JP2013163796A5 - - Google Patents

Description

Method and apparatus for producing resin raw material from lignocellulosic biomass

  The present invention relates to a resin raw material production method using lignocellulosic biomass as a raw material and an apparatus therefor, and more specifically, a resin raw material mainly composed of a low molecular weight lignin derivative using a lignocellulosic biomass as a grease. The present invention relates to a continuous process for producing a resin raw material that can be separated in a state and an apparatus therefor.

  Conventionally, many technological developments have been performed for the purpose of producing pulp raw materials (cellulose) from lignocellulosic biomass, particularly woody biomass. Here, pulping when producing a pulp raw material (cellulose) means that hemicellulose and lignin are decomposed and solubilized from hemicellulose, cellulose and lignin, which are the main components of lignocellulosic biomass, and cellulose is isolated. It is a method, using Na2S and NaOH as cooking chemicals, heating for several hours at 140-170 ° C is using kraft pulp, and using sulfite aqueous solution as cooking chemicals, heating for several hours at 150 ° C. Is sulfite pulp.

  In both cases, lignin and hemicellulose are separated as black liquor and used as boiler fuel. On the other hand, as a cooking liquid, an organic solvent, that is, a mixed liquid of acetic acid, ethyl acetate and water, is heated at 170 to 180 for 1 to 3 hours to solubilize lignin and hemicellulose, and to isolate cellulose. This is called an organosolv pulping method, in which lignin is separated into an organic solvent phase and hemicellulose (decomposed product) is separated into an aqueous phase.

  In recent years, many studies for efficiently separating cellulose have been conducted for the purpose of pulping and producing biodegradable plastic raw materials. In JP-A-4-506544 (Patent Document 1), as a pulping method, an active delignification agent comprising sodium hydroxide containing sodium sulfide in an ammonia-based solvent containing water up to about 12% under supercritical conditions. Shows a method for delignification at a temperature of 5 to 250 ° C. and a pressure of 400 to 3500 ps.

  In JP 2004-306021 (Patent Document 2), for the purpose of obtaining cellulose as a biodegradable plastic raw material, the raw material is compressed at 180 to 300 ° C. and 15 to 28 MPa, and hot water at 180 to 200 ° C. is used. Has been proposed to solubilize lignin and hemicellulose and separate cellulose as a solid.

  This method is extremely interesting without using any special cooking chemicals, but the raw materials are corn cob (corn core), bagasse, rice straw and herbaceous biomass. In the case of woody biomass, the lignin component is 180. Considering that it is hardly solubilized with hot water at ˜200 ° C., it is highly possible that the lignin component (molecular weight) is different from the woody biomass.

  Japanese Patent Application Laid-Open No. 2008-248202 (Patent Document 3) discloses a method and apparatus for extracting high-purity (nearly 100%) cellulose from lignocellulosic plant materials. The treatment process is composed of three stages. First, a part of hemicellulose and lignin is decomposed with pressurized hot water at 180 to 250 ° C. and 10 to 20 MPa, and separated as a soluble component. By this treatment, a part of the lignin is separated into a soluble lignin having many hydrophilic groups and an insoluble hydrophobic lignin having few hydrophilic groups, and most of the cellulose remains in a solid state.

  Next, the residual solids here are treated at 350 to 390 ° C., 25 to 35 MPa, for 0.5 seconds to solubilize the cellulose in high-temperature and high-pressure water, and then the liquid (cellulose-soluble) is cooled. However, since the cellulose immediately after it is soluble, after high-pressure filtration, it is depressurized and sent to a storage tank, where it is left at room temperature for 2 hours to 2 days to precipitate solids. Almost 100% of cellulose is obtained.

  Although there is no description in the patent document, hydrophobic lignin is presumed to be separated by high-pressure filtration in the final treatment, but in the second step, it is inevitable that cellulose undergoes hydrolysis, and in the examples. Although not described, the yield of 100% cellulose is assumed to be very low. In this patent, the example is only bagasse (squeezed sugar cane), and it is unclear whether this method can be applied to woody biomass.

  As mentioned above, the use of lignocellulosic biomass components has been mainly limited to cellulose, but in recent years, research focused on lignin has been vigorously conducted by thermochemical conversion of lignocellulosic woody biomass. Various technologies for extracting cellulose, hemicellulose, and lignin solutions, which are constituents of woody biomass, have been developed.

  As prior art, for example, woody biomass is hydrothermally treated at 180 ° C. to separate soluble hemicellulose, and then insoluble lignin, cellulose is treated with an acetone / water mixture at 230 ° C. to dissolve insoluble cellulose and soluble A process for producing a lignin solution by a two-stage process for separating lignin is known (Non-Patent Document 1).

  As another prior art, woody biomass is hydrothermally treated at 300 ° C. to separate soluble hemicellulose and cellulose, and then insoluble lignin is extracted with acetone at room temperature to obtain high molecular lignin and low molecular weight lignin. A process for producing a low-molecular-weight lignin by a single-stage process is known (Patent Documents 4 and 5).

  Here, the solvent is distilled off from the acetone-soluble component is a lignin derivative containing a phenolic hydroxyl group and an alcoholic hydroxyl group in a molar ratio of 9: 1 to 8: 2, which includes hexamethylenetetramine and the like. It has been shown that a lignin resin composition can be obtained by mixing a crosslinking agent.

  Traditionally, including other prior art, treatment processes aimed at separating soluble lignin or low molecular weight lignin by a one-step or two-step process have been reported. This is due to a distribution process. Until now, the continuous manufacturing process which can isolate | separate the lignin derivative which can become a resin raw material from lignocellulosic biomass is not established.

