WO2019196165A1 - 一种连续分离木质纤维素组分的方法 - Google Patents

一种连续分离木质纤维素组分的方法 Download PDF

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WO2019196165A1
WO2019196165A1 PCT/CN2018/087760 CN2018087760W WO2019196165A1 WO 2019196165 A1 WO2019196165 A1 WO 2019196165A1 CN 2018087760 W CN2018087760 W CN 2018087760W WO 2019196165 A1 WO2019196165 A1 WO 2019196165A1
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aqueous solution
lignocellulose
alkali
cellulose
residue
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PCT/CN2018/087760
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English (en)
French (fr)
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应汉杰
唐成伦
朱晨杰
陈勇
单军强
张宇
李明
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南京高新工大生物技术研究院有限公司
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Publication of WO2019196165A1 publication Critical patent/WO2019196165A1/zh

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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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
    • 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
    • C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • 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
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/14—Disintegrating in mills
    • D21B1/18—Disintegrating in mills in magazine-type machines
    • D21B1/22—Disintegrating in mills in magazine-type machines with screw feed
    • 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

  • the invention belongs to the field of biochemical and bioenergy, and particularly relates to a method for continuously separating lignocellulose components.
  • Lignocellulosic resources which are an important component of renewable resources, are carriers of green plants that convert solar energy into chemical energy through photosynthesis. It can be converted into solid, liquid, gaseous fuels by physical, chemical or biological means, or it can be converted into a variety of chemical raw materials. At the same time, biomass is also the only renewable carbon source. Its effective utilization can realize the transformation from “Petrochemical Carbon” economy to “Photosynthetic Carbon” economy, and has positive significance for maintaining the carbon balance of the ecological environment.
  • Lignocellulose forms the cell wall of the plant and protects the cells. It is mainly composed of cellulose, hemicellulose and lignin. At present, the utilization of cellulose, hemicellulose and lignin has been thoroughly studied and many industrialization results have been achieved. However, the current utilization method is only to separate and utilize the single component of lignocellulose. For example, in the typical cellulosic ethanol industry, patents CN101509018 and CN101525636 use steam explosion to pretreat lignocellulosic feedstock, which improves the enzymatic hydrolysis efficiency of cellulose and hemicellulose, but neglects that the separation and extraction of lignin is more favorable for cellulose.
  • Patent CN103790056A uses a double screw extruder to pretreat lignocellulose, which is only a single component of lignocellulose separation, which improves the efficiency of enzymatic saccharification, but the cellulase efficiency under the condition of simultaneous cellulose and hemicellulose Decreased, the enzymatic hydrolysis time is prolonged. Therefore, at present, the lignocellulose pretreatment technology is mostly a single component separation. Although the cellulose enzymatic hydrolysis efficiency is improved, the three components are not effectively utilized.
  • the technical problem to be solved by the present invention is to provide a method for continuously separating lignocellulose components to solve the problems of the prior art and the like.
  • a method for continuously separating lignocellulosic components comprising the steps of:
  • step (3) transporting the alkali-removing material obtained in the step (2) to the continuous cooking reactor, introducing steam into the steam for cooking, and discharging the blasting to collect the materials;
  • the sprayed material obtained in the step (3) is sent to a screw extruder, and the residue is squeezed to obtain a hemicellulose hydrolyzate and a cellulose-containing residue.
  • the straw is chopped, washed with water, and the washing water is filtered and sedimented, and then subjected to anaerobic treatment after circulating a plurality of batches.
  • the lignocellulose is straw and/or various kinds of agricultural and forestry lignocellulosic processing wastes; wherein the straw is a common crop straw such as corn stover, wheat straw, rice straw, sorghum straw, agricultural and forestry wood.
  • Fiber processing waste is processing waste from forestry such as sugar cane, bamboo, Chinese fir, poplar, and pine.
  • the lignocellulose is previously treated into a section of 2 to 8 cm in length.
  • the washing refers to conveying the lignocellulose to the drum washing machine to clean the sediment and the soluble matter, and the washing water is filtered and then used for anaerobic treatment after circulating a plurality of batches.
  • the washed lignocellulose is extruded to free water and then fed into a twin screw extruder.
  • the alkaline agent is a combination of any one or a combination of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous potassium carbonate solution.
  • the alkaline agent has a concentration of 2 to 12% by weight.
  • the mass of the alkaline agent is 1 to 20%, preferably 4 to 12%, based on the dry weight of the lignocellulose.
  • the mass ratio of the lignocellulose dry weight to the water is 1:1 to 10, preferably 1:4.
  • the temperature in the holding chamber is 60 to 120 ° C, and the reaction time is 0.5 to 5 hours.
  • the reagent used for rinsing is water.
  • an acid solution is introduced into the continuous cooking reactor while introducing steam; wherein the acid solution is any one of a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, a phosphoric acid aqueous solution, an aqueous formic acid solution, and an aqueous acetic acid solution.
