JP2015149957A - Pretreatment method for saccharifying lignocellulosic biomass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pretreatment method of biomass, allowing an ammonia separation pretreatment product before saccharification to be easily cooled without injection of cooling water into a reactor.SOLUTION: The pretreatment method of biomass includes a step of obtaining an ammonia separation pretreatment product before saccharification, in which the internal pressure of a reactor 2 is reduced to a pressure P at the atmospheric pressure or less and the saturated vapor pressure of water at an optimal temperature of amylase or more, so that ammonia is dissipated from the ammonia-containing pretreatment product before saccharification and the temperature of the ammonia separation pretreatment product before saccharification is lowered to a temperature T corresponding to the pressure P.

Description

  The present invention relates to a saccharification pretreatment method for lignocellulosic biomass used for bioethanol production.

  In recent years, it has been studied to use a gasoline-ethanol mixed fuel as a fuel for automobiles. For use in the gasoline-ethanol mixed fuel, a technique for producing ethanol using lignocellulosic biomass has been studied.

  The lignocellulosic biomass contains cellulose, and it can be decomposed into sugars such as glucose by subjecting the cellulose to a saccharification treatment using a saccharifying enzyme, and the resulting sugar can be fermented to obtain ethanol.

  However, the lignocellulosic biomass mainly contains hemicellulose and lignin in addition to cellulose, and usually the cellulose and the hemicellulose are firmly bound to the lignin. It is difficult to carry out the reaction. Therefore, when enzymatically saccharifying the cellulose, it is desirable that the lignocellulosic biomass is pretreated in advance so that the enzymatic saccharification reaction is possible.

  In order to make the lignocellulosic biomass ready for enzymatic saccharification, a method is known in which the lignocellulosic biomass is pretreated as follows (see, for example, Patent Document 1).

  First, in a sealed reaction vessel, a lignocellulosic biomass as a substrate and aqueous ammonia are mixed to obtain a substrate mixture. Next, the substrate mixture is heated to a predetermined temperature in the reaction vessel and held at the temperature for a predetermined time to dissociate lignin from the substrate or swell the substrate under high temperature and pressure, thereby saccharifying the ammonia. A pre-treatment product is obtained.

  In addition, in this application, dissociation means cut | disconnecting at least one part coupling | bonding among the binding sites of lignin couple | bonded with cellulose etc. Swelling means that voids are formed in cellulose or the like constituting crystalline cellulose by the ingress of liquid, or the voids are generated inside the cellulose fibers to expand.

  Next, the sealed reaction vessel is released to release ammonia from the ammonia-containing saccharification pretreatment product and release it to the outside of the reaction vessel to obtain an ammonia separation saccharification pretreatment product. Next, the ammonia-separated saccharification pretreatment product is cooled to the optimum temperature of the saccharification enzyme used for the enzyme saccharification reaction, and a solution containing the saccharification enzyme and an aqueous acid solution as necessary are added, whereby a substrate / saccharification is performed. An enzyme mixture is obtained.

  Then, after the substrate / saccharifying enzyme mixture obtained by such a pretreatment method is kept at the optimum temperature for a predetermined time in the sealed reaction vessel for an enzyme saccharification reaction, the resulting saccharification solution is fermented. Then, bioethanol can be obtained by distillation.

  In the conventional pretreatment method, the ammonia separation saccharification pretreatment product is introduced into the reaction vessel in which the ammonia separation saccharification pretreatment material is accommodated or the jacket of the reaction vessel, whereby the ammonia separation saccharification pretreatment material is treated as the optimum. It is conceivable to cool to temperature.

JP 2011-234688 A

  However, when cooling water is introduced into the reaction vessel, the ammonia separation saccharification pretreatment product is diluted, resulting in a disadvantage that the processing efficiency is lowered. In addition, when cooling water is introduced into the jacket of the reaction vessel, not only the energy to be added is increased, but also the facilities are complicated and the cost is increased.

