WO2013188401A1 - Procédé de production d'énergie à partir de lignine - Google Patents

Procédé de production d'énergie à partir de lignine Download PDF

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Publication number
WO2013188401A1
WO2013188401A1 PCT/US2013/045177 US2013045177W WO2013188401A1 WO 2013188401 A1 WO2013188401 A1 WO 2013188401A1 US 2013045177 W US2013045177 W US 2013045177W WO 2013188401 A1 WO2013188401 A1 WO 2013188401A1
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WO
WIPO (PCT)
Prior art keywords
lignin
black liquor
phase
carbonated liquid
process according
Prior art date
Application number
PCT/US2013/045177
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English (en)
Inventor
Michael A. Lake
John C. Blackburn
Original Assignee
Liquid Lignin Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liquid Lignin Company filed Critical Liquid Lignin Company
Publication of WO2013188401A1 publication Critical patent/WO2013188401A1/fr

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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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for

Definitions

  • the present invention relates to a process for producing energy from lignin. More particularly, the present invention relates to a process for carbonating black liquor from a pulp mill to recover carbonated liquid-lignin and burning the lignin to create energy.
  • Lignin a component of wood, is the second most abundant biopolymer in the world behind cellulose. Lignin is primarily recovered from the black liquor stream produced in a kraft pulp mill. Black liquor is removed from the pulp mill's recovery system downstream of an efficiently performing soap separator, since tall oil impurities in the black liquor are deleterious to the operation of the unit operations of the process and the downstream applications. Alternatively, lignin can be recovered from enzymatic conversions of biomass cellulose, where lignin remains in a byproduct or waste stream.
  • lignin Although there are a number of uses for lignin, their high ash content - mainly Na + , K + , and other active cations associated either with anions or carboxylic or phenolic groups on the lignin itself - limits lignin' s usefulness.
  • lignin With its high energy density and variety of functional groups and structure, lignin holds promise to be an efficient biofuel source or green chemical precursor. Thus, one use for lignin is to recover lignin as a solid and bum the solid lignin as a fuel or to use the lignin as a binder for energy producing fuel pellets.
  • the present invention is a process comprising introducing a black liquor stream from a pulp mill into an absoiption column at an elevated pH; carbonating the black liquor, at elevated temperature and pressure, with C0 2 to neutralize NaSH and/or NaOH; and allowing the carbonated black liquor and carbonated lignin to undergo a phase separation creating a carbonated liquid- lignin phase and a lignin-depleted carbonated black liquor phase.
  • the lignin-depleted carbonated black liquor phase being mostly black liquor, is returned to the pulp mill recovery boiler at a temperature higher than the temperature of the black liquor received, thus, removing a major impediment for commercial implementation by a pulp and paper mill.
  • the carbonated liquid-lignin phase is a homogeneous stream exiting the carbonating column at an operating temperature >200°F.
  • the pressure is maintained at about 50 psi to prevent boiling.
  • the carbonated liquid-lignin may be fed directly to a power boiler with enthalpy loss less than 10% from the water vaporization where the carbonated liquid-lignin is burned to produce energy.
  • the carbonated liquid-lignin is separated; passed to a flash tank to remove the water; then the friable mostly solid lignin is pulverized; and sent to the power boiler and burned to form energy.
  • a slip stream of carbonated liquid-lignin is passed to a lignin recovery system where the slip stream of carbonated liquid-lignin is acidified to form a dense lignin phase and further treated to recover a purified lignin.
  • the amount of carbonated liquid-lignin in the slip stream will be determined by the capacity of the pulp mill recovery boiler. The remainder of the carbonated liquid-lignin is sent to the power boiler and burned.
  • Another object of the present invention is to provide both relief of a constricted pulp mill recovery boiler and an efficient platform for lignin recovery processes.
