JP2013112802A - Device for producing biomass-thermal-decomposition oil and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device for producing biomass-thermal-decomposition oil, the device recovering carbon from biomass at a high yield and requiring no drying of a raw material; and to provide a method for producing the same.SOLUTION: The device for producing biomass-thermal-decomposition oil includes: a means which kneads biomass, a carbon material and water together to produce a biomass raw material, and sends by means of pressure, the biomass raw material to a microwave reaction tube which is formed with a microwave-unabsorbable material and has a pressure-controlling means, and then heats the biomass raw material in the microwave reaction tube at a temperature range of 120-347°C in a microwave heater to produce crude biomass-thermal-decomposition oil; a condensation means which discharges the crude biomass-thermal-decomposition oil to a solid-liquid separator from a pressure controller to condense the biomass-thermal-decomposition oil, the condensation means being provided to connect it to the gas outlet of the solid-liquid separator; and a separation means which separates the biomass-thermal-decomposition oil from the solid carbon material.

Description

  The present invention relates to a biomass pyrolysis oil production apparatus and production method, and more specifically, biomass pyrolysis oil produced by pyrolyzing biomass and water using a microwave heating apparatus, and produced biomass pyrolysis oil The present invention relates to an apparatus and a method for producing biomass pyrolysis oil that continuously gasifies gas.

As an alternative to fossil fuels such as coal, oil, or natural gas, developments are underway to utilize biomass as fuel or industrial feedstock.
In order to use biomass as a fuel or industrial raw material, it is important to convert solid biomass into liquid or gas.

  As an approach for producing industrial raw materials from solid fuel, a method of producing “water gas” containing carbon monoxide and hydrogen by incomplete combustion of coal in the presence of steam is a basic reaction in coal chemistry. Established from the first century to the first half of the 20th century. In Germany, aviation fuel was produced from coal during World War II, and in South Africa, gasoline was produced during the oil embargo by apartheid.

Attempts have been made to apply a reaction for producing water gas to biomass, to produce synthesis gas from biomass, and to produce fuel and industrial raw materials. For example, a catalyst in which a metal is supported on a perovskite-type complex oxide, which is used to decompose tar generated when producing an aqueous gas containing hydrogen and carbon monoxide from biomass, is disclosed (for example, Patent Documents). 1). Methods for producing methanol (see, for example, Patent Document 2), ethanol, dimethyl ether (see, for example, Patent Document 3) and the like from water gas produced from biomass have already been disclosed.
Even now, “water gas” can be regarded as a promising common raw material for producing industrial raw materials from biomass.

  Note that the “water gas” in a narrow sense refers to a mixed gas (also referred to as synthesis gas) containing hydrogen gas and carbon monoxide obtained by reacting a carbon compound such as coke with water vapor at 900 ° C. or higher. In the present invention, a mixed gas containing hydrogen gas and carbon monoxide is referred to as “water gas”. In the present invention, as will be described later, water gas is produced from a mixed gas generated by the reaction of a carbon compound and water vapor, and hydrogen gas and carbon monoxide are separately taken out using a membrane separator, and the component ratio is adjusted. After mixing, it is used as “water gas”.

  Since the conventional method for producing water gas is performed at a reaction temperature of 900 ° C. or higher, part of the biomass has to be used as a fuel in order to maintain the reaction temperature. For this reason, there has been a problem that the reaction yield of the water gas is lowered. In addition, since the water gas reaction is basically an incomplete combustion reaction, the reaction is unstable and difficult to control. In particular, it is difficult to adjust the mixing ratio of carbon monoxide and hydrogen to be generated.

As a recent technology, a method for producing a carbon material by heating biomass with a microwave heating apparatus has been proposed (see, for example, Patent Document 4). In addition, a method for producing “water gas” from a carbon material using a microwave heating apparatus has been reported (see, for example, Patent Document 5). However, since these methods also use a large amount of energy in the microwave heating apparatus, the carbon yield and the energy recovery rate are low, and it is said that this method cannot be industrialized for economic reasons.
A method for industrially producing “water gas” from biomass has not yet been established.

  In a method of treating woody biomass with hot water at high temperature and high pressure, hydrolyzing the cellulose contained therein to produce glucose, and producing bioethanol by fermentation from glucose, cellulose is produced using a solid acid catalyst produced from biomass. A method for hydrolysis is disclosed (see, for example, cited document 6). However, although this method can accelerate the hydrolysis rate, it cannot raise the yield of ethanol to the industrial practical level.

