AU2013357649B2 - Use of sodium dithionite in a cellulose pulping process - Google Patents
Use of sodium dithionite in a cellulose pulping process Download PDFInfo
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- AU2013357649B2 AU2013357649B2 AU2013357649A AU2013357649A AU2013357649B2 AU 2013357649 B2 AU2013357649 B2 AU 2013357649B2 AU 2013357649 A AU2013357649 A AU 2013357649A AU 2013357649 A AU2013357649 A AU 2013357649A AU 2013357649 B2 AU2013357649 B2 AU 2013357649B2
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- 239000001913 cellulose Substances 0.000 title claims abstract description 25
- 229920002678 cellulose Polymers 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 83
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 title claims description 28
- 238000004537 pulping Methods 0.000 title description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010411 cooking Methods 0.000 claims description 62
- 230000029087 digestion Effects 0.000 claims description 44
- 239000002023 wood Substances 0.000 claims description 27
- 239000012978 lignocellulosic material Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 8
- CPMVCRMQKZREQQ-UHFFFAOYSA-L ctk4c8528 Chemical compound [Ca+2].[O-]S(=O)S([O-])=O CPMVCRMQKZREQQ-UHFFFAOYSA-L 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
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 229920005610 lignin Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011122 softwood Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000006887 Ullmann reaction Methods 0.000 description 4
- GOYYUYNOGNSLTE-UHFFFAOYSA-N copper;2-azanidylethylazanide Chemical compound [Cu+2].[NH-]CC[NH-].[NH-]CC[NH-] GOYYUYNOGNSLTE-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 102100030386 Granzyme A Human genes 0.000 description 3
- 101001009599 Homo sapiens Granzyme A Proteins 0.000 description 3
- 241000218657 Picea Species 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- -1 Alkali metal salts Chemical class 0.000 description 2
- 241000609240 Ambelania acida Species 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
- 240000000731 Fagus sylvatica Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 235000014676 Phragmites communis 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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000010905 bagasse Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 239000003265 pulping liquor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 244000283070 Abies balsamea Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 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
- 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
- 241000604152 Macrochloa tenacissima 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 230000003247 decreasing effect 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
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 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
- 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a method for producing cellulose from material containing lignocellulose by means of sulfite decomposition or sulfate decomposition in the presence of a salt of dithionous acid, characterized in that the salt of dithionous acid is used in an amount in the range of 0.1 to 4.0 wt% with respect to the amount of kiln-dry material containing lignocellulose.
Description
PF 74186 1 USE OF SODIUM DITHiONITE IN A CELLULOSE PULPING PROCESS Description
The present invention relates to a method of producing cellulose from lignocellulosic material by sulfite digestion or sulfate digestion, as defined in the claims.
Methods of obtaining cellulose from lignocellulosic material, such as wood, are known and described for example in Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 17, "Paper, fibrous raw materials", pp. 531-576, Verlag Chemie Weinheim, New York (1979). Typically, cellulose is obtained from the lignocellulosic material, for example wood, by chemical processes of destructurization. Examples of such chemical methods of destructurization are sulfite digestion as used for these purposes and the similarly familiar process of sulfate digestion. Sulfite digestion and sulfate digestion are described in the above-cited Ullmann reference for example.
Put simply, lignocellulosic material is treated in the two abovementioned processes as follows to obtain cellulose.
In the sulfite process (hereinafter also called "sulfite digestion"), lignocellulosic material, typically wood, is treated with a cooking liquor in an acidic or neutral medium in the presence of sulfites (salts of sulfurous acid H2SO3), whereby the lignin is typically sulfonated and water-solubilized and thus can be removed from the fibers to leave behind the cellulose.
There are various types of the sulfite process in existence, which differ inter alia in the pH of their cooking liquor. Examples are: a) the acidic bisulfite process with magnesium dihydrogensulfite (hereafter also "Mg(HS03)2") and sulfur dioxide, SO2, as well as water as a component of the cooking liquor, b) the bisulfite process with Mg(HSC>3)2 as a component of the cooking liquor, c) the neutral-sulfite process with disodium sulfite (hereinafter also "Na2SC>3") and sodium carbonate (hereinafter also "Na2C03"), as components of the cooking liquor, and d) the alkali-sulfite process with Na2SC>3 and sodium hydroxide (hereinafter also "NaOH") as well as water as components of the cooking liquor.
