WO2012112108A1 - Method for producing a lignin fiber - Google Patents
Method for producing a lignin fiber Download PDFInfo
- Publication number
- WO2012112108A1 WO2012112108A1 PCT/SE2012/050141 SE2012050141W WO2012112108A1 WO 2012112108 A1 WO2012112108 A1 WO 2012112108A1 SE 2012050141 W SE2012050141 W SE 2012050141W WO 2012112108 A1 WO2012112108 A1 WO 2012112108A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- fractionated
- hardwood
- softwood
- fiber
- Prior art date
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- 229920005610 lignin Polymers 0.000 title claims abstract description 235
- 239000000835 fiber Substances 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000011121 hardwood Substances 0.000 claims abstract description 91
- 239000003513 alkali Substances 0.000 claims abstract description 83
- 239000011122 softwood Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 31
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 26
- 239000004917 carbon fiber Substances 0.000 claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 11
- 230000006641 stabilisation Effects 0.000 claims description 11
- 238000011105 stabilization Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920005611 kraft lignin Polymers 0.000 description 54
- 238000002360 preparation method Methods 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000002955 isolation Methods 0.000 description 10
- 238000004537 pulping Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000000108 ultra-filtration Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000014633 carbohydrates Nutrition 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- 239000012466 permeate Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001720 carbohydrates Chemical class 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 235000018185 Betula X alpestris Nutrition 0.000 description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 241000183024 Populus tremula Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000003265 pulping liquor Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 235000014466 Douglas bleu Nutrition 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 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
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 241000218922 Magnoliophyta Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 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
- 241000218683 Pseudotsuga Species 0.000 description 1
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000592342 Tracheophyta Species 0.000 description 1
- 241000218685 Tsuga Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
Definitions
- the present invention relates to methods of producing lignin fibers and structural carbon fibers from softwood and/or hardwood alkali lignin.
- Carbon fibers are high-strength light-weight materials commonly produced by heat treatment and pyrolysis of polyacrylonitrile, a synthetic material made from petroleum feedstock but other precursors are also used to a minor extent such as petroleum- or coal-based pitch and rayon fibers.
- the current precursors such as the high price of polyacrylonitrile and its slow graphitization and the uneven quality of pitch.
- the two major commercial precursors used are from non-renewable sources.
- Lignin is present in all vascular plants making it second to cellulose in abundance among polymers in nature.
- pulp and paper industry large quantities of lignin are produced as a byproduct with primary use as the source of internally generated energy in pulp mills.
- the kraft process is predominant in the world for liberating cellulosic fibers from wood for further processing to paper, board and tissue products.
- lignin becomes dissolved in the alkali pulping liquor, denoted black liquor, from where it can be further processed to energy by combustion of the partly evaporated black liquor or, alternatively, isolated in solid form by addition of acid.
- lignin may occur in several steps since a major portion of lignin can precipitate out from the black liquor already at high pH-values as described in the book Lignins (Eds K.V. Sarkanen and C.H. Ludwig, Wiley-Interscience 1971 , p 672 ). Such lignin precipitate will still contain appreciable amounts of sodium and other inorganic species making the lignin unsuitable as precursor for structural carbon fibers (see below).
- Alkali lignins are obtained from black liquors obtained from either kraft or soda pulping. Commercially, these pulping processes are applied on softwoods, hardwoods as well as on annual plant biomass. On pulping, some of the wood polymers, notably lignin and
- hemicelluloses are to a major extent chemically modified and solubilized in the black liquor.
- major gymnosperm species softwood
- major angiosperm species hardwood
- birch aspen
- poplar eucalypt species
- acacia acacia
- maple acacia
- lignin might be an alternative precursor of carbon fiber due to its potentially large availability, its expected lower cost, and its high content of carbon (>60%).
- lignin is a renewable material.