  • the concentration of the acid solution is 0.05 to 5 wt%, preferably 0.2 to 3 wt%; wherein the solid-liquid ratio of the dry weight of the lignocellulose to the acid solution is 1:2 to 10, preferably 1: 3.
  • the cooking temperature is 140 to 190 ° C
  • the cooking time is 20 min to 2 h
  • the cooking pressure is 0.3 to 1.3 MPa.
  • the present invention has the following advantages:
  • the invention can effectively separate the three major components of cellulose, hemicellulose and lignin, and can jointly produce high-purity lignin, hemicellulose hydrolyzate and highly dissociated cellulose.
  • the strong fiber dissociation ability and mixing ability of the double screw extruder greatly improve the catalytic efficiency of the chemical liquid.
  • the spiral displacement washing and de-alkali machine has high-efficiency de-alkali effect, and the water-saving effect is 50%-80% less than that of the conventional washer.
  • the single-spiral tubular reactor realizes continuous cooking compared with the kettle or the pot reactor, and improves the cooking efficiency.
  • the residue obtained by the invention has high cellulose content, high dissociation degree, large specific surface area, and greatly improved enzymatic saccharification effect.
  • Figure 1 is a schematic flow chart of the present invention.
  • composition of the straw was analyzed using the standard method of the American Renewable Energy Laboratory.
  • separation rate of hemicellulose, the lignin removal rate and the cellulose retention rate were calculated as follows:
  • M 0 is the hemicellulose content of a certain amount of M straw
  • M 1 is the hemicellulose content of the M amount of straw treatment
  • M 2 is the hemicellulose content of a certain amount of M straw
  • M 3 is the hemicellulose content of the M amount of straw treatment
  • M 5 is the cellulose content in a certain amount of M straw; M 4 is the cellulose content after the treatment of M amount of straw.
  • the apparatus used is as shown in FIG.
  • the lignocellulose is transported into the device by the straw conveyor, and the lignocellulose is washed with a drum washing machine, filtered through a filter, and then introduced into the twin screw extruder 4, and simultaneously passed from the chemical liquid feeding port 9 to the double screw extruder 4
  • the alkaline reagent is added; the filtered lignocellulose and the alkaline reagent are thoroughly mixed in the double screw extruder 4, and then enter the heat preservation device 5 for the heat preservation reaction; after the heat retention reaction is completed, the obtained material is transported by the conveyor 10 to
  • the spiral displacement washing and alkali removal machine 6 separates and obtains the lignin alkaline black liquor and the alkali-removing material after rinsing, and transports the alkali-depleted material to the vertical tower continuous digester 11 through the conveyor for cooking and cooking.
  • the obtained sprayed material is collected and sent to a screw extruder, and the residue is squeezed to obtain
  • the corn stalks are cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 5wt% NaOH aqueous solution was pumped in (the NaOH aqueous solution accounted for 10% of the dry weight of lignocellulose), and the alkaline catalyzed straw was obtained, and the heat preservation chamber was kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali-removing material is sent to the screw feeder in the front stage of the single-spiral tubular reactor to form a plug, and 180°C high-temperature steam is introduced into the reactor, and the high-temperature steam penetrates into the fiber, and the continuous cooking is performed for 60 minutes while maintaining the intermittent operation.
  • Continuous explosion the material is sprayed into the discharge bin 8, and the spray material is sent to a screw extruder, and the residue is squeezed to obtain a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 70%
  • the yield of xylose and oligosaccharide is 60%
  • the removal rate of lignin is 70%
  • the retention rate of cellulose is 96%
  • the proportion of cellulose in the residue is 65. %.
  • the corn stalks are cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 2wt% NaOH solution was pumped (the quality of NaOH water solution accounted for 4% of the dry weight of lignocellulose), and the alkaline catalyzed straw was obtained, and it was kept in the holding chamber for 30 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to a screw feeder in the front section of the single spiral tubular reactor to form a plug, and 140 ° C high temperature steam and 0.2 wt% sulfuric acid aqueous solution are introduced into the reactor (the quality of the solute sulfuric acid accounts for the lignocellulose dry Heavy 1%), high-temperature steam infiltrates into the fiber, and is continuously cooked for 30 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge bin 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 70%
  • the yield of xylose and oligosaccharide is 58%
  • the removal rate of lignin is 50%
  • the retention rate of cellulose is 96%
  • the proportion of cellulose in the residue is 68. %.
  • the corn stalks are cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 4wt% NaOH aqueous solution (the NaOH aqueous solution mass accounts for 8% of the dry weight of lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the heat preservation chamber is kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to a screw feeder in the front section of the single spiral tubular reactor to form a plug, and 160 ° C high temperature steam and 0.5 wt% sulfuric acid aqueous solution are introduced into the reactor (the quality of the solute sulfuric acid accounts for the lignocellulose dry Heavy 1%), high-temperature steam penetrates into the fiber, and is continuously cooked for 45 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 80%
  • the yield of xylose and oligosaccharide is 70%
  • the removal rate of lignin is 70%
  • the retention rate of cellulose is 93%
  • the proportion of cellulose in the residue is 73. %.