There is liquefaction of biomass as a third method for converting biomass or the like into industrially usable materials. Add metal salt to biomass and water and irradiate microwaves to rapidly heat and liquefy biomass, "biomass pyrolysis oil", non-condensable component (gas component), solid carbon material, Has been disclosed (see, for example, Patent Document 7). The carbon yield in the “biomass pyrolysis oil” of this method can be 80 to 90%, and even if the properties of the raw material change, it is said that the produced biomass has little change in properties. .
However, the produced “biomass pyrolysis oil” is unstable and contains a large amount of water, so its calorific value per unit weight is low. Therefore, its use is limited to boiler fuel and the like.

In order to use biomass as an industrial raw material, the following problems peculiar to biomass must be solved.
(1) Biomass has a lower calorific value per unit weight than fossil fuels, and has a high impurity content and low purity.
(2) Biomass is a large variety of solids that are bulky and small in volume, and are difficult to transport.
(3) Some biomass contains a large amount of water.

Since biomass is a common problem, the method of using biomass as an industrial raw material is said to have a limit of 20% for the carbon yield (%) defined below.
Carbon yield = (number of carbon atoms in product / number of carbon atoms in raw material) x 100 (1)
(However, the amount of energy consumed in the production process is converted to the amount of carbon having the same amount of combustion energy and subtracted from the amount of carbon in the product.)

Moreover, it is said that the energy recovery rate defined below of biomass is 0.2.
Energy recovery rate = energy of products / (energy of raw materials + energy consumed in manufacturing process)
An industrially feasible method for producing water gas from biomass has not been put into practical use so far.

Japanese Patent Laid-Open No. 2008-238012 Japanese Patent Laid-Open No. 2005-13239 JP 2003-64016 A JP 2002-161278 A JP 2007-146115 A JP 2006-257234 A Special table 2009-543926

  An object of the present invention made to solve the above problems is to provide a biomass pyrolysis oil production apparatus and production method that can be used industrially without a high carbon recovery rate from biomass and having to dry the raw material. There is to do.

  Another object is to continuously produce water gas from biomass continuously by connecting a pyrolysis oil gasification step to a biomass pyrolysis oil production step.

  The apparatus for producing a biomass pyrolysis oil of the present invention for solving such problems is a biomass raw material production means for producing a biomass raw material by kneading with biomass, a carbon material, and water, and does not absorb the biomass, Raw material supply means formed of a material and pumped to a microwave reaction tube equipped with pressure control means, and raw biomass in the microwave reaction tube is heated to a temperature range of 120 ° C. to 347 ° C. with a microwave heating apparatus, and crude biomass And microwave heating means for producing pyrolysis oil.

  The present invention also includes a biomass material production means for producing biomass material by kneading biomass, a carbon material, a solid acid catalyst, and water, and the biomass material is formed of a material that does not absorb microwaves and includes a pressure control valve. A raw material supply means for pumping to a microwave reaction tube, and a microwave heating means for producing a crude biomass pyrolysis oil by heating a biomass raw material in the microwave reaction tube to a temperature range of 120 ° C. to 347 ° C. with a microwave heating device; It is preferable to have.

In the present invention, the solid acid catalyst is preferably a carbon-based acid catalyst.
Moreover, it is preferable that this invention has a pre-processing means which heats a biomass raw material and manufactures pre-processed biomass, and a raw material supply means which pumps a pre-processed biomass raw material to a microwave reaction tube.

The microwave heating means of the present invention includes a microwave oscillator and a container having a cylindrical space made of metal at least on the inner surface, the direction is parallel to the central axis of the space, and the size is the center of the space. A microwave resonator having an axially symmetric microwave electromagnetic field constant in the axial direction and the circumferential direction of the space, and a microwave reaction tube formed of a material that does not absorb microwaves,
Preferably, the microwave reaction tube shares the central axis of the microwave resonator and passes through the inside of the microwave resonator, is connected to the raw material supply means at one end, and is provided with a pressure control valve at the other end. .

  Moreover, it is preferable that this invention further has a means to remove a solid acid catalyst from pretreated biomass.