The acidic bisulfite process generally utilizes magnesium in the form of magnesium oxide (MgO) as a base, which is then converted to the dihydrogensulfite. Instead of magnesium (Mg), the acidic bisulfite process can also utilize calcium (Ca), sodium (Na) or ammonium (NH4+) as a base for the cooking liquor, which is then used similarly to magnesium in the form of the corresponding oxides/hydroxides. These metals except for calcium can typically also be used in similar fashion in the bisulfite process. PF 74186 2
Of the sulfite processes, the acidic magnesium bisulfite process is currently the most frequently used.
Softwoods such as sprucewood, also firwood and the wood of the hemlock fir generally come into consideration as lignoceliulose material for the sulfite process. Some hardwood species such as beech, poplar and birch are also suitable. Sprucewood is preferred for the sulfite process.
The abovementioned various types of the sulfite process typically each operate at pressures ranging from 0.1 to 10 bar and generally at certain pH ranges. The typical pH is in the range from 2 to 3 for the acidic bisulfite process a), in the range from 3 to 5 for the bisulfite process b), in the range from 6 to 9 for the neutral sulfite process c) and around 11 for the alkali-sulfite process d).
The digestion temperatures in the sulfite process differ in line with the pH range. Thus, the temperature range is generally from 120°C to 150°C for the acidic bisulfite process a), from 150°C to 160°C for the bisulfite process b) and in the range from 160°C to 180°C for both the sodium sulfite process c) and the alkali-sulfite process d).
The cooking liquor in the sulfite process typically comprises so-called free sulfur dioxide (SO2), which is present as SO2 and sulfurous acid (hereinafter also "H2SO3") and bound SO2, which is bound to a cation (base). Free SO2 and bound SO2 are generally reported as total SO2. The cooking liquor in the sulfite process generally has the following composition: M2SO3 + H2SO3 + SO2 + H2O, of which the H2SO3 and the SO2 are assigned to the free SO2 and the M2SO3 to the bound SO2. M here is the respective so-called base, for example magnesium.
The proportion of base and of SO2 in the cooking liquor is reported in weight percent. For instance, a cooking liquor having a total SO2 content of 80 g per liter comprises 8% of total SO2. The base fraction is reported in the particularly corresponding oxide form for the base, such as MgO, CaO, Na20. A cooking liquor is typically prepared via an absorption of SO2 on water and base vehicles. The equation hereinbelow shall serve as an example of the principle of cooking-liquor production in the bisulfite process using magnesium as base (magnesium bisulfite).
Mg(OH)2 + 2 S02 Mg(HS03)2 PF 74186 3
In the sulfate process (also known as "kraft digestion or "sulfate digestion" among those skilled in the art), cellulose is typically obtained from lignocellulosic material for example the wood of trees or else from annual plants, for example reed, grain (straw), sugarcane (bagasse), corn.
Typically, in the sulfate process, chips of the lignocellulosic material, for example wood or comminuted stems of plants, are 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, typically in a mixture of aqueous sodium hydroxide solution (aqueous NaOH), sodium sulfide (Na2S) and sodium sulfate (hereinafter also "NapSOV) and optionally sodium carbonate (hereinafter also "Na2CC>3").
This produces the so-called "black liquor" (soluble alkali metal lignin), which is separated from the cellulose by filtration.
Using the sulfite and sulfate processes mentioned, cellulose can be separated from lignin, but it continues to be desirable to increase the pulp yield and to achieve this more particularly with a simultaneously low lignin content for the pulp.
It is known, for example for the destructurization of wood into pulp, that there is a relationship between the so-called "degree of destructurization", as expressed by the "kappa number" for example, and the pulp yield.
The kappa number is a measure of the lignin content of the pulp. A very low kappa number, i.e,, a very low lignin content of the pulp, typically correlates with a low pulp yield. This is because, typically, it is not just more and more lignin which is remote with increasing destructurization, but increasingly also pulp (components) (predominantly hemicelluloses) being dissolved out of the wood into the cooking liquor. The result is a lower quantity of isolated cellulose relative to the wood used.
One disadvantage of pulp digestion by the sulfate process is the formation of malodorants such as mercaptans, especially methyl mercaptan.