  • FIG. 1 is a schematic flow diagram illustrating an embodiment of the process of the present invention showing the black liquor carbonating step, the liquid-lignin separation step and the energy producing step;
  • FIG. 2 is a schematic flow diagram illustrating an embodiment of the process of the present invention showing the black liquor carbonating step, the liquid-lignin separation step, the lignin purification step and the energy producing step.
  • Black liquor is removed from the pulp mill's recovery plant downstream of an efficiently perforrning soap separator because tall oil impurities are deleterious to the operation of the unit operations of the process.
  • the use of lignin for fuel in the present process involves two major unit operations: a black liquor carbonation system for producing liquid-lignin and a powe boiler for burning the lignin.
  • pressurized black liquor at a high pH (e.g. , above pH 13) is introduced through line 2 to a C0 2 absorption column Q.
  • Black liquor, leaving the soap separator in the pulp mill, is pumped at a pressure of about 50 psig.
  • black liquor, removed midway in the evaporator train is 25-45% solids and has a temperature of about 180°F to about 250°F. Keeping the heat of reaction in the system raises the temperature significantly.
  • the heat of reaction of black liquor with C0 2 typically raises the temperature 25°F.
  • the black liquor is introduced into the top Q of a two part C0 2 absorption column C.
  • the size of the column will depend upon the volume of black liquor being treated. For example, in a column designed to process 50,000 tons of lignin per year the upper portion of the column may be approximately 5' diameter, 20' tall.
  • the black liquor with a high NaOH content and a pH above pH 13, more normally about pH 14, reacts with the C0 2 injected through line 3 to form NaHC0 3 .
  • the column operates at a nominal pressure of about 50 psig and a temperature betwee4n about 180°F and about 350°F, preferably about 200°F to about 300°F, most preferably about 200°F to 250°F.
  • the NaOH is neutralized, lowering the pH to 8-11, preferably about pH 8 to 10.
  • This reaction causes the release of a substantial exotherm, increasing the temperature of the stream about 25°F, depending on the NaOH content and the solids level of the stream.
  • the viscosity of the lignin in the black liquor decreases as the temperature rises above the melt point.
  • the melt point of lignin depends strongly on the level of Na + ions, the source of the lignin, and water within the liquid-lignin phase, so the viscosity is difficult to predict.
  • vent gases leave the top of column C ⁇ through line 4 and contain essentially H 2 S and C0 2 with no air and are scrubbed completely by bubbling through as little as two feet of 10% caustic solution (not shown).
  • the bubbles collapse completely as the H 2 S and C0 2 react rapidly with NaOH near ambient temperature.
  • Vent gases from the C0 2 absorption column can be scrubbed with a white liquor solution from the paper mill forming NaSH from the absorbed H 2 S, creating value as a pulping agent in the papermaker's host system.
  • Other non-condensable sulfur gases that escape a NaOH scrubber can be treated with thermal oxidation efficiently with the absence of air.
  • the carbonated black liquor and carbonated liquid-lignin flow into the bottom portion of the column C 2 , where the two phases undergo complete separation.
  • the high temperature and pressure separation preserve heat from the heats of reaction of the reaction with C0 2 that enables sending that heat back to the recovery plant in the lignin- depleted black liquor and improves the phase separation.
  • the lower portion C 2 of the C0 2 column provides a large, quiet zone for phase separation.
  • C 2 may be approximately 5,000 gal vessel for a 50,000 ton lignin per year column.
  • the lignin-depleted carbonated black liquor separates as the light (top) phase and is returned to the recovery plant of the pulp mill through line 5.
  • the lignin-depleted carbonated black liquor is returned to the host mill at a higher temperature than the black liquor withdrawn, due to the heat of reaction with C0 2 with black liquor components.
  • the carbonated liquid-lignin stream 6 leaving the bottom of the carbonation column C 2 contains approximately 40% moisture.
