WO2004106624A1 - Procede de production de pate a papier et de lignine - Google Patents

Procede de production de pate a papier et de lignine Download PDF

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Publication number
WO2004106624A1
WO2004106624A1 PCT/CA2003/001901 CA0301901W WO2004106624A1 WO 2004106624 A1 WO2004106624 A1 WO 2004106624A1 CA 0301901 W CA0301901 W CA 0301901W WO 2004106624 A1 WO2004106624 A1 WO 2004106624A1
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WIPO (PCT)
Prior art keywords
acid
lignocellulosic material
lignin
aqueous
solution
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PCT/CA2003/001901
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English (en)
Inventor
David Tarasenko
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Pacific Pulp Resources Inc.
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Publication date
Application filed by Pacific Pulp Resources Inc. filed Critical Pacific Pulp Resources Inc.
Priority to AU2003291874A priority Critical patent/AU2003291874A1/en
Publication of WO2004106624A1 publication Critical patent/WO2004106624A1/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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/04—Pretreatment of the finely-divided materials before digesting with acid reacting compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes

Definitions

  • This invention pertains to a method for producing pulp (comprising cellulose) and lignin from lignocellulosic material such as wood chips.
  • Wood is a composite material comprising cellulose, lignin and hemicellulose.
  • Cellulose is the strong, fibrous component which consists of long chains of glucose molecules and which is used to make paper.
  • Lignin is a phenolic polymeric matrix which holds the cellulose fibres together.
  • Hemicellulose is the component comprised of short, branched chains of glucose and other like molecules.
  • Pulp refers to cellulose fibres or material containing cellulose fibres which may be used in the production of paper or paper containing products.
  • the two main types of pulping processes in use today are mechanical pulping and chemical pulping though there are other pulping processes, such as chemi-thermal mechanical pulping, which are a combination thereof.
  • Mechanical pulping involves the physical separation of individual fibres of the wood by forcing debarked logs and hot water between large rotating steel discs with teeth that tear the wood apart, or alternatively, by, pressing logs against grindstones.
  • pulps produced by mechanical pulping are of lower quality than pulps produced according to chemical pulping, and thus are used to produce newsprint and cardboard type products.
  • Kraft pulping involves subjecting wood to heat and chemicals in order to dissolve the lignin and hemicellulose binding materials, thereby separating the cellulosic fibres.
  • Kraft pulping is an example of a chemical pulping process, and involves involves cooking wood chips in a pressurized vessel known as a digester in the presence of hot caustic soda (NaOH) and sodium sulfide (Na 2 S).
  • NaOH hot caustic soda
  • Na 2 S sodium sulfide
  • Kraft pulping is a variation of the soda process where only NaOH is used to break down and remove the lignin. Relative to the soda process, the addition of the sodium sulfide in the Kraft process assisted in dissolving the lignin with less damage to cellulosic fibres.
  • the digestion process dissolves the lignin that "glues" the cellu- losic fibers to each other in the wood.
  • the resultant solution containing the dissolved ligneous material is referred to as a "black liquor”.
  • the cellulose-containing pulp is separated from the black liquor and washed.
  • the resultant colored slurry of cellulose fibres is referred to as "brownstock” .
  • the color of the slurry is the result of some residual lignin remaining within the slurry with the cellulosic fibres.
  • a further step of bleaching the slurry can be carried out to remove some additional components of the lignin, thereby brightening the pulp.
  • the pulp is bleached in multiple stages with various combinations of oxygen, hydrogen peroxide and sodium hydroxide. Chelation stages can be utilized in the bleaching process to remove transition metals in the pulp which may otherwise interfere with peroxide bleaching.
  • Kraft pulping typically involves pressures of approximately 120 p.s.i., temperatures of approximately 160 - 180 °C and initial pH values over 12 in the digestion stage. In part, these reaction conditions are required by the fact that reactions carried out in Kraft pulping are oxidation reactions. These harsh conditions result in a loss of some cellulose and the destruction of much of natural form lignin from the wood chips.
  • Lignin typically is not recovered as an end-product in typical Kraft pulping processes. Instead, in Kraft pulping processes the black liquor is typically condensed in recovery boilers in the process of recovering chemicals such as sodium hydroxide for reuse. Solids such as lignin are burned as fuel to run the pulp mill utilizing the Kraft process. It would be advantageous to recover as much lignin as possible in a pulping process since lignin is a valuable component in its own right, having a wide range of industrial applications such in the manufacture of fertilizers, asphalt emulsifiers, soil stabilizers, wood products (such as plywood and particle board), oil well drilling fluids and dispersing agents for preparing concrete.
  • the invention provides for methods for producing pulp and lignin from lignocellulosic material, the pulp comprising cellulose.
