WO2015108409A1 - An integrated process for fractionation of oil palm empty fruit bunch and conversion of the cellulosic solid to ethanol - Google Patents

An integrated process for fractionation of oil palm empty fruit bunch and conversion of the cellulosic solid to ethanol Download PDF

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WO2015108409A1
WO2015108409A1 PCT/MY2015/050002 MY2015050002W WO2015108409A1 WO 2015108409 A1 WO2015108409 A1 WO 2015108409A1 MY 2015050002 W MY2015050002 W MY 2015050002W WO 2015108409 A1 WO2015108409 A1 WO 2015108409A1
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solid
organic acid
solid phase
process according
liquid stream
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PCT/MY2015/050002
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English (en)
French (fr)
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Soh Kheang LOH
Yuen May Choo
Zhao XUEBING
Liu DEHUA
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Malaysian Palm Oil Board
Tsinghua University
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Publication of WO2015108409A1 publication Critical patent/WO2015108409A1/en

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    • 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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention discloses an integrated process for fractionation of oil palm empty fruit bunch (EFB) to obtain cellulosic solid, hemicellulosic sugars and high-purity lignin, and conversion of the cellulosic solid to ethanol by enzymatic hydrolysis and microbial fermentation.
  • the end-products of the disclosed integrated process comprises cellulosic solid, hemicellulosic sugars, high-purity lignin and cellulosic ethanol.
  • Lignocellulose is one of the most abundant organic materials on the planet and has long been recognized as a potential feedstock for producing fuels, chemicals and materials.
  • biorefining of lignocellulosic biomass to produce multi-products has attracted great interest all over the world due to the shortage of fossil-based oil and increasing environmental pollution.
  • Lignocellulose is composed of carbohydrate polymers (cellulose and hemicelluloses) and an aromatic polymer (lignin), all of which show promising uses in a biorefinery platform.
  • Cellulose is a polysaccharide consisting of a linear chain of several hundred to over ten thousand ⁇ (1 ⁇ 4) linked D-glucose units. It can be used in many industrial applications, such as to make paper or other pulp-derived products.
  • the cellulose can also be converted into glucose which can be further used as carbon source for producing many fuels and chemicals, such as ethanol.
  • Hemicellulose is a diverse group of short-chain branched, substituted polymer of sugars with degree of polymerization ⁇ 70 to 200. After hydrolysis, the obtained constituent sugars (referred to herein as "hemicellulosic sugar”) can also be converted into fuels and chemicals by either biological or chemical ways, or a combination of both.
  • Lignin obtained from lignocellulosic biomass has value as a solid fuel and also as an energy feedstock to produce liquid fuels, syn-gas or hydrogen. It is also useful as an intermediate to make a variety of polymeric compounds and many other lignin-derived chemicals, such as vanillin, syringic acid, ferulic acid, etc.
  • lignocellulosic biomass It will be beneficial to fractionate lignocellulosic biomass and further utilize the resulting components respectively.
  • a major disadvantage of previous biomass fractionation technologies is that the process is usually conducted using high temperatures with associated high pressures.
  • the ethanol organosolv delignification process is usually conducted at higher than 160 °C in order to effectively remove lignin (Zhao et al., Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis"; Applied Microbiology and Biotechnology 82 (5): 815-827; 2009).
  • Another disadvantage associated with fractionation at high temperature relates to the degradation of fermentable sugars to other compounds such as furfural (Li et al., "Fractionating pretreatment of sugarcane bagasse by aqueous formic acid with direct recycle of spent liquor to increase cellulose digestibility - the Formiline process”; Bioresour Technol. 117:23 - 32; 2012).
  • Traditional biomass pulping to produce paper and related goods is also a biomass fractionation process, in which cellulose is recovered in high yields, but lignin is primarily consumed by combustion for heat recovery. Moreover, the lignin products are always not of high purity which limits its utilization.
  • '330 Publication disclosed a method for utilization of lignocellulose waste of palm oil production, first of all, empty fruit bunches (EFB) after separation of oil-bearing fruit.
  • the method for utilization is based on peculiarities of the structure of cell tissue of bunches and provides obtaining soluble sugars useful for ethanol production and obtaining solid fuel enriched in lignine.