The addition of sodium dithionite (hereinafter also "Na2S204") in the pulpmaking operation is known in principle from the following references. G. Jayme and G. Worner describe an alkaline sulfite pulping process for sprucewood at 170°C, 24 hours, wherein 100 cm3 of the pulping liquor comprised 3 g of NaOH, 1.56 g of sodium dithionite (Na2S204) and 4.69 g of Na2S03(G. Jayme, G. Worner, Papier, volume 6, No. 11, pp. 220-222 (1952)). Relatively large quantities of sodium dithionite, based on the wood to be treated, are described indirectly therein via the quantitative schedule of chemicals as well as the liquor ratio" (page 221, left-hand column, numerical table and the subsequent paragraph).
Jayme and Worner further describe in Hoiz a/s Roh- und Werkstoff10 (1952) 6, pp. 244-249, the use of relatively large amounts of sodium dithionite (Na2S204) in a sulfate liquor (65%
NaOH, 25% Na2S and 10% Na2COs) in the sulfate pulping of sprucewood. The amount of PF 74186 4 sodium dithionite, based on the wood to be treated, is also described here indirectly via the quantitative schedule of chemicals and also the "liquor ratio" (page 246, left-hand column from "Effect of sodium hypodisulfite in sulfate pulping liquors" through table 2). The 1 : 7.5 "liquor ratio" described therein indicates that 7.5 parts by mass of cooking liquor were used per 1 part by mass of wood.
The problem addressed by the present invention was that of obtaining a high pulp yield coupled with a simultaneously low lignin content on the part of the pulp in the digestion of lignocellulosic material while reducing the creation of malodorous emissions in the sulfate process in particular.
The problem was solved by adding small amounts of a salt of dithionous acid (hereinafter also "H2S2O4") in the sulfite or sulfate process and otherwise as described in the claims.
Cellulose is known and described for example in "Ullmanns Enzyklopadie der technischen Chemie”, 4th edition, volume 17, "Paper, fibrous raw materials", Verlag Chemie Weinheim, New York (1979) in chapter 1. Lignocellulosic material herein is any material, preferably natural material, which comprises lignin and cellulose.
Preferred lignocellulosic material comprises wood, including comminuted woods, such as wood cuts from saw mills.
Softwoods, preferably spruce or pine or hardwoods such as beech are very useful woods.
Lignocellulose material herein further comprehends grasses and annual plants, for example straw, reed, espartogras, bamboo and bagasse, although these are typically not digested using the sulfite process, but preferably using alkaline processes of digestion or the neutral-sulfite process.
Sulfite digestion and sulfate digestion to obtain cellulose are known and are described at the beginning and in more detail in Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 17, "Paper, fibrous raw materials", Verlag Chemie Weinheim, New York (1979) pp. 535-549 in chapter 1.4.
Salts of dithionous acid (H2S2O4) herein are any metal salts or substituted (NFV) or unsubstituted (NH4+) ammonium salts of this acid.
Alkali metal salts, alkaline earth metal salts, salts of metals of group 12 of the periodic table and also ammonium (NH4+) salts are very useful salts of dithionous acid.
Preferred salts of dithionous acid are sodium dithionite (Na2S204), potassium dithionite (K2S2O4), calcium dithionite (CaSaCU), zinc dithionite (ZnS204), ammonium dithionite ((NH4)2S204). PF 74186 5
Salts of dithionous acid, including the above-preferred ones, also comprise, as will be appreciated, those species which comprise water of crystallization and/or additives, the latter for stabilization for example.
The sodium dithionite product marketed by BASF SE as Biankit® or Blankit®S is a very useful salt of dithionous acid.
Any version of the sulfite process as described at the outset and in Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 17, "Paper, fibrous raw materials", pp. 531-576, Verlag Chemie Weinheim, New York (1979) is in principle suitable for the method of the present invention.
Pulping temperature in sulfite digestion is typically in the range from 100°C to 160°C.
The bisulfite process with Mg(HSC>3)2 as a component of the cooking liquor is a very useful sulfite process of the method of the present invention and will now be more particularly described.
The lignocellulosic material used comprises softwoods, preferably sprucewoods, more preferably as chips. Chips are typically used in the forest-fresh state (i.e., with a dry matter content of about 50 wt%). The amount used is computed as oven-dry substance in order that the yield of pulp may subsequently be determined for example.