  • the carbonated liquid-lignin stream is homogeneous at operating temperatures of >250°F.
  • the pressure is maintained at about 50 psig to prevent boiling.
  • the carbonated liquid-lignin stream is fed through pump P and line 7 directly to a power boiler at an elevated temperature (>250°F) so that sensible heat needed to raise the carbonated liquid-lignin to burning temperature is minimized.
  • the enthalpy loss is less than 10% from the water vaporization.
  • the steam produced from the burning lignin exits through line 8, while the sodium carbonate exits through line 9 and is recycled to the host mill.
  • the carbonated liquid-lignin goes through a pressure-reducing valve water is flashed from the carbonated liquid-lignin.
  • the resulting material is a solid but porous lignin structure having lava-like appearance.
  • This porous carbonated liquid- lignin solid is friable, e.g., easily crushed by hand. This friable solid easily dewaters.
  • the power boiler is fed with solidified carbonated liquid-lignin that has been dewatered.
  • the moisture content of the solid carbonated liquid-lignin is less than 20%), and the water that drains away has high levels of sodium bicarbonate that may be mixed with lignin-depleted carbonated black liquor at the same pH (about 8) and returned to the host mill.
  • the ash loading of the power boiler would be reduced but the capital would be increased from the flashing and dewatering equipment.
  • the carbonation system can be designed flexibly to allow scale-up by oversizing the carbonation column diameter and pump; the height of the column remains the same.
  • the equipment used in the process of the present invention can be sized to fit the need of increasing throughput to the recovery furnace in the short term.
  • the power boiler is designed to meet this demand. As the market development of kraft lignin expands, a lignin recovery system may be added as part of the process. The power boiler size would be unchanged as lignin production is ramped upward.
  • FIG. 2 An embodiment of the lignin recovery system that may be used with the process for producing energy is shown in FIG. 2 wherein the carbonating step is the same as for the process shown in FIG. 1.
  • a slip steam of carbonated liquid-lignin is continuously passed through line 10 to an acidifier where the carbonated liquid-lignin stream is acidified to neutralize residual NaOH and other basic components, thereby generating an acidified dense lignin phase.
  • the acidifying step is accomplished with an acid, such as a strong acid, like sulfuric acid in an amount sufficient to reduce the pH to less than 4, preferably a pH between 1.5 and 3.5.
  • the acidifying step is carried out at a temperature up to 390°F, preferably at a
  • SLRP Sequential Liquid-Lignin Recovery and Purification
  • biomass-burning power boilers A wide variety of biomass-burning power boilers are under development.
  • the list of companies offering biomass power boilers includes major manufacturers such as Alstom Power, Andritz Oy, Babcock & Wilcox, and ThyssenKrupp VDM, as well as smaller manufacturers such as Heuristic Engineering, Keystone, and Kansas Boilers.
  • 50,000 ton/yr of lignin about 100,000 lb/hr of steam and about 20 tons/day of sodium as ash will be generated.
  • the carbonated liquid-lignin either as a true liquid or as the lava-like solid, requires evaluation by the boiler manufacturer. If the carbonated liquid-lignin is burned as a true liquid, the 40% water in the phase actually can assist combustion by creating small particles as the pressure is reduced within the burner by the rapid expansion of the water.
  • the ash content of the carbonated liquid-lignin is relatively high compared to most biofuels. Carbonated liquid-lignin has an ash content of 25% based on solids, whereas typical biofuels have ash contents less than 10%. However, the inorganics contributing to the ash in carbonated liquid-lignin are constrained to relatively few components; whereas the variety of ash components in waste biofuels is relatively broad.
  • the carbonated liquid-lignin ash is primarily sodium bicarbonate (NaHC0 3 ) at pH 8 which converts readily at combustion temperatures to Na 2 C0 3 and/or Na 2 0, depending on the temperature and residence time in the boiler. Some sulfur is present in the carbonated liquid-lignin as sodium sulfate and organically-bound sulfur, but this latter component is readily converted to Na 2 S0 4 in an oxygen-rich combustion zone.