  • '330 Publication disclosed a method which consists of several stages including conversion of polysaccharides (cellulose and hemicellulose) of lignocellulose feedstock into soluble sugars, biotechnological conversion of soluble sugars in methanol by microorganisms.
  • Malaysian Patent No. MY-142233-A (hereinafter referred to as '233 Patent) disclosed a process of producing ethanol from a fibrous lignocellulosic raw material.
  • SSF simultaneous saccharification and fermentation
  • the recovered cellulose is often recalcitrant to subsequent hydrolysis to form glucose.
  • the hydrolysis is often done enzymatically, and the resistance of the cellulose to hydrolysis is often compensated for by using high enzyme loading.
  • the objective of delignification is to remove lignin and maintain fiber strength and degree of polymerization (DP) of cellulose.
  • DP polymerization
  • Oil palm empty fruit bunch is a by-product of palm oil extraction and milling process.
  • EFB Oil palm empty fruit bunch
  • Malaysia has a ready source of biomass in EFB conveniently collected and available for exploitation in all palm oil mills.
  • As a lignocellulosic biomass EFB similarly shows many applications in various fields (Sumathi et al., "Utilization of oil palm as a source of renewable energy in Malaysia”; Renewable and Sustainable Energy Reviews 12(9):2404 - 2421 ; 2008).
  • EFB is fractionated into its primary components such as cellulose, hemicellulosic sugars and lignin, it would be used more easily in potentially distinct downstream process with more revenues.
  • One aspect of the present invention is to provide an integrated process for fractionation of oil palm empty fruit bunch (EFB) into cellulosic solid.
  • EFB oil palm empty fruit bunch
  • a further aspect of the present invention is to provide an integrated process for converting the said cellulosic solid into ethanol and specifically employing simultaneous saccharification and fermentation (SSF) process.
  • SSF simultaneous saccharification and fermentation
  • another aspect of the present invention is to provide a process for utilizing the produced spent liquor comprises lignin product and hemicellulosic sugars in more beneficial way via biological or chemical procedures which may include production of polymer substitutes or derivatives like surfactant.
  • FIG. 1 is the flow sheet of the integrated process for fractionation of EFB into cellulosic solid (pulp), hemicellulosic sugars and lignin
  • FIG. 2 is the graph showing enzymatic hydrolysis of cellulosic solid at different solid consistency characterized in the form of (a) Sugar concentration; (b) Enzymatic glycan conversion
  • FIG. 3 is the graph showing Simultaneous Saccharification and Fermentation (SSF) of cellulosic solid for ethanol production characterized independently in the form of (a) Glucose concentration during SSF; (b) Ethanol concentration during SSF
  • SSF Simultaneous Saccharification and Fermentation
  • FIG. 4 is the flow sheet of the general mass balance of fractionation of EFB for ethanol, lignin and hemicellulosic syrup production DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the present invention relates to an integrated process for fractionation of oil palm empty fruit bunch (EFB) to obtain cellulosic solid, hemicellulosic sugars and high-purity lignin, and conversion of the cellulosic solid to ethanol by enzymatic hydrolysis and microbial fermentation i.e. simultaneous saccharification and fermentation (SSF).
  • EFB oil palm empty fruit bunch
  • biomass pretreatment is a prerequisite step for effective saccharification of cellulose for producing glucose.
  • the objective of pretreatment is to increase cellulose accessibility and thus cellulase enzymes can contact cellulose to perform the hydrolysis process.
  • Conventional biomass pretreatment such as steam explosion, dilute acid pretreatment, hydrothermal pretreatment showed some merits to increase cellulose digestibility.
  • lignin is often of low quality and only can use as a fuel.
  • Organosolv pretreatment has been recognized as a promising biomass fractionation due to the following advantages: (1 ) organic solvents are always easy to recover by distillation and recycled for pretreatment; (2) the chemical recovery in organosolv pretreatment can isolate lignin as a solid material and hemicellulose as syrup, both of which show promise as chemical feedstocks; (3) the isolated lignin are of high purity, which can be used for polymer substitution and production of other high-value-added products.
  • the present invention provides a process for fractionation of oil palm empty fruit bunch (EFB) for producing cellulosic solid (pulp), hemicellulosic sugars and lignin as illustrated in FIG. 1 , and comprises the following steps:
  • the process advantageously produces cellulose pulp from EFB which can be further used for paper production.