  The present invention also provides a discharge means for discharging the crude biomass pyrolysis oil from the pressure controller to the solid-liquid separator and a condensing means that is connected to the gas outlet of the solid-liquid separator and condenses the biomass pyrolysis oil. And separating means for separating the biomass pyrolysis oil and the solid carbon material.

  Further, the present invention is a discharge stage for discharging crude biomass pyrolysis oil from a pressure control valve to a pyrolysis oil gasification means comprising a hydrogen permeable membrane means, a high-frequency electromagnetic induction heating device, and a heating element, Pyrolysis oil gasification means for heating crude biomass pyrolysis oil by a high-frequency electromagnetic induction heating device and a heating element, and pyrolyzing the crude biomass pyrolysis oil to produce hydrogen gas and carbon monoxide. It is preferable.

Further, the pyrolysis oil gasification means of the present invention is a cylindrical container formed of a non-magnetic material, provided at one end thereof, an inlet for supplying crude biomass pyrolysis oil pressurized at a high temperature, An outer tube having an expansion portion for vaporizing the crude biomass pyrolysis oil at normal pressure, an outlet provided at the other end of the container, and a high-frequency electromagnetic induction coil wound around the outer periphery; and an inner portion of the outer tube One or more inner tubes provided with a hydrogen permeable membrane and having a hydrogen gas outlet penetrating a part of the outer tube, and a space formed between the outer tube and the inner tube formed of a magnetic material are heated. And a heating element.
Having

Moreover, it is preferable that the pyrolysis oil gasification means of the present invention further has a catalyst for promoting the decomposition of the crude biomass pyrolysis oil.
In the present invention, the catalyst is preferably a nickel-doped perovskite oxide catalyst.

In the present invention, it is preferable that the hydrogen permeable membrane means includes a zeolite membrane having hydrogen permeability, and further includes a separation generating means that allows only one of hydrogen gas and water vapor to pass therethrough.
In the present invention, it is preferable that the hydrogen permeable membrane means includes a hydrogen permeable metal film, and the hydrogen permeable metal film acts as a heating element.

  According to the present invention, the metal film having hydrogen permeability is a metal film containing one or more metal elements selected from platinum, palladium, vanadium, niobium, tungsten, and molybdenum. it can.

  According to the method for producing biomass pyrolysis oil of the present invention, biomass pyrolysis oil can be produced as a “liquid” that can be used for industrial continuous production at a high yield from a small amount of many types of biomass.

  The carbon yield of biomass pyrolysis oil is as high as 80-90%.

  Since the biomass pyrolysis oil is a dispersion using water as a solvent, the raw material biomass can be used without drying.

It is a figure which shows the biomass pyrolysis oil manufacturing apparatus which concerns on 1st Embodiment of this invention. It is the schematic which shows the biomass pyrolysis oil manufacturing apparatus which concerns on 2nd Embodiment of this invention. It is the schematic which shows the biomass pyrolysis oil manufacturing apparatus which concerns on 3rd Embodiment of this invention. It is a figure of the pyrolysis oil gasification apparatus of the biomass pyrolysis oil manufacturing apparatus which concerns on 3rd Embodiment of this invention. It is a figure of the isolation | separation and refinement | purification apparatus of the biomass pyrolysis oil manufacturing apparatus which concerns on 3rd Example of this invention. It is a figure of the water gas component adjustment apparatus of the biomass pyrolysis oil manufacturing apparatus which concerns on 3rd Example of this invention. It is a figure of the pyrolysis oil gasification apparatus of the biomass pyrolysis oil manufacturing apparatus which concerns on 3rd Embodiment of this invention. It is a figure of the isolation | separation and refinement | purification apparatus of the biomass pyrolysis oil manufacturing apparatus which concerns on 3rd Example of this invention. It is the schematic of a dimethyl ether manufacturing apparatus.

The present invention relates to a biomass pyrolysis oil production apparatus and production method for producing biomass pyrolysis oil from biomass.
The term “biomass” often refers to organic resources derived from living organisms. However, in the present invention, the term “biomass” is broader and includes “all renewable organic resources excluding fossil fuels”.
Specific examples of biomass include wood, bamboo, rice straw, wheat straw, herbs, agricultural products, seaweed, food waste, household waste, manure, industrial waste, agricultural waste, livestock waste, activated sludge waste Can do.