  • the corn stalks are cut into small pieces of 2 to 6 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, a 4wt% KOH aqueous solution (the KOH aqueous solution mass accounts for 8% of the dry weight of the lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the thermal insulation chamber is kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and is pumped into clean water for washing to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to a screw feeder in the front stage of the single spiral tubular reactor to form a plug, and 160 degree high temperature steam and 0.5 wt% hydrochloric acid aqueous solution are introduced into the reactor (the mass of the solute HCl accounts for the lignocellulose dry Heavy 1%), high-temperature steam penetrates into the fiber, and is continuously cooked for 45 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 78%
  • the yield of xylose and oligosaccharide is 70%
  • the removal rate of lignin is 75%
  • the retention rate of cellulose is 92%
  • the proportion of cellulose in the residue is 70. %.
  • the corn stalks are cut into small pieces of 2 to 6 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 8wt% KOH aqueous solution was pumped (the quality of KOH aqueous solution accounted for 16% of the dry weight of lignocellulose), and the alkaline catalyzed straw was obtained, and it was kept in the holding chamber for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and is pumped into clean water for washing to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 180 degree high temperature steam and 2wt% phosphoric acid aqueous solution are introduced into the reactor (the mass of the solute phosphoric acid accounts for the dry weight of the lignocellulose) 10%) high-temperature steam penetrates into the fiber, and is continuously cooked for 60 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder to obtain the squeeze residue. Hydrolysate of hemicellulose and cellulose-rich residue. Among them, the separation rate of hemicellulose is 88%, the yield of xylose and oligosaccharide is 79%, the removal rate of lignin is 85%, the retention rate of cellulose is 90%, and the proportion of cellulose in the residue is 78. %.
  • the wheat straw is cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 4wt% NaOH aqueous solution (the NaOH aqueous solution mass accounts for 8% of the dry weight of lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the heat preservation chamber is kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 160 ° C high temperature steam and 0.2 wt % sulfuric acid aqueous solution are introduced into the reactor (the quality of the solute sulfuric acid accounts for the lignocellulose dry Heavy 1%), high-temperature steam penetrates into the fiber, and is continuously cooked for 45 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 80%
  • the yield of xylose and oligosaccharide is 70%
  • the removal rate of lignin is 70%
  • the retention rate of cellulose is 93%
  • the proportion of cellulose in the residue is 70. %.
  • the rice straw is cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 5wt% NaOH aqueous solution (the NaOH aqueous solution mass accounts for 10% of the dry weight of lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the heat preservation chamber is kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 160 ° C high temperature steam and 0.2 wt % sulfuric acid aqueous solution are introduced into the reactor (the quality of the solute sulfuric acid accounts for the lignocellulose dry Heavy 1%), high-temperature steam penetrates into the fiber, and is continuously cooked for 50 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge bin 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 77%
  • the yield of xylose and oligosaccharide is 71%
  • the removal rate of lignin is 68%
  • the retention rate of cellulose is 92%
  • the proportion of cellulose in the residue is 62. %.
  • the sorghum straw is cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, 5wt% NaOH aqueous solution (10% of the dry weight of lignocellulose) was pumped in to obtain alkaline catalyzed straw, and it was kept in the holding chamber for 70 min.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 160 ° C high temperature steam and 0.3 wt% sulfuric acid aqueous solution are introduced into the reactor (the quality of the solute sulfuric acid accounts for the lignocellulose dry 1.5% heavy), high-temperature steam penetrates into the fiber, and is continuously cooked for 60 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge bin 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 78%
  • the yield of xylose and oligosaccharide is 69%
  • the removal rate of lignin is 70%
  • the retention rate of cellulose is 92%
  • the proportion of cellulose in the residue is 68. %.
  • the bagasse is added to the drum washing machine 2, and the soluble matter is rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches.
  • the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4.
  • 4wt% NaOH aqueous solution (the NaOH aqueous solution mass accounts for 8% of the dry weight of lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the heat preservation chamber is kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 150 ° C high temperature steam and 0.2 wt% sulfuric acid aqueous solution are introduced into the reactor (the quality of the solute sulfuric acid accounts for the lignocellulose dry Heavy 1%), high-temperature steam penetrates into the fiber, and is continuously cooked for 60 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder for extrusion cleaning.
  • the residue obtained a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the separation rate of hemicellulose is 80%
  • the yield of xylose and oligosaccharide is 74%
  • the removal rate of lignin is 72%
  • the retention rate of cellulose is 94%
  • the proportion of cellulose in the residue is 70. %.
  • the bamboo chips are added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and the sand is circulated and used for anaerobic treatment.
  • the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4.