  • the methods comprise: (a) contacting the lignocellulosic material with an aqueous acid solution to impregnate the lignocellulosic material, the aqueous acid solution comprising from about 10% to about 40% by weight of the acid; (b) heating the lignocellulosic material in two stages, the first heating stage being carried out for a period of time which is sufficient to depolymerize lignin within the lignocellolosic material without substantially degrading the cellulose or lignin in the ligncellulosic material, the second heating stage being carried out at or above the boiling point of the acid to distill off the acid; (c) contacting the lignocellulosic material with an aqueous alkaline solution under heat to solubilize lignin in the alkaline solution, leaving a black liquor; (d)
  • the acid in step (a) may be nitric acid.
  • the aqueous acid solution in step (a) may comprise, without limitation, from about 10% to about 30%, from about 15% to about 30%, from about 20% to about 25%, or from about 10% to about 15%, by weight of the acid.
  • the lignocellulosic material may be contacted with the aqueous acid solution in step (a) for at least 30 minutes, including without limitation, from about 12 hours to about 24 hours.
  • the lignocellulosic material may be contacted with the aqueous acid solution in step (a) under heat.
  • the lignocellulosic material may be contacted with the aqueous nitric acid solution in step (a) at a temperature from about 50 °C to below the boiling point of the nitric acid.
  • the temperature during the second heating stage of step (b) may be, without limitation, from about 73 °C to below 100 °C or from about 90 °C to about 95 °C.
  • the temperature during the first heating stage of step (b) may be, without limita- tion, up to about 75 °C, from about 50 °C to about 75 °C, from about 60 °C to about 70 °C, from about 50 °C to about 60 °C, or from about 70 °C to about 75 °C.
  • the first heating stage in step (b) may be carried out for at least 15 minutes.
  • the aqueous alkaline solution may comprise sodium hydroxide or potassium hydroxide or a combination of sodium hydroxide and potassium hydroxide.
  • the aqueous alkaline solution may comprise an amount of alkali solute which is at least the normal equivalent of the nitric acid in the aqueous acid solution in step (a).
  • the aqueous alkaline solution may comprise an amount of alkali solute which is at least the molar equivalent of the nitric acid in the aqueous acid solution in step (a).
  • the acid used in step (e) may be sulfur ic acid.
  • the amount of acid added in step (e) may be at least the molar amount of the alkali in the aqueous alkaline solution in step (c).
  • the amount of acid added in step (e) may be at least the normal amount of the alkali in the aqueous alkaline solution in step (c).
  • the black liquor may cooled from the temperature in step (c) before the acid is added in step (e).
  • the temperature of the black liquor when the acid is added in step (e) may be, without limitation, up to about 75 °C, from about 5 °C to about 75 °C, from about 5 °C to about 50 °C, from about 25 °C to about 50 °C, or from about 50 °C to about 75 °C.
  • Any aqueous acid solution not absorbed by the lignocellulosic material in step (a) may be removed prior to heating the lignocellulosic material in step (b).
  • the methods may comprise collecting any aqueous acid solution which is removed prior to step (b) and recycling the collected aqueous acid solution for use in step (a), and comprising collecting any acid which is distilled off in step (b) and recycling the collected acid for use in step (a).
  • the starting moisture content of the lignocellulosic material may be from about 30% to about 55% by weight of water.
  • the method may comprise contacting the lignocellulosic material with water before step (a) to increase the moisture content in the lignocellulosic material.
  • the starting lignocellulosic material may comprise, without limitation, wood chips, wood shavings, sawdust, pieces of rye, wheat, hemp and combinations of two or more of the foregoing.
  • the starting lignocellulosic material may comprise undigested lignocellulosic material previously subjected to the method.
  • An amber liquor may be left following the removal of the lignin, and the method may comprise processing the amber liquor after the lignin has been removed, for example, to produce unicellular proteins or alcohols or both. Any water which is produced as a reaction byproduct in one or more of the steps in the method may be collected and recycled for use in the method. Steps (a) and (c) and the first heating stage in step (b) may each carried out at a temperature from about 50 °C to about 75 °C.
  • One or more of the heating of the impregnated lignocellulosic material in step (b), the contacting the lignocellulosic material with the aqueous alkaline solution in step (c) and the adding the acid in step (e) may be carried out with agitation.
  • the methods may be carried out at atmospheric pressure.
  • the pulp removed in step (d) may be washed, pressed, bleached and dried.
  • the lignin removed in step (f) may be dried. Any residual liquor that is removed from the pulp by pressing may be collected and added to the black liquor prior to adding the acid in step (e). Similarly, any residual liquor which is removed from the lignin during drying may be collected and added to the liquor after step
  • Enough acid may be added to the solution in step (e) to lower the pH of the solution to an acidic pH.
  • step (c) may be carried out at a temperature up to about 75 °C, from about 5 °C to about 75 °C, from about 50 °C to about 75 °C, from about 20 °C to about 50 °C, from about 30 °C to about 40 °C, or from about 40 °C to about 50 °C.
  • Step (a) may comprise immersing the lignocellulosic material in the aqueous acid solution in step (a), or spraying the lignocellulosic material with aqueous nitric acid solution.