  An object of the present invention is to provide a biomass pretreatment method that can easily cool the ammonia separation saccharification pretreatment product without introducing cooling water into the reaction vessel and the jacket, eliminating such disadvantages. And

  In order to achieve such an object, the present invention comprises a step of mixing a lignocellulosic biomass as a substrate and aqueous ammonia in a sealed reaction vessel to obtain a substrate mixture; Heating to a temperature and maintaining the temperature for a predetermined time to dissociate lignin from the substrate or swell the substrate to obtain an ammonia-containing saccharification pretreatment product, and ammonia from the ammonia-containing saccharification pretreatment product A step of obtaining an ammonia separation saccharification pre-treatment product by releasing and releasing it from the reaction vessel; and a step of obtaining a substrate / saccharification enzyme mixture by adding a solution containing a saccharification enzyme to the ammonia separation saccharification pre-treatment product. In the pretreatment method for saccharification of lignocellulosic biomass comprising: After releasing the sealing and allowing ammonia to spontaneously dissipate from the ammonia-containing saccharification pretreatment product until the internal pressure of the reaction vessel drops to a first pressure of atmospheric pressure or higher, the internal pressure of the reaction vessel is increased to a high level. By reducing the pressure to a second pressure that is equal to or lower than the atmospheric pressure and equal to or higher than the saturated vapor pressure of water at the optimum temperature of the saccharifying enzyme, ammonia is released from the ammonia-containing saccharification pretreatment product and the ammonia separation saccharification pretreatment product is The temperature is lowered to a temperature corresponding to the second pressure.

  In the pretreatment method of the present invention, the step of obtaining the ammonia separated saccharification pretreatment product by releasing ammonia from the ammonia-containing saccharification pretreatment product is performed as follows.

  First, in order to perform the step of obtaining the ammonia-containing saccharification pretreatment product, the sealing of the reaction vessel which is sealed and is at a high temperature and high pressure is released. Thereby, ammonia is naturally diffused from the ammonia-containing pre-saccharification product until the internal pressure of the reaction vessel is reduced to a first pressure equal to or higher than atmospheric pressure, and is released to the outside of the reaction vessel. The first pressure is, for example, a pressure equal to or higher than atmospheric pressure and close to atmospheric pressure.

  Next, by reducing the internal pressure of the reaction vessel to a second pressure not lower than the saturated vapor pressure of water and not higher than atmospheric pressure at the optimum temperature, ammonia can be further dissipated from the ammonia-containing saccharification pretreatment product. In addition, an ammonia separation saccharification pretreatment product can be obtained.

  At this time, the temperature of the ammonia-containing saccharification pretreatment product is first lowered to a temperature corresponding to the saturated vapor pressure of ammonia water. And the temperature of the said ammonia containing saccharification pre-processing thing falls to the temperature corresponding to the saturated vapor pressure of water by the ammonia concentration becoming low in the latter half of emission. Along with this, the ammonia separation saccharification pretreatment product accommodated in the reaction vessel can be lowered to a temperature corresponding to the second pressure.

  Therefore, according to the pretreatment method of the present invention, the ammonia separation saccharification pretreatment product can be easily brought to a temperature corresponding to the second pressure by simply reducing the internal pressure of the reaction vessel to the second pressure. Can be cooled.

  In the pretreatment method of the present invention, the second pressure can be, for example, the saturated vapor pressure of water at a temperature 5 to 20 ° C. higher than the optimum temperature.

  In this case, when the internal pressure of the reaction vessel is reduced to the second pressure, the ammonia separation saccharification pretreatment product can be cooled to a temperature 5 to 20 ° C. higher than the optimum temperature of the saccharification enzyme. Next, the optimum temperature can be adjusted by adding a solution containing the saccharifying enzyme.

The system block diagram which shows the apparatus structure which implements the pre-processing method of this embodiment. Explanatory drawing which shows schematically an example of the line of the binary system heat pump shown in FIG.

  Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

  In the present embodiment, as a pretreatment, a substrate mixture obtained by mixing a substrate and aqueous ammonia is heated to obtain an ammonia-containing saccharification pretreatment product, and then ammonia is removed from the ammonia-containing saccharification pretreatment product to separate ammonia saccharification. A pre-treatment product is obtained. Further, the substrate / saccharifying enzyme mixture obtained by adding a solution containing saccharifying enzyme to the ammonia separation saccharification pre-treated product is subjected to enzymatic saccharification treatment.

  The pretreatment method of this embodiment can be implemented using the pretreatment apparatus 1 shown in FIG.

  The pretreatment device 1 includes a reaction vessel 2, an ammonia water condenser 3, an ammonia water absorption tower 4, and an ammonia water tank 5.