  In addition, the use of organic solvents such as acetone is essential for the separation of lignin derivatives in the prior art, and even if reuse is taken into consideration, the cost of raw materials for acetone replenishment and the energy cost for acetone separation are large. And it left a problem economically. Therefore, in this technical field, a continuous production process of lignin resin is developed to produce lignin resin economically and efficiently from woody biomass such as wood flour and bark, and herbaceous biomass such as rice straw and corn. There was a strong demand.

Japanese National Patent Publication No. 4-506544 JP 2004-306021 A JP 2008-248202 A JP 2009-84320 A JP 2009-227890 A

Isao Hasegawa et al. Energy & Iuels, 2004, 18, 755-760

  Under such circumstances, the present inventors have conducted intensive research with the goal of developing a high-efficiency manufacturing process for resin raw materials mainly composed of lignin derivatives from lignocellulosic biomass in view of the above-described conventional technology. As a result, we succeeded in establishing a technology for separating and recovering resin raw materials economically and efficiently without using an organic solvent by a continuous process using subcritical water treatment, and completed the present invention. It came to do.

  The present invention provides an economical high-efficiency production method and apparatus for resin raw materials mainly composed of lignin derivatives from woody biomass such as wood powder and bark using subcritical water, and herbaceous biomass such as rice straw and corn. It is intended to do. Another object of the present invention is to provide a high-efficiency production method and apparatus for a resin raw material mainly composed of a lignin derivative, which is free from problems of piping blockage and precipitates in the reactor outlet line.

The present invention for solving the above-described problems comprises the following technical means.
(1) In a method for producing a resin raw material from lignocellulosic biomass mainly composed of hemicellulose, cellulose and lignin,
The biomass is pulverized and mixed with water to form a water slurry, and the water slurry is subjected to continuous treatment at a temperature of 250 ° C. or higher and 374 ° C. or lower under a pressure equal to or higher than the saturated water vapor pressure at that temperature for 30 minutes or longer. After completion of the reaction, solid-liquid separation is performed at 200 to 250 ° C. to separate the solid and the high-temperature hot water soluble component, and the temperature is lowered to 100 ° C. or lower to lower the temperature. A continuous process for producing a resin raw material from lignocellulosic biomass, characterized in that it is separated into a hot water soluble component and a grease-like resin raw material.
(2) The continuous manufacturing method of the resin raw material as described in said (1) which processes a water slurry at the temperature of 300 degrees C or less.
(3) The continuous manufacturing method of the resin raw material as described in said (1) or (2) whose solid-liquid separation operation at 200-250 degreeC is operation by filtration or specific gravity difference separation.
(4) A method of lowering the temperature of a high-temperature hot water-soluble component separated at 200 to 250 ° C. to 100 ° C. or less is received by a high-temperature and high-pressure recovery receiver while maintaining 200 to 250 ° C. The resin raw material according to any one of the above (1) to (3), which is cooled to 100 ° C. or lower, or directly flushed from 200 to 250 ° C. to atmospheric pressure to 100 ° C. or lower. Production method.
(5) The continuous manufacturing method of the resin raw material in any one of said (1)-(4) whose solid substance density | concentration in water slurry is 15% at maximum (water content 85% or more).
(6) An apparatus used in the continuous production method of the resin raw material according to (1), wherein a pump system for supplying water slurry at a high pressure, a reactor for performing a subcritical water reaction, and the reactor are used. A reactor outlet line for discharging the reactant, a receiver for recovering the reactant from the reactor outlet line, and a solid-liquid separator installed in the middle of the reactor outlet line as constituent elements. The treated high temperature hot water soluble component at 200 to 250 ° C. and the solid are separated by the solid-liquid separator, and the high temperature hot water soluble component is received at the receiver while maintaining 200 to 250 ° C. The resin raw material is recovered by lowering the temperature to 100 ° C. or lower in order to precipitate the resin raw material as a grease-like solid and separate it from the low-temperature hot water soluble component. Lignocellulosic biomas Continuous production apparatus for resin material from.
(7) The apparatus according to (6), wherein the solid-liquid separator is a filter or a specific gravity difference separator.
(8) The apparatus according to (6) or (7), further including a heat-retaining and heating unit that keeps the reactor outlet line (from the reactor outlet to the receiver) at 200 to 250 ° C.
(9) The apparatus according to (8), wherein the heat retaining heating means is heating medium heating.
(10) The apparatus according to any one of (6) to (9), further including means for cooling the high temperature hot water soluble component accommodated in the receiver to 100 ° C. or lower.
(11) The receiver has a piston inside, accepts a high temperature hot water soluble component on one side of the piston, and discharges the high pressure water filled on the opposite side of the piston at a predetermined pressure, whereby the pressure of the entire apparatus The apparatus according to any one of (6) to (10), wherein adjustment is performed and a high-temperature hot water-soluble component is recovered.
(12) The device according to (10), wherein the means for cooling to 100 ° C. or lower is a cooling jacket installed outside the receiver.
(13) The pressure of the entire apparatus is adjusted by filling the receiver with an inert gas at a predetermined pressure in advance and discharging the gas pressure increase due to receiving the high-temperature hot water soluble component at the predetermined pressure. And the apparatus in any one of said (6)-(10) which collect | recovers high temperature hot water soluble components.
(14) The apparatus according to (10), wherein the means for cooling to 100 ° C. or lower is a cooling coil inserted into the receiver.
(15) An apparatus used in the continuous production method of the resin raw material according to (1), wherein a pump system for supplying water slurry at a high pressure, a reactor for performing a subcritical water reaction, and the reactor are used. Reactor outlet line for discharging the reactants, solid-liquid separator installed in the middle of the reactor outlet line, and liquid (high temperature hot water soluble component) from the solid-liquid separator is flushed directly under atmospheric pressure And a receiver for recovering the reaction product after flushing as components, and the 200-250 ° C. high-temperature hot water soluble component and solid material treated in the reactor are separated by the solid-liquid separator. The resin raw material is precipitated as a grease-like solid in the receiver by reducing the temperature of the high-temperature hot water soluble component directly from 200 to 250 ° C. to atmospheric pressure and lowering the temperature to 100 ° C. or lower. By separating from low temperature hot water soluble components , Continuous production apparatus for resin material from the lignocellulosic biomass characterized in that so as to recover the resin material.
(16) The apparatus according to (15), wherein the solid-liquid separator is a filter or a specific gravity difference separator.
(17) The apparatus according to (15) or (16), further including a heat-retaining and heating unit that maintains the reactor outlet line (from the reactor outlet to the receiver) at 200 to 250 ° C.
(18) The apparatus according to (17), wherein the heat retaining heating means is heating medium heating.
(19) The separator according to (15)-(18), having a separator that separates the reaction product after flashing into a vapor and a solid-liquid mixture, wherein the vapor is evaporated into condensed water by a condenser, and the solid-liquid mixture is received in a receiver. The device according to any one of the above.

