this lye ratio is usually in the range of 4: 1 to 4.5: 1, for example 4.2: 1, depending on the filling density of wood in the digester.
- the concentration of active alkali in the cooking liquor for example in the range of 45 to 60 g / l.
- the content of sodium sulfide (Na 2 S) in the total effective alkali is the sulfidity (expressed in%).
- the cooking liquor for the sulfate process according to the invention contains a salt of dithionic acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, in an amount in the range of 0.1 to 4 wt .-% based on the amount of oven-dried lignocellulose -containing material.
- the pH of the cooking liquor for the sulphate process according to the invention is usually about 14 at the beginning of the cooking process.
- the cooking of the lignocellulosic material with the cooking liquor for the sulphate process according to the invention takes place in the usual digesters discontinuous or continuous.
- the total cooking time for the sulfate process of the invention is usually in the range of 200 to 400 minutes, preferably 240 to 300 minutes.
- the boiling temperature for the sulfate process of the invention is in the range of 160 to 185 ° C, for example at 170 ° C.
- the salt of the dithionic acid preferably selected from the group consisting of sodium dithionite, zinc dithionite, calcium dithionite, most preferably sodium dithionite, in the sulphate process of the invention, is blended between the lignocellulosic material and the cooking liquor in an amount ranging from 0.1 to 4.0 % By weight, preferably 1.0 to 2.0% by weight, in each case based on the oven-dried lignocellulose-containing material.
- the salt of the dithionic acid is added in the final phase of the digestion of the sulphate process according to the invention.
- the inventive method for the production of cellulose from lignocellulose-containing material by sulfite pulping or sulfate pulping provides pulp in good yield good delignification of the lignocellulosic material. The whiteness of the unbleached pulp is improved.
- a salt of the dithionic acid in the sulfate process of the invention reduces the concentration of malodorous substances, preferably mercaptans in the exhaust gas of the sulfate cooking process.
- Lignocellulose-containing material A) Lignocellulose-containing material:
- Spruce wood chips pre-sorted and pre-dried in the room air for 2 to 3 days before cooking water content in the range of 23.4 to 33.2 wt .-%, on average about 30 wt .-%
- the stove had an acid circulation and electrical jacket heating and a temperature controller, pressure gauge, temperature sensor and pH electrode, and connected computer system.
- the total digestion time was 510 min (8 h 30 min).
- the pressure in the digester was 8 to 9 bar at the end of the final cooking time.
- Sodium dithionite (Blankit®S BASF SE) was dissolved in water by dosing pump within 10 min in the digester added to the mixture and that 32 g of pure Na 2 S 2 O 4 (1 wt .-% Na 2 S 2 O 4 or 64 g of pure Na 2 S 2 O 4 (2% by weight of Na 2 S 2 O 4, based on the amount of wood used, calculated on the amount of wood used).
- the addition times of the sodium dithionite were, per experiment, as follows: At the beginning of the holding time (impregnation phase), about 105 minutes after the start of the experiment or at the beginning of the final cooking time, about 255 minutes after the start of the experiment or in the half of the finished cooking time, approx 360 min after the start of the experiment.
- the pulp was removed, mixed with water and defibered with a stirrer.
- the shredded pulp was filled into a sieve, washed with water and dehydrated in a centrifuge.
- Table 1 shows the experiments: Table 1: test series Auxiliary agent [2] Adding time- min [1] Temp. On addition W7 1% Start of finished cooking time 255 min 155 ° C W8 1% Beginning impregnation phase 105 min 105 ° C W9 1% Half finished cooking time 360 min 155 ° C W10 2% Beginning impregnation phase 105 min 105 ° C W11 2% Start of finished cooking time 255 min 155 ° C W12 1% Beginning impregnation phase 105 min 105 ° C W14 without - - - W15 1% Beginning impregnation phase 105 min 105 ° C W16 1% before digestion process - - [1] The values mean number of minutes after the start of the experiment, ergo start of the first heating up [2] Sodium dithionite Na 2 S 2 O 4
- Table 2 summarizes the results of the experiments in Table 1: Table 2: test series aids addition Adding time- Acceptance yield [%] Kappa number / whiteness [%] Viscosity [ml / g] W7 1% Start of finished cooking time 54.2 24.5 / 60.7 676.1 W8 1% Beginning impregnation phase 54.9 19.0 / 62.9 640.6 W9 1% Half finished cooking time 55.3 27.9 / 59.1 689.0 W10 2% Beginning impregnation phase 54.5 25.5 / 59.1 679.8 W11 2% Start of finished cooking time 53.1 17.2 / 63.6 660.8 W12 1% Beginning impregnation phase 54.7 16.0 / 63.3 645.1 W14 without - 55.6 36.1 / 58.6 708.8 W15 1% Beginning impregnation phase 54.3 20.6 / 61.7 677.4 W16 1% before digestion process 55.0 29.0 / 57.1 694.9
- Acceptance yield means amount of pulp received (without coarse or splinter content) in relation to the wood used; It was determined by weighing and dry content measurement.