- Carbon Fibers Two types have been discerned; 1) continuously spun, solid and homogeneous carbon fibers used as strength-giving reinforcement elements in construction materials (herein also referred to as structural carbon fibers) and 2) activated porous carbon fibers with large internal pore structure for adsorption of gases and liquids where the activation can be done chemically with e.g. potassium or sodium hydroxide, zinc chloride or phosphorous acid, or physically with e.g. steam or carbon dioxide, or by applying the latter to chemically pre-activated fibers (Carbon Fiber Application, in the 3 ed. of the book Carbon Fiber, Eds. Donnet, Wang, Rebouillat and Peng, Marcel Dekker 1998, p. 463).
- structural carbon fibers Two types have been discerned; 1) continuously spun, solid and homogeneous carbon fibers used as strength-giving reinforcement elements in construction materials (herein also referred to as structural carbon fibers) and 2) activated porous carbon fibers with large internal pore structure for adsorption of gases and liquids where the
- Fibers from extensively purified hardwood kraft lignin have been made by extrusion of the lignin after admixing with softening agents such as poly-ethyleneterephtalate (PET) or poly-ethyleneoxide (PEO).
- PET poly-ethyleneterephtalate
- PEO poly-ethyleneoxide
- a method of producing a continuous lignin fiber comprising the following steps:
- unfractionated softwood alkali lignin and/or unfractionated hardwood alkali lignin herein below also collectively referred to as "unfractionated lignin", or simply “lignin"
- lignin unfractionated lignin
- the amount of fractionated and isolated hardwood alkali lignin is in one embodiment 100% of the material to be extruded. In another embodiment, the amount of fractionated and isolated softwood alkali lignin is 100% of the material to be extruded.
- unfractionated softwood alkali lignin and/or unfractionated hardwood alkali lignin may be mixed with the fractionated and isolated hardwood alkali lignin.
- the latter has advantageously been fractionated according to the principle of ultra filtration as described herein.
- the fractionated hardwood alkali lignin provided may be obtained by fractionation of e.g. hardwood black liquor.
- the fractionated and isolated hardwood alkali lignin in one embodiment amounts to 1.5- 100% by weight of the material to be extruded. In one embodiment, fractionated and isolated hardwood alkali lignin amounts to from 2, 2.5, 3, 3.5, 4 up to 100 % by weight of the material to be extruded.
- the fractionated and isolated hardwood alkali lignin may amount to 5-100, or 5-95% by weight, of the material to be extruded.
- the range of addition of fractionated and isolated hardwood alkali lignin is 25-75% by weight of the material to be extruded.
- a material constituting fractionated and isolated hardwood alkali lignin, unfractionated softwood alkali lignin and/or unfractionated hardwood alkali lignin, and wherein less than 1.5% of the material constitutes fractionated hardwood alkali lignin will behave as e.g. 100% unfractionated softwood alkali lignin (or 100% unfractionated hardwood alkali lignin) and no continuous fibers can be obtained.
- fractionated and isolated softwood alkali lignin may be mixed with unfractionated hardwood alkali lignin.
- the fractionated and isolated softwood alkali lignin has advantageously been fractionated according to the principle of ultra filtration as described herein.
- the fractionated softwood alkali lignin provided may be obtained by fractionation of e.g. softwood black liquor.
- the fractionated and isolated softwood alkali lignin in one embodiment amounts to 50-100% by weight of the material to be extruded. Alternatively, the fractionated and isolated softwood alkali lignin amounts to 60-90% by weight of the material to be extruded. In yet an alternative, the fractionated and isolated softwood alkali lignin amounts to 75-85% by weight of the material to be extruded.
- a material constituting fractionated and isolated softwood alkali lignin, unfractionated hardwood alkali lignin and wherein less than 50% of the material constitutes fractionated and isolated softwood alkali lignin will behave as e.g. 100% unfractionated softwood alkali lignin (or 100% unfractionated hardwood alkali lignin) and no continuous fibers can be obtained.
- Fractionation is preferably carried out using ultra filtration of black liquor, inert at the conditions present, i.e. high alkalinity at high temperatures, with a filter that permits a lignin- rich permeate while high molecular weight lignin particles, high molecular weight lignin- carbohydrate complexes, and non-lignin residues are left in the retentate.