  The reaction vessel 2 is provided with a substrate supply conduit 6, an ammonia water supply conduit 7, a saccharification enzyme solution supply conduit, an acid aqueous solution supply conduit, and an ion exchange water supply conduit (not shown) at the top, and ammonia gas. A first exhaust pipe 8 that discharges water vapor and guides it to the ammonia water condenser 3 is disposed via an exhaust valve 9 and a bag filter 10.

  The substrate supply conduit 6 supplies lignocellulosic biomass as a substrate, such as rice straw, to the reaction vessel 2, and the ammonia water supply conduit 7 supplies ammonia water to the reaction vessel 2 from an ammonia water tank (not shown). The saccharifying enzyme solution supply conduit supplies a solution containing saccharifying enzyme (hereinafter abbreviated as saccharifying enzyme solution) to the reaction vessel 2, and the acid aqueous solution supply conduit supplies an acid aqueous solution such as dilute sulfuric acid to the reaction vessel 2. To supply.

  In addition, the reaction vessel 2 includes a motor 11 disposed in the upper portion, a rotary shaft 12 hanging from the motor 11 into the reaction vessel 2, and a stirring blade 12 a extending from the rotary shaft 12 in the horizontal direction. .

  Further, a pressure sensor 13 for detecting pressure is provided inside the reaction vessel 2.

  A jacket 14 through which a heat medium is circulated is disposed outside the reaction vessel 2, and a hot water conduit 15 is connected to the jacket 14.

  The hot water conduit 15 passes hot water derived from the upper part of the jacket 14 as a first heat medium through a hot water tank 16, a hot water pump 17, an air cooling fan 18, a two-way heat pump 19, a check valve 20, and an on-off valve 21. And is circulated to the bottom of the jacket 14.

  The hot water conduit 15 includes a hot water bypass conduit 22 that branches from between the check valve 20 and the on-off valve 21. The hot water bypass conduit 22 is connected to the hot water tank 16 via an on-off valve 23 and includes a flow meter 24 downstream of the on-off valve 23.

  The hot water tank 16 is provided with a first make-up water conduit 25, and the first make-up water conduit 25 is connected to the first make-up water tank 26 through a first water supply valve 25a.

  The ammonia water condenser 3 cools at least a part of the ammonia gas and water vapor introduced from the first exhaust pipe 8 to condense the ammonia gas and water vapor into ammonia water. Is provided with a first drainage conduit 27. The first drainage conduit 27 is connected to the ammonia water tank 5 through a condensed water tank 28 and a first drainage pump 29 for further cooling the condensed ammonia water.

  The ammonia water condenser 3 includes a second exhaust conduit 30 that discharges ammonia gas and water vapor that have not been condensed and guides them to the ammonia water tank 5. The second exhaust conduit 30 is connected via an on-off valve 31. The ammonia water tank 5 is connected. The second exhaust conduit 30 branches from the third exhaust conduit 32 upstream of the on-off valve 31. The third exhaust conduit 32 includes a vacuum pump 33 on the way and joins the second exhaust conduit 30 downstream of the on-off valve 31. doing.

  An open / close valve 34 is provided upstream of the vacuum pump 33 in the third exhaust conduit 32, and an open / close valve 35 is provided downstream of the vacuum pump 33. The third exhaust conduit 32 branches the fourth exhaust conduit 36 between the vacuum pump 33 and the on-off valve 35. The fourth exhaust conduit 36 is provided with an open / close valve 37, and the other end of the fourth exhaust conduit 36 is open to the atmosphere.

  The ammonia water absorption tower 4 communicates with the top surface of the ammonia water tank 5 at the bottom, and absorbs (dissolves) ammonia gas and water vapor guided to the ammonia water tank 5 by the second exhaust conduit 30 in the ammonia water. For this reason, the ammonia water absorption tower 4 is provided with a showering device 39 for showering the ammonia water supplied from the ammonia water tank 5 via the ammonia water circulation conduit 38 at the top.

  The ammonia water circulation conduit 38 is connected from the ammonia water tank 5 to the showering device 39 via the circulation pump 40, the ammonia water heat exchanger 41, and the ammonia concentration sensor 42. The ammonia water heat exchanger 41 has a function of cooling the ammonia water circulated through the ammonia water circulation conduit 38. The ammonia water absorption tower 4 is provided with a second makeup water conduit 43, and the second makeup water conduit 43 is connected to a second makeup water tank 45 via a second water supply valve 44.

