WO1992013849A1 - Reduction en pate de matieres lignocellulosiques et recuperation des sous-produits qui en resultent - Google Patents

Reduction en pate de matieres lignocellulosiques et recuperation des sous-produits qui en resultent Download PDF

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Publication number
WO1992013849A1
WO1992013849A1 PCT/US1992/000720 US9200720W WO9213849A1 WO 1992013849 A1 WO1992013849 A1 WO 1992013849A1 US 9200720 W US9200720 W US 9200720W WO 9213849 A1 WO9213849 A1 WO 9213849A1
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WO
WIPO (PCT)
Prior art keywords
black liquor
lignin
furfural
organic solvent
alcohol
Prior art date
Application number
PCT/US1992/000720
Other languages
English (en)
Inventor
Jairo H. Lora
Raphael Katzen
Malcolm Cronlund
Chih Fae Wu
Goyal C. Gopal
Stephen R. Winner
Ron Leblanc
Original Assignee
Alcell Technologies Inc.
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 Alcell Technologies Inc. filed Critical Alcell Technologies Inc.
Priority to JP4509563A priority Critical patent/JPH06511043A/ja
Priority to BR9205576A priority patent/BR9205576A/pt
Publication of WO1992013849A1 publication Critical patent/WO1992013849A1/fr
Priority to BR9305819A priority patent/BR9305819A/pt
Priority to AU36649/93A priority patent/AU676829B2/en
Priority to JP5513540A priority patent/JPH08500854A/ja
Priority to CA002116544A priority patent/CA2116544A1/fr
Priority to PCT/US1993/001256 priority patent/WO1993015261A1/fr
Priority to EP93905902A priority patent/EP0746650A4/fr
Priority to FI933418A priority patent/FI933418A/fi
Priority to NO93932758A priority patent/NO932758L/no
Priority to FI943541A priority patent/FI943541A/fi
Priority to NO942824A priority patent/NO942824L/no
Priority to AU12398/97A priority patent/AU1239897A/en
Priority to AU12397/97A priority patent/AU1239797A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • 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
    • 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
    • D21C11/0042—Fractionating or concentration of spent liquors by special methods
    • 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
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment

Definitions

  • This invention generally relates to the pulping of lignocellulosic materials and the recovery of the resultant by-products resulting from the pulping process. More specifically, this invention relates to pulping of lignocellulosic materials in a water miscible organic solvent (e.g. lower aliphatic alcohol) and recovering and recycling the organic solvent and various by-products of the pulping process (e.g. cellulose, lignin, furfural hemicellulose and sugars). Pulping of the lignocellulosic material and the recovery of the resultant by-products may be carried out in either continuous or batch processes.
  • a water miscible organic solvent e.g. lower aliphatic alcohol
  • Pulping of the lignocellulosic material and the recovery of the resultant by-products may be carried out in either continuous or batch processes.
  • Lignin has been recovered from the black liquor in this patent by first stripping (preferably vacuum stripping) alcohol from the black liquor and then separating the lignin which precipitates from the stripper bottoms or tails (preferably by thickening and then centrifuging the settled solids from the stripper bottoms).
  • a portion of the lignin has tended to precipitate as a sticky tar or gum on the internal surfaces of the stripper, thereby fouling the stripper and reducing its efficiency in recovery of alcohol from the black liquor.
  • the lignin also has tended to precipitate from the stripper bottoms as a sticky amorphous mass which has been difficult to handle and has required substantial crushing to convert the lignin mass into a powder.
  • lignin and other by-products of the pulping process are recovered from a "black liquor" produced when wood or other lignocellulosic material is contacted with a water miscible organic solvent (e.g. ethanol/water solvent) at elevated temperatures and pressures.
  • a water miscible organic solvent e.g. ethanol/water solvent
  • the Lora process successfully allows for the recovery of many by-products, including most of the lignin liberated during pulping. It has also been discovered through improvements of the Lora et al patent as set forth herein that additional by ⁇ products, including lower molecular weight lignin and furfural, may be recovered while simultaneously increasing the overall energy efficiency of the process, reducing the consumption of solvent required throughout the system and significantly reducing or eliminating environmentally undesirable effluent.
  • the invention described herein includes the foregoing improvements and additionally accelerates delignification of the black liquor and allows for the recovery of additional by-products and streams from the pulping process.
  • This invention not only recovers furfural from the residual black liquor filtrates produced during lignin recovery but uses same to recover low molecular weight lignin by recycling same into the system.
  • Also incorporated herein is a system which not only accommodates novel bleaching techniques but provides for the recycling of bleaching effluent filtrates, which accelerate delignification and mitigate against pollution.
  • This invention provides for the recovery of lignin and other by-products from pulping of fibrous material.
  • solvents and filtrates are recovered and recycled for reuse. This results in a significant solvent and energy savings.
  • filtrates from the bleaching and delignification of the pulp of this invention are recycled for reuse in the continuous pulping, separation and recovery of lignin and other by ⁇ products.
  • the reuse of the bleaching filtrates results in accelerated delignification and greater operating efficiency. The net result is a significant energy savings and mitigation if not the elimination of pollution typically associated with bleaching.
  • lignin is recovered from a black liquor comprising a solution of lignin, hemicellulose, and a water miscible organic solvent by precipitating lignin solids by diluting the black liquor with water and acid under conditions to form a diluted residual black liquor including a diluted residual black liquor supernatant and precipitated lignin solids which are free from the formation of tarry lignin precipitates and recovering the lignin by separating the lignin solids from the diluted residual black liquor supernatant.
  • a novel lignin is precipitated by the process of this invention.
  • a preferred lignin is characterized by: a number average molecular weight of about 800 to 1500 g/mol; a polydispersity of less than about 4; and a methoxyl content approximately equal to that of native lignin.