  • a 12wt% Na 2 CO 3 aqueous solution (the mass of the Na 2 CO 3 aqueous solution accounts for 20% of the dry weight of the lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the heat preservation chamber is kept for 2 hours.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and is pumped into clean water for washing to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 150 degree high temperature steam and 1 wt% sulfuric acid aqueous solution are introduced into the reactor (the mass of the solute sulfuric acid accounts for the dry weight of the lignocellulose) 5%), high-temperature steam penetrates into the fiber, and is continuously cooked for 45 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder to squeeze the residue.
  • a hemicellulose hydrolyzate and a cellulose-rich residue are obtained.
  • the separation rate of hemicellulose is 90%
  • the yield of xylose and oligosaccharide is 78%
  • the removal rate of lignin is 75%
  • the retention rate of cellulose is 88%
  • the proportion of cellulose in the residue is 76. %.
  • the chopped wood chips are added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and the sand is circulated and used for anaerobic treatment.
  • the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4.
  • 8wt% NaOH aqueous solution (the quality of the NaOH aqueous solution accounts for 16% of the dry weight of the lignocellulose) is pumped, and the alkaline catalyzed straw is obtained, and the heat preservation chamber is kept for 90 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and is pumped into clean water for washing to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to a screw feeder in the front stage of the single spiral tubular reactor to form a plug, and 160 degree high temperature steam and 3 wt% acetic acid aqueous solution are introduced into the reactor (the mass of the solute acetic acid accounts for the dry weight of the lignocellulose) 15%), high-temperature steam penetrates into the fiber, and is continuously cooked for 90 minutes under pressure. At the same time, intermittent continuous explosion is realized.
  • the material is sprayed into the discharge bin 8, and the material is sent to the screw extruder to squeeze the residue.
  • a hemicellulose hydrolyzate and a cellulose-rich residue are obtained.
  • the separation rate of hemicellulose is 76%
  • the yield of xylose and oligosaccharide is 70%
  • the removal rate of lignin is 74%
  • the retention rate of cellulose is 93%
  • the proportion of cellulose in the residue is 73. %.
  • the wood chips are added to the drum type washing machine 2, and the discharge material is sent to a screw extruder, and the residue is squeezed to obtain a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4.
  • a 10wt% K 2 CO 3 aqueous solution was pumped (the mass of the K 2 CO 3 aqueous solution accounted for 20% of the dry weight of the lignocellulose), and the alkaline catalyzed straw was obtained, and the heat preservation chamber was kept for 3 hours.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and is pumped into clean water for washing to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to a screw feeder in the front section of the single spiral tubular reactor to form a plug, and a 170 degree high temperature steam and a 2wt% formic acid aqueous solution are introduced into the reactor (the mass of the solute formic acid accounts for the dry weight of the lignocellulose) 10%), high-temperature steam penetrates into the fiber, and is continuously cooked for 120 minutes under pressure.
  • the material is sprayed into the discharge bin 8, and the spray material is transported to the screw extruder to squeeze the residue.
  • a hemicellulose hydrolyzate and a cellulose-rich residue are obtained.
  • the separation rate of hemicellulose is 80%
  • the yield of mannose and oligosaccharide is 70%
  • the removal rate of lignin is 70%
  • the retention rate of cellulose is 87%
  • the proportion of cellulose in the residue is 70%. %.
  • the pine wood chips are added to the drum type washing machine 2, and the discharge material is sent to a screw extruder, and the residue is squeezed to obtain a hemicellulose hydrolyzate and a cellulose-rich residue.
  • the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4.
  • the alkali removal material is sent to the screw feeder in the front section of the single spiral tubular reactor to form a plug, and 180 degree high temperature steam and 1 wt% sulfuric acid aqueous solution are introduced into the reactor (the mass of the solute sulfuric acid accounts for the dry weight of the lignocellulose) 5%), high-temperature steam penetrates into the fiber, and is continuously cooked for 120 minutes under pressure.
  • intermittent continuous explosion is realized, the material is sprayed into the discharge tank 8, and the material is sent to the screw extruder to squeeze the residue. A hemicellulose hydrolyzate and a cellulose-rich residue are obtained.
  • the separation rate of hemicellulose is 85%
  • the yield of mannose and oligosaccharide is 73%
  • the removal rate of lignin is 72%
  • the retention rate of cellulose is 89%
  • the proportion of cellulose in the residue is 74. %.
  • the corn stalks are cut into small pieces of 2 to 8 cm. It is added to the drum type washing machine 2, the sediment and the soluble matter are rinsed, and the washed water is filtered and sedimented, and then subjected to anaerobic treatment after recycling a plurality of batches. After the cleaned corn stover passes through the filter 3, it is squeezed and dehydrated and then enters the first stage twin screw extruder 4. At the same time, a 4wt% NaOH aqueous solution (the mass of the NaOH aqueous solution accounts for 8% of the dry weight of the lignocellulose) is pumped, and the alkali-catalyzed straw is obtained, and the heat preservation chamber is kept for 60 minutes.