The cooking liquor can be prepared by suspending magnesium carbonate (hereinafter also "MgCOa") in water and then passing SO2 into the suspension, generally until the suspension has turned into a clear solution, which has a pH of about 3.8 for example. At this stage, it is typically the case that substantially the entire dissolved substance is present as Mg(HS03)2. On continued introduction of SO2, the pH would continue to decrease as the proportion of sulfurous acid increases.
Cooking the so-called lignocellulosic material with the cooking liquor takes place in the customary cookers, batchwise or else continuously. Total cooking time is in the range from 400 to 600 minutes. A temperature profile is preferably used for cooking in the herein recited bisulfite processes, preferably the bisulfite process with Mg(HSOa)2 as a component of the cooking liquor. A very useful temperature profile is as follows: 1st phase: heating up from a temperature in the range from 15°C to 30°C to a temperature in the range from 100 to 110°C, within from 60 to 120 minutes; PF 74186 6 2nd phase (impregnating phase): 60 to 90 minutes' pausing at a temperature in the range from 100 to 110°C; 3rd phase: heating up from a temperature in the range from 100 to 110°C up to a temperature in the range from 150 to 160°C, within from 45 to 90 minutes; 4th phase (ready-cook time): 150 to 250 minutes' pausing at a temperature in the range
from 150 to 160°C 5th phase: cooling down to a temperature in the range from 100 to 90°C.
The salt of dithionous acid, preferably sodium dithionite (Na2S204), calcium dithionite (CaS204), zinc dithionite (ZnS204), more preferably sodium dithionite, is added into the mixture of lignocelluiosic material, preferably the chips of sprucewood and the cooking liquor, as described above, in an amount from 0.1 to 4.0 wt%, preferably 1.0 to 2.0 wt%, all based on the oven-dry lignocelluiosic material, preferably the oven-dry chips of sprucewood.
In principle, the salt of dithionous acid can be added at any stage during the cooking process or else therebefore. The dosing regimens which follow are preferable, however: a) at the start of the 2nd phase b) at the start of the 4th phase c) approximately halfway through the 4th phase
Preferably, the salt of dithionous acid is added at the start of the 2nd phase, i.e., the impregnating phase. A sulfate process which is very useful for the method of the present invention will now be described.
Woods, such as hard- or preferably softwoods, more preferably sprucewoods, preferably in the form of chips, are used as lignocelluiosic material.
The cooking liquor used can in principle be the familiar sulfate-process mixture of aqueous sodium hydroxide solution (aqueous NaOH), sodium sulfide (Na2S) and sodium sulfate (hereinafter also "Na2S04n) and optionally sodium carbonate (hereinafter also "Na2C03"), admixed with the salt of dithionous acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite and calcium dithionite, in an amount from 0.1 to 4 wt%, based on the amount of oven-dry lignocelluiosic material. A cooking liquor which is very suitable for the sulfate method of the present invention will now be described: PF 74186
The cooking liquor for the sulfate process typically comprises NaOH and sodium sulfide (Na2S) as active cooking chemicals. The sum total of the two substances (expressed as NaOH) relative to the lignocellulosic material, preferably wood (reckoned oven-dry), is the alkali ratio. This ratio is typically in the range from 20 to 24 wt%.
The concentration in which these substances have to be present in the cooking liquor is typically dependent on the so-called "liquor ratio". This is understood by a person skilled in the art to refer to mass fractions of cooking liquor in relation to mass fractions of lignocellulosic material, preferably wood (reckoned oven-dry). In the case of softwoods, for example spruce and pine, this liquor ratio is generally in the range from 4 :1 to 4.5 :1, for example 4.2 : 1, typically according to the fill density of wood in the cooker. Therefore, the concentration of active alkali in the cooking liquor is in the range from 45 to 60 g/l for example.
The proportion of total active alkali which is accounted for by sodium sulfide (Na2S) is the sulfidity (reported in %). Sulfidity is generally in the range from 30 to 38%, for example 30%.
The cooking liquor for the sulfate method of the present invention comprises a salt of dithionous acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite and calcium dithionite, in an amount from 0.1 to 4 wt% based on the amount of oven-dry lignocellulosic material.
The pH of the cooking liquor for the sulfate method of the present invention is typically about 14 at the start of the cooking process.
Cooking the lignocellulosic material with the cooking liquor for the sulfate method of the present invention takes place batchwise or continuously in customary cookers.