  • the invention provides for methods for producing pulp and lignin from lignocellulosic material, the pulp comprising cellulose, the methods comprise: (a) contacting the lignocellulosic material with an aqueous nitric acid solution to impregnate the lignocellulosic material, the aqueous nitric acid solution comprising from about 10% to about 40% by weight of the nitric acid; (b) heating the impregnated lignocellulosic material in two stages, the first heating stage being carried out a temperature from about 50 °C to about 75 °C for a period of time which is sufficient to depolymerize lignin within the lignocellolosic material without substantially degrading the cellulose or lignin in the ligncellulosic material, the second heating stage being carried out at or above the boiling point of the nitric acid to distill off the nitric acid; (c) contacting the lignocellulosic material with an a
  • the invention provides for methods for producing pulp and lignin comprising the steps of contacting lignocellulosic material with an acid and, after removing any acid not absorbed by the lignocellulosic material, heating the lignocellulosic material at a temperature up to about 75 °C to effect the acid- catalyzed hydrolytic depolymerization of the lignin in the lignocellulosic material without substantially degrading the cellulose or lignin in the lignocellulosic material, the acid-contacting and heating steps being carried out before the lignocellulosic material is digested in an alkaline liquor, the pulp being removed following the digestion of the lignocellulosic material in the alkaline liquor, the lignin being removed after being precipitated out with the addition of an acid to the black liquor produced following the digestion of the lignocellulosic material in the alkaline liquor, wherein the pulp comprises cellulose.
  • the acid-contacting step may comprise immersing the lignocellulosic material in an aqueous solution of the acid, and wherein the acid is nitric acid and the aqueous solution comprises from about 10 % to about 40 % by weight of nitric acid.
  • the lignocellulosic material may be heated, after depolymerizing the lignin but before digesting the lignocellulosic material, at a temperature above the boiling point of the acid in order to distill off the acid.
  • the invention provides methods for treating lignocellulosic material comprising: (a) contacting the lignocellulosic material with an aqueous acid solution to impregnate the lignocellulosic material, the aqueous acid solution comprising from about 10% to about 40% by weight of the acid; (b) heating the lignocellulosic material in two stages, the first heating stage being carried out for a period of time which is sufficient to depolymerize lignin within the lignocellolosic material without substantially degrading the cellulose or lignin in the ligncellulosic material, the second heating stage being carried out at or above the boiling point of the acid to distill off the acid, wherein any aqueous acid solution not absorbed by the lignocellulosic material in step (a) is removed prior to heating the lignocellulosic material in step (b); (c) contacting the lignocellulosic material with an aqueous alkaline
  • the invention provides methods for producing pulp and lignin from lignocellulosic material, the pulp comprising cellulose, the methods comprising: (a) contacting the lignocellulosic material with an aqueous nitric acid solution to impregnate the lignocellulosic material, the aqueous acid solution comprising from about 10% to about 40% by weight of the nitric acid; (b) heating the lignocellulosic material in two stages, the first heating stage being carried out for a period of time which is sufficient to depolymerize lignin within the lignocellolosic material without substantially degrading the cellulose or lignin in the ligncellulosic material, the second heating stage being carried out at or above the boiling point of the acid to distill off the acid, wherein any aqueous acid solution not absorbed by the lignocellulosic material in step (a) is removed prior to heating the lignocellulosic material in step (b
  • Figure 1 is an illustration of the mechanism of acid-catalyzed hydrolysis of an ester
  • Figure 2 is a schematic illustration of a method according to the present invention.
  • the invention includes methods involving contacting lignocellulosic material with an acid, preferably nitric acid, in order to impregnate the lignocellulosic material and then heating the lignocellulosic material to de-polymerize the lignin within the lignocellulosic material prior to digesting the lignocellulosic material in an alkaline solution to solubilize lignin in the alkaline solution, leaving a black liquor (comprising the solubilized lignin) and pulp.
  • the pulp is then removed and processed (e.g. pressing, washing, bleaching, drying).
  • the solubilized lignin is precipitated out of the black liquor with the addition of an acid and then removed for processing.
  • the remaining solution can be further processed to produce other useful by-products such as unicellular proteins, alcohols or both.
  • lignocellulosic material refers to any material which contains cellulose and lignin and, without limitation, includes pieces or particles (for example wood chips, wood shavings, sawdust) from any type of tree (for example pine, oak, maple, fir, spruce) and other vegetative material (for example rye, wheat , hemp) and combinations thereof.
  • impregnating refers to the absorption of an impregnating material by lignocellulosic material.
  • impregnating wood chips can be accomplished by immersing or soaking the wood chips in a sufficient volume of the impregnating material (e.g. nitric acid solution) to saturate all or part of the wood chips.
  • a sufficient volume of the impregnating material e.g. nitric acid solution
  • spraying could also be used to accomplish the impregnation.
  • the hydroxyl (-OH) groups can react with each other or with the aldehyde or ketone groups.