  • the produced celluose is suitable for enzymatic hydrolysis into sugars, which can be further fermented into alcohols such as ethanol and/or butanol.
  • the said organic acid is selected from formic acid, acetic acid or propanoic acid; more preferably, the said organic acid is formic acid. Since organic acid, in particular formic acid and acetic acid have ⁇ value around 1 1 cal 1/2 /cm "3 2 , they are good solvents for lignin fragmentation. Moreover, the carboxyl group of organic acid can easily form hydrogen bond with lignin molecule, thus aqueous organic acids have high lignin solubility.
  • the FT dissociated from organic acid can play as a catalyst to accelerate the formation of lignin fragments and hydrolysis of hemicellulose.
  • an exogenous acid such as sulfuric acid or hydrochloric acid is unnecessary.
  • the used aqueous organic acid should have an organic acid concentration of 50-90%. Too low organic acid concentration is negative to lignin solubilization; however, too high organic acid concentration can lead to high acylation of cellulose, which can further affect the utilization of cellulose. More preferably, the organic acid concentration should not be higher than 90% by weight in order to control the acyl group content of lower than 5% by weight.
  • the organic acid concentration should not be less than 50% by weight, in order to obtain a high degree of delignification.
  • the obtained slurry is further separated.
  • the said separation process is performed by squeezing, filtration or centrifugation; more preferably, after separation the said solid phase contains dry solid mater of 20-50% by weight. It should be careful to control the liquid content of the obtained solid phase.
  • the liquid content should not be less than 50% (corresponding dry solid matter content higher than 50%); otherwise the mechanical pressing power would collapse the pore structure of the cellulosic solid, which whereby could decrease the cellulose digestibility.
  • the solid phase (2) In order to further remove the residual lignin fragments remaining in the said solid phase (2) obtained in step b), the solid phase (2) must be washed with fresh organic acid as shown in step c).
  • the said organic acid in step c) is selected from formic acid, acetic acid or propanoic acid; more preferably, the said organic acid is the same as that used for cooking in both organic acid type and concentration.
  • the said solid phase (2) cannot be directly washed with water in order to avoid the precipitation of dissolved lignin onto cellulosic fiber which will affect the subsequent enzymatic hydrolysis of cellulose.
  • the washing step can be conducted by either batch or continuous flow.
  • the solid phase (2) is washed with fresh medium comprising the same organic acid as that used in step a) in a counter flow or cross flow manner.
  • a separating step is performed as that used in step b) to obtain a solid phase (5).
  • the said solid phase (5) is wet with some residual organic acid that must be recovered.
  • the said solid phase (5) is heated under vacuum to recover the residual organic acid by evaporation and obtained an evaporated solid phase (7).
  • the evaporation temperature should be well controlled. Too high a temperature might cause significant hornification of the said cellulosic solid, and whereby decreases the subsequent enzymatic hydrolysis.
  • the evaporation is conducted at 20- 80 °C under pressure of 1 -13 kPa; more preferably, the recovery condition meets the demand that the said evaporated solid phase (7) has a liquid content of less than 5% by weight. By this evaporation process, more than 95% of the residual organic acid can be recovered.
  • the evaporated solid phase (7) still contains some residual organic acid, which might inhibit the microorganism growth in the subsequent fermentation process. Therefore, the said evaporated solid phase (7) is further washed with water to remove the residual organic acid.
  • the said washing process in step e) is conducted at 30-60 °C with water-to-solid ratio of 20-5:1 by weight. More preferably, the said washing process is conducted in a counter flow or cross flow manner.
  • This invention also comprises a step for recovering the organic acid from the spent liquor obtained in step b) and c).
  • the spent liquor contains dissolved lignin and sugars that mainly come from hemicellulose hydrolysis.
  • the said spent liquor is evaporated under vacuum to recover organic acid.
  • the spent liquor is distillated under vacuum to obtain the recovered fresh aqueous organic acid at the top as the top liquid stream (10) and a concentrated spent liquor stream (1 1 ).
  • the said top liquid stream (10) is further recycled to step a) for delignification of EFB and step c) for washing the said solid phase 2). More preferably, 90% of the organic acid in spent liquor should be recovered by distillation.