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Abstract

L'invention concerne un procédé de production d'énergie à partir de lignine. Une liqueur noire provenant d'une usine de pâte est introduite dans une colonne d'absorption à un pH élevé et carbonatée à température élevée et pression élevée avec du CO2 pour neutraliser NaSH et/ou NaOH. La liqueur noire et la lignine sont amenées à subir une séparation de phases créant une phase liquide carbonaté-lignine et une phase de liqueur noire carbonatée appauvrie en lignine. La phase de liqueur noire carbonatée appauvrie en lignine est renvoyée à l'installation de récupération. Le liquide carbonaté-lignine est introduit directement dans une chaudière de production d'énergie et brûlé pour produire de l'énergie. En variante, la phase liquide carbonaté-lignine est séparée et amenée à passer dans un réservoir éclair pour éliminer l'eau ; ensuite la lignine solide, pour la plupart friable, est pulvérisée et envoyée à la chaudière de production d'énergie. Dans un autre mode de réalisation, un courant de glissement du liquide carbonaté-lignine peut être amené à passer dans un système de récupération de lignine pure.
PCT/US2013/045177 2012-06-13 2013-06-11 Procédé de production d'énergie à partir de lignine WO2013188401A1 (fr)

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US201261659032P 2012-06-13 2012-06-13
US61/659,032 2012-06-13

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WO2013188401A1 true WO2013188401A1 (fr) 2013-12-19

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3161210A4 (fr) * 2014-06-25 2018-01-31 Michael A. Lake Procédé de réduction de poids moléculaire de lignine liquide
EP3527577A1 (fr) * 2014-07-09 2019-08-21 Virdia, Inc. Procédés de séparation et de raffinage de lignine à partir de liqueur noire et compositions correspondantes
EP3684891A4 (fr) * 2017-09-18 2021-05-05 Valmet AB Procédé et système de production de granulés ou de briquettes combustibles
US11053558B2 (en) 2012-05-03 2021-07-06 Virdia, Llc Methods for treating lignocellulosic materials
US11993624B2 (en) 2013-05-03 2024-05-28 Virdia, Llc Methods for preparing thermally stable lignin fractions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4764596A (en) * 1985-11-05 1988-08-16 Repap Technologies Inc. Recovery of lignin
WO2008156397A1 (fr) * 2007-06-20 2008-12-24 Metso Power Ab Procédé pour récupérer des produits chimiques et production de vapeur
WO2009104995A1 (fr) * 2008-02-21 2009-08-27 Lignoboost Ab Procédé pour séparer la lignine de la liqueur noire, produit de lignine, et utilisation d'un produit de lignine pour la production de combustibles ou de matériaux
US20110294991A1 (en) * 2009-09-25 2011-12-01 Lake Michael A Process for recovering lignin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4764596A (en) * 1985-11-05 1988-08-16 Repap Technologies Inc. Recovery of lignin
WO2008156397A1 (fr) * 2007-06-20 2008-12-24 Metso Power Ab Procédé pour récupérer des produits chimiques et production de vapeur
WO2009104995A1 (fr) * 2008-02-21 2009-08-27 Lignoboost Ab Procédé pour séparer la lignine de la liqueur noire, produit de lignine, et utilisation d'un produit de lignine pour la production de combustibles ou de matériaux
US20110294991A1 (en) * 2009-09-25 2011-12-01 Lake Michael A Process for recovering lignin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUN, RUNCANG ET AL.: "Effects of precipitation pH on the physico-chemical properties of the lignins isolated from the black liquor of oil palm empty fruit bunch fibre pulping", POLYMER DEGRADATION AND STABILITY, vol. 63, no. 2, 28 February 1999 (1999-02-28), pages 195 - 200 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11053558B2 (en) 2012-05-03 2021-07-06 Virdia, Llc Methods for treating lignocellulosic materials
US11993624B2 (en) 2013-05-03 2024-05-28 Virdia, Llc Methods for preparing thermally stable lignin fractions
EP3161210A4 (fr) * 2014-06-25 2018-01-31 Michael A. Lake Procédé de réduction de poids moléculaire de lignine liquide
EP3527577A1 (fr) * 2014-07-09 2019-08-21 Virdia, Inc. Procédés de séparation et de raffinage de lignine à partir de liqueur noire et compositions correspondantes
US10767308B2 (en) 2014-07-09 2020-09-08 Virdia, Inc. Methods for separating and refining lignin from black liquor and compositions thereof
EP3684891A4 (fr) * 2017-09-18 2021-05-05 Valmet AB Procédé et système de production de granulés ou de briquettes combustibles

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