  • a novel low molecular weight lignin is obtained.
  • a preferred lignin is characterized by: a number average molecular weight in the range of less than 500 g/mol, a glass transition in the range of from about 24° to 60°C and a syringhaldehyde to vanillin molar ratio of about 5.3:1, especially as it relates to hardwoods. It is expected that a more soluble lignin having a novel structure is produced.
  • a purified furfural product is recovered.
  • the furfural product contains from about 95 to 98% furfural, from about 0.1 to 0.5% ethanol and from about 0.1 to 2% water.
  • Figure 1 is a flow chart of a process for producing cellulose pulp from wood by treating the wood with an aqueous alcohol solvent, and for recovering lignin and other by-products from the alcohol/water black liquor.
  • Figure 2 is a schematic sectional view of an example of an apparatus for precipitating lignin from the alcohol/water black liquor from the processes of Figures 1, 3 and 4.
  • Figures 3 and 4 represent a flow chart of a continuous process for producing cellulose pulp from wood by treating the wood with an aqueous alcohol solvent and for recovering lignin, and other by-products from the alcohol/water black liquor produced in the pulping Drocess.
  • Figure 5 is a schematic representation of crude furfural upgrading and purification by liquid/liquid cross-current extraction followed by pervaporation.
  • Figure 6 is a schematic representation of crude furfural upgrading and purification by liquid/liquid counter-current extraction followed by pervaporation.
  • Figure 7 is a flow chart for the recovery of low molecular weight lignin.
  • Figure 8 is a schematic representation of a continuous co-current/counter-current extractor used in the processes of Figures 3 and 4.
  • the process shown in Figure 1 initially involves pulping a batch of wood chips or other fibrous material that are loaded from a hopper 1 into an extractor 2.
  • the extractor 2 is operated in accordance with Diebold et al U.S. Patent 4,100,016 at an elevated temperature (e.g., about 180° to 210°C) and an elevated pressure (e.g., about 20 to 35 atmospheres) and with a solvent comprising: about 40 to 80% (by volume) of a water miscible lower aliphatic alcohol of 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol or tert- butanol); 20 to 60% water; and if needed, a small amount of a strong water soluble acid, such as a mineral aid (e.g., hydrochloric, sulfuric, phosphoric or nitric acid) or an organic acid (e.g., oxalic acid, preferably acetic, formic or peroxy acids).
  • the wood chips in the extractor 2 are preheated with low pressure steam, and then, a twice- used 60% ethanol/40% water, primary solvent from a primary
  • EET solvent accumulator 3 contacts the wood chips in the extractor 2.
  • the primary solvent is rapidly recirculated through the extractor 2 and through a peak load (e.g., steam-heated) heat exchanger 4 to raise the temperature of the wood chips to about 190° to 200°C in a few minutes (preferably not more than about 5 minutes). Alternatively, in large scale plant operations, a time of from about 5 to 60 minutes is required.
  • the resulting extract or "black liquor" in the extractor 2 is displaced into a recovery feed accumulator 5 by a once-used 60% ethanol/40% water, secondary solvent (preferably heated to 190° to 200°C) from a secondary solvent accumulator 6.
  • the black liquor which contains lignin, hemicelluloses, other saccharides and extractives (e.g., resins, organic acids, phenols and tannins) from the wood and the ethanol is recovered at a temperature of from about 180° to 210°C and under a pressure of from about 20 to 35 atmospheres in the recovery feed accumulator 5.
  • the secondary solvent in the extractor 2 is displaced into the primary solvent accumulator 3 by a fresh 60% ethanol/40% water solvent (preferably heated to 190° to 200°C) from a fresh solvent accumulator 7.
  • the fresh solvent in the extractor 2 is then drained into the secondary solvent accumulator 6.
  • the extractor 2 Once the extractor 2 has been drained, it is vented, alcohol-rich vapors from the extractor are condensed in a water-cooled (“C.W.") condenser 8, and the resulting ethanol/water mixture from the condenser 8 is recycled to the fresh solvent accumulator 7. After venting the extractor 2, residual alcohol in the pulp in the extractor is then stripped with low pressure steam, and the resulting alcohol/water vapors are condensed and recovered as discussed below. After steam stripping, the pulp in the extractor 2 is sluiced with water, piped to a holding tank 9 and pumped through a pulp screen 10. The pulp can then be suitably subjected to a conventional pulp handling, bleaching and paper-making procedures. The extractor 2 can be loaded with another batch of wood chips from the hopper 1, and the wood chips can be contacted by the primary, secondary and fresh solvents from accumulators 3, 6 and 7 as described above.
  • C.W. water-cooled
  • FIG. 3 a continuous pulping process is shown in Figures 3 and 4.
  • wood chips (50% moisture) or other fibrous material are pre-steamed in steaming bin 31.
  • Saturated steam is injected into steaming bin 31 at atmospheric pressure.
  • the chips are wetted and passed into metering screw 32 which is positioned at an angle.
  • the excess water from the steam condensates in metering screw 32 and the wet chips are passed thru a first low pressure sluice 33, heated in line 46 by direct steam injection at a temperature of from about 270°F to about 330°F and at a pressure of from about 30 to about 100 psig.
  • Line 46 is equipped with a steam barrier which helps prevent backup of alcohol-containing vapors into low pressure sluice 33.
  • the steamed wood chips are passed thru a second low pressure sluice 34 and are mixed in line 45 with a solvent from line 36.
  • the solvent is mixed with the chips in high pressure sluice 35 and partially impregnates the chips.
  • the resultant slurry passes through line 37 and enters extractor 100 at inlet 38.
  • a liquid separator 101 regulates the flow of the mixture into extractor 100.