Next, the present invention will be described in more detail.
The present invention relates to a method for producing a resin raw material from lignocellulosic biomass mainly composed of hemicellulose, cellulose and lignin. The biomass is pulverized and mixed with water to form a water slurry, and the water slurry is 250 ° C or higher. At a temperature of 374 ° C. or lower, under a pressure equal to or higher than the saturated water vapor pressure at that temperature, continuous treatment is performed for 30 minutes or longer. After the reaction is completed, solid-liquid separation is performed at 200 to 250 ° C. A soluble component is separated, and the high temperature hot water soluble component is separated into a low temperature hot water soluble component and a grease-like resin raw material by lowering the temperature to 100 ° C. or lower. .

Further, the present invention is an apparatus used in the continuous production method of the resin raw material, which is a pump system for supplying water slurry at a high pressure, a reactor for performing subcritical water reaction, and a reaction product treated in the reactor. A reactor outlet line for discharging the reactor, a receiver for recovering the reactants from the reactor outlet line, and a solid-liquid separator installed in the middle of the reactor outlet line as components, and processed in the reactor. The high temperature hot water soluble component at 200 to 250 ° C. and the solid matter are separated by the solid-liquid separator, and the high temperature hot water soluble component is received at the receiver while maintaining the temperature of 200 to 250 ° C. The resin raw material is recovered by lowering the temperature to 100 ° C. or less by precipitating the resin raw material as a grease-like solid and separating it from the low-temperature hot water soluble component. It is.

  In the present invention, in developing a high-efficiency production process of a resin raw material mainly composed of a lignin derivative from lignocellulosic biomass, in order to establish basic conditions for hydrothermal treatment of lignocellulosic biomass with subcritical water, A batch test was conducted. A high-temperature and high-pressure autoclave (design condition: 500 ° C./45 MPa) having an internal volume of 200 cc was used as a test apparatus.

  The biomass raw material used for the test was cedar wood powder (0.5 mm or less) discharged during building material processing. The test was performed using a reaction temperature of 180 to 360 ° C., a reaction time of 30 minutes, a pressure of saturated vapor pressure at the reaction temperature, water added to cedar powder, and a solid adjusted to 10% by weight. .

  Cooling was started immediately after the reaction time elapsed, and after the internal temperature became 100 ° C. or lower, the residual pressure was released and the treated product was recovered. The recovered material was fractionated and analyzed by the method shown in FIG. 1, and the solid matter residual rate, the Klarson lignin rate, and the acetone soluble component rate were calculated as evaluation indexes.

  Here, Klason lignin is a solid that is treated with a strong acid (72% sulfuric acid) to solubilize hemicellulose and cellulose, and the remaining insoluble matter is evaluated as acid-insoluble lignin. It is considered in the literature (Japanese Patent Application Laid-Open No. 2009-84320, 227890) that lignin is considered to be a low molecular weight derivative and becomes a resin raw material. The definition of each yield is as follows.

Residual rate of solids = solids after treatment (dry weight: B) / biomass input (dry weight A)
Klarson lignin ratio = Amount of acid insoluble component (C) / Solid matter after treatment (B)
Acetone soluble component ratio = Acetone soluble component amount (D) / Solid matter after treatment (B)

  FIG. 2 shows the results of the batch test. From the figure, in the subcritical water treatment (180 to 360 ° C.), the solids remaining rate (FIG. 2-1) decreases and the Klarson lignin rate (FIG. 2-2) increases but the solids remaining as the temperature increases. It was revealed that both the ratio and the Klarson lignin ratio showed a saturation tendency at about 300 ° C.

  It was found that in the treatment at 300 ° C. or higher, the solid residue ratio was reduced to about 50%, most of which was evaluated as Klarson lignin. However, since the Klarson lignin in the raw material (cedar wood flour) is 35%, it is considered that the residual solid contains not only lignin but also cellulose-derived carbides and oils. On the other hand, the acetone soluble component ratio (FIG. 2-2) considered to be a lignin derivative (resin raw material) increased up to 300 ° C., but decreased at higher temperatures.

  Specifically, the result of several percent in the treatment at 180 ° C. is about 40% in the treatment at 300 ° C., and the lignin depolymerization (lignin derivative) progressed with the increase in temperature. Conversely, the acetone soluble component ratio decreased. Further, it is presumed that the acetone-soluble component contains a small amount of cellulose-derived oil in addition to the lignin derivative.

  Furthermore, the resin raw material yield (FIGS. 2-3) is compared with the biomass ratio (= acetone soluble component amount (D) / biomass input amount (A)) and the total lignin ratio during biomass input (= acetone soluble component amount). As a result of calculation using two types of (D) / biomass input amount (A) × 0.35), the maximum was 300 ° C. to 330 ° C., and the decrease was 360 ° C.