  • the material completed by the heat preservation reaction is sent to a spiral displacement washing and de-alkali machine, and the water is pumped into a countercurrent cleaning to obtain a lignin alkaline black liquor and a de-alkali material.
  • the alkali removal material is sent to the vertical tower continuous digester, and 160 ° C high temperature steam and 0.5 wt% sulfuric acid aqueous solution (the mass of the solute sulfuric acid accounts for 1% of the dry weight of the lignocellulose) is introduced into the reactor, and the high temperature steam infiltrates into the fiber. Internally, the pressure is continuously cooked for 45 minutes, and intermittent continuous explosion is realized at the same time.
  • the material is sprayed into the discharge tank 8, and the discharge material is sent to the screw extruder, and the residue is squeezed to obtain the hemicellulose hydrolyzate and the rich.
  • Cellulose-containing residue The separation rate of hemicellulose is 79%, the yield of xylose and oligosaccharide is 70%, the removal rate of lignin is 70%, the retention rate of cellulose is 92%, and the proportion of cellulose in the residue is 72. %.

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Abstract

一种连续分离木质纤维素组分的方法，包括如下步骤：将秸秆切碎，用水清洗后，将木质纤维素输送到双螺旋挤压机（4）中，通入碱性试剂，充分混合反应后输送至保温仓（5）中，进行保温反应；将所得物料输送到螺旋置换洗涤脱碱机（6）中，漂洗后分离得到木质素碱性黑液和脱碱物料，并回收黑液中的细小纤维；将脱碱物料输送到连续蒸煮反应器（11）中，通入水蒸汽进行蒸煮并喷放爆破，收集喷放物料；将喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和含纤维素的残渣。

Description

一种连续分离木质纤维素组分的方法 技术领域
本发明属于生物化工与生物能源领域，具体涉及一种连续分离木质纤维素组分的方法。
背景技术
由于石化能源(煤炭、石油、天然气等)的开发和利用，人类社会得到快速的发展。然而，随着人口的增长和和社会生产力的发展，能源短缺与环境恶化已成为二十一世纪人类面临和亟待解决的重大问题，也是制约我国社会与经济可持续发展的主要因素。因此，开发利用绿色、可再生的代替资源关乎人类未来命运，引起各国政府和科技界的普遍关注。作为可再生资源重要组成部分的木质纤维素资源是绿色植物通过光合作用将太阳能转化为化学能的载体。它可以通过物理、化学或生物手段转化为固态、液态、气态燃料，也可转化为多种化工原料。同时，生物质也是唯一的可再生碳源，它的有效利用可以实现由“石化碳”经济向“光合碳”经济的转变，对维持生态环境的碳平衡有积极意义。
木质纤维素构成了植物的细胞壁，对细胞起着保护作用，它主要由纤维素、半纤维素和木质素3部分组成。目前，纤维素、半纤维素和木质素的利用已经做了深入的研究并取得了很多产业化的成果。但目前利用方式只是将木质纤维素的单一组分分离并进行高效利用。例如典型的纤维素乙醇行业中，专利CN101509018和CN101525636采用蒸汽爆破预处理木质纤维素原料，提高了纤维素与半纤维素的酶解效率，但忽视了木质素的分离提取会更有利于纤维素的酶解糖化，同时木质素也未得到高效利用。专利CN103898788A采用单螺杆蒸汽爆破设备进行木质纤维素的预处理，相对于罐式蒸爆，极大的提高了预处理的效率和酶解糖化效率，但该技术只是单纯破坏植物纤维结构同时水解半纤维素，依然没有有效分离木质素。专利CN103790056A采用双螺旋挤压机预处理木质纤维素，仅仅是分离木质纤维素的单一组分，提高了酶解糖化效率，但是纤维素与半纤维素同时存在的条件下，纤维素酶解效率下降，酶解时间延长。所以，目前木质纤维素预处理技术多为单一组分的分离，虽然实现了纤维素酶解效率的提升，但并未实现三大组分高效利用。
因此，能够实现木质纤维素三大组分的有效分离，将对木质纤维素的全值化利用产生重大意义。
发明内容
本发明要解决的技术问题是提供一种连续分离木质纤维素组分的方法，以解决现有技术存在的效果不佳等问题。
为解决上述技术问题，本发明采用的技术方案如下：
一种连续分离木质纤维素组分的方法，包括如下步骤：
(1)将将秸秆切碎，用热水清洗后，将木质纤维素输送到双螺旋挤压机中，通入碱性试剂，充分混合反应后输送至保温仓中，进行保温反应；
(2)将步骤(1)中保温反应所得物料输送到螺旋置换洗涤脱碱机中，漂洗后分离得到木质素碱性黑液和脱碱物料，并回收黑液中的细小纤维；