  The ammonia water tank 5 includes a second drainage conduit 46 that discharges ammonia water, and the second drainage conduit 46 is connected to an ammonia water tank (not shown) via a second drainage pump 47. Note that an ammonia water supply conduit 7 for supplying ammonia water to the reaction vessel 2 is connected to the ammonia water tank.

  The ammonia water condenser 3 is connected to a low temperature water conduit 48 for cooling ammonia gas and water vapor introduced from the first exhaust conduit 8. The low temperature water conduit 48 converts low temperature water derived from the ammonia water condenser 3 as a second heat medium into a low temperature water primary tank 49, a low temperature water primary pump 50, a two-way heat pump 19, a first switching valve 51, The ammonia water heat exchanger 41 and the condensed water tank 28 are circulated to the ammonia water condenser 3.

  A low temperature water bypass conduit 52 is connected to the first switching valve 51, and the other end of the low temperature water bypass conduit 52 is connected to the low temperature water primary tank 49 via the second switching valve 53. A cold water conduit 55 is connected to the second switching valve 53, and the other end of the cold water conduit 55 is connected to the low temperature water secondary tank 56. The first switching valve 51 and the second switching valve 53 can switch the flow path of the low-temperature water.

  The low temperature water secondary tank 56 is provided with a cold water supply conduit 57, and the cold water supply conduit 57 is connected to the low temperature water conduit 48 downstream of the first switching valve 51 via the low temperature water secondary pump 58. Yes. The low temperature water primary tank 49 is provided with a third make-up water conduit 59, and the third make-up water conduit 59 is connected to the third make-up water tank 61 through the third water supply valve 60.

  Next, the operation of the pretreatment device 1 of this embodiment will be described.

  In the pretreatment apparatus 1, first, the saccharification product obtained in the previous treatment is discharged from a discharge port (not shown) at the bottom of the reaction vessel 2 and transferred to the next step.

  Next, after starting the supply of lignocellulosic biomass as a new substrate from the substrate supply conduit 6, for example, rice straw to the reaction vessel 2, the operation of the binary heat pump 19 is started. Further, hot water as a heating heat medium is supplied from the hot water conduit 15 to the jacket 14, and circulation is started between the jacket 14 and the binary heat pump 19, and the temperature of the warm water itself and the jacket 14 as the heat medium is increased. To do.

  Next, ammonia water is supplied to the reaction vessel 2 from the ammonia water supply conduit 7. At this time, in the reaction vessel 2, the rotating shaft 12 is rotationally driven by the motor 11, and the rice straw and the ammonia water are stirred by the stirring blade 12a, whereby the substrate mixture is prepared. In the present embodiment, the operation corresponds to a step of obtaining a substrate mixture.

  The substrate mixture is heated to a predetermined temperature, for example, in the range of 80 to 85 ° C., in the reaction vessel 2 by the hot water supplied from the hot water conduit 15 to the jacket 14. The stirring by the stirring blade 12a is continued until the substrate mixture reaches the predetermined temperature.

  Next, after the substrate mixture is heated to the predetermined temperature, the agitation and hot water pump 17 and the binary heat pump 19 are stopped, the heating is finished, and the substrate mixture is kept at the predetermined temperature for a predetermined time. For example, for 1 to 6 hours. As a result, it is possible to obtain an ammonia-containing saccharification pretreatment product in which lignin is dissociated from the substrate or the substrate is swollen so that rice straw as the substrate can be enzymatically saccharified. In this embodiment, the said operation | movement corresponds to the process of obtaining an ammonia containing saccharification pre-processing thing.

  Next, in the pretreatment device 1, the operation of the binary heat pump 19 is restarted and the supply of hot water to the jacket 14 is started in order to start the step of obtaining the ammonia separation saccharification pretreatment product. By opening the exhaust valve 9, ammonia and water vapor contained in the ammonia-containing saccharification pretreatment product are diffused as gas and guided to the ammonia water condenser 3 from the first exhaust pipe 8 through the bag filter 10. At this time, the pressure in the reaction vessel 2 is higher than the atmospheric pressure due to the heating, and by opening the exhaust valve 9, ammonia gas and water vapor can be easily released from the ammonia-containing saccharification pretreatment product. it can.

  The ammonia gas and water vapor are cooled by the low-temperature water supplied from the low-temperature water conduit 48 to the ammonia water condenser 3, part of which is condensed and liquefied to become ammonia water, which is condensed via the first drainage conduit 27. It is discharged to the water tank 28. The ammonia water is further cooled by the low temperature water supplied from the low temperature water conduit 48 in the condensed water tank 28, and then sent to the ammonia water tank 5 through the first drainage pump 29.