Total cooking time for the sulfate method of the present invention is typically in the range from 200 to 400 minutes, preferably 240 to 300 minutes.
The cooking temperature for the sulfate method of the present invention is in the range from 160 to 185°C, for example 170°C.
The salt of dithionous acid, preferably selected from the group consisting of sodium dithionite, zinc dithionite and calcium dithionite, more preferably sodium dithionite, is added in the sulfate process of the present invention to the mixture of lignocellulosic material and cooking liquor in an amount from 0.1 to 4.0 wt%, preferably 1.0 to 2.0 wt%, all based on the oven-dry lignocellulosic material.
In principle, the salt of dithionous acid can be added at any stage during the cooking process of the sulfate method according to the present invention. PF 74186 8
The salt of dithionous acid is preferably added in the impregnating phase, the end phase of digestion or the main phase of digestion in the sulfate method of the present invention, more preferably in the end phase of digestion or in the main phase of digestion in the sulfate method of the present invention.
The method which the present invention provides for producing cellulose from lignocellulosic material by sulfite digestion or sulfate digestion delivers pulp in high yield combined with good delignification of the lignocellulosic material. There is an improvement in the brightness of the unbleached puip.
The addition of a salt of dithionous acid in the suifate method of the present invention reduces the concentration of malodorants preferably mercaptans in the off-gas of the sulfate cooking process.
Examples (I) Sulfite digestion by the bisulfite process with Mg(HSC>3)2 as a component of the cooking liquor. A) Lignocellulosic material:
Sprucewood chips presorted and predried in the ambient air for 2 to 3 days before cooking, water content ranging from 23.4 to 33.2 wt%, averaging about 30 wt%. B) Cooking liquor:
Arithmetically 2.7 wt% of MgO per liter. pH before cooking (initial pH) 3.8. 1100 g of MgC03 were suspended in 17 liters of deionized water to obtain an arithmetic MgO concentration of about 2.7 wt%. Gaseous sulfur dioxide (SO2) was passed into the suspension until the pH was 3.8. C) Cooking 3200 g (reckoned oven-dry) of sprucewood chips having an original water content as described in A) and 16 (iters of the cooking liquor from B) were filled into the 25-liter capacity batch cooker, corresponding to a 5 :1 mixing ratio for cooking liquor: oven-dry wood. The cooker was equipped with a liquor recirculator, an electrical-type jacket heater, a temperature controller, a manometer, a temperature sensor, a pH electrode, and a connected electronic data processing system.
The following heating program was implemented:
1st phase: 105 min heat-up time from room temperature (23°C) to 105°C
2nd phase: 90 min hold time (impregnating phase) at 105°C
3rd phase: 60 min high-heat time from 105°C to ready-cook temperature of 155°C PF 74186 9 4th phase: 195 min ready-cook time at ready-cook temperature of 155°C 5th phase: about 60 min off-gas time (heating off on reaching cooking time) until temperature below 100°C.
Digestion time totaled 510 min (8 h 30 min). The pressure in the cooker at the end of the ready-cook time was in the range from 8 to 9 bar.
Sodium dithionite (B!ankit®S from BASF SE) was added in the form of a solution in water to the mixture in the cooker within 10 min by metering pump, specifically at 32 g of pure Na2S204 (1 wt% of Na2S204 based on employed wood reckoned oven-dry) and/or 64 g of pure Na2S204 (2 wt% of Na2S204 based on employed wood reckoned oven-dry).
The times of addition for the sodium dithionite were as follows per experiment:
At the start of the holding time (impregnating phase), about 105 min after beginning the experiment or from the start of the ready-cook time, about 255 min after beginning the experiment or halfway through the ready-cook time, about 360 min after beginning the experiment.
In the case of experiment W 16, the chips were impregnated with sufficient aqueous solution of sodium dithionite (Blankit®S from BASF SE) to correspond to 1 wt% of pure Na2S204 based on employed wood reckoned oven-dry, immediately prior to digestion.