- the kappa number indicates the hardness of the pulp and was determined in accordance with ISO 302. Put simply, when determining the kappa number in an aqueous pulp suspension in an acidic medium under defined conditions, the potassium permanganate consumption (KMnO 4 consumption) is measured. The higher the lignin content in the pulp, the higher the potassium permanganate consumption and thus the kappa number. The higher the kappa number, the higher the residual lignin content of the pulp, the harder is usually the pulp.
- Whiteness means remission at 457nm and was determined on the Datacolor Elrepho® instrument according to ISO 2470.
- the viscosity determination was carried out in accordance with ISO 5351/1 (International Standard ISO 5351/1, Cellulose in dilute solutions - Determination of limping viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) solution, First edition 1981-12-01 ).
- a solution of cellulose in copper ethylenediamine solution is prepared.
- the concentration of the solvent is fixed.
- the concentration of cellulose in the solution should be determined according to the sample used in the determination.
- the throughput time of both the solvent and the cellulose solution is measured by a capillary viscometer at 25 ° C.
- the calculation of the intrinsic viscosity is based on the results of the determination and the known concentration of the cellulose solution according to the Martin equation.
- the measurement was carried out according to Alternative A of the determination method (International Standard ISO 5351/1, Cellulose in dilute solutions - Determination of limping viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) solution, First edition 1981-12-01 ). It works at low cellulose concentration and used to measure the transit times of solvent and cellulose solution, the same capillary.
- A) Lignocellulosic material is Lignocellulosic material:
- the cooking liquor was prepared by adding commercial laboratory chemicals in water from sodium hydroxide (NaOH) and sodium sulfide (Na 2 S). The amount of chemicals used was calculated so that an alkali ratio of 23% was used at a sulphidity of 20%.
- Table 3 shows the experiments: Table 3 Cooking no. Auxiliary agent [1] Adding time- Temperature on addition 1 without ------------ -- -------- 2 (Cf.) 2% main phase 170 ° C 3 2% final phase 170 ° C [1] Sodium dithionite Na 2 S 2 O 4
- Table 4 shows the yield of the accepts and the kappa number.
- Table 4 Cooking no. Auxiliary agent [1] Acceptance of raw material [%] Kappa number 1 without 43.3 20.1 2 (Cf.) 2% in the main phase 46,4 19.4 3 2% in final phase 47.1 19.9 [1] Sodium dithionite Na 2 S 2 O 4
- Acceptance yield and kappa number are as defined under (I) above.
- exhaust gases gases from the digester
- exhaust samples were taken at different times with a tracer pump.
- concentration of methylmercaptan in these samples was measured with methylmercaptan-specific gas detector tubes.
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Claims (6)
- Procédé de fabrication de cellulose à partir d'un matériau lignocellulosique par décomposition par des sulfites ou décomposition par des sulfates en présence d'un sel de l'acide dithionique, caractérisé en ce que le sel de l'acide dithionique est utilisé en une quantité dans la plage allant de 0,1 à 4,0 % en poids dans le cas de la décomposition par des sulfites et en une quantité dans la plage allant de 1,0 à 2,0 % en poids dans le cas de la décomposition par des sulfates, à chaque fois par rapport à la quantité de matériau lignocellulosique séché au four, et, en cas de décomposition par des sulfites, le sel de l'acide dithionique est ajouté dès que le mélange de l'acide de Koch et du matériau lignocellulosique à décomposer atteint lors du chauffage une température dans la plage allant de 60 °C à 110 °C, et le mélange ainsi obtenu est laissé à une température dans la plage allant de 100 à 110 °C pendant 30 à 90 minutes (phase d'imprégnation), et, en cas de décomposition par des sulfates, le sel de l'acide dithionique est ajouté lors de la phase terminale de la décomposition.
- Procédé selon la revendication 1, dans lequel le sel de l'acide dithionique est choisi dans le groupe constitué par : le dithionite de sodium, le dithionite de zinc, le dithionite de calcium.
- Procédé selon les revendications 1 à 2, dans lequel le sel de l'acide dithionique est le dithionite de sodium.
- Procédé selon les revendications 1 à 3, dans lequel la décomposition par des sulfates est réalisée dans la plage de température allant de 160 à 185 °C.