(3)将步骤(2)中所得的脱碱物料输送到连续蒸煮反应器中，通入水蒸汽进行蒸煮并喷放爆破，收集物料；
(4)将步骤(3)中所得的喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和含纤维素的残渣。
步骤(1)中，优选的是，将秸秆切碎，用水清洗后，洗涤水过滤泥沙后循环使用多批次后进行厌氧处理。
步骤(1)中，所述的木质纤维素为秸秆和/或各类农林木质纤维类加工废弃物；其中，秸秆为玉米秸秆、小麦秸秆、水稻秸秆、高粱秸秆等常见的农作物秸秆，农林木质纤维类加工废弃物为甘蔗、竹、杉木、杨木、松木等林产的加工废弃物。
步骤(1)中，所述的木质纤维素预先被处理成2～8cm长的段。
步骤(1)中，所述的清洗是指将木质纤维素输送到鼓式水洗机中清洗泥沙和可溶性物质，洗涤水过滤泥沙后循环使用多批次后进行厌氧处理。
步骤(1)中，清洗后的木质纤维素经挤压至无游离水，再输送进双螺旋挤压机中。
步骤(1)中，所述的碱性试剂为氢氧化钠水溶液、氢氧化钾水溶液、碳酸钠水溶液、碳酸钾水溶液中的任意一种或几种的组合。所述的碱性试剂的浓度为2～12wt％。其中，碱性试剂的质量为木质纤维素干重的1～20％，优选4～12％。
步骤(1)中，木质纤维素干重和水的质量比为1：1～10，优选1：4。
步骤(1)中，保温仓中温度为60～120℃，反应时间为0.5～5h。
步骤(2)中，漂洗所用试剂为水。
步骤(3)中，在通入水蒸气的同时，向连续蒸煮反应器中通入酸溶液；其中，所 述的酸溶液为硫酸水溶液、盐酸水溶液、磷酸水溶液、甲酸水溶液和乙酸水溶液中的任意一种或几种的组合；所述的酸溶液的浓度为0.05～5wt％，优选0.2～3wt％；其中，木质纤维素干重与酸溶液的固液比为1：2～10，优选1:3。
步骤(3)中，蒸煮温度为140～190℃，蒸煮时间为20min～2h，蒸煮时压力为0.3～1.3MPa。
有益效果：
与现有技术相比，本发明具有如下优势：
1、本发明可以实现纤维素、半纤维素和木质素三大组分的有效分离，且可以联产高纯度木质素、半纤维素水解液和高度解离纤维素。
2、双螺旋挤压机强力的纤维解离能力和混合能力，使化学药液催化效率大幅度提升。
3、螺旋置换洗涤脱碱机具有高效脱碱效果，且节水效果比通常洗浆机节水50％～80％。
4、单螺旋管式反应器相对釜式或锅式反应器实现了蒸煮连续化，提高了蒸煮效率。
5、本发明得到的残渣纤维素含量高，解离程度高，比表面积大，酶解糖化效果也大幅提升。
附图说明
图1为本发明的流程示意图。
附图标记说明：1、秸秆输送机；2、鼓式水洗机；3、过滤器；4、双螺旋挤出机；5、保温仓；6、螺旋置换洗涤脱碱机；8、喷放仓；9、化学药液加料口；10、输送机；11、立塔式连续蒸煮器。
具体实施方式
为了能够更清楚的理解本发明，下面通过具体的实施例对本发明进行进一步的描述。
下述实施例中，秸秆的组分含量分析采用美国再生能源实验室标准方法，半纤维素的分离率、木质素脱除率和纤维素保留率的计算方法如下：
半纤维素的分离率＝1–(M 1/M 0)×100％
木质素脱除率＝1–(M 3/M 2)×100％
纤维素保留率＝(M 5/M 4)×100％
注：M 0为一定量M秸秆中半纤维素含量；M 1为M量秸秆处理后半纤维素含量；
M 2为一定量M秸秆中半纤维素含量；M 3为M量秸秆处理后半纤维素含量；
M 5为一定量M秸秆中纤维素含量；M 4为M量秸秆处理后纤维素含量。
下述实施例中，所用的装置如图1所示。木质纤维素由秸秆输送机输送进入装置内，木质纤维素经鼓式水洗机水洗后经过滤器过滤后进入双螺旋挤出机4中，同时由化学药液加料口9向双螺旋挤出机4中加入碱性试剂；过滤后的木质纤维素和碱性试剂在双螺旋挤出机4中充分混合后，进入保温装置5中进行保温反应；保温反应结束后，所得物料由输送机10输送至螺旋置换洗涤脱碱机6中，漂洗后分离得到木质素碱性黑液和脱碱物料，并将脱碱物料经输送机输送至立塔式连续蒸煮器11中进行蒸煮蒸煮并在喷放仓中喷放爆破后，收集所得的喷放物料再输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和含纤维素的残渣。
实施例1
首先将玉米秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入5wt％NaOH水溶液，(NaOH水溶液质量占木质纤维素干重的10％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入180℃高温蒸汽，高温蒸汽渗入纤维内部，保压连续蒸煮60min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为70％，木糖与低聚糖的得率为60％，木质素的脱除率为70％，纤维素的保留率96％，残渣中纤维素比例为65％。
实施例2
首先将玉米秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入2wt％NaOH溶液(NaOH水 溶液质量占木质纤维素干重的4％)，获得碱性催化的秸秆，并进入保温仓保温30min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入140℃高温蒸汽与0.2wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮30min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为70％，木糖与低聚糖的得率为58％，木质素的脱除率为50％，纤维素的保留率96％，残渣中纤维素比例为68％。
实施例3
首先将玉米秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入4wt％NaOH水溶液(NaOH水溶液质量占木质纤维素干重的8％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入160℃高温蒸汽与0.5wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮45min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为80％，木糖与低聚糖的得率为70％，木质素的脱除率为70％，纤维素的保留率93％，残渣中纤维素比例为73％。