  The resin raw material yield (to biomass ratio) in the treatment at 300 ° C. was about 20%, which was found to be 55% when converted to the total lignin ratio during biomass input. From this result, it became clear that the target value (50%) based on the separately estimated economic efficiency can be achieved by the treatment at 300 ° C. · 9 MPa to 330 ° C. · 13 MPa. Therefore, the 300 ° C. treatment was determined to be optimal from the viewpoint of energy and the required pressure resistance of the apparatus.

  Next, in order to evaluate how the lignocellulosic biomass (woody / herbaceous, conifer / broadwood, etc.), that is, lignin content and lignin structure, affects the treatment, in addition to cedar (conifer) A batch test similar to that described above was conducted on bamboo shoots (broadwood), bamboo, and rice straw (herbaceous). However, the reaction conditions were set to 300 ° C. · 9 MPa · 30 minutes.

  Table 1 summarizes the experimental results [results of subcritical water treatment batch test (difference in lignocellulosic biomass)]. As a result, the lignin content and structure seem to be different depending on the type of biomass, but the solids remaining rate does not show a significant difference in the range of 40 to 50%, and the Klarson lignin rate is Was over 90%.

  On the other hand, the acetone-soluble component ratio was 32%, which was lower than that of cedar, but rice straw and bamboo, on the contrary, showed 48%, which was about 10% larger than cedar. When these results are converted into resin raw material yield, the other three types (cedar, rice straw, bamboo) are about 20% although the cocoon is as low as 14.5%. It was concluded that it could be applied.

  A continuous processing apparatus was constructed from the results of the batch test. FIG. 3 shows a block flow sheet of the continuous processing apparatus. 1 is a slurrying device, 2 is a high-pressure pump system, 3 is a reactor, 4 is a heating medium heater, 5 is a cooler, 6 is a cooling tower, 7 is a decompression device, and 8 is a product storage tank.

  The design conditions of the reactor as the main apparatus were 320 ° C. and 12 MPa, and the capacity and capacity of each device were determined at a maximum processing capacity of 20 g / min. In this test, a pulverized cedar raw material (0.5 mm or less) was obtained and used, so a pulverizer was not installed. For this pulverization, a general mechanical pulverizer such as a ball mill was used. It is possible. Here, the slurrying apparatus 1 is installed in order to add a predetermined amount of water to the pulverized raw material to obtain a uniform slurry.

  Depending on how much shearing force is applied to the object, various methods such as a mill method, a rotary method, a high-pressure method, an ultrasonic method, and a stone mortar device are adopted for the slurrying device. A system is adopted in which the processed material passes through the screen slit portion to increase the speed and obtain a large shearing force by rotating the rotor at a high speed while maintaining a small clearance with the screen.

  The high-pressure pump system 2 needs to supply a high-pressure / quantitative slurry with poor fluidity to the reactor, and a special piston pump can be used, but this continuous processing apparatus has a maximum throughput of 20 g / min. Due to its small size, a commercially available pump system could not be used, and a dedicated high-pressure pump system was constructed.

  Specifically, it is composed of an injection tank having a piston inside, a low-pressure slurry pump (Mono pump) and a high-pressure water pump (plunger pump). The low-pressure slurry pump fills the injection tank with slurry, and the high-pressure water passes through the piston. A system was adopted in which slurry was supplied in a fixed amount under high pressure by a pump.

  The reactor 3 is a vertical upflow type high-pressure vessel, and is loaded with a screw scraper at the bottom inside and two J-type scrapers at the top. This is because a slurry with almost no fluidity enters in the lower part of the reactor, so a screw scraper that actively pushes it up is used. It uses a J-type scraper that has the ability and mixing effect.

  The slurry was heated with an electric heating medium heater 4. Usually, electric heating such as nichrome heating is generally used for laboratory scale heating, but a heating medium heating method is used to avoid scorching (→ clogging) due to local heating inside the reactor. did. The high-temperature and high-pressure product after the reaction was a coil (slurry) / shell (cooling water) type cooler 5, and the cooling water was supplied from the cooling tower 6. The high-pressure product after cooling is normally controlled to a predetermined pressure by a pressure control valve, but here the piston is placed inside, taking into consideration that the object contains a large amount of solids and the amount of processing is extremely small. A pressure reducing device 7 having the above was manufactured and used.

  Specifically, the product was received in the upper part of the piston, and the high-pressure water filled on the opposite side of the piston was controlled to a predetermined pressure by a spring-type holding valve (primary pressure regulating valve). In this method, the product is received under high pressure, and when the piston reaches the bottom, the valve connected to the reactor (cooler) is closed, the high pressure water is reduced by adjusting the holding valve, and the slurry discharge pump is operated. The product was discharged into the product storage tank 8 while pushing up the piston. The detailed flow of this continuous processing apparatus is shown in FIG.

  Using this continuous processing apparatus, first, after confirming that the press-fitting performance, heating performance, cooling performance, and decompression performance of this equipment operate as planned with fresh water, cedar powder (0.5 mm or less) was used. Transitioned to continuous testing. Water was previously added to the cedar wood powder, and a slurry with a solid concentration of 5% by weight was prepared with the above slurrying apparatus.

  Using this slurry, continuous operation was carried out under the conditions of a reaction temperature of 250 ° C., a pressure of 5 MPa, and a flow rate of 20 g / min. As a result, the pressure gradually increased during the operation, and clogging occurred in the reactor outlet line. After the operation was completed, the reactor outlet line, the cooler, and the line from the cooler to the decompression device were disassembled to identify the blockage site. The blockage occurred in the cooler, and the line from the reactor to the cooler. Then it was found that no obstruction occurred.

  The deposit was black, the surface was smooth, and it was found that the piping was completely blocked. This occlusion was clearly different from the residual solids obtained in the batch test, suggesting the possibility that only certain components were deposited, not just the residual solids were occluded.