  • a ether linkage is formed when a hydroxyl group reacts with another hydroxyl group, a hemiacetal is formed when a hydroxyl group reacts with an aldehyde and a ketal is formed when a hydroxyl group reacts with a ketone.
  • Lignin molecules are three- dimensional and heavily cross-linked.
  • a typical lignin molecule can have a molecular weight of about 15,000 amu.
  • Lignin molecules are susceptible to harsh chemical concentrations and temperature exposure.
  • a lignin polymeric matrix may be broken down at temperatures as low as 100°C. Lignin is unstable, light sensitive, and breaks down into acid compound as it ages, and its presence in paper items contributes to their degradation over time.
  • the present invention utilizes the acid-catalyzed hyrolysis of lignocellulosic material.
  • the lignin within lignocellulosic material includes ester functional groups.
  • Figure 1 illustrates the mechanism of the acid-catalyzed hydroly- sis of an ester.
  • the rate of ester hydrolysis is very slow because their leaving groups are basic. The rate can be increased by the presence of a catalyst, such as an acid. In such an acid catalyzed reaction all organic reactants, intermediates, and products are positively charged.
  • the following steps take place within the hydroly- sis of the ester:
  • the carboxylic acid product obtained in (F) is a de-polymerized form of lignin. Because water (H 2 0) and methanol (CH 3 OH) have approximately the same basicity, it will be equally easy for the tetrahedral intermediates to collapse to reform the ester as it would be for the formation of the carboxylic acid. Hence, at equilibrium both the ester and the carboxylic acid will be obtained. However, an excess of water will shift the equilibrium towards the formation of the carboxylic acid product, de-polymerized lignin. Thus, methods of the present invention will render higher yields with the addition of water and, for this reason, it is possible to use lignocellulosic material which has a relatively high moisture content (e.g. "green" wood chips) or which has been previously contacted with water in order to increase the moisture content prior to impregnating the lignocellulosic material with the acid.
  • lignocellulosic material which has a relatively high moisture content (e.
  • the ability to use lignocellulosic materials with a relatively high moisture content in the present invention is an advantage compared to existing Kraft type pulping processes.
  • many existing processes it is necessary to dry wood chips prior to pulping in order to remove or reduce moisture to meet stringent requirements.
  • chips are preferred in many existing processes on a BDU (bone dry unit) basis. Requiring a drying step adds expense to such processes.
  • the present invention overcomes this disadvantage since "wet" starting materials can be used, thus removing the need to dry the wood chips or other starting materials.
  • excess water drives the depolymerization reaction to favor the formation of a carboxylic acid instead of collapsing to reform an ester, additional moisture in the chips improves yields in methods according to this invention.
  • the lignocellulosic material is digested in the presence of an alkali such as sodium hydroxide (NaOH) and/or potassium hydroxide (KOH).
  • the positive cations K + or Na + or another suitable ion
  • the hydrogen cation then bonds with the negatively charged hydroxyl ion to form water.
  • the lignin is then water-soluble and drops into solution, thereby separating the dissolved lignin from the cellulose-containing pulp. Due to more modest temperature, pressure and reactant concentrations involved, the lignin and cellulose produced are subject to less degradation than products obtained through a Kraft type process, thereby providing increased yield and purity.
  • FIG. 2 is a schematic illustration of a method 10 according to the present invention.
  • Lignocellulosic material such as wood chips (not shown) is used as the starting raw material in an impregnating tank 12.
  • the wood chips are prepared by chipping wood into a convenient size, for example, chips of roughly 0.5 - 2.0 inches in diameter. This can be done with a standard mill. Other sizes and shapes of lignocellulosic material can be used.
  • “green" wood chips are used, or in other words, chips having a starting moisture content of approximately 30 - 55%, or even higher, by weight of water.
  • a pre-treatment stage could be utilized wherein the wood chips were immersed or otherwise contacted with water prior to being placed in the impregnating tank in order to increase the moisture content within the chips up to or beyond 30 - 55% by weight of water, though this step is not necessary to produce lignin, pulp and other ancillary products according to this invention.
  • Impregnating bone dry chips with an acid solution could be done, but this will result in higher consumption rates of the acid impregnant, thereby increasing costs.
  • Wood chips are loaded into impregnating tank 12 where they are contacted with an acid in order to impregnate the wood chips with the acid.
  • the acid is preferably provided within an aqueous solution, and in such a case, the acid impregnates the wood chips as part of the solution. That is, the wood chips absorb both acid and water.
  • the aqueous solution comprises from about 10% to about 40% by weight of the acid.
  • the invention also includes utilizing other, narrower acid concentration ranges within this range.
  • the aqueous acid solution may comprise from about 15% to about 30%, from about 10% to about 25%, from about 10% to about 15%, or from about 20% to about 25 % , by weight of the acid.
  • the aqueous acid solution is provided to impregnating tank 12 from acid solution tank 14 in a sufficient volume to immerse the wood chips.
  • the acid used is preferably nitric acid, but those skilled in the art will appreciate that other acids could instead be used within the scope of the present invention. Nitric acid is used herein for illustration purposes.