  The remaining ammonia gas and water vapor are introduced into the ammonia water tank 5 through the second exhaust conduit 30 by opening the on-off valve 31. The pressure of the ammonia gas and water vapor decreases as it is diffused, and when it becomes equal to the atmospheric pressure, it becomes difficult to dissipate further.

  Therefore, when the pressures of the ammonia gas and the water vapor become equal to the atmospheric pressure, the on-off valve 31 is closed, the on-off valve 34 and the on-off valve 35 are opened, and the vacuum pump 33 is operated, whereby the reaction vessel The ammonia gas and water vapor in the tank 2 are sucked and introduced into the ammonia water tank 5 through the second exhaust conduit 30 and the third exhaust conduit 32.

  The ammonia gas and water vapor introduced into the ammonia water tank 5 are then introduced into the ammonia water absorption tower 4 communicating with the ammonia water tank 5. In the ammonia water absorption tower 4, the ammonia gas circulated by the circulation pump 40 through the ammonia water circulation conduit 38 is showered by the showering device 39, thereby absorbing (dissolving) the ammonia gas and water vapor in the ammonia water and Condense.

  In the present embodiment, the condensation of the ammonia gas and water vapor in the ammonia water condenser 3 and the absorption in the ammonia water absorption tower 4 correspond to a process of recovering the diffused ammonia gas and water vapor as ammonia water.

  At this time, the heat and latent heat generated when the ammonia water and water vapor are absorbed (dissolved) and condensed in the ammonia water by the ammonia water heat exchanger 41 provided in the middle of the ammonia water circulation conduit 38 are converted into the low temperature water conduit. The ammonia water is cooled while being recovered by the low-temperature water flowing through 48.

  The ammonia water stored in the ammonia water tank 5 is, for example, in the range of 15 to 20 ° C. as a result of condensation and cooling in the ammonia water condenser 3 and the condensed water tank 28 and dissolution in the ammonia water in the ammonia water absorption tower 4. Is cooled to a temperature of The ammonia water cooled to the temperature in the above range is taken out by the second drainage pump 47 through the second drainage conduit 46 and reused for the preparation of the substrate mixture in the reaction vessel 2.

  In the reaction vessel 2, the ammonia-separated saccharification pretreatment product from which ammonia has been separated can be obtained as a result of the ammonia water being diffused from the ammonia-containing saccharification pretreatment product as described above.

  Next, the acid aqueous solution is supplied to the reaction vessel 2 via the acid aqueous solution supply conduit and stirred, and the saccharification enzyme solution is supplied and stirred via the saccharification enzyme solution supply conduit. As a result, a substrate / saccharifying enzyme mixture in which the ammonia separation saccharification pretreatment product and the saccharifying enzyme solution are mixed can be obtained. At this time, if necessary, ion-exchanged water may be supplied via an ion-exchanged water supply conduit to adjust the water content of the substrate / saccharifying enzyme mixture.

  Next, by performing an enzymatic saccharification treatment in the reaction vessel 2, at least a part of the substrate / saccharifying enzyme mixture is saccharified, and the resulting saccharification treatment product is discharged from the bottom of the reaction vessel 2 as described above. It is discharged from (not shown) and transferred to the next process. Then, the next process is prepared in the reaction vessel 2.

  Next, the heating of the substrate mixture for obtaining the ammonia-containing saccharification pretreatment product in the reaction vessel 2 will be described in more detail.

  First, the heating of the substrate in the reaction vessel 2 will be described. After the substrate starts to be supplied to the reaction vessel 2 through the substrate supply conduit 6, hot water is supplied to the jacket 14 of the reaction vessel 2 through the hot water conduit 15. As a result, heating of the heat medium (warm water) itself and the jacket 14 is started. Thereafter, ammonia water is supplied through the ammonia water supply conduit 7, and the substrate and the ammonia water are stirred and mixed by the stirring blade 12a to prepare a substrate mixture.

  In the pretreatment method of the present embodiment, heating of the heating medium and the jacket 14 is started before the substrate mixture is prepared, and an ammonia separation pretreatment product is obtained in the hot water tank 16 during the previous pretreatment. Since the hot water recovered during the process can be used, the time required for the substrate mixture to rise to the predetermined temperature can be shortened. In addition, stirring is performed by the stirring blade 12a until the temperature of the substrate mixture is raised to the predetermined temperature, but the stirring time can be shortened and energy required for stirring can be reduced.