  In order to avoid clogging in the reactor outlet line, in order to verify the relationship between temperature and solids precipitation, the control temperature of the discharge line from the reactor outlet to the pressure reducing device receiver is changed to change the temperature and clogging, ie solids The relationship of product precipitation was investigated. As a result, as shown in FIG. 5, it was found that only when the temperature in the cooling process was controlled and the temperature of the reactor discharge line was maintained at 210 ° C. or higher, there was no clogging of pipes and solid matter precipitation.

  Next, in order to evaluate the processed solids of Run-06 in FIG. 5, the solids recovered from the reactor through the discharge line to the pressure reducing device receiver, that is, the processed solids were examined. As a result, the material to be treated in the reactor contained untreated slurry and was 78% Klarson lignin and 3% acetone-soluble component, whereas the solid after treatment in the reactor was Klarson lignin. 100%, acetone-soluble component was 95%, and the solid after treatment was found to be a resin raw material mainly composed of a lignin derivative.

  This result shows the possibility of separating the resin raw material without using an organic solvent such as acetone, and is extremely important. In FIG. 6, the evaluation result of the solid substance after a process of Run-06 (FIG. 5) was shown. As described above, in the batch test results using the same cedar powder, although Klason lignin was as high as 97%, the acetone-soluble component was 38%. confirmed. This suggests that the lignin derivative, which is an acetone-soluble low molecular weight lignin, is dissolved in subcritical water at 210 ° C. or higher and selectively separated and recovered.

  In the present invention, lignocellulosic biomass is pulverized and mixed with water to form a water slurry. In this case, the water slurrying method and apparatus can use appropriate means, and the means is particularly It is not limited. The present invention provides a method and an apparatus for producing a resin raw material mainly composed of a lignin derivative from lignocellulosic biomass using subcritical water with high efficiency.

The present invention is a method for producing a lignin resin raw material from lignocellulosic biomass, pulverizing lignocellulosic biomass and mixing with water to form a water slurry, the water slurry at a temperature of 250 ° C or more and 374 ° C or less, The treatment is performed for 30 minutes or more under a pressure equal to or higher than the saturated water vapor pressure at that temperature, and solid-liquid separation is performed at 200 to 250 ° C. after completion of the reaction.

In the present invention, the polymeric lignin components as a solid separated, which divides hemicellulose hydrolyzate as high temperature water soluble component, cellulose hydrolyzate, low molecular lignin derivative as a resin material, 200 to 250 ° C. Is held in a high-temperature and high-pressure recovery receiver, and cooled to 100 ° C. or lower in the receiver, or flushed from 200 to 250 ° C. directly to atmospheric pressure to 100 ° C. or lower.

  In the present invention, the hemicellulose hydrolyzate and the cellulose hydrolyzate are separated as they are in a low-temperature hot water soluble component, and the resin raw material mainly composed of a lignin derivative is separated in the form of grease, thereby providing a reactor. It is possible to provide a method and apparatus for efficiently producing a resin raw material mainly composed of a lignin derivative by avoiding clogging in the outlet line, and the hemicellulose recovered as a low temperature hot water soluble component and By using sugar or organic acid, which is a hydrolyzate of cellulose, as a fermentation raw material or other raw material, it is possible to provide an economical method for continuously producing a resin raw material mainly composed of a lignin derivative.

The present invention has the following effects.
(1) By the subcritical water treatment, it is possible to provide a resin raw material continuous production method and apparatus capable of separating and recovering a resin raw material mainly composed of a lignin derivative from lignocellulosic biomass as a grease-like solid.
(2) By combining temperature control at 200 to 250 ° C. and high-temperature and high-pressure solid-liquid separation operation, it is possible to selectively extract and separate high molecular weight lignin and low molecular weight lignin derivatives. It is possible to selectively separate lignin derivatives.
(3) By keeping the temperature of the reactor outlet line at 200 to 250 ° C. , it is possible to avoid clogging with solid matter.
(4) In the treatment of cedar raw materials at 300 ° C., the resin raw material yield is a value close to 20%, and when converted to the total lignin ratio during biomass input, 55% can be achieved.
(5) This treatment can be applied to many lignocellulosic biomass such as cedar (woody / coniferous), firewood (woody / hardwood), bamboo (woody), rice straw (herbaceous) and the like.
(6) Without using an organic solvent such as acetone, it is possible to selectively separate a resin raw material mainly composed of a lignin derivative.
(7) It is possible to provide a continuous production method of a resin raw material mainly containing a lignin derivative without using an organic solvent.
(8) According to the present invention, a high-concentration slurry having a biomass solids concentration of 15% by weight can be operated, and a continuous process for producing a resin raw material mainly composed of a lignin derivative can be provided.
(9) The present invention is useful as a method for providing a continuous process for producing a resin raw material mainly composed of a lignin derivative, which can separate sugars and organic acids, which are hydrolysates of hemicellulose and cellulose, as water-soluble components. .

It is explanatory drawing which shows the classification and analysis method of the solid substance after a process obtained by subcritical water treatment. The result of a subcritical water treatment batch test (Sugigi powder) is shown. The block flow sheet of a continuous processing device is shown. The detailed flow sheet of a continuous processing apparatus is shown. The examination result of reactor outlet line-solid matter blockage is shown. It is explanatory drawing about evaluation of the solid substance after the process of Run-06 of FIG. An example of embodiment of the continuous manufacturing apparatus of the resin raw material which has a lignin derivative as a main component is shown. It is explanatory drawing of the flow diagram of a subcritical water extraction apparatus. The result of subcritical water extraction experiment is shown.

Next, embodiments of the present invention will be specifically described with reference to the accompanying drawings. Below, an example of embodiment of the continuous manufacturing apparatus of the resin raw material which has a lignin derivative as a main component is shown. Figure 7 is performed by filtering the solid-liquid separation at 200 to 250 ° C., illustrates a block flow when carrying out the cooling operation of 100 ° C. or less from 200 to 250 ° C. by flash to atmospheric pressure (rapid decompression) .