  • the wood chips are impregnated by allowing them to soak in the aqueous nitric acid solution in the impregnating tank 12.
  • the impregnation time may last for as little as 30 minutes or less and may extend for any length of time before the degradation of the wood chips begins to occur. For example, impregnation may last from about 2 hours and 45 minutes to about 48 hours. It is contemplated that the impregnation time may fall within a narrower time ranges such as, for example, from about 12 to about 24 hours and ranges within this range.
  • Heating the chips during the impregnation step may decrease the impregnation time.
  • impregnation of the wood chips could occur from about 30 minutes or less to about 13 hours with the addition of heat, or up to 48 hours or longer, without the addition of heat.
  • Heating during impregnation can be achieved by any number of well known techniques that could be used to heat the wood chips within impregnating tank 12.
  • the exterior of impregnating tank could be heated with steam to heat the tank 12.
  • any excess nitric acid solution is removed from the wood chips, by drainage for example, and passed to spent solution tank 16. Any collected excess nitric acid solution may then be recycled for use in the impregnating tank 12.
  • any excess nitric acid solution is filtered and purified using conventional techniques before being reconstituted back up to strength.
  • Filtration and/or purification could be accomplished by passing any spent nitric acid solution from spent acid solution tank 16 to a conventional filtration and/or purification apparatus (not shown) before the solution is passed to acid solution tank 14.
  • a conventional filtration and/or purification apparatus not shown
  • the impregnated wood chips are then passed to a heating tank 18. This transfer can be accomplished by gravity feed, if impregnating tank 12 is located above the heating tank 18, or by a suitable transfer mechanism if not.
  • the impregnated chips are heated within heating tank 18.
  • the exterior of heating tank 18 is heated with steam produced by steam boiler 20, thereby heating the chips within heating tank 18.
  • Heating of the chips in heating tank 18 may be carried out in two heating stages; the first heating stage to depolymerize the lignin within the wood chips without substantially degrading the cellulose or lignin, and the second heating stage to distill off the acid following depolymerization of the lignin.
  • the distilled off nitric acid is recycled for use in the impregnation stage.
  • the distilled off nitric acid is collected and passed to a condenser 22 and then to spent solution tank 16 to be reconstituted to a desired strength and then passed back to nitric acid tank 14 for eventual use in impregnating tank 12.
  • the nitric acid attacks the cross-links or ester groups of the lignin polymeric matrix during the first heating stage.
  • the first heating stage is carried out for a period of time which is sufficient to depolymerize the lignin within the wood chips without substantially degrading the cellulose or lignin.
  • the first heating stage is carried out at a temperature up to about 75 °C, but above the freezing point of the aqueous acid solution It is within the scope of the invention for the first heating stage to be carried out within a narrower temperature range, for example from about 50 °C to about 75 °C, from about 50 °C to about 60 °C, from about 70 °C to about 75 °C, or from about 60 °C to about 70 °C, when nitric acid is used as the impregnating acid. It is desirable to maintain these more modest temperatures (relative to Kraft pulping temperatures) in order to prevent the unwanted degradation and destruction of the lignin and cellulose within the wood chips, thus providing improved product yield and purity.
  • heating tank 18 is fitted with an agitator 24 to provide agitation during the heating of chips within heating tank 18. Aggressive agitation by agitator 24 . helps to both bring about a homogeneous temperature within heating tank 18 and to begin breaking apart the fibers in the wood chips.
  • the temperature is then brought above the boiling point of the acid for a sufficient time (for example, 30 minutes) to distill off the nitric acid.
  • a sufficient time for example, 30 minutes
  • the temperature of the boiling point of the acid in this stage may depart slightly from the temperature that one would expect the acid to boil. This discrepancy results from various factors including the interaction of the acid with the wood, the moisture content within the wood, and, for nitric acid, the formation of azeotropes with water.
  • some scientific literature establishes the boiling point of nitric acid to be 83 °C
  • the inventor has observed boiling for nitric acid with wood chips as low as 73 °C.
  • the temperature of the second heating stage within heating tank 18 be at least about 73 °C where nitric acid is utilized.
  • the second heating stage could be carried out from about 73 °C to below 100 °C.
  • narrower ranges for example from about 90 °C to about 95 °C, within this larger range.
  • the amount of time for the first and second heating stages will vary depending upon a number of factors, including the particular temperatures involved.
  • the first heating stage may be carried out for as little as 15 minutes, and could be carried out for a longer period of time.
  • the wood chips are then transferred to a digester 26.
  • a caustic solution or in other words, an aqueous alkaline solution wherein the solute is an alkali such as sodium hydroxide, potassium hydroxide, or a combination of these.
  • the wood chips are contacted with the aqueous alkaline solution under heat to solubilize the lignin in the solution.
  • the resultant solution is darker in color due to the solubilized lignin and is thus referred to as black liquor.
  • This digestion step thereby separates the lignin and the black liquor from the pulp.