- Ultra filtration was in accordance with the invention performed using a ceramic membrane.
- One ceramic membrane used had a cut-off value of 15 kDa (Orelis, France).
- the temperature during ultra filtration may be a temperature in the interval of from 80°C to 150°C, e.g. 90, 100, 110, 120, 130, 140°C, or any interval therein between.
- Further permeate treatment involves
- Softwood alkali lignin may be isolated from fractionated softwood black liquor by means of precipitation and involving the following steps; addition of acid to black liquor until lignin precipitation occurs, filtration and re-dispersing the lignin cake in aqueous mineral acid, filtration, washing with water, and drying. In a preferred mode of lignin isolation the procedure described in EP 1794363 is applied. The resulting dried lignin has a purity that is sufficient for its further processing into lignin fiber. Thus, the content of non-lignin residues such as ash is below 1% and carbohydrates below 4%. Softwood alkali lignin alone cannot be converted into solid homogeneous lignin fiber, since, the material cannot soften enough to be extruded into continuous fibers.
- hardwood alkali lignin can be isolated from fractionated hardwood black liquor. Direct mixing of this lignin in any proportion with softwood alkali lignin was shown not to provide continuous spinnability through melt extrusion for the formation of solid fibers required for structural carbon fiber applications.
- the fractionated hardwood alkali lignin is isolated preferably as described below. Isolation is initiated by acidification of the fractionated hardwood alkali lignin permeate to a pH in the interval of from 2 to 11, e.g. a pH of approximately 9. Acidification may be obtained by the use of carbon dioxide, whereby acidification may be to a pH in the interval of from 5.5 to 11, e.g. from pH 8 to 11. Alternatively, for obtaining low pH values, acidification can be done using any other acid such as sulfuric acid.
- the precipitated lignin permeate is separated. The separation may be done by filtering. Thereafter, the lignin cake obtained may be suspended in a solvent, e.g. water.
- the solvent may be acidified to a pH in the interval of from 1 to 6, e.g. a pH of approximately 2. Acidification may be carried out by using any acid such as sulfuric acid. Isolation of fractionated softwood alkali lignin, hardwood alkali lignin and softwood alkali lignin may be performed mutatis mutandis.
- a narrow single glass transition with a single glass transition temperature demonstrates that a homogeneous lignin material suitable for extrusion has been obtained.
- the lignin material is in one embodiment melt extruded at a temperature exceeding the glass transition temperature of the lignin material by 20-85 °C, for the formation of a continuous lignin fiber. In one embodiment, said temperature interval is 25-50 °C. In another embodiment, melt extrusion is performed at a temperature in the range of 110-250 °C, for the formation of a continuous lignin fiber.
- the chosen temperature interval for extrusion is dependent on the proportions between unfractionated softwood and/or unfractionated hardwood alkali lignin on one hand and fractionated hardwood alkali lignin on the other.
- Figure 1 shows the relationship between proportions of unfractionated softwood alkali lignin on the one hand and fractionated hardwood alkali lignin on the other.
- the extrusion temperature should be chosen between T g (glass transition temperature) and T d
- composition temperature For the lowest possible portion of fractionated hardwood alkali lignin (1.5%), an extrusion temperature of 175-215°C may advantageously be chosen while for 100% fractionated hardwood alkali lignin the preferred extrusion temperature is in the range of 135-210°C. For other proportions between unfractionated and fractionated lignins, intermediate temperatures according to the figure may be chosen.
- All lignin ratios in accordance with the invention containing at least 1.5 % fractionated hardwood alkali lignin, resulted in continuous lignin fibers that were found to be solid and homogeneous without cracks and pores as revealed by analysis with scanning electron microscopy (SEM).
- Lignin fibers from 100% fractionated softwood alkali lignin were also found to be solid and homogeneous without cracks and pores as revealed by analysis with scanning electron microscopy (SEM).