On completion of the digestions, the pulp was removed, admixed with water and defiberized with a stirrer. The defiberized pulp was filled into a sieve, washed with water and dewatered in a centrifuge. D) Inventory and evaluation
Table 1 shows the experiments:
Table 1:
Experimental series Auxiliary addition [2] Time of addition min [1] Temperature at addition W7 1% Beginning of ready-cook time 255 min 155°C W8 1% Start of impregnating phase 105 min 105°C W9 1% Halfway through ready-cook time 360 min 155°C W10 2% Start of impregnating phase 105 min 105°C W11 2% Beginning of ready-cook time 255 min 155°C 5 PF 74186 10 W12 1% Start of impregnating phase 105 min 105°C W14 none - - - W15 1% Start of impregnating phase 105 min 105°C W16 1% Before digestion process - “ [1] The values denote numbers of minutes after beginning the experiment, i.e., commencement of the first heat-up [2] sodium dithionite Na2S204 PF 74186 11
The results of the experiments in table 1 are collated in table 2: Table 2:
Experimental series Auxiliary addition Time of addition Accepts yield [%] kappa number/brightness [%3 Viscosity [ml/g] W7 1% Beginning of ready-cook time 54.2 24.5/60.7 676.1 W8 1% Start of impregnating phase 54.9 19.0 62.9 640.6 W9 1% Halfway through ready-cook time 55.3 27.9/59.1 689.0 W10 2% Start of impregnating phase 54.5 25.5 59.1 679.8 W11 2% Beginning of ready-cook time 53.1 17.2/63.6 660.8 W12 1% Start of impregnating phase 54.7 16.0 63.3 645.1 W14 none - 55.6 36.1/58.6 708.8 W15 1% Start of impregnating phase 54.3 20.6/61.7 677.4 W16 1% Before digestion process 55.0 29.0/57.1 694.9
The following definitions apply therein:
Accepts yield is the amount of pulp obtained (without rejects/shives) as a proportion of the wood used; It was determined by weighing and dry matter content measurement. 10
The kappa number indicates the hardness of the pulp and was determined according to ISO 302. Put simply, the potassium permanganate consumption (KMn04 consumption) is measured to determine the kappa number in an aqueous pulp suspension in an acidic medium under defined conditions. The higher the lignin content of the pulp, the higher the potassium 15 permanganate consumption and thus the higher the kappa number. The higher the kappa number, the higher the residual lignin content of the pulp and the harder the pulp generally is.
Brightness (R457) denotes reflectance at 457 nm and was determined on an Elrepho® from Datacolor in accordance with ISO 2470. PF 74186 12
Viscosity was determined in accordance with ISO 5351/1 (International Standard ISO 5351/1, Cellulose in dilute solutions-- Determination of limiting viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) solution, First edition 1981-12-01). A solution of cellulose in copper-ethylene-diamine solution is prepared. The concentration of the solvent is a fixed value. The concentration of cellulose in the solution is decided according to the sample to be determined. What is measured is the flow time of both the solvent and the cellulose solution through a capillary viscometer at 25°C. The limiting viscosity number is computed from 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 method of determination (International Standard ISO 5351/1, Cellulose in dilute solutions - Determination of limiting viscosity number, Part 1: Method in cupri-ethylene-diamine (CED) solution, First edition 1981-12-01). A low concentration is employed for the cellulose and the same capillary is used for measuring the flow times of the solvent and of the cellulose solution.
It is apparent that adding the auxiliary, particularly when it is added at the start of the impregnation phase, delivers an improved combination of accepts yield with kappa number/ brightness. (II) Sulfate digestion A) Lignocellulosic material:
Mixed spruce-pine chips having a 7:3 spruce:pine mixing ratio, undried, water content 57%. B) Cooking liquor:
The cooking liquor was prepared from aqueous sodium hydroxide solution (NaOH) and sodium sulfide (Na2S) by incorporating commercial laboratory-grade chemicals in water. The amount of chemicals used was determined such as to apply an alkali ratio of 23% coupled with a sulfidity of 20%. C) Cooking:
Sufficient chips were introduced into a 10 I cooker to ensure that at the given dry matter content of the wood 1300 g of oven-dry wood matter were used. The cooker was filled with cooking liquor. This cooking liquor comprised 239.2 g of NaOH and 59.8 g of Na2S (reckoned as NaOH) for a desired alkali ratio of 23% and a sulfidity of 20%. The cooker contents were then heated to 170°C and maintained at 170°C until the desired digestion time was reached.
The so-caiied H-factor was used to calculate the desired digestion time. The calculation was made on the basis of the temperature dependence of the relative reaction rate for the alkaline digestion. An H-factor of 3500 was realized for all cookings.