  • the alkaline solution is provided to digester 26 from caustic solution tank 28.
  • the concentration of the alkaline solution is such to just make the lignin water soluble. This is accomplished by the positive cations (K + or Na + or another suitable ion) attaching to the exposed cleavage sites on the lignin monomers and the lignin then dissolving into the water.
  • the temperature during the digestion stage is preferably up to about 75 °C, but above the freezing point of the aqueous alkaline solution. It is however within the scope of the invention to increase the temperature above 75 °C up to the boiling point of the alkaline solution.
  • the alkaline solution comprises an aqueous sodium hydroxide solution
  • the digestion stage prefferably be carried out within a narrower temperature range, for example, from about 5 °C to about 75 °C, from about 50 °C to about 75 °C, from about 20 °C to about 50 °C, from about 30 °C to about 40 °C, or from about 40 °C to about 50 °C.
  • Heat is provided to digester 26 by heater 30, which may be any conventional apparatus or arrangement for providing heat to the digester 26.
  • Digester 26 may be fitted with an agitator 32 to provide agitation during the digestion of the chips.
  • Aagitation helps to bring about a homogeneous temperature within the digester 26 and to break up the wood chips. Agitation also increases the rate that the cation (e.g. K + , Na + , etc.) binds to the exposed lignin cleavage sites thus minimizing any possible caustic action on the cellulose.
  • the cation e.g. K + , Na + , etc.
  • the alkaline solution may include an amount of alkali which is at least the normal equivalent of the nitric acid in the solution used in the impregnation stage. Adding excess alkali will increase costs by requiring more acid to be added at a later step. Further, the alkali concentration in the aqueous alkaline solution should be main- tained below 17.5% by weight of the solution since beta and gamma cellulose dissolve at this level.
  • the resultant pulp (containing cellulose) and black liquor (containing solubilized lignin) is transferred to pulp tank 34 .
  • the black liquor is removed, for example by drainage, and transferred to black liquor tank 36.
  • the cellulose-containing pulp is then processed according to the user's needs. Typically, processing would involve washing, pressing, bleaching and drying the pulp following the separation from the black liquor.
  • the pulp would be pressed in a pulp press 38 to remove any residual black liquor (which would also be transferred to black liquor tank 36), and then bleached and dried with bleaching apparatus 40 and dryer 42.
  • Bleaching apparatus 40 and dryer 42 could be any conventional known apparatuses for these purposes.
  • the lignin is precipitated out of the black liquor in black liquor tank 36 after the addition of an acid from acid solution tank 44.
  • the acid added is a mineral acid, such as sulfuric acid.
  • the acid added to the black liquor strips off the cation from the caustic solute, thereby precipitating out the lignin and a caustic salt (e.g. where sulfuric acid is used, the salts Na ⁇ O ⁇ K 2 SO 4 , or other similar salts depending upon the alkali solute used in digestion, would result).
  • Addition of the acid to the black liquor lowers the pH of the liquor until it is just slightly acidic.
  • the acid may be added to the black liquor within an aqueous solution.
  • Black liquor tank 36 may be fitted with an agitator 46 to provide agitation during the addition of the acid from tank 44.
  • the contents of black liquor tank 36 may be cooled, for example by cooler 48, in order to faciliate the precipitation of lignin.
  • Cooler 48 can be any known apparatus for cooling purposes.
  • the black liquor may be cooled from the digestion temperature before the addition of the acid. Preferably the temperature is up to about 75 °C, but above the freezing point of the black liquor.
  • the precipitated lignin can then be removed from the resultant amber liquor (which is lighter in color than the black liquor due to the removal of the lignin) and processed using any conventional technique.
  • the resultant amber liquor and lignin slurry may be passed from black liquor tank 36 through a lignin filter 50, with the lignin then being transferred to a lignin dryer 52 and dried at temperatures that will not degrade the lignin.
  • the resultant lignin contains natural form lignin.
  • the filtrate passing through lignin filter 50 is the amber liquor, which is then transferred to an amber liquor tank 54. Any residual amber liquor removed during the drying of lignin in lignin dryer 52 is also transferred to amber liquor tank 54, as illustrated in Figure 2.
  • Amber liquor is an aqueous solution containing starches, sugars, and other minerals and compounds found in plants that are not cellulose or lignin.
  • amber liquor tank 54 the amber liquor can be processed to yield various other products of value including alcohols, unicellular proteins or both.
  • the amber liquor could be used as a starting culture for various bacteria to produce various products, such as ammal feeds and alcohols.
  • Amber liquor tank 54 may be fitted with an agitator 56 to provide agitation if desired.
  • Any proteins produced during the processing of the amber liquor may be removed by filtration (via protein filter 58) and dried (via protein dryer 60). Suitable apparatus modifications and/or additions could be made to accommodate alcohol processing and/or the production of other desired end products.