  • Excess cooking mixture liquid overflows extractor 100 at outlet 39, is recycled thru line 57 and pumped back into high pressure sluice 35.
  • the excess cooking liquid from high pressure sluice 35 is pumped thru line 58 and recycled back into surge tank 50.
  • the cooking mixture in surge tank 50 is mixed internally thru line 51.
  • any overflow cooking mixture from surge tank 50 is pumped thru line 54 into line 37.
  • the partially impregnated chips in extractor 100 are digested and extracted with solvent which is fed into extractor 100 at inlets 52 and 53.
  • the solvent is similar to that used in the process shown in Figure 1.
  • the alcohol concentration in the solvent is regulated by mixing appropriate quantities of makeup alcohol, introduced at 49, with recovered alcohol from the alcohol and by-products recovery system introduced at 7, and with alcohol/water filtrate from counter-current washer 44.
  • the solvent contained in line 36 is heated in pressure diffuser 47 by heat exchange with the pulp leaving extractor 100 at outlet 41.
  • extractor 100 is operated in a continuous co- current/counter-current mode and at a pressure range of from about 200 to about 650 psig.
  • Such an extractor is comprised of sequential reaction zones and means to add and remove solvent.
  • the latter can be in the form of liquor extraction screens equipped with wipers or other cleaning devices that prevent screen plugging such as steam injectors.
  • the cooking mixture which typically contains 5% chips in 95% solvent passes through extractor 100 and is exposed sequentially to six reaction zones.
  • further alcohol impregnation of the chips occurs at a constant temperature of from about 100° to 130°C in separation zone (a) for about 2 to about 20 minutes.
  • separation zone (a) a vapor head space is maintained with the level of the solvent in the cooking mixture higher than the level of the chips. Any excess solvent is removed thru outlet 39 and recycled as described above.
  • the temperature of the cooking mixture chips is elevated as the cooking mixture passes into preheating zone (b) and is preheated to from about 150° to 180°C in about 50 minutes.
  • the heating of the cooking mixture in preheating zone (b) is achieved by circulating the cooking solvent counter- currently thru a heat exchanger (typically of the tube and shell type) which is heated with steam.
  • the heat exchanger temperature is maintained at a level sufficient to cause the cooking mixture in preheating zone (b) to heat to from about 150° to 180° C.
  • the preheated cooking mixture is further heated in primary extraction zone (c) to from about 160° to 205° C and subjected to digestion and extraction for about 70 minutes.
  • the cooking mixture is heated in primary extraction zone (c) by circulating the cooking solvent co-currently through a heat exchanger as described above. In zone (c) , a hot ethanol/water extract or "black liquor" is produced during the digestion and extraction process.
  • the hot black liquor which contains lignin, hemicellulose, other saccharides and extractives e.g. resins, organic acids, phenols and tannins
  • lignin, hemicellulose, other saccharides and extractives e.g. resins, organic acids, phenols and tannins
  • the cooking mixture is further digested and extracted for about 60 minutes in secondary extraction zone (d) at a temperature of from about 150° to 180°C.
  • the temperature is cooled in secondary extraction zone (d) by recirculating the cooking solvent in a heat exchanger as describe above.
  • the heat exchanger temperature is maintained at a level sufficient to achieve the cooling of the cooking mixture to maintain a temperature of from about 150° to 180° C in secondary extraction zone (d).
  • the cooking mixture is further digested and extracted for about 45 minutes in tertiary extraction zone (e) and the mixture is cooled to a temDerature of from about 130° to
  • EET 160°C by recirculating the cooking solvent co-currently thru a heat exchanger as described above.
  • the cooking mixture is further cooled to from about 70° to 100°C in cooling zone (f) for about 22 minutes and broken up into pulp with mixer 102. Cooling of the cooking mixture in cooling zone (f) is achieved by mixing the mixture with the solvent introduced at inlet 52 in a counter-current fashion and at inlet 53 in a co-current fashion.
  • the solvent mixture consists of makeup alcohol, recycled alcohol from the alcohol and by-product recovery and alcohol/water filtrate from counter-current washer 44.
  • the pulp is separated from the cooking mixture and exits extractor 100 through line 41.
  • the pulp is washed in pressure diffuser 47 with recycled alcohol through line 7 and cooled to a temperature below 80°C while simultaneously additional lignin is removed and recycled through line 36 and the kappa number is reduced to a bleachable grade. Further defiberisation occurs as the pulp passes through pressure reduction valve 42.
  • Pressure reduction valve 42 is preferably a blow valve.
  • the pulp is further washed in multistage counter-current washer 44 by water introduction through line 43 and cooled to a temperature of from about 40° to 70°C. Counter- current washer 44 replaces conventional, less energy efficient, steam stripping methods and removes from about 50 to about 90% additional alcohol from the pulp.
  • the pulp is piped to tank 9 and pumped through a pulp screen 10. The pulp can then be suitably subjected to conventional pulp handling, bleaching and paper-making procedures.
  • the pulp now referred to as brownstock can be delignified by treating with oxygen coupled with a prior peroxy treatment using a peroxy compound such as peracetic acid or hydrogen Deroxide.
  • Filtrates thus obtained under acidic conditions can be recycled as wash water for brown stock washing. These filtrates are introduced at inlet 43, mixed with water and become part of the solvent in line 36. Since the rate of delignification is directly proportional to the acidity of the solvent, it is believed that these acidic filtrates will accelerate the rate of delignification. It is also believed that the presence in the filtrates of organic acids of sodium lignate accelerate the rate of delignification.
  • filtrates from alkaline oxygen delignification can also be used.
  • delignification of pulp with oxygen can be carried by first mixing a pulp slurry at from about 9 to 15% consistency by weight of pulp solids with a solution of sodium hydroxide (caustic) and further mixing at high shear with oxygen gas.