In the case of selected cookings, 2 wt% of sodium dithionite were added in each case relative to the introduced quantity of wood (reckoned oven-dry). The time of addition was during the main phase of digestion in one cooking and during the end phase of digestion in a further cooking. PF 74186 13
On reaching the H-factor of 3500, the cookings were discontinued by ending the heating and cooling down in conjunction with depressurization ("off-gassing"). The pulp was defiberized by vigorous stirring and washed. D) Inventory and evaluation
Table 3 presents the experiments:
Table 3 Cooking No. Auxiliary addition [1] Time of addition Temperature at addition 1 none 2 2% main phase 170°C 3 2% end phase 170°C [1] Sodium dithionite Na2Sa04
Table 4 presents the accepts yield and the kappa number. Table 4:
Cooking No. Auxiliary addition [1] Accepts yield % kappa number 1 none 43,3 20.1 2 2 % in main phase 46.4 19.4 3 2 % in end phase 47.1 19.9 [1] sodium dithionite Na2S204
Accepts yield and kappa number are as defined under (i), above.
It is apparent that adding the sodium dithionite is associated with a distinct increase in yield (by 3 to 4 percentage points) and even a slight reduction in the kappa number. E) Reduction of methyl mercaptan emissions A sulfate digestion of softwood was carried out as described above.
During the release of gases from the cooker ("off-gassing"), off-gas samples were taken at different times using a detection pump. The concentration of methyl mercaptan in these samples was measured using gas testing tubes specific to methyl mercaptan.
The first measurement in each case was carried out immediately after terminating cooking; the temperature in the cooker was 172°C. Subsequent measurements were carried out at further decreased cooker temperatures, see table 5. The results are complied in table 5.
Tabie 5: Methyl mercaptan concentrations
Test wt% [1] of Sulfidity Cooker temperature Methyl mercaptan- 14 N32S204 [%] at time of measurement [°C] concentration [ppm] 1b 0 30 162 890 2b 0 20 162 410 3b 2 30 162 400 4b 2 20 162 180 [1]: based on oven-dry wood 2013357649 01 May 2017
Sulfidity is: Na2S fraction in active alkali 5 The methyl mercaptan concentration is highest at high sulfidity. Using Na2S204 results in a decrease of the methyl mercaptan in the off-gas.
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge 10 in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. 15 to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention. 9004722,
(GHMattere) P99897.AU
Claims (6)
- We claim:-1. A method of producing cellulose from lignocellulosic material by sulfite digestion or sulfate digestion in the presence of a salt of dithionous acid, which method comprises using the salt of dithionous acid in an amount from 0.1 to 4.0 wt.% in case of the sulfite digestion and in an amount from 1.0 to 2.0 wt.% in case of the sulfate digestion, each amount respectively based on the amount of oven-dry lignocellulosic material, wherein the salt of dithionous acid is added in said sulfite digestion as soon as the mixture of cooking liquor and lignocellulosic material to be digested has attained a temperature in the range from 60°C to 110°C in the course of being heated up, and the mixture thus obtained is left at a temperature from 100°C to 110°C for from 30 to 90 minutes (impregnation phase), and wherein the salt of dithionous acid is added in said sulfate digestion in the end phase of digestion.
- 2. The method according to claim 1 wherein the salt of dithionous acid is selected from the group consisting of sodium dithionite, zinc dithionite and calcium dithionite.
- 3. The method according to claim 1 or 2 wherein the salt of dithionous acid is sodium dithionite.
- 4. The method according to claim 1 or 2 or 3 wherein said sulfite digestion is conducted in the temperature range from 100°C to 160°C and said sulfate digestion is conducted in the temperature range from 160°C to 185°C.
- 5. The method according to claim 1 or 2 or 3 or 4 wherein the lignocellulosic material is wood.
- 6. The method according to claim 1 or 2 or 3 or 4 or 5 as a batch operation.
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DA3 | Amendments made section 104 |
Free format text: THE NATURE OF THE AMENDMENT IS: AMEND THE NAME OF THE INVENTOR TO READ ERREN, STEFAN; SCHOENHABER, DIETER; SCHACHTL, MARTIN; FISCHER, STEFFEN AND BAEURICH, CHRISTIAN |
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FGA | Letters patent sealed or granted (standard patent) |