  • the final filtrate can be recovered and treated in water treater 62 to remove any contaminants, thereby allowing the recycling of water within various steps in the method, for example in reuse in washing in pulp tank 34, preparation of the alkaline solution in caustic solution tank 28 and in steam boiler 20. Any recovered water could also be used in steam boiler 20 or in the preparation of the aqueous acid solutions in acid solution tank 14 and/or acid solution tank 44.
  • wet starting materials can be used. Since water is essential to the hydrolysis of the lignocellulosic material, this removes the need to dry the starting materials prior to the pulping process, thus resulting in lower costs relative to certain existing pulping methods.
  • the method of the present invention does not require added pressure, but may be carried out at atmospheric pressure. This reduces costs relative to certain existing pulping methods, as does the fact that the method of the present invention does not require the addition of heat at temperatures approaching those used in typical Kraft type pulping processes. 3) Weak concentrations of strong acids and strong bases may be used, thereby minimizing raw material costs and degradation of final products.
  • the acid catalyst can be recovered and recycled for reuse, allowing im- proved cost efficiency. These factors also allow a closed system, minimize pollution, and therefore environmental impact. Very little pollution is caused by methods according to this invention.
  • Water used in the method may be recovered in saleable byproducts (such as alcohols and animal feeds) treated and reused or vented as steam, with suitable apparatus and process modifications.
  • the vented steam could be used in providing energy for the method, thereby eliminating even this small loss of water.
  • the method is flexible in terms of starting materials.
  • the ability to process a wide variety of lignocellulosic material without retooling any apparatus or changing the methods involved gives flexibility in pulp production.
  • mills are typically designed to produce specific pulp types and utilize specific wood species as raw materials.
  • most Kraft mills require chips meeting stringent quality specifications to remain economically viable.
  • the present method may utilize not only any number of differently sized chips, but also sawdust, and also chips that would be considered "green” and unusable by current pulp mill standards.
  • the flexibility pro- vided by methods of this invention eliminates or simplifies the need for chip mills designed to produce chips of stringent standards, thereby offering the potential for lower operating and capital costs.
  • the yield of alpha cellulose is high using the method, while the method also allows for a high yield of lignin, which is a valuable component itself.
  • lignin which is a valuable component itself.
  • other useful and potentially valuable byproducts may be recovered using methods of this invention.
  • the amber liquor is suitable for fermentation of unicellular protein following precipitation and removal of lignin.
  • the protein can be used in animal feeds or for research purposes.
  • Methods of the invention may be applied to different sized and configured apparatuses, thereby improving the flexibility of use.
  • Mills utilizing a method of the present invention will be highly efficient, with lower operating costs than mills using typical Kraft pulping processes.
  • This example comprises 19 trials which were run to illustrate the yields of pulp and lignin obtained using methods according to this invention, and also to illustrate the recovery of the acid used in the impregnation stage.
  • the starting lignocellulosic material in Trials 1 - 18 comprised 200 grams of a mixture of hardwood and softwood wood chips obtained from a sawmill and chip mill operation in Kelowna, British Columbia, Canada. 600 grams of wood chips were used as the starting material in Trial 19. All of the different species of trees that the chips originated from were not ascertained, but at least some of the chips came from Ponderosa Pine, Douglas Fir, Maple, Oak and Spruce.
  • the moisture content of the wood chips was between 35 - 50 % water by weight.
  • the moisture content was calculated by drying separate samples of the wood chips (which were not subjected to the steps of the method) and measuring the weight difference in the wood chips following the drying step.
  • the acid used in the impregnating step was nitric acid (HNO 3 ).
  • Nitric acid solu- tions were prepared by diluting an amount (chosen depending upon the strength of solution desired) of 70% (w/w) nitric acid with distilled water.
  • 1 L of an aqueous nitric acid solution was used in the impregnating step, with the exception that Trials 17 and 18 each used 750 mL, and Trial 19 used 2250 mL.
  • a 2500 mL beaker sealed with laboratory film was used as the impregnating tank.
  • nitric acid solution was removed from the wood chips before they were heated in the heating step.
  • the heating step was carried out in a 2000 ml round bottom triple neck boiling flask, which was fitted with a distillation setup so that nitric acid distilled out in the heating step would be collected.
  • samples from the excess acid solution collected following the impregnating step and from the distilled nitric acid which was collected during the heating step were each titrated using a 10% (w/w) % solution that was prepared by dissolving 100 g NaOH in distilled water and topped up in a 1 L volumetric flask.
  • Titration of the excess nitric acid solution collected from after the impregnation step permitted the calculation of the number of moles of nitric acid recovered after the impregnating step, which in turn permitted the calculation of the number of moles of nitric acid which were absorbed by the wood chips, since the moles of nitric acid in the initial 1 L solution was known.
  • the chips were digested in a round stainless steel tank with a 9.283 liter capacity (22.86 cm diameter, 11.43 cm height).
  • the alkaline solution used in digestion was prepared by diluting an amount of 2.5 molar sodium hydroxide (NaOH) solution, 2.5 molar potassium hydroxide (KOH) solution, or a combination thereof, with distilled water.