  In the figure, 1 is a slurrying device, 2 is a high-pressure pump system, 3 is a reactor, 4 is a heating medium heater, 6 is a cooling tower, 8 is a product storage tank, 9 is a high-temperature high-pressure filter, 10 is a flash device, 11 Indicates a solid-liquid separator, and 12 indicates a condenser. Although not shown in the figure, if the lignocellulosic biomass is in an unground state, it is necessary to install a pulverizing device for converting the biomass powder to 0.5 mm or less before the slurrying device. For this pulverization, a general mechanical pulverizer such as a ball mill can be used.

  A predetermined amount of water was added to the pulverized raw material, and a uniform water slurry was prepared by the slurrying apparatus 1. Various apparatuses such as a mill system, a rotary system, a high pressure system, an ultrasonic system, and a stone mill system are employed as the slurrying apparatus. The water slurry is supplied to the reactor 3 at a high pressure and a fixed amount by the high pressure pump system 2, but as described above, since it has almost no fluidity, it is difficult to supply with a normal slurry pump, and a special piston is used. Limited to the use of pumps.

  For example, there are double piston pumps of Putzmeister and Weil Minerals, but there are many types of lignocellulosic biomass, which may not be press-fit depending on the properties. In that case, it is also possible to employ a dedicated high-pressure pump system (consisting of a low-pressure slurry pump, an injection tank with a piston, and a high-pressure water pump) described in FIG.

  The pressurized water slurry is introduced from the lower part of the reactor 3 and heated while passing through the vertical upflow type high-pressure vessel to cause the reaction. A special scraper as described above is installed in the reactor. The slurry is heated by the heat medium heater 4. If the heat source is small, an electric type is selected, and if the capacity is large, city gas, LPG, kerosene, heavy oil, or the like is selected. As the heat medium, a dedicated heat medium oil such as Dowtherm A or NeoSK-OIL is selected in order to reduce the operating pressure.

  The state of the heat medium during heating may be either a gas phase or a liquid phase, but is appropriately selected in consideration of the heat transfer capability and the system configuration. In the reactor, the treatment is carried out at 250 to 300 ° C. for 30 minutes or more, and hemicellulose and cellulose, which are components of lignocellulosic biomass, are mostly hydrolyzed and are in a water-soluble state such as sugars and organic acids. Become. However, some become carbide and oily substances.

  On the other hand, lignin is hydrolyzed into a low molecular weight lignin derivative having a hydrophilic group and a hydrophobic polymer lignin. At the outlet of the reactor, these are discharged as a mixed high-temperature and high-pressure product and introduced into the high-temperature and high-pressure filter 9. The filter is composed of a high-pressure vessel and a filter installed inside the vessel, and a metallic mesh or sintered metal is used for the filter.

The solid matter supplemented by the filter 9 maintained at 200 to 250 ° C. is mainly composed of a high-molecular hydrophobic lignin, but also includes a solid matter obtained by carbonizing cellulose or the like. On the other hand, the liquid (high temperature hot water soluble component) that has passed through the filter contains a small amount of hemicellulose hydrolyzate, cellulose hydrolyzate, low molecular weight lignin derivative, and cellulose-derived oily substance. .

Since filtration is a batch operation, in order to perform a complete continuous operation, it is possible to perform a continuous operation by installing a plurality of filters and switching using the differential pressure before and after the filter as an index. . The liquid (high-temperature hot water soluble component) that has passed through the filter is introduced into the flash device 10 while maintaining the temperature at 200 to 250 ° C. The flash device is composed of a pressure control valve for high temperature and high pressure, and a separator that separates a mixture ejected under atmospheric pressure into vapor and liquid / solid matter.

  The pressure control valve can be a valve used in a coal liquefaction device or a sludge oiling device, such as an angle valve (manufactured by Yamatake Corporation). For example, if tungsten carbide, ceramics, diamond-like carbon (DLC) or the like is used, there is no particular problem even with a general control valve. The separator is a cylindrical vertical container, in which a jetted mixture is allowed to flow in from a tangential direction, and a method of separating a vapor into an upper part and a liquid / solid substance into a lower part using a centrifugal force is used.

  The vapor | steam isolate | separated here flows in into the condenser 12, is cooled, and is divided into evaporative condensed water and non-condensable gas. The evaporated condensed water contains an organic acid having low volatility, and the gas is mainly composed of carbon dioxide. On the other hand, the liquid / solid mixture discharged from the lower part of the separator is stored in the product storage tank 8 and processed by the solid-liquid separator 11 as needed.

  As the solid-liquid separation device, a specific gravity difference separation method or a centrifugal separation method can be adopted, and a liquid containing a low-temperature hot water-soluble component such as a hemicellulose hydrolyzate or a cellulose hydrolyzate and a lignin derivative as main components. Separated into a greasy solid. As described above, by using this apparatus, lignocellulosic biomass can be continuously processed in a subcritical water state, and if separation is appropriately performed in a specific temperature range, a resin raw material mainly composed of a lignin derivative can be obtained. It can be continuously produced without using an organic solvent.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

  In this example, it was experimentally verified whether the lignin derivative is soluble in high-temperature hot water. First, by using the batch-type apparatus described above, a mixture of cedar wood powder and water (solids concentration 10% by weight) was treated at 300 ° C., 9 MPa, 30 minutes, and the resulting solid residue (Klason lignin ratio 90%, About 3 g of acetone-soluble component ratio) was charged in a specially constructed subcritical water extraction apparatus, and extraction with subcritical water was attempted at various temperatures. An outline of the subcritical water extraction apparatus is shown in FIG.