  Next, the circulation route of the low temperature water stored in the low temperature water primary tank 49 is shown. When obtaining the ammonia-containing pre-saccharification product, the first switching valve 51 is operated to switch the low-temperature water conduit 48 and the low-temperature water bypass conduit 52 to be connected.

  In this way, the low-temperature water stored in the low-temperature water primary tank 49 passes through the low-temperature water primary pump 50, and the low-temperature water primary pump 50, It is circulated through a path returning to the low-temperature water primary tank 49 through the original heat pump 19, the first switching valve 51, and the second switching valve 53.

  At this time, the low-temperature water circulated through the low-temperature water conduit 48 exchanges heat with the carbon dioxide in the first heat exchanger 74 of the binary heat pump 19 as described above, so that the ammonia water condenser 3 The target is cooled to a temperature at which ammonia gas can be condensed, for example, a temperature in the range of 10 to 15 ° C. However, since it is higher than the temperature at the time of start-up, it is circulated through a path returning to the low-temperature water primary tank 49.

  Next, when the temperature of the low-temperature water detected by the temperature sensor 54 is cooled to a target temperature in the range of 10 to 15 ° C., the second switching valve 53 is connected to the low-temperature water bypass conduit 52 and the cold water conduit 55. Can be switched to connect. As a result, low-temperature water having a temperature in the range of 10 to 15 ° C. or lower (hereinafter referred to as cold water) is stored in the low-temperature water secondary tank 56 and used in the step of obtaining the ammonia separation saccharification pretreatment product.

  Next, the binary heat pump 19 will be described in detail. The two-way heat pump 19 is a heat pump using two types of heat medium, and includes two types of heat medium circulation systems of a first circulation conduit 71 and a second circulation conduit 72 as shown in FIG. ing. As the two types of heat medium, for example, carbon dioxide is circulated through the first circulation conduit 71 and trifluoroethanol is circulated through the second circulation conduit 72.

  The first circulation conduit 71 is circulated to the expansion valve 73 and the first heat exchanger 74 that exchanges heat with the low-temperature water circulated to the low-temperature water conduit 48, the compressor 75, and the second circulation conduit 72. A second heat exchanger 76 that exchanges heat with fluoroethanol is provided. The second circulation conduit 72 is circulated to the expansion valve 77, the second heat exchanger 76 that exchanges heat with the carbon dioxide circulated to the first circulation conduit 71, the compressor 78, and the hot water conduit 15. A third heat exchanger 79 for exchanging heat with warm water is provided.

  The low-temperature water is cooled to a temperature at which ammonia gas can be condensed in the ammonia water condenser 3 by exchanging heat with carbon dioxide in the first heat exchanger 74 of the binary heat pump 19, for example, 10 to 15 ° C. The The carbon dioxide is heated by exchanging heat with the low-temperature water in the first heat exchanger 74 of the binary heat pump 19.

  In the binary heat pump 19, the trifluoroethanol circulated through the second circulation conduit 72 exchanges heat with the carbon dioxide supplied through the first circulation conduit 71 in the second heat exchanger 76. Heated. The trifluoroethanol is cooled by exchanging heat with hot water supplied by the hot water conduit 15 in the third heat exchanger 79. As a result, the hot water supplied to the third heat exchanger 79 through the hot water conduit 15 is heated to a temperature at which the substrate mixture can be heated in the reaction vessel 2.

  Next, cooling and condensation of ammonia gas and water vapor by the ammonia water condenser 3 will be described in more detail.

  In the pretreatment device 1, first, in the normal time except for the initial stage of obtaining the ammonia separation pretreatment product, the first switching valve 51 connects the upstream and downstream of the low temperature water conduit 48, and the low temperature water primary pump 50. Is activated.

  As a result, the low-temperature water stored in the low-temperature water primary tank 49 is taken out by the low-temperature water conduit 48, and the low-temperature water primary pump 50, the two-way heat pump 19, the first switching valve 51, the ammonia water heat exchanger. 41, the condensed water tank 28 and the ammonia water condenser 3, and then circulated through a path returning to the low temperature water primary tank 49.