  • Various volumes of the initial 2.5 molar solutions were added to make the final alkaline solution used in digestion and various volumes of the final alkaline solution prepared were used for the various trials.
  • the moles of each alkali solute(s) and the total volume of the aqueous alkaline solution prepared for Trials 1 - 19 are found in Tables 1 - 5.
  • the black liquor (containing solubilized lignin) was vaccum filtered in a buchner funnel without filter paper to remove the pulp, which was washed with distilled water and then air-dried at room temperature and weighed.
  • the black liquor was transferred to a 2500 mL beaker, where the lignin was precipitated with the addition of a sulfuric acid (H 2 SO 4 ) solution.
  • the sulfuric acid solution was prepared by diluting an volume (depending upon the concentration sought) of pure sulfuric acid in a 1 L volumetric flask with distilled water.
  • the temperature of the black liquor was allowed to cool from the digestion step for the lignin precipitation step. The various temperatures are shown in Tables 1 - 5.
  • the lignin was vacuum filtered in a buchner funnel without filter paper and thus removed from the amber liquor. The lignin was air-dried at room temperature and weighed. The lignin was not however dried and weighed for Trials 17 and 18. In these trials, the lignin did precipitate and was, by visual inspection, found to have a similar relative amount and appearance as the lignin produced in Trials 1 - 16.
  • heat was applied during the heating and digestion steps and in five trials, during the impregnation step. Where so indicated, the heat was supplied in various steps by using a heating mantle made by Glas-Col Apparatus Co., Cat 10 0-410, having 465 total watts and 110 volts.
  • the mantle controller was a Powerstat variable autotransformer, Type 3PN116B, made by The Superior Electric Co. of Bristol, Conn. Agitation was provided during the digestion step by a cold steel impeller which was 8 inches in diameter with 1/2 inch separation between 45 ° offset blades. A 18 volt DEWALTTM XRP cordless drill was used to power the agitator. Agitation was provided during the lignin precipitation step by manual stirring using a glass stir rod for approximately 30 - 45 seconds in each trial.
  • This example comprised a trial that was similar to Trials 1 - 19 in example 1 except that the starting lignocellulosic material was 150 grams of shavings and sawdust from Hemlock, Oak and Pine tree species. Impregnation was done for 30 minutes in 15% (w/w) HNO 3 solution under heat of 50 °C. The impregnated shavings and sawdust were heated for 60 minutes between 50 - 75 °C, and then for 10 minutes over 80 °C. Following the heating step, the shavings and sawdust were contacted with an alkaline solution having 1.25 moles of NaOH and 2600 mL total volume at a temperature of 52 °C for 7 minutes.
  • lignin was precipitated with the addition of 20 % (v/v) H 2 S0 4
  • the pulp and lignin were not weighed, but a visual inspection showed satisfactory appearance and yield for each, proving that the method of this invention can be carried out with relatively small pieces of lignocellulosic material such as shavings and sawdust.
  • the present invention also includes pulp produced according to the methods herein, as well as paper products comprising cellulose from pulp produced according to the methods herein.
  • the present invention also includes lignin produced according to the methods herein, as well as numerous other products and compositions comprising lignin produced according to the methods herein, including for example, fertilizers, asphalt emulsif ⁇ ers, soil stabilizers, wood products (such as plywood and particle board), oil well drilling fluids and dispersing agents for preparing concrete.

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Abstract

L'invention concerne des procédés permettant de produire de la pâte à papier (comprenant de la cellulose) et de la lignine à partir d'une matière lignocellulosique, telle que des copeaux de bois. Lesdits procédés impliquent une hydrolise catalysée par un acide. La matière lignocellulosique qui possède une teneur en humidité relativement élevée peut être utilisée comme matière de départ. Ladite matière lignocellulosique est imprégnée d'acide (de préférence, d'acide nitrique) puis chauffée. Pendant le chauffage, la lignine est dépolymérisée à des températures relativement basses et le catalyseur acide est éliminé par distillation Ledit catalyseur acide peut être collecté et recyclé après imprégnation et chauffage. La matière lignocellulosique est ensuite digérée dans une solution alcaline soumise à un chauffage, ce qui permet de dissoudre la lignine et de retirer la pâte à papier. L'acide est ajouté à une liqueur noire afin de précipiter la lignine qui est ensuite retirée. La liqueur ambre résultante peut ensuite être traitée afin d'obtenir d'autres produits d'additifs tels que des alcools et/ou des protéines monocellulaires.
PCT/CA2003/001901 2003-06-03 2003-12-05 Procede de production de pate a papier et de lignine WO2004106624A1 (fr)

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WO2014101867A1 (fr) * 2012-12-31 2014-07-03 钟祥金汉江精制棉有限公司 Technologie de production de coton raffiné à ultra-haute viscosité et appareil de transport à sec pour la pâte de coton raffiné
EP4261343A1 (fr) 2022-04-13 2023-10-18 SCA Forest Products AB Conversion de résidus de biomasse en bio-huile
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