- Fiber diameters were in the range of 25-125 ⁇ . According to the invention, there is provided a method of producing structural carbon fiber, wherein the lignin fiber produced according to the first aspect undergoes the following subsequent process steps: a) Stabilization of the lignin fiber
- the lignin fiber produced is stabilized by air or oxygen. Subsequently, carbonization may proceed in inert, e.g. nitrogen, atmosphere.
- the structural carbon fiber produced was shown by SEM analysis to be completely solid and homogeneous (i.e.
- T g Glass transition temperature, defined as the inflection point value.
- T d Decomposition temperature, defined as the temperature at which 95% of the material remains.
- Figure 1 shows the relationship between amount of added fractionated hardwood alkali lignin and glass transition temperature (T g , (open circles) of a mixture between softwood alkali lignin and fractionated hardwood alkali lignin, as well as for neat fractionated hardwood alkali lignin.
- T g glass transition temperature
- the preferred temperature range for melt extrusion at various mixture ratios is also shown (i.e. 25 and 50 °C above T g respectively).
- Softwood kraft lignin was isolated from black liquor obtained through pulping of a mixture of pine and spruce wood with kraft pulping liquor. The lignin isolation procedure was done following the steps described in EP 1794363. The following characteristics were obtained: Ash 0.9%, carbohydrates 2%, glass transition temperature (T g ) 140 °C, decomposition temperature (T d ) 273 °C.
- Hardwood kraft lignin was isolated from black liquor obtained through pulping of a mixture of birch and aspen wood with kraft pulping liquor. The lignin isolation procedure was done following the steps described in EP 1794363. The following characteristics were obtained: Ash 0.8%, carbohydrates 4%, glass transition temperature (T g ) 139 °C, decomposition temperature (T d ) 274 °C.
- Black liquor obtained from kraft pulping of a mixture of birch and aspen wood, was subjected to ultra filtration using ceramic membrane (15kDa) at a temperature of 120 °C.
- the collected permeate was acidified by gaseous carbon dioxide at 60 °C to pH ⁇ 9.
- the lignin cake was suspended in water and acidified to pH ⁇ 2 with sulfuric acid. Filtration of the lignin followed by washing with water and drying afforded purified hardwood kraft lignin with the following characteristics: ash 0.9%, carbohydrates 0.4%, glass transition temperature (T g ) 114°C, decomposition temperature (T d ) 274°C.
- Black liquor obtained from kraft pulping of a mixture of pine and spruce wood, was subjected to ultra filtration using ceramic membrane (15kDa) at a temperature of 120°C.
- the collected permeate was acidified by gaseous carbon dioxide at 70°C to pH ⁇ 9.
- the lignin cake was suspended in water and acidified to pH ⁇ 2 with sulfuric acid. Filtration of the lignin followed by washing with water and drying afforded purified softwood kraft lignin with the following characteristics: ash 0.9%, carbohydrates 0.4%, glass transition temperature (T g ) 140°C, decomposition temperature (Td) 280°C.
- Dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 97:3 by weight (7 grams in total) and introduced in a laboratory extruder kept at 200°C.
- the two lignins were mixed at that temperature in the extruder by rotating the two screws at a speed of -25 rpm for at least 10 minutes before extrusion of the lignin fiber through a die of 0.5 mm in diameter.
- the resulting continuous lignin fiber was collected on a bobbin using a winding speed of 30 m/min.
- Example 5 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 9: 1 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5.
- Example 1 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 75:25 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5. 11. Preparation of softwood lignin fiber containing 25% fractionated hardwood lignin at 164 °C
- Example 5 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 75:25 (by weight) and introduced in a laboratory extruder kept at 164 °C. Lignin fibers were produced as described in Example 5.
- Example 5 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 50:50 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5.
- Example 1 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 50:50 (by weight) and introduced in a laboratory extruder kept at 178 °C. Lignin fibers were produced as described in Example 5. 15. Preparation of softwood lignin fiber containing 75% fractionated hardwood lignin at 200 °C
- Example 5 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 25:75 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5.