  The extraction container was composed of a 1/2 inch tube, L: 150 mm, volume: 13.5 ml, and a filter (opening 7 μm) was installed in front and back to prevent the solid matter from flowing out. Subcritical water (150 to 300 ° C., pressure is constant at 9 MPa) having a predetermined temperature and pressure was produced in this extraction vessel with an electric heater and allowed to flow for about 3 hours at a flow rate of 2.5 g / min. The subcritical water exiting the extraction vessel was cooled to near room temperature with a double tube type cooler, passed through a filter, and then reduced in pressure while maintaining the system pressure at 9 MPa with a spring pressure holding valve.

  The inner tube of the double tube cooler used here is the same 1/2 inch tube as the extraction container, the outer tube is a 3/4 inch tube, and the annular portion of the inner tube and the outer tube is cooled with water. . The reason why the inner tube of the cooler is a 1/2 inch tube is to prevent the high temperature hot water soluble components that flowed out of the extraction vessel together with hot water from clogging even if it precipitates in the cooler and causing pressure rise. It is.

  The relationship between the temperature in subcritical water extraction, the solids outflow rate (%), and the acetone soluble component extraction rate (%) was investigated. The result is shown in FIG. The solids outflow rate was defined as the ratio of the solids outflowed to the weight of the remaining solids charged, but actually the amount remaining in the extraction container was measured and obtained as the difference.

  The extraction ratio of acetone-soluble components with subcritical water was defined as the ratio of the amount of acetone-soluble components in the spilled solids to the amount of acetone-soluble components in the charged residual solids. It was determined as 100% acetone soluble. However, as a result of extracting the recovered effluent with acetone, it was experimentally confirmed that it was 100% acetone soluble. As shown in the figure, it can be seen that in the experiment at 250 ° C., almost all of the acetone-soluble component in the charged residual solid was extracted. In contrast, at 200 ° C., the result was a little less than 60%.

  However, in the result of the continuous experiment shown in FIG. 5 described above, by setting the temperature to 210 ° C. or higher, clogging is eliminated and solid matter precipitation in the line can be prevented. At that time, almost all of the solid matter recovered in the receiver is obtained. Subcritical water experiments have evaluated the solubility in pure high-temperature hot water, while the continuous experimental system uses hemicellulose and cellulose hydrolyzate. It is soluble in the coexistence state with a certain organic acid, and it is considered highly possible that the entire amount was dissolved in a lower temperature range.

  In addition, in the experiment at 300 ° C., the acetone soluble component ratio was evaluated as 120%, which is more than the charged amount. This is because lignin was further reduced in the molecular weight in the process of subcritical extraction at 300 ° C. It suggests. In any case, this example clearly showed the possibility of separating the resin raw material by controlling the temperature without using an organic solvent such as acetone.

  In this example, the Klarson lignin ratio and the acetone-soluble component ratio were examined together with the solid matter adhering to the filter in the continuous operation. A high-temperature and high-pressure filter was installed in the reactor outlet line of the continuous processing apparatus shown in FIG. 4, and the operation from the reactor outlet to the pressure reducing device receiver was held at 210 ° C. or higher with a heat medium to perform continuous operation. The object was cedar powder, and water was added to adjust the solid concentration to a 10% by weight water slurry. The reaction conditions were 300 ° C. and 9 MPa, and the flow rate was 20 g / min.

  The continuous operation was completed without causing problems such as blockage, with almost no fluctuations in temperature and pressure. On the next day of operation, the high-temperature and high-pressure filter was removed, and the solid matter attached to the filter was collected. In parallel, a grease-like solid was collected in the vacuum apparatus receiver, and the Klarson lignin ratio and the acetone-soluble component ratio were measured together with the filter-attached solid.

  As a result, the Klarson lignin rate was almost 100% in both samples, but the acetone soluble component rate was 2% for the filter-attached solids, while the grease-like solids were almost 100%. The results were different. As a result, the solid matter blocked by the high-temperature high-pressure filter is a component mainly composed of polymer lignin, and the grease-like solid obtained by the pressure reducing device receiver is mainly composed of a low-molecular lignin derivative. It was shown to be a resin raw material.

  In this example, the solid concentration capable of continuous press-fitting was examined. The biomass solids concentration in the biomass / water slurry directly affects the scale and energy balance of the processing apparatus, and the higher the solids concentration, the better the economy. However, as the solid concentration increases, the fluidity deteriorates, and continuous press-fitting becomes virtually impossible above a certain concentration.

  The object was cedar wood powder, water was added so that the solids concentration would be 5, 10, 15, and 20% by weight, and homogenization was performed with a slurrying device (high-speed shearing homogenizer). The slurry of various concentrations after the homogenization treatment was filled in the low-pressure slurry pump (Mono pump) hopper of the continuous treatment apparatus shown in FIG. 4 and examined whether it could be inserted into the reactor.

  As a result, a slurry with a solids concentration of up to 15% could be sent with almost no problem. However, with a 20% slurry, the solids remained in the pipe and only water was sent (ie, pressing). Eventually, a pressure increase occurred and the automatic stop occurred. Thereafter, this high-concentration slurry was treated again for a long time using a slurrying apparatus, and the same experiment was conducted. The result was the same. From the above results, it was concluded that the solid concentration capable of stable continuous injection was 15% by weight.

As described above in detail, the present invention relates to a method and apparatus for producing a resin raw material mainly composed of a lignin derivative using lignocellulosic biomass as a raw material, and according to the present invention, lignocellulosic based on subcritical water is provided. It is possible to provide a continuous process for producing a resin raw material and a device thereof that can separate and recover a low molecular weight lignin derivative from biomass as a solid. In the present invention, by combining temperature control and high-temperature and high-pressure solid-liquid separation, it is possible to selectively extract and separate high molecular weight lignin and low molecular weight lignin derivative. Can be separated. In the present invention, by keeping the temperature of the reactor outlet line at 200 to 250 ° C. , it is possible to avoid clogging by solids, and the resin raw material yield (ratio of low molecular weight lignin derivative to biomass input) is Nearly 20% can be achieved for many lignocellose biomass. The present invention provides an economical and highly efficient method for continuously producing a resin raw material comprising a lignin derivative as a main component and its apparatus, which can selectively separate a low molecular weight lignin derivative without using an organic solvent such as acetone. Useful for providing.