实施例4
首先将玉米秸秆切成2～6cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入4wt％KOH水溶液(KOH水溶液质量占木质纤维素干重的8％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料 塞，同时向反应器中通入160度高温蒸汽与0.5wt％盐酸水溶液(溶质HCl的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮45min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为78％，木糖与低聚糖的得率为70％，木质素的脱除率为75％，纤维素的保留率92％，残渣中纤维素比例为70％。
实施例5
首先将玉米秸秆切成2～6cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入8wt％KOH水溶液(KOH水溶液质量占木质纤维素干重的16％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入180度高温蒸汽与2wt％磷酸水溶液(溶质磷酸的质量占木质纤维素干重的10％)高温蒸汽渗入纤维内部，保压连续蒸煮60min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为88％，木糖与低聚糖的得率为79％，木质素的脱除率为85％，纤维素的保留率90％，残渣中纤维素比例为78％。
实施例6
首先将小麦秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入4wt％NaOH水溶液(NaOH水溶液质量占木质纤维素干重的8％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入160℃高温蒸汽与0.2wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮45min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得 半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为80％，木糖与低聚糖的得率为70％，木质素的脱除率为70％，纤维素的保留率93％，残渣中纤维素比例为70％。
实施例7
首先将水稻秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入5wt％NaOH水溶液(NaOH水溶液质量占木质纤维素干重的10％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入160℃高温蒸汽与0.2wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮50min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为77％，木糖与低聚糖的得率为71％，木质素的脱除率为68％，纤维素的保留率92％，残渣中纤维素比例为62％。
实施例8
首先将高粱秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入5wt％NaOH水溶液(NaOH水溶液质量占木质纤维素干重的10％)，获得碱性催化的秸秆，并进入保温仓保温70min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入160℃高温蒸汽与0.3wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1.5％)，高温蒸汽渗入纤维内部，保压连续蒸煮60min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为78％，木糖与低聚糖的得率为69％，木质素的脱除率为70％，纤维素的保留率92％，残渣中纤维素比例为68％。
实施例9
首先将甘蔗渣加入到鼓式水洗机2中，漂洗可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入4wt％NaOH水溶液(NaOH水溶液质量占木质纤维素干重的8％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入150℃高温蒸汽与0.2wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮60min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为80％，木糖与低聚糖的得率为74％，木质素的脱除率为72％，纤维素的保留率94％，残渣中纤维素比例为70％。
实施例10
首先将竹屑加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入12wt％Na 2CO 3水溶液(Na 2CO 3水溶液的质量占木质纤维素干重的20％)，获得碱性催化的秸秆，并进入保温仓保温2h。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入150度高温蒸汽与1wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的5％)，高温蒸汽渗入纤维内部，保压连续蒸煮45min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为90％，木糖与低聚糖的得率为78％，木质素的脱除率为75％，纤维素的保留率88％，残渣中纤维素比例为76％。
实施例11