- Example 5 A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 10:90 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5. 18. Preparation of softwood lignin fiber containing 95% fractionated hardwood lignin at 200 °C A total of 7 grams of dry kraft lignin from Example 1 and Example 3 were mixed in the proportions 5:95 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5.
- Dry fractionated hardwood kraft lignin (7 grams) was prepared as described in Example 3 and introduced in a laboratory extruder kept at 165 °C. Lignin fibers were produced as described in Example 5.
- Dry fractionated hardwood kraft lignin (7 grams) was prepared as described in Example 3 and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5.
- Dry fractionated hardwood kraft lignin (7 grams) was prepared as described in Example 3 and introduced into a laboratory extruder kept at 210 °C. Lignin fibers were produced as described in Example 5.
- Example 5 A total of 7 grams of dry kraft lignin from Example 4 and Example 2 were mixed in the proportions 75:25 (by weight) and introduced in a laboratory extruder kept at 190 °C. Lignin fibers were produced as described in Example 5.
- Example 2 A total of 7 grams of dry kraft lignin from Example 2 and Example 3 were mixed in the proportions 95:5 (by weight) and introduced in a laboratory extruder kept at 170 °C. Lignin fibers were produced as described in Example 5, using a winding speed of the bobbin of 30 m/minute.
- a total of 7 grams of dry kraft lignin from Example 2 and Example 3 were mixed in the proportions 80:20 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5, using a winding speed of the bobbin of 74 m/minute.
- Preparation of hardwood lignin fiber containing 40% fractionated hardwood lignin at 200 °C A total of 7 grams of dry kraft lignin from Example 2 and Example 3 were mixed in the proportions 60:40 (by weight) and introduced in a laboratory extruder kept at 200 °C. Lignin fibers were produced as described in Example 5, using a winding speed of the bobbin of 74 m/minute. 29. Preparation of solid and homogeneous carbon fiber based on hardwood lignin fiber
- Lignin fibers from Example 28 were thermally stabilized in air at 250 °C during 60 min using a temperature increase of 0.2 °C/min from room temperature. Subsequent heating of the fibers with 1 °C/min up to 600 °C then 3 °C/min to a final temperature of 1000 °C afforded solid carbon fibers.
- Softwood kraft lignin fibers from Example 23 were stabilized in air in a temperature controlled oven using a heating rate of 15 °C/min from ambient to 250 °C, where it was isothermally treated for 30 min.
- Example 31 Stabilization of single softwood kraft lignin fibers at 250 °C
- Single softwood kraft lignin fibers from Example 23 were stabilized according to Example 30 using a heating rate of 70 °C/min from ambient to 250 °C, where it was isothermally treated for 10 min at that temperature.
- Single softwood kraft lignin fibers from Example 23 were stabilized according to Example 30 using a heating rate of 40 °C/min from ambient to 220 °C, where it was isothermally treated for 10 min at that temperature. 33. Stabilization of single softwood kraft lignin fibers at 200 °C
- Example 23 Single softwood kraft lignin fibers from Example 23 were stabilized according to Example 30 using a heating rate of 70 °C/min from ambient to 200 °C, where it was isothermally treated for 30 min.
- Kraft lignin fibers from Example 9 were stabilized according to Example 30 using a heating rate of 3 °C/min from ambient to 250 °C, where it was isothermally treated for 30 min.
- Example 9 Single kraft lignin fibers from Example 9 were stabilized according to Example 30 using a heating rate of 70 °C/min to 250 °C, where it was isothermally treated for 10 min.
- Example 9 Single kraft lignin fibers from Example 9 were stabilized according to Example 30 using a heating rate of 70 °C/min from ambient to 200 °C, where it was isothermally treated for 30 min.