- Procédé selon les revendications 1 à 4, dans lequel le matériau lignocellulosique est le bois.
- Procédé selon les revendications 1 à 5, dans lequel le procédé est réalisé de manière discontinue.
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PL13805310T PL2931968T3 (pl) | 2012-12-12 | 2013-12-02 | Zastosowanie ditioninu sodu w sposobie warzenia masy celulozowej |
EP13805310.3A EP2931968B1 (fr) | 2012-12-12 | 2013-12-02 | Utilisation de dithionite de sodium dans un processus de cuisson de cellulose |
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EP12196636 | 2012-12-12 | ||
PCT/EP2013/075193 WO2014090609A1 (fr) | 2012-12-12 | 2013-12-02 | Utilisation de dithionite de sodium dans un processus de cuisson de cellulose |
EP13805310.3A EP2931968B1 (fr) | 2012-12-12 | 2013-12-02 | Utilisation de dithionite de sodium dans un processus de cuisson de cellulose |
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EP2931968B1 true EP2931968B1 (fr) | 2018-10-31 |
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JP (1) | JP6290244B2 (fr) |
KR (1) | KR20150093825A (fr) |
CN (1) | CN104838065A (fr) |
AR (1) | AR093929A1 (fr) |
AU (1) | AU2013357649B2 (fr) |
BR (1) | BR112015013578B1 (fr) |
CA (1) | CA2892725A1 (fr) |
CL (1) | CL2015001406A1 (fr) |
ES (1) | ES2708216T3 (fr) |
MX (1) | MX2015007586A (fr) |
PH (1) | PH12015501255A1 (fr) |
PL (1) | PL2931968T3 (fr) |
PT (1) | PT2931968T (fr) |
RU (1) | RU2649301C2 (fr) |
TW (1) | TWI607041B (fr) |
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CN112900130B (zh) * | 2021-02-02 | 2022-08-12 | 大连工业大学 | 一种减少植物纤维蒸煮后白度下降的方法 |
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DE912169C (de) * | 1952-02-22 | 1954-05-24 | Georg Jayme Dr Ing | Verfahren zum alkalischen Aufschluss von Pflanzenstoffen |
FR1150451A (fr) * | 1956-05-04 | 1958-01-14 | Saint Gobain | Perfectionnement aux procédés de fabrication des pâtes cellulosiques mi-chimiques |
FR2615874B1 (fr) * | 1987-05-25 | 1992-02-21 | Atochem | Procede de preparation de pates chimicothermomecaniques |
AU2007253774C1 (en) * | 2006-05-19 | 2012-03-22 | The Research Foundation Of State University Of New York | Methods for carbonate pretreatment and pulping of cellulosic material |
US20080105392A1 (en) * | 2006-11-03 | 2008-05-08 | Duggirala Prasad Y | Method and composition for improving fiber quality and process efficiency in mechanical pulping |
US20090090478A1 (en) * | 2007-10-05 | 2009-04-09 | Hollomon Martha G | Selectivity improvement in oxygen delignification and bleaching of lignocellulose pulp using singlet oxygen |
US20120168102A1 (en) * | 2009-04-02 | 2012-07-05 | Sung-Hoon Yoon | Pulping process for quality protection including methods for hemicellulose extraction and treatment of hemicellulose-extracted lignocellulosic materials |
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RU2649301C2 (ru) | 2018-03-30 |
CA2892725A1 (fr) | 2014-06-19 |
BR112015013578A2 (pt) | 2017-08-15 |
AU2013357649A1 (en) | 2015-06-11 |
PL2931968T3 (pl) | 2019-04-30 |
ZA201504934B (en) | 2017-11-29 |
JP6290244B2 (ja) | 2018-03-07 |
PT2931968T (pt) | 2019-01-11 |
KR20150093825A (ko) | 2015-08-18 |
TW201428031A (zh) | 2014-07-16 |
AR093929A1 (es) | 2015-07-01 |
CN104838065A (zh) | 2015-08-12 |
AU2013357649B2 (en) | 2017-06-08 |
WO2014090609A1 (fr) | 2014-06-19 |
CL2015001406A1 (es) | 2016-02-05 |
RU2015127891A (ru) | 2017-01-19 |
ES2708216T3 (es) | 2019-04-09 |
PH12015501255A1 (en) | 2015-08-17 |
TWI607041B (zh) | 2017-12-01 |
BR112015013578B1 (pt) | 2021-07-06 |
EP2931968A1 (fr) | 2015-10-21 |
JP2015537130A (ja) | 2015-12-24 |
MX2015007586A (es) | 2016-05-05 |
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