Claims (19)

In a method for producing a resin raw material from lignocellulosic biomass mainly composed of hemicellulose, cellulose and lignin,
The biomass is pulverized and mixed with water to form a water slurry, and the water slurry is subjected to continuous treatment at a temperature of 250 ° C. or higher and 374 ° C. or lower under a pressure equal to or higher than the saturated water vapor pressure at that temperature for 30 minutes or longer. After completion of the reaction, solid-liquid separation is performed at 200 to 250 ° C. to separate the solid and the high-temperature hot water soluble component, and the temperature is lowered to 100 ° C. or lower to lower the temperature. A continuous process for producing a resin raw material from lignocellulosic biomass, characterized in that it is separated into a hot water soluble component and a grease-like resin raw material.   The continuous manufacturing method of the resin raw material of Claim 1 which processes a water slurry at the temperature of 300 degrees C or less. The method for continuously producing a resin raw material according to claim 1 or 2, wherein the solid-liquid separation operation at 200 to 250 ° C is an operation by filtration or specific gravity difference separation. A method of lowering the temperature of a high-temperature hot water-soluble component separated at 200 to 250 ° C. to 100 ° C. or lower is received by a high-temperature and high-pressure recovery receiver while maintaining 200 to 250 ° C. The method for continuous production of a resin raw material according to any one of claims 1 to 3, wherein the resin raw material is cooled to 100 ° C or lower by being directly cooled to 200 ° C or 250 ° C under atmospheric pressure.   The continuous manufacturing method of the resin raw material in any one of Claims 1-4 whose solid substance concentration in a water slurry is 15% at the maximum (water content 85% or more). It is an apparatus used with the continuous manufacturing method of the resin raw material of Claim 1, Comprising: The pump system which supplies a water slurry at high pressure, the reactor which performs subcritical water reaction, The reaction material processed by this reactor is discharged | emitted A reactor outlet line, a receiver for recovering the reactant from the reactor outlet line, and a solid-liquid separator installed in the middle of the reactor outlet line as components, and processed in the reactor 200 The high-temperature hot water-soluble component at ˜250 ° C. and the solid are separated by the solid-liquid separator, and the high-temperature hot water-soluble component is received at the receiver while maintaining the temperature of 200-250 ° C. Lignocellulosic system characterized in that the resin raw material is recovered by lowering the temperature to below ℃ to precipitate the resin raw material as a grease-like solid and separating it from the low-temperature hot water soluble component From biomass Continuous production apparatus fat feedstock.   The apparatus according to claim 6, wherein the solid-liquid separator is a filter or a specific gravity difference separator. The apparatus of Claim 6 or 7 which has a heat insulation heating means which maintains a reactor exit line (reactor exit to a receiver) at 200-250 degreeC .   The apparatus according to claim 8, wherein the heat retaining heating means is heating medium heating.   The apparatus in any one of Claims 6-9 which has a means to cool the high temperature hot water soluble component accommodated in the receiver to 100 degrees C or less.   The receiver has a piston inside, receives high-temperature hot water soluble components on one side of the piston, and discharges high-pressure water filled on the opposite side of the piston at a predetermined pressure, thereby adjusting the pressure of the entire device And the apparatus in any one of Claims 6-10 which collect | recovers high temperature hot water soluble components.   The apparatus according to claim 10, wherein the means for cooling to 100 ° C. or lower is a cooling jacket installed outside the receiver.   The receiver is filled with an inert gas at a predetermined pressure in advance, and the gas pressure increase caused by receiving the high-temperature hot water soluble component is discharged at a predetermined pressure, thereby adjusting the pressure of the entire apparatus and The apparatus in any one of Claims 6-10 which collect | recovers a hot water soluble component.   The apparatus according to claim 10, wherein the means for cooling to 100 ° C. or less is a cooling coil inserted into the receiver. It is an apparatus used with the continuous manufacturing method of the resin raw material of Claim 1, Comprising: The pump system which supplies a water slurry at high pressure, the reactor which performs subcritical water reaction, The reaction material processed by this reactor is discharged | emitted A reactor outlet line, a solid-liquid separator installed in the middle of the reactor outlet line, a pressure reducing valve that flushes liquid (high temperature hot water soluble component) directly from the solid-liquid separator under atmospheric pressure, A receiver for recovering the reaction product after flushing is included as a component, and the high-temperature hot water soluble component at 200 to 250 ° C. and the solid material treated in the reactor are separated by the solid-liquid separator. By reducing the soluble component directly from 200 to 250 ° C. to atmospheric pressure and lowering the temperature to 100 ° C. or less, the resin raw material is precipitated as a grease-like solid in the receiver, and low temperature hot water is allowed. By separating it from the dissolved components, Continuous production apparatus for resin material from the lignocellulosic biomass characterized in that so as to recover.   The apparatus according to claim 15, wherein the solid-liquid separator is a filter or a specific gravity difference separator. The apparatus of Claim 15 or 16 which has a heat insulation heating means which maintains a reactor outlet line (reactor outlet to a receiver) at 200-250 degreeC .   The apparatus according to claim 17, wherein the heat retaining heating means is heating medium heating.   The apparatus according to any one of claims 15 to 18, further comprising a separator for separating the reaction product after flashing into a vapor and a solid-liquid mixture, wherein the vapor is evaporated into condensed water by a condenser and the solid-liquid mixture is received in a receiver. .

Images