  • the concentrated spent liquor stream (1 1 ) is further treated for lignin and hemicellulosic sugar recovery.
  • Lignin can be easily precipitated from the concentrated spent liquor as a solid phase while hemicellulosic sugars are recovered as a liquid syrup.
  • the volume of the water added to the said concentrated spent liquor should be at least five times that of the concentrated spent liquor. More preferably, the water added to the concentrated spent liquor is the liquid stream (12) obtained in step e).
  • This invention also provides a process for converting the said cellulosic solid to ethanol comprising the steps of:
  • step b) adjusting the pH value of the said first slurry mixture obtained in step a) to 4.5-6.5 to obtain a second slurry mixture;
  • alkali is used to catalyze the deacylation process.
  • the said alkali is selected from sodium hydroxide, potassium hydroxide, lime or ammonia. More preferably, the said alkali is selected from lime or ammonia, since lime is cheap and ammonia can be used as nitrogen source for yeast growth.
  • the alkali loading is important to deacylation.
  • the used alkali loading is 0.1 -10% by weight based on the dry cellulosic solid.
  • liquid-to-solid ratio is also important since it can affect the alkali concentration for deacylation.
  • the liquid-to-solid ratio is 20-3:1 . More preferably, when alkali loading is low, a low liquid-to-solid ratio should be used, but the mixing might not be homogenous at a low liquid- to-solid ratio.
  • Deacylation temperature also significantly affects the degree of deacylation.
  • the temperature should be in the range of 20-120 °C.
  • the deacylation condition should meet the requirement i.e.
  • the treated cellulosic solid has an acyl group content of less than 1 % by weight based on dry matter.
  • the obtained slurry mixture showed excellent enzymatic digestibility for ethanol production by a SSF process.
  • the slurry mixture is preferably neutralized and its pH adjusted in the range of 4.5-6.5. More preferably, in most cases, since the released organic acid by deacylation process can react with the excess alkali, no other acid is required to adjust the pH value of the slurry.
  • the neutralized slurry is thus suitable for ethanol production.
  • the said SSF is conducted with 5-30 FPU/g solid of cellulase loading, at 30-40 °C and 5-20% solid consistency.
  • the cellularosic solid obtained by this invention showed very good enzymatic digestibility, and can obtain a high ethanol concentration. Removing most of the lignin by organic acid delignification not only eliminates the physical barrier of lignin, but also decreases the nonproductive adsorption of cellulase enzymes onto the residual lignin matrix. Moreover, the high cellulose content in the obtained cellulosic solid would increase glucose concentration in the enzymatic hydrolyzate, which whereby would increase the subsequent ethanol concentration. Increasing ethanol concentration has important significance for decreasing the energy consumption in ethanol recovery. A significant increase in energy demand is observed at an ethanol concentration below 4%. However, with the process provided by this invention, ethanol concentration can be higher than 5%, which is important to decrease the energy consumption for ethanol recovery.
  • the said hemicellulosic sugars obtained in the process provided are further utilized for the production of corresponding products by biological or chemical ways; more preferably, the said hemicellulosic sugars is converted to furfural and 5-(Hydroxymethyl)-furfural (5-HMF); most preferably, the said conversion of the hemicellulosic sugars to furfural and 5-HMF is employed under the catalysis of the residual organic acid and no additional mineral acids need to be added.
  • the obtained lignin product is of high purity and can be used for polymer substitution.
  • the present invention will be further illustrated by the following, non-limiting examples.
  • Example 1 fractionation with aqueous formic acid
  • the oil palm EFB's main chemical components were determined according to Laboratory Analytical Procedure (LAP) of National Renewable Energy Laboratory (Sluiter et al., Determination of Structural Carbohydrates and Lignin in Biomass, Technical Report NREL/TP-510-42618, 5 April, 2008). The results are shown in Table 1 .
  • the main chemical components of the dried pretreated solid are shown in Table 2. It can be calculated according to mass balance that after the treatment, 7.9% of cellulose, 89.32% of hemicellulose and 87.27% of lignin were respectively dissolved into the liquid phase, corresponding to 92.1 % of cellulose, 10.68% hemicellulose and 12.73% lignin recovered as solid phase. This result indicates that aqueous formic acid treatment can obtain a good degree of delignification and hemicellulose recovery.