  At this time, the low-temperature water is cooled by exchanging heat with hot water via the binary heat pump 19. The low-temperature water is heat-exchanged with ammonia water by the ammonia water heat exchanger 41 and the condensed water tank 28 to cool the ammonia water, and heat-exchanged with ammonia gas and water vapor by the ammonia water condenser 3. Cool ammonia gas and water vapor. On the other hand, the low-temperature water itself is heated by the ammonia water, the ammonia gas, and water vapor.

  Next, the initial stage of the process for obtaining the ammonia separation pretreatment product will be described. When the exhaust valve 9 is opened and ammonia gas and water released from the ammonia-containing saccharification pretreatment product in the reaction vessel 2 are introduced into the ammonia water condenser 3, the second switching valve 53 The low temperature water secondary pump 58 is operated in a state where the low temperature water bypass conduit 52 and the cold water conduit 55 are connected. By doing so, the cold water stored in the low temperature water secondary tank 56 is condensed with the ammonia water via the cold water supply conduit 57 and the low temperature water conduit 48, via the ammonia water heat exchanger 41 and the condensed water tank 28. Is supplied to the vessel 3.

  Since the pretreatment method of the present embodiment is a batch (batch) type, when ammonia gas and water vapor are condensed in the ammonia water condenser 3, a high concentration is obtained from the ammonia-containing saccharification pretreatment product in the initial stage of the emission. A large amount of ammonia gas and a small amount of water vapor are diffused, and a high concentration ammonia gas and a small amount of water vapor are introduced into the ammonia water condenser 3. For this reason, in the initial stage, large cooling heat energy is required to cool the high concentration ammonia gas and a small amount of water vapor. Therefore, as described above, by supplying the cold water stored in the low temperature water secondary tank 56 to the ammonia water condenser 3, the high concentration ammonia gas and a small amount of water vapor are efficiently cooled, Can be fully condensed.

  Thereafter, if it is detected by a water level sensor (not shown) that the water level of the cold water stored in the low temperature water secondary tank 56 has reached the lower limit, the first switching valve 51 is moved to the low temperature water as described above. It is switched to connect the upstream and downstream of the conduit 48.

  Then, the low-temperature water derived from the ammonia water condenser 3 is transferred to the low-temperature water primary tank 49, the low-temperature water primary pump 50, the two-way heat pump 19, the first switching valve 51, the ammonia water heat exchange by the low-temperature water conduit 48. Transition to the normal cooling state circulated to the ammonia water condenser 3 via the condenser 41 and the condensed water tank 28. At this time, since the concentration and amount of the ammonia gas diffused have already been reduced, the ammonia gas and water vapor can be sufficiently cooled and condensed by the low-temperature water in the normal cooling state.

  Further, in the pretreatment method of the present embodiment, in the step of obtaining ammonia separation saccharification pretreatment product by releasing ammonia from the ammonia-containing saccharification pretreatment product, the ammonia separation saccharification pretreatment product is obtained as follows. Reduce temperature.

  First, the on-off valve 34, the on-off valve 35, and the on-off valve 37 are closed, and the on-off valve 31 is opened to release the sealing of the reaction vessel 2 that has been sealed and is at high temperature and high pressure. As a result, ammonia is naturally diffused from the ammonia-containing saccharification pretreatment product in the reaction vessel 2, and the ammonia gas and water vapor are introduced into the ammonia water tank 5 through the first exhaust conduit 8 and the second exhaust conduit 30. The Thereby, the temperature of the said ammonia containing saccharification pre-processing thing falls to the temperature corresponding to the saturated vapor pressure of ammonia water.

  Next, after the pressure in the reaction vessel 2 becomes equal to the atmospheric pressure, the on-off valve 31 is closed, the on-off valve 34 and the on-off valve 35 are opened, and the vacuum pump 33 is operated. Thereby, ammonia gas and water vapor in the reaction vessel 2 are sucked by the vacuum pump 33 and introduced into the ammonia water tank 5 through the first exhaust conduit 8, the second exhaust conduit 30, and the third exhaust conduit 32.