  • the amount of caustic added can preferably be from about 2 to 8%, more preferably from about 3 to 6% based on % wt/wt of oven dry (o.d.) pulp.
  • the temperature of the reaction mixture can preferably be between about 60°C and 110°C, more preferably between about 70°C and 90°C, and oxygen pressure in the bleaching vessel can preferably be maintained at from about 40 to 110 psig, more preferably at from about 80 to 100 psig for oxygen delignification and at from about 32 to 60 psig for delignification using oxidative extraction.
  • the reaction time with oxygen can preferably be from about 6 to 60 minutes, more preferably from about 40 to 50 minutes.
  • Additional chemical agents which may be added to help preserve strength properties include 0.5% to 1% magnesium sulfate, 0.5% diethylene triamine pentaacetic acid (DTPA), and up to 3% sodium silicate.
  • peroxy treatment of pulp can be achieved by mixing peracetic acid with the pulp at a pH cf about 2 to about 10 and in amounts of from about 0.5 to about 4% by weight of peracetic acid per weight of oven dried pulp.
  • the pulp can be of any consistency, but is preferably between about 10 and 12% by weight of pulp solids.
  • the reaction time can preferably be from about 20 minutes to about 3 hours at a temperature of from about 40°C to 90°C.
  • peroxy treatment of pulp can also be achieved by mixing hydrogen peroxide with the pulp in amounts of from about 0.5% to about 4% hydrogen peroxide and at a pH of from about 2 and 11.
  • the pulp can be of any consistency, but is preferably between about 10% and 12% by weight of pulp solids and the temperature of the reaction can be maintained at from about 40° and 90°C.
  • Magnesium sulfate at from about 0.5% to 1.0% may be added for viscosity protection of the pulp, and DTPA may be added at from about 0.05 to 0.5% to prevent catalytic decomposition of the peroxide by metal ions such as manganese, copper, and iron.
  • the black liquor is flashed into a flash tank 11 to recover part of the ethanol.
  • the flash tank 11 can be at atmospheric pressure for simplicity of operation or at reduced pressure to further cool the black liquor and enhance the alcohol recovery.
  • the reduction in pressure in the flash tank 11 causes partial vaporization of the ethanol and leaves the residual black liquor in the flash tank with an ethanol content of about 30 to 45%, preferably abou'_ 35 to 40%.
  • the residual black liquor is cooled during this step to a temperature of less than about 95°C, preferably down to about 80° to 92°C, but not below about 70°C to avoid premature precipitation of lignin in the flash tank 11.
  • the black liquor can be heated by steam injection or indirect heating before flashing in flash tank 11 to vaporize more ethanol, therefore decreasing the ethanol concentration of the liquor to from about 25 to 34% and reducing the amount of dilution water needed for precipitation by from about 20 to 70%.
  • Steam injection or indirect heating can also be introduced directly into flash tank 11 or in any of the flash tanks that can be used in sequential series with flash tank 11.
  • the ethanol/water vapors obtained are condensed in condenser 8 and recycled, along with any makeup ethanol, water and/or acid, for use in treating subsequent batches of wood chips.
  • the ethanol/water vapors from flash tank 11 can be recycled in reboiler 24, thus providing energy for distillation in solvent recovery tower 14.
  • Solvent recovery can be further enhanced by interfacing solvent recovery tower 14 with additional solvent recovery towers and reboilers arranged in sequential series with solvent recovery tower 14.
  • lignin is then separated from the residual black liquor discharged from the flash tank 11.
  • This step is carried out by diluting and preferably cooling the residual black liquor, as it leaves the flash tank 11, with water and acid to form a diluted residual black liquor with: a) an alcohol content of less than about 30% (by volume), preferably about 10 to 25%, particularly about 12 to 21%, with an alcohol content of about 8% being a practical minimum for subsequently recovering the alcohol economically; b) a temperature of less than about 75°C, preferably less than about 60°C, particularly about 35° to 55°C; and c) a pH of less than about 3, preferably less than about 2.5, particularly about 1.5 to 2.5.
  • temperatures are not critical, although providing higher temperatures in the diluted residual black liquor will generally increase settling rates of the lignin but will yield a darker colored lignin and may decrease its yields.
  • About 75°C is a maximum temperature to avoid the formation of tarry lignin precipitates
  • ambient temperatures e.g., about 20°C
  • lower temperatures e.g., down to about 0°C
  • Temperatures below about 65°C, particularly below 60°C provide a significantly lighter colored lignin precipitate.
  • about 30°C is a maximum temperature in order to avoid the formation of tarry lignin precipitates.
  • pH's of the diluted residual black liquor are not critical in this step, but lower pH's increase the yield of precipitated lignin from the diluted residual black liquor and permit the use of higher temperatures in the diluted residual black liquor.
  • lowering pH below about 1 provides little or no additional improvement in yield, and for this reason, a pH of about 1 is a practical minimum although lower pH's can be used.
  • lignin will precipitate from the diluted residual black liquor in high yield and at a high rate as fine solids. These lignin solids can then be separated from the remaining diluted residual black liquor supernatant in a conventional manner.
  • the lignin solids are separated by: allowing them to settle out as a paste of about 6 to 12% (by weight) solids in a conventional clarifier or settling tank 12; then concentrating this paste of lignin solids in a conventional centrifugal separator to form a wet cake of about 30 to 40% solids; and then drying this wet cake to form a uniform fine, free flowing powder.
  • the lignin solids are preferably separated by using large scale filters (e.g. belt filter and filter press, preferably drum filter) which allows easy washing of the lignin cake.
  • any conventional water soluble acid can be utilized which will provide the diluted residual black liquor with a pH of less than about 3.0, preferably less than about 2.50.