首先将杉木屑加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入8wt％NaOH水溶液(NaOH水溶液的质量占木质纤维素干重的16％)，获得碱性催化的秸秆，并进入保温仓保温90min。将保温反应 完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入160度高温蒸汽与3wt％乙酸水溶液(溶质乙酸的质量占木质纤维素干重的15％)，高温蒸汽渗入纤维内部，保压连续蒸煮90min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为76％，木糖与低聚糖的得率为70％，木质素的脱除率为74％，纤维素的保留率93％，残渣中纤维素比例为73％。
实施例12
首先将杨木屑加入到鼓式水洗机2中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入10wt％K 2CO 3水溶液(K 2CO 3水溶液的质量占木质纤维素干重的20％)，获得碱性催化的秸秆，并进入保温仓保温3h。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入170度高温蒸汽与2wt％甲酸水溶液(溶质甲酸的质量占木质纤维素干重的10％)，高温蒸汽渗入纤维内部，保压连续蒸煮120min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为80％，甘露糖与低聚糖的得率为70％，木质素的脱除率为70％，纤维素的保留率87％，残渣中纤维素比例为70％。
实施例13
首先将松木屑加入到鼓式水洗机2中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入2wt％NaOH水溶液与6wt％Na 2CO 3水溶液的混合溶液(NaOH水溶液的质量占木质纤维素干重的4％，Na 2CO 3水溶液的质量占木质纤维素干重的12％)，获得碱性催化的秸秆，并进入保温仓保温4h。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到单螺旋管式反应器前段的螺旋喂料器中形成料塞，同时向反应器中通入180度高温蒸汽与1wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的5％)，高温蒸汽渗入纤维内部，保压连续蒸煮120min，同时实现间歇式连续喷爆，物料 喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为85％，甘露糖与低聚糖的得率为73％，木质素的脱除率为72％，纤维素的保留率89％，残渣中纤维素比例为74％。
实施例14
首先将玉米秸秆切成2～8cm小段。加入到鼓式水洗机2中，漂洗泥沙和可溶性物质，且清洗后的水过滤泥沙后循环利用多批次后进行厌氧处理。清洗后的玉米秸秆经过过滤器3时，挤压脱水后进入第一段双螺旋挤压机4。同时泵入4wt％NaOH水溶液(NaOH水溶液的质量占木质纤维素干重的8％)，获得碱性催化的秸秆，并进入保温仓保温60min。将保温反应完成的物料输送到螺旋置换洗涤脱碱机，泵入清水进行逆流清洗，获得木质素碱性黑液和脱碱物料。将脱碱物料输送到立塔式连续蒸煮器，同时向反应器中通入160℃高温蒸汽与0.5wt％硫酸水溶液(溶质硫酸的质量占木质纤维素干重的1％)，高温蒸汽渗入纤维内部，保压连续蒸煮45min，同时实现间歇式连续喷爆，物料喷放到喷放仓8中，喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和富含纤维素的残渣。其中，半纤维素的分离率为79％，木糖与低聚糖的得率为70％，木质素的脱除率为70％，纤维素的保留率92％，残渣中纤维素比例为72％。

Claims (9)

  1. 一种连续分离木质纤维素组分的方法，其特征在于，包括如下步骤：
    (1)将秸秆切碎，用水清洗后，将木质纤维素输送到双螺旋挤压机中，通入碱性试剂，充分混合反应后输送至保温仓中，进行保温反应；
    (2)将步骤(1)中保温反应所得物料输送到螺旋置换洗涤脱碱机中，漂洗后分离得到木质素碱性黑液和脱碱物料，并回收黑液中的细小纤维；
    (3)将步骤(2)中所得的脱碱物料输送到连续蒸煮反应器中，通入水蒸汽进行蒸煮并喷放爆破，收集喷放物料；
    (4)将步骤(3)中所得的喷放物料输送到螺旋挤压机中，挤压清洗残渣获得半纤维素的水解液和含纤维素的残渣。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中，将秸秆切碎，用水清洗后，洗涤水过滤泥沙后循环使用多批次后进行厌氧处理。
  3. 根据权利要求1或2所述的方法，其特征在于，步骤(1)中，所述的木质纤维素为秸秆和/或农林木质纤维类加工废弃物。
  4. 根据权利要求1或2所述的方法，其特征在于，步骤(1)中，所述的碱性试剂为氢氧化钠水溶液、氢氧化钾水溶液、碳酸钠水溶液、碳酸钾水溶液、碳酸氢钠水溶液和碳酸氢钾水溶液中的任意一种或几种的组合；所述的碱性试剂的浓度为2～12wt％；其中，碱性试剂的质量为木质纤维素干重的4～20％。
  5. 根据权利要求1或2所述的方法，其特征在于，步骤(1)中，木质纤维素干重和水的质量比为1：1～6。
  6. 根据权利要求1或2所述的方法，其特征在于，步骤(1)中，保温仓中温度为60～120℃，保温反应时间为0.5～5h。
  7. 根据权利要求1或2所述的方法，其特征在于，步骤(3)中，连续蒸煮反应器为单螺旋管式连续蒸煮器或立塔式连续蒸煮器。
  8. 根据权利要求1或2所述的方法，其特征在于，步骤(3)中，在通入水蒸气的同时，向连续蒸煮反应器中通入酸溶液；其中，所述的酸溶液为硫酸水溶液、盐酸水溶液、磷酸水溶液、甲酸水溶液和乙酸水溶液中的任意一种或几种的组合；所述的酸溶液的浓度为0.01～5wt％；其中，木质纤维素干重和酸溶液质量的固液比为1：5～15。
  9. 根据权利要求1或2所述的方法，其特征在于，步骤(3)中，蒸煮温度为140～190℃，蒸煮时间为20min～2h，蒸煮时压力为0.3～1.3MPa。
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