Then, the reaction vessel 2, the water in the optimum temperature _{T 1} of the said saccharifying enzyme used in the enzymatic saccharification process the next step (e.g., 50 ° C.) from 5 to 20 ° C. higher temperature _{T 2} (e.g. 55 to 70 ° C.) The pressure is reduced to a pressure P corresponding to the saturated vapor pressure. This is effective when a large amount of an acid aqueous solution or a saccharifying enzyme solution adjusting solution described later can be supplied. Further, lower than 5 ° C., since become lower than the optimum temperature T ₁ of the saccharifying enzyme by the adjusting solution, hardly enzymatic saccharification. When the temperature is higher than 20 ° C., a larger amount of the adjustment solution is required to obtain the optimum temperature T ₁ , and the ammonia separation saccharification pretreatment product is diluted.

More preferably, it is preferably a temperature T ₂ (for example 55 to 60 ° C.) that is 5 to 10 ° C. higher than the optimum temperature T ₁ (for example 50 ° C.) of the saccharifying enzyme. In this case, since the adjustment solution can be minimized, the concentration of the ammonia separation saccharification pretreatment product can be further increased.

When the internal pressure of the reaction vessel 2 having a constant volume is reduced, the temperature of the ammonia-containing saccharification pretreatment product is lowered to a temperature corresponding to the saturated vapor pressure of water due to a decrease in the ammonia concentration. Along with this, it is possible to reduce the temperature of the ammonia separation saccharification pretreated product contained in the reaction vessel to a temperature T _2.

  Therefore, according to the pretreatment method of this embodiment, the ammonia separation saccharification pretreatment product can be easily cooled without introducing cooling water into the reaction vessel 2 or the jacket 14 of the reaction vessel 2.

  Next, the acid aqueous solution is supplied to the reaction vessel 2 through the acid aqueous solution supply conduit, and the saccharification enzyme solution is supplied through the saccharification enzyme solution supply conduit and stirred. As a result, a substrate / saccharifying enzyme mixture in which the ammonia separation saccharification pretreatment product and the saccharifying enzyme solution are mixed can be obtained. The substrate / saccharifying enzyme mixture is neutralized by being mixed with the aqueous acid solution and adjusted to the optimum pH of the saccharifying enzyme.

The obtained substrate / saccharifying enzyme mixture is mixed with the saccharifying enzyme solution and the acid aqueous solution, whereby the temperature can be lowered to the optimum temperature T _{1 of the} saccharifying enzyme. The substrate / saccharifying enzyme mixture that has been cooled to the optimal temperature T ₁ of the saccharifying enzyme and adjusted to the optimal pH of the saccharifying enzyme can be subjected to an enzymatic saccharification treatment using the saccharifying enzyme.

  Therefore, according to the pretreatment method of the present embodiment, the ammonia-separated saccharification pretreatment product can be quickly cooled, and can be quickly subjected to an enzymatic saccharification treatment using the saccharifying enzyme.

  DESCRIPTION OF SYMBOLS 1 ... Pretreatment apparatus, 2 ... Reaction container.

Claims (2)

A step of mixing a lignocellulosic biomass as a substrate with ammonia water in a sealed reaction vessel to obtain a substrate mixture;
Heating the substrate mixture to a predetermined temperature in the reaction vessel and maintaining the temperature for a predetermined time to dissociate lignin from the substrate or swell the substrate to obtain an ammonia-containing saccharification pretreatment product;
A step of obtaining ammonia-separated saccharification pre-treatment product by releasing ammonia from the ammonia-containing saccharification pre-treatment product and releasing it from the reaction vessel;
In the pretreatment method for saccharification of lignocellulosic biomass comprising the step of obtaining a substrate / saccharification enzyme mixture by adding a solution containing a saccharification enzyme to the ammonia separation saccharification pretreatment product,
In the step of obtaining the ammonia separation saccharification pretreatment product, the ammonia is removed from the ammonia-containing saccharification pretreatment product until the reaction vessel is closed and the internal pressure of the reaction vessel is reduced to a first pressure of atmospheric pressure or higher. After being naturally diffused, the ammonia-containing saccharification pretreatment is performed by reducing the internal pressure of the reaction vessel to a second pressure not higher than atmospheric pressure and not lower than the saturated vapor pressure of water at the optimum temperature of the saccharifying enzyme. A method for pre-saccharification of lignocellulosic biomass, wherein ammonia is diffused from a product and the ammonia-separated saccharification pre-treatment product is lowered to a temperature corresponding to the second pressure. In the pre-saccharification pretreatment method for lignocellulosic biomass according to claim 1,
The pretreatment for saccharification of lignocellulosic biomass, wherein the second pressure is a saturated vapor pressure of water at a temperature 5 to 20 ° C higher than the optimum temperature.

Images