  • a strong mineral acid e.g., hydrochloric, nitric, sulfuric or phosphoric acid
  • a strong organic acid e.g., oxalic acid, preferably acetic, formic or peroxy acids
  • filtrates from the bleaching step can also be used. They can be added to the water in line 43 and alternatively, they can be added to mixing tank 20.
  • oxygen delignification filtrates after pH adjustment, are able to precipitate lignin at a pH above 3.0, preferably between approximately 3.5 and approximately 4.0.
  • the water and acid are mixed together before they are used to dilute the residual black liquor.
  • a particularly preferred mixture of acid and water is a residual black liquor supernatant that is derived from a previous batch of wood chips and that has been recycled and used to dilute the residual black liquor from the flash tank 11 after: a) the supernatant has been separated from the lignin solids from the previous batch of wood chips in the settling tank 12 and the centrifugal separator 13, or as shown in Figure 4, in large scale filter 63; and b) the alcohol content of the supernatant has been recovered in a conventional solvent condenser 15 as described below.
  • the recycled residual black liquor supernatant or stripper bottoms when used for diluting the residual black liquor from the flash tank 11, provides higher yields and faster settling of lignin solids precipitating in the settling tank 12 and centrifugal separator 13.
  • the method of diluting the residual black liquor with the water and acid also is not critical, so long as there is rapid and intimate mixing of the residual black liquor with the acid and water.
  • the residual black liquor can be suitably diluted by adding it to the acid and water in a conventional static dispersion mixer or a mixing tank, generally 20.
  • the residual black liquor can also be diluted by adding it as a finely divided stream to a stream comprising a solution of the water and acid, for example, by means of a venturi-type device, generally 20, as shown schematically in Figure 2.
  • the residual black liquor from flash tank 11 in Figures 1, 3 and 4 can be pumped through a small nozzle 21 located at about the center of a pipe 22 in the venturi-type device 20 in Figure 2, and the acid and water solution can flow in the pipe 22 towards the settling tank 12.
  • the residual black liquor is injected by the nozzle 21 into the acid and water solution in the pipe 22, the residual black liquor is rapidly diluted and cooled by the acid and water in the pipe 22.
  • Lignin rapidly precipitates as fine solids from the resulting diluted residual black liquor in the pipe 22, which solids can be easily collected and concentrated in the settling tank 12 and centrifugal separator 13.
  • the residual black liquor exits mixing tank 20 and enters a liquid/solid separation system consisting of large scale filter 63 (e.g. belt filter, filter press, preferably drum filter), and dryer 66. Filtrates of alcohol and dissolved solids, including hemicellulose, are extracted from filter 63 to be distilled in solvent recovery tower 14. Precipitated lignin cake is discharged from filter 63 and is dried to a powder-like form in dryer 66.
  • large scale filter 63 e.g. belt filter, filter press, preferably drum filter
  • dryer 66 Filtrates of alcohol and dissolved solids, including hemicellulose, are extracted from filter 63 to be distilled in solvent recovery tower 14. Precipitated lignin cake is discharged from filter 63 and is dried to a powder-like form in dryer 66.
  • the yield and settling rates of the lignin are generally a function of: a) the wood species; b) the process conditions utilized in the extractor 2; c) the temperature, pH and solids content of (i) the residual black liquor from the flash tank 11 and (ii) the acid and water used to dilute it; and d) the ratio of residual black liquor to the acid and water used to dilute it.
  • the lignin from softwoods, such as spruce is preferably precipitated at a temperature after dilution of about 40° to 60°C using an acid and water solution with a pH of about 1.5 to 2.5 and with a ratio of residual black liquor to the acid and water solution of about 0.5 to about 1.
  • an acid and water solution with a pH of about 1.2 to 2.2 and a temperature after dilution of less than about 50°C.
  • a ratio of residual black liquor to the acid and water solution of: a) about 0.2 to 0.8 if the temperature after dilution is about 40°C; and b) about 0.6 to 1.0 if the temperature after dilution is less than about 40°C (e.g., down to ambient temperature).
  • a temperature after dilution of about 40° to 60°C, an acid and water solution with a pH of about 1.5 to 2.5, and a ratio of residual black liquor to the acid and water solution of about 0.35 to 0.7.
  • the clarified residual black liquor filtrate from the lignin solids separation step contain alcohol, furfural, wood sugars, acetic acid and low molecular weight lignin fragments that were not captured in the precipitation procedure.
  • the ethanol content is preferably recovered in the solvent recovery tower 14 and solvent condenser 15.
  • the ethanol content of the supernatant can be stripped (e.g., down to about 200 ppm) in a conventional manner in the solvent recovery tower 14 at atmospheric pressure.
  • the tower 14 is heated by heating and recycling a portion of the bottoms stream from the tower 14 in a heat exchanger 24, using the low pressure steam used to strip residual ethanol from the pulp in the extractor 2.
  • the tower 14 can be operated under vacuum or pressurized.
  • the ethanol/ water vapors from the tower 14 are condensed in a conventional manner in the water-cooled condenser 15 (or by heat exchange with the stripper feed) and are then recycled together with the ethanol/water mixture which condenses from the low pressure steam in the heat exchanger 24.
  • the ethanol content of the supernatant from the settling tank 12 and centrifugal separator 13, or alternatively from large scale filter 63 as shown in Figure 4 can be suitably recovered in high yield in a simple manner, without lignin precipitating within the solvent recovery tower 14 and forming tarry or gummy deposits on the internal surfaces of the tower.
  • the clarified residual black liquor filtrates from the lignin solids separation step typically contains from about 0.2 to 0.8% furfural, from about 10 to 15% alcohol, from about 0.5 to 10% dissolved solids, and water.
  • the black liquor is fed to solvent recovery tower 14 and a furfural side draw is removed which contains from about 12 to 30% furfural.