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CN201280008568.7A CN103459686B (en) | 2011-02-14 | 2012-02-13 | For the method producing lignin fibre |
BR112013020652-7A BR112013020652B1 (en) | 2011-02-14 | 2012-02-13 | METHOD FOR PRODUCTION OF A LIGNIN FIBER |
US13/985,255 US9446955B2 (en) | 2011-02-14 | 2012-02-13 | Method for producing a lignin fiber |
RU2013141916/05A RU2591939C2 (en) | 2011-02-14 | 2012-02-13 | Method of producing lignin fibres |
JP2013553399A JP6050762B2 (en) | 2011-02-14 | 2012-02-13 | Method for producing lignin fiber |
CA2826061A CA2826061C (en) | 2011-02-14 | 2012-02-13 | Method for producing a lignin fiber |
EP12747498.9A EP2675946B1 (en) | 2011-02-14 | 2012-02-13 | Method for producing a lignin fiber |
AU2012218169A AU2012218169B2 (en) | 2011-02-14 | 2012-02-13 | Method for producing a lignin fiber |
KR1020137023918A KR101853158B1 (en) | 2011-02-14 | 2012-02-13 | Method for producing a lignin fiber |
ZA2013/05439A ZA201305439B (en) | 2011-02-14 | 2013-07-18 | Method for producing a lignin fiber |
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WO2014046826A1 (en) * | 2012-09-20 | 2014-03-27 | Graftech International Holdings Inc. | Carbon fibers derived from lignin |
DE102014004797A1 (en) | 2013-05-24 | 2014-11-27 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Precursor fibers of lignin-based carbon fibers, their preparation and use |
CN104870701A (en) * | 2012-11-13 | 2015-08-26 | 斯托拉恩索公司 | Thermally reactive thermoplastic intermediate product and method of manufacturing thereof |
DE102015120377A1 (en) | 2015-11-25 | 2017-06-01 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Process for the preparation of a lignin-based composition |
US9758905B2 (en) | 2012-11-16 | 2017-09-12 | Graftech International Holdings Inc. | Process of making carbon fibers derived from lignin/carbon residue |
US10011492B2 (en) | 2013-09-05 | 2018-07-03 | Graftech International Holdings Inc. | Carbon products derived from lignin/carbon residue |
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US20140271443A1 (en) * | 2013-03-15 | 2014-09-18 | University Of Tennessee Research Foundation | High Glass Transition Lignins and Lignin Derivatives for the Manufacture of Carbon and Graphite Fibers |
US10626523B2 (en) * | 2015-06-11 | 2020-04-21 | Stora Enso Oyj | Fiber and a process for the manufacture thereof |
CN108138440B (en) | 2015-07-07 | 2023-07-07 | 索理思科技公司 | Method for inhibiting deposition of organic contaminants in pulp and papermaking systems |
CN106400206A (en) * | 2016-05-25 | 2017-02-15 | 南通慧源塑胶有限公司 | Preparation method for lignin-based carbon fiber |
JP6662423B1 (en) * | 2018-09-06 | 2020-03-11 | 日本製紙株式会社 | How to separate lignin |
CN110518243B (en) * | 2019-08-20 | 2021-03-23 | 台州立拓能源有限公司 | Application of lignin in preparation of lithium battery graphite negative electrode material |
WO2023147451A1 (en) * | 2022-01-28 | 2023-08-03 | Board Of Trustees Of Michigan State University | Waterborne lignin-based polyurethane dispersions, related compositions, and related methods |
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US9683313B2 (en) | 2012-09-20 | 2017-06-20 | Graftech International Holdings Inc. | Method of making carbon fibers from lignin |
CN104870701A (en) * | 2012-11-13 | 2015-08-26 | 斯托拉恩索公司 | Thermally reactive thermoplastic intermediate product and method of manufacturing thereof |
US10941297B2 (en) | 2012-11-13 | 2021-03-09 | Stora Enso Oyj | Thermally reactive thermoplastic intermediate product and method of manufacturing thereof |
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US20140219909A1 (en) | 2014-08-07 |
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BR112013020652B1 (en) | 2020-08-11 |
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US9446955B2 (en) | 2016-09-20 |
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CA2826061A1 (en) | 2012-08-23 |
EP2675946A4 (en) | 2015-01-21 |
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