  • Example 2 fractionation with aqueous acetic acid
  • the EFB used was the same as that in Example 1 .
  • the main chemical components of the dried pretreated solid are shown in Table 3. It can be calculated according to mass balance that after the treatment, 9.6% of cellulose, 73.4% of hemicellulose and 68.7% of lignin were respectively dissolved into the liquid phase, corresponding to 90.4% of cellulose, 26.6% hemicellulose and 31 .3% lignin recovered as solid phase.
  • This example indicates that aqueous acetic acid treatment also can obtain a satisfying degree of delignification and hemicellulose recovery.
  • the EFB used was the same as that used in Example 1 .
  • the EFB used was the same as that used in Example 1 .
  • 30 gram of EFB was packed in a 1 -L three-neck flask followed by addition of 300 ml 78% (by weight) formic acid.
  • the mixture was then heated to the normal boiling point at atmospheric pressure for 1 .5 hours.
  • a mechanical stirring was employed to ensure a good reaction.
  • the mixture was filtered to obtain a solid phase with liquid content of about 75%.
  • the obtained solid phase was first washed by 300 ml 78% (by weight) formic acid and then filtered to remove as much liquid as possible.
  • the solid was deformylated with 4% Ca(OH) 2 based on dry pulp weight at 120 °C for 1 hour.
  • the solid was washed with water until neutrality and stored at 4°C in a fridge prior to enzymatic hydrolysis.
  • the cellulosic solid was further digested by cellulase loading of 15 FPU/g solid at 50 ⁇ 0.5°C and pH 4.8 (0.1 M sodium acetate buffer) in an air-bath shaker at 130 rpm for 5 days.
  • the solid consistency was 2.5-10%.
  • the enzymatic digestibility of the cellulosic solid was described as enzymatic sugar concentrations and glycan conversion, which is respectively defined as follows:
  • Example 5 Simultaneous Saccharafication and Fermentation (SSF) of cellulosic solid for ethanol production
  • the EFB used was the same as that used in Example 1 .
  • the solid was washed with water until neutrality and stored at 4°C in a fridge prior to SSF.
  • the SSF was performed in 150-ml Erienmeyer flasks with 50 ml liquid medium.
  • the yeast used was Saccharomices cerevisiae CICC 31014.
  • the liquid medium contained 2 g/L (NH 4 ) 2 S0 4 , 5 g/L KH 2 P0 4 , 5 g/L yeast extracts, 1 g/L MgS0 4 and 0.2 g/L CaCI 2 .
  • the cellulosic solid was mixed with the liquid medium until the solid consistency was 15% (w/v) followed by sterilization at 121 °C for 20 min.
  • the EFB used was the same as that used in Example 1 .
  • FIG. 4 A general mass balance of fractionation of EFB for ethanol, lignin and hemicellulosic syrup production is illustrated in FIG. 4.
  • the present invention may be embodied in other specific forms without departing from its essential characteristics.
  • the described embodiments are to be considered in all respects only as illustrative and not restrictive.
  • the scope of the invention is, therefore indicated by the appended claims rather than by the foregoing description. All changes, which come within the meaning and range of equivalency of the claims, are to be embraced within their scope.

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WO2021024025A1 (en) * 2019-08-08 2021-02-11 Thai Eastern Pulp And Paper Co., Ltd. A hopper and a system for preparing empty fruit bunch fiber in a paper and/or pulp production process
WO2021024026A1 (en) * 2019-08-08 2021-02-11 Thai Eastern Pulp And Paper Co., Ltd. A method for preparing empty fruit bunch fiber in a paper and/or pulp production process
CN113026409A (zh) * 2021-03-29 2021-06-25 边静 一种利用棕榈纤维制生物无硫半化学浆的方法
WO2022235212A1 (en) * 2021-05-03 2022-11-10 Asia Pacific Resources International Holdings Ltd. Process for treating non-wood feedstock
CN116084198A (zh) * 2018-05-28 2023-05-09 皮尔森生物工程技术(北京)有限公司 用于从植物材料的有机酸预处理回收产物的有效方法和组合物
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