  • the furfural side draw is taken at a plate above the feed plate at line 700.
  • the furfural side draw is cooled by indirect heat exchange in heat exchanger 701 to a temperature of less than about 50° C and separates in decanter 71 into a crude furfural layer which contains from about 60 to 75% furfural, and an alcohol rich layer which is returned directly to solvent recovery tower 14.
  • the crude furfural can be upgraded to from about 85 to 91% furfural using liquid/liquid extraction and can be further purified to from about 95 to 98% furfural using pervaporation.
  • Other purification techniques include freeze concentration, dehydration and the use of a desiccant.
  • the crude furfural layer which typically contains from about 60 to 75% furfural, from about 5 to 15% ethanol, from about 0.5 to 2% methanol and from about 7 to 15% water can be upgraded using liquid/liquid extraction.
  • Cross-current liquid extraction can be used, and as shown in Figure 5, the crude furfural is mixed in mixer 71 using mechanical agitation with a solvent, preferably water. When the crude furfural and water separate in settler 72, a furfural raffinate and an alcohol rich water extract are obtained.
  • N extraction steps in Figure 5
  • upgrading of the crude layer can be satisfactorily achieved with preferably two or three sequential cross-current extractions.
  • Water and crude furfural are mixed in a volume ratio of from about 1:1 to 3:2, for about 30 minutes, and at a temperature of from about 0° to 50° C.
  • the alcohol extract which contains from about 0.5 to 6% ethanol, from about 0.2 to 1% methanol and from about 6 to 10% furfural is returned to solvent recovery tower 14.
  • a furfural raffinate is obtained which contains from about 89 to 91% furfural, from about 0.1 to 0.2% ethanol, and from about 4.2 to 4.6% water.
  • the crude furfural can be upgraded using counter-current extraction.
  • the crude furfural is extracted with a solvent, preferably water in counter-current extractor 73.
  • a temperature of from about 0° to 50°C is used, and the flow of crude furfural to water is about 3:2.
  • An upgraded furfural raffinate is obtained which contains from about 85 to 90% furfural, from about 0.2 to 1% ethanol and from about 4 to 7% water.
  • An alcohol extract typically containing from about 1 to 12% ethanol, from about 0.4 to 1.5% methanol and from about 6 to 10% furfural is returned to solvent recovery tower 14.
  • the upgraded furfural raffinate can be further purified to remove the water (e.g. by dehydration or pervaporation) .
  • FIGS 5 and 6 are illustrative of purification by pervaporation.
  • the pervaporation system 80 is comprised of a cell separated by a membrane 82 into two compartments 81 and 83.
  • Membrane 82 is preferably a hydrophyllic membrane, for example, a polyvinyl alcohol membrane.
  • the upgraded furfural is fed into compartment 81 and the water contained in the upgraded furfural is preferentially attracted by membrane 82.
  • the water travels thru membrane 82 into compartment 83.
  • a vacuum pressure of from about 0.8 to 8 psia (preferably from about 1 to 2 psia) is maintained in tank 83 to vaporize the water.
  • a final furfural product is obtained which contains from about 95 to 98% furfural, from about 0.1 to 0.5% ethanol and from about 0.1 to 2% water and removed from compartment 81.
  • the crude furfural can be upgraded using conventional distillation.
  • An upgraded furfural distillate is obtained which contains from about 95 to 99% furfural, from about 0.2 to 1% ethanol and from about 0.2 to 1% water.
  • upgrading and purification of furfural using liquid/liquid extraction and pervaporation is the preferred method over a single distillation since this results in an energy savings of at least two-fold and the resultant furfural product contains less ethanol and water.
  • the bottoms stream removed from the solvent recovery tower 14 contains wood sugars, low molecular weight lignins, acetic acid, ash and other minor components.
  • a portion of the bottoms stream is preferably concentrated in a conventional manner, for example, in multiple effect evaporators 26. In this step, scaling or fouling cf the evaporation equipment is not a significant problem because there are no substantial amounts of high molecular weight lignin in the bottoms stream from the solvent recovery tower 14.
  • the resulting syrup containing hemicelluloses together with small amounts of other saccharides, extractives and very low molecular weight lignin (i.e., lignin with a molecular weight of less than about 400 g/ mol), can be burned to recover its fuel value, use as animal feed, or converted to other chemical products. Alternatively, the low molecular weight lignin can be recovered.
  • the low molecular weight lignin corresponds to lignin fragments that were not captured by the precipitation process due to their low molecular weight and water solubility and several different fractions can be isolated.
  • low molecular weight lignin can be characterized by a low molecular weight fraction in the range of less than 500 g/ mol and a low glass transition temperature in the range of from about 24° to 60°C.
  • Another characteristic, when hardwoods are pulped, is that the low molecular weight lignin is predominantly of the syringyl type, since by nitrobenzene oxidation, it yields a syringaldehyde to vanillin molar ratio of about 5.3:1.
  • This low molecular weight lignin can be used as an extender in phenolic wood adhesive systems. It can also be used in applications requiring water solubility during processing (e.g. fiberglass binders) and as an intermediate for the production of syringaldehyde and other chemicals.
  • Figure 7 illustrates the recovery of low molecular weight lignin.
  • a portion of the bottom streams removed from solvent recovery tower 14 is concentrated by multiple effect evaporator 600 to a syrup containing from about 10 to 30% solids.
  • the pH of the syrup is raised to a pH of from about 2.0 to about 6.0 by alkaline addition before concentrating the bottom streams.
  • the low molecular weight lignin fragments separate as a tarry organic phase 90 which contains from about 30 to 70% of the low molecular weight lignin that was present in the bottoms stream, and an aqueous fraction.
  • This tarry organic phase 90 contains from about 60 to 90% low molecular weight lignin solids and at a temperature of from about 60 to 95°C, it has a viscosity of from about 400 to 3000 cps.
  • This organic phase is separated in decanter 91 from the aqueous phase.
  • the aqueous phase containing the remaining low molecular weight lignin is concentrated in evaporator 92 to from about 40 to 65% solids, and is extracted with an organic solvent (preferably 1:1 volume ratio) in counter-current liquid/ liquid extraction column 93.
  • Organic solvents such as dieth l ether, cyclohexane, furan, and 3-hexanol can be used, however furfural is a particularly preferred solvent since it removes in excess of 70% of the low molecular weight lignin present in the aqueous phase in a single extraction.
  • the furfural obtained by upgrading and purification as shown in Figures 5 and 6 can also be used to extract the low molecular weight lignin as described above.
  • the raffinate from column 93 contains from about 5 to 20% low molecular weight lignin, from about 70 to 85% furfural and from about 5 to 15% water.
  • the raffinate is vacuum distilled in column 94.
  • the bottoms stream from column 94 contain low molecular weight lignin and the condensate from condenser 940 containing primarily from about 85 to 95% furfural and from about 5 to 15% water is recycled to column 93.
  • the extract from column 93 containing from about 6 to 10% furfural, from about 4 to 5% sugars and from about 50 to 80% water is stripped from furfural in column 95.
  • the condensate from column 95 in condenser 950 is decanted in decanter 96 and the heavy layer containing from about 85 to 95% furfural and from about 5 to 15% water is recycled to column 93.
  • the stripper bottoms from column 95 contain sugars, mostly xyloses, which can be further used for furfural production by acid catalyzed dehydration.
  • a second portion of the bottoms stream removed from the tower 14 is preferably used as the acid and water solution for diluting the residual black liquor from the flash tank 11 in order to precipitate lignin therefrom.
  • the second portion of the bottoms stream from the tower 14 is preferably cooled to a temperature of less than about 50°C, preferably about 25° to 40°C (about 0 ⁇ C being a practical minimum), and its pH is adjusted, if necessary, to about 1.0 to 3.0 by adding a strong water soluble acid to it.
  • the cooled and acidified second portion of the bottoms stream (hereinbefore called the "recycled residual black liquor supernatant") is intimately and rapidly mixed (e.g., in the venturi-type device 20 of Figure 2) with the residual black liquor to dilute and cool the residual black liquor and precipitate lignin.
  • the very pure lignin which precipitates as fine solids from the diluted residual black liquor in the settling tank 12, can be subsequently removed from the centrifugal separator 13, or alternatively from large scale filter 63 as shown in Figure 4 , water-washed and dried in a conventional manner (e.g., by spin flash drying) to form a fine (e.g., -80 mesh) uniform, free flowing, water insoluble powder.
  • a fine e.g., -80 mesh
  • This lignin can be characterized as having: a relatively low number average molecular weight of about 800 to 1500 g/mol, preferably about 900 to 1300 g/mol and a glass transit i on temperature which is preferably about 100° to 170°C, particularly about 130° to 150°C, although a glass transition temperature of preferably about 80° to 170°C, particularly about 90° to 150°C is also observed; a narrow molecular weight distribution, i.e., a polydispersity of less than about 4, preferably no more than about 3, particularly only about 1.5 to 2.7; and a methoxyl content approximately equal to the methoxyl content of native lignin (i.e., about 20% for hardwoods and about 14% for softwoods).
  • This lignin also has a softening temperature which is preferably about 120° to 150°C, particularly about 130° to 150°C. These characteristics show, inter alia, the purity and low degree of chemical modification of the lignin of this invention.
  • This lignin can be used for example, as a phenol formaldehyde resin extender in the manufacture of particle board and plywood.
  • This lignin can also be used in the manufacture of molding compounds, urethane and epoxy resins, antioxidants, controlled-release agents and flow control agents.
  • the process for precipitating the lignin of this invention can alternatively be carried out by separately adding an acid and water to a solution of lignin dissolved in a water miscible organic solvent to form a diluted aqueous solution with a pH of less than about 3, an organic solvent content of less than about 30% and a temperature of less than about 75°C, from which diluted solution the lignin will precipitate as uniform fine solids.
  • the acid can be separately added to the residual black liquor from the flash tank 11 in Figure 1 by adding the acid to the primary solvent from the primary solvent accumulator 3 before the primary solvent is used in the extractor 2 for pulping wood chips to produce the black liquor (which becomes, after removal of ethanol in the flash tank 11, the residual black liquor).
  • the process of this invention can be carried out with a water miscible organic solvent other than a lower aliphatic alcohol (preferably ethanol), such as acetone, glycol or glycerol, or with a mixture cf such solvents.
  • these processes can be carried out using any fibrous plant material, such a bamboo, bagasse, kenaf, cereal straws, and not just wood.

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Abstract

Des filtrats provenant du blanchiment et de la délignification de la pâte sont recyclés afin d'être ré-utilisés dans les procédés de réduction en pâte, de séparation et de récupération de lignine (66) et d'autres sous-produits, ce qui permet de réaliser d'importantes économies d'énergie ainsi que de diminuer sinon d'éliminer la pollution généralement associée au processus de blanchiment. L'invention se rapporte aussi à des produits dérivés du procédé et à un appareil servant à effectuer ce procédé. Des lignines de différents poids moléculaires et des sous-produits du procédé de réduction en pâte sont aussi récupérés (66). Les lignines sont précipitées avec un rendement élevé et à une vitesse élevée à partir d'une liqueur noire (40) produite lorsqu'on réduit du bois en pâte à des températures et à des pressions élevées avec un solvant aqueux à base d'alcool aliphatique inférieur. Un produit composé de furfural purifié est aussi récupéré (71) comme sous-produit du procédé. Le furfural peut être recyclé afin d'être utilisé pour la récupération de la lignine de faible poids moléculaire de ce procédé.
PCT/US1992/000720 1991-02-01 1992-01-29 Reduction en pate de matieres lignocellulosiques et recuperation des sous-produits qui en resultent WO1992013849A1 (fr)

Priority Applications (14)

Application Number Priority Date Filing Date Title
JP4509563A JPH06511043A (ja) 1991-02-01 1992-01-29 リグノセルロース原料のパルプ化及び生成する副生物の回収
BR9205576A BR9205576A (pt) 1991-02-01 1992-01-29 Produção de polpa a partir de materiais lignocelulósicos e recuperação dos subprodutos resultantes.
EP93905902A EP0746650A4 (fr) 1992-01-29 1993-01-29 Reduction en pate de materiaux vegetaux fibreux et recuperation de sous-produits resultants
PCT/US1993/001256 WO1993015261A1 (fr) 1992-01-29 1993-01-29 Reduction en pate de materiaux vegetaux fibreux et recuperation de sous-produits resultants
AU36649/93A AU676829B2 (en) 1992-01-29 1993-01-29 Pulping of fibrous plant materials and recovery of resultantby-products
JP5513540A JPH08500854A (ja) 1992-01-29 1993-01-29 繊維質植物原料のパルプ化及び生成する副生物の回収
CA002116544A CA2116544A1 (fr) 1992-01-29 1993-01-29 Procede de preparation d'une pate a partir de plantes fibreuses, et recuperation des sous-produits
BR9305819A BR9305819A (pt) 1992-01-29 1993-01-29 Processo para produção de polpa de materiais de plantas fibrosos e recuperação dos subprodutos resultantes
FI933418A FI933418A (fi) 1991-02-01 1993-07-30 Foerfarande foer defibrering av lignocellulosamaterial och aotervinning av biprodukter
NO93932758A NO932758L (no) 1991-02-01 1993-08-02 Fremstilling av masse fra lignocelluloseholdige materialer, samt gjenvinning av biprodukter
FI943541A FI943541A (fi) 1992-01-29 1994-07-28 Kuitupitoisen kasvimateriaalin kuidutus ja syntyvien sivutuotteiden talteenotto
NO942824A NO942824L (no) 1992-01-29 1994-07-29 Oppslutning av fiberholdig plantemateriale, samt gjenvinning av dannede biprodukter
AU12398/97A AU1239897A (en) 1992-01-29 1997-01-30 Washing of pulp
AU12397/97A AU1239797A (en) 1992-01-29 1997-01-30 Washing of pulp

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US64968391A 1991-02-01 1991-02-01
US649,683 1991-02-01

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AU (2) AU1744892A (fr)
BR (1) BR9205576A (fr)
CA (1) CA2101754A1 (fr)
FI (1) FI933418A (fr)
MX (1) MX9200444A (fr)
NO (1) NO932758L (fr)
WO (1) WO1992013849A1 (fr)
ZA (1) ZA92566B (fr)

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WO1996041052A1 (fr) * 1995-06-07 1996-12-19 Alcell Technologies Inc. Fabrication de pate a papier avec un solvant organique modifie
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WO2009028969A1 (fr) * 2007-08-31 2009-03-05 Biojoule Ltd Lignine et autres produits isolés de matières végétales, procédés et compositions associés
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AT510812A1 (de) * 2010-10-29 2012-06-15 Annikki Gmbh Verfahren zur gewinnung von lignin
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US9127325B2 (en) 2008-07-24 2015-09-08 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock
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US5788812A (en) * 1985-11-05 1998-08-04 Agar; Richard C. Method of recovering furfural from organic pulping liquor
DE4334422A1 (de) * 1993-10-08 1995-04-13 Fraunhofer Ges Forschung Streckmittel für Holzwerkstoff-Bindemittel und Verfahren zu seiner Herstellung
WO1996041052A1 (fr) * 1995-06-07 1996-12-19 Alcell Technologies Inc. Fabrication de pate a papier avec un solvant organique modifie
US8822657B2 (en) 2006-05-08 2014-09-02 Vertichem Corporation Recovery of lignin and water soluble sugars from plant materials
US7649086B2 (en) 2006-05-08 2010-01-19 Biojoule Ltd. Integrated processing of plant biomass
US7985847B2 (en) 2006-05-08 2011-07-26 Biojoule Ltd. Recovery of lignin and water soluble sugars from plant materials
WO2009028969A1 (fr) * 2007-08-31 2009-03-05 Biojoule Ltd Lignine et autres produits isolés de matières végétales, procédés et compositions associés
US8053566B2 (en) 2007-08-31 2011-11-08 Vertichem Corporation Methods for isolating and harvesting lignin and isolated lignin preparations produced using the methods
US9010522B2 (en) 2008-07-24 2015-04-21 Abengoa Bioenergy New Technologies, Llc Method and apparatus for conveying a cellulosic feedstock
US9127325B2 (en) 2008-07-24 2015-09-08 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock
US8778084B2 (en) 2008-07-24 2014-07-15 Abengoa Bioenergy New Technologies, Llc. Method and apparatus for treating a cellulosic feedstock
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EP0569526A4 (en) 1993-12-22
AU1140995A (en) 1995-03-30
JPH06511043A (ja) 1994-12-08
MX9200444A (es) 1992-08-01
ZA92566B (en) 1993-07-28
BR9205576A (pt) 1994-11-08
EP0569526A1 (fr) 1993-11-18
FI933418A0 (fi) 1993-07-30
NO932758L (no) 1993-09-24
NO932758D0 (no) 1993-08-02
AU1744892A (en) 1992-09-07
CA2101754A1 (fr) 1992-08-02

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