  “Biomass pyrolysis oil” is a dark solution using water as a solvent, and is a complex mixture having a different composition depending on the type of raw material and the degree of decomposition. However, it is assumed that “biomass pyrolysis oil” is not an aqueous solution but a dispersion of fine particle components. Depending on the production conditions, it may be separated into two layers of an aqueous component and an oily component.

Biomass pyrolysis oil has the following characteristics.
(1) Biomass pyrolysis oil is obtained from various biomass as a “liquid” that can be used for industrial continuous production.
(2) The carbon yield of biomass pyrolysis oil is as high as 80 to 90%.
(3) Since the biomass pyrolysis oil is a dispersion using water as a solvent, the biomass as a raw material can be used without drying.
(4) The problem that the biomass pyrolysis oil is unstable is solved by making the biomass pyrolysis oil production process a continuous reaction with the next production process.

Biomass pyrolysis oil is produced by pyrolyzing and carbonizing biomass by rapid heat treatment of biomass in water in an oxygen-free state at a speed on the order of [° C./millisecond] with a microwave heating device.
The reaction of treating woody biomass with hot water at high temperature and high pressure to hydrolyze cellulose to produce monosaccharides such as glucose and xylose is known, but the production reaction of the biomass pyrolysis oil of the present invention is different from this. It is a reaction.

The production reaction of biomass pyrolysis oil is
(1) By rapidly heating the biomass, it is speculated that the dehydration reaction in the biomass molecule takes precedence over the hydrolysis reaction by the bimolecular reaction between the biomass and the water molecule,
(2) As a side reaction, it involves a water gas reaction and a water gas shift reaction that generate hydrogen gas, and thus is a reaction under reducing conditions.
(3) Biomass produces a 6-membered ring because there are many C6 compounds including cellulose, which is the main component,
(4) It is presumed that a condensed aromatic ring compound condensed with a carbon 6-membered ring is given as a main product.

The condensed aromatic ring compound contained in the biomass pyrolysis oil is presumed to have many types of side chains derived from reaction intermediates and lignin.
As an example of the intramolecular dehydration reaction of cellulose, for example, in Patent Document 6, when cellulose is heated in an inert gas stream at 250 ° C. for 15 hours, a condensed aromatic ring compound having a hydrocarbon skeleton in which many benzene rings are condensed is obtained. It is described.

  It is presumed that the condensed aromatic ring compound is stable against heat, and is polymerized further when heated at a high temperature and high pressure in an oxygen-free atmosphere to generate carbon having a final graphite structure. The high carbon recovery rate of biomass pyrolysis oil is presumed to be due to the formation of a stable condensed aromatic ring compound.

The biomass pyrolysis oil production reaction is outlined below from a macro perspective.
Since biomass is an organic resource, it is mainly composed of carbon, hydrogen, and oxygen. Therefore, the biomass can be schematically described as (C _n H _m O _p ). However, m, n, and p are often not integers.
The production reaction of biomass pyrolysis oil proceeds under reducing conditions using a hydroxyl group elimination reaction (dehydration reaction) as a trigger, and therefore, a heavy hydrocarbon compound (C _x H _y ) having a low oxygen content is the main component.
Since cellulose, which is a main component of biomass, is a compound having 6 carbon atoms, a unit of 6 carbon atoms is generated by a dehydration reaction, and a condensed aromatic ring compound (nC ₆ ) is generated. If this reaction is described typically, the following formula (Chemical Formula 1) is obtained.

The reaction for forming the fused aromatic ring compound is described in Patent Document 6, for example.
On the other hand, it is estimated that the fragment of the reaction intermediate produced in the condensed aromatic ring formation reaction is further decomposed to generate non-condensable gases such as carbon (C), carbon dioxide, carbon monoxide, hydrogen gas, methane. The
Therefore, the production reaction of biomass pyrolysis oil from biomass (C _n H _m O _p ) can be approximately expressed as follows.

(About the biomass pyrolysis oil production method of the present invention)
In the method for producing bio-oil of the present invention, biomass is dispersed in water and rapidly heated and thermally decomposed using a microwave heating device as a heating means.
However, water absorbs microwaves and generates heat, but the absorption and heat generation efficiency is not good. Moreover, although this invention includes the temperature range of 100 degreeC or more as a reaction area | region, water vapor | steam does not absorb a microwave.

In the method for producing biomass pyrolysis oil according to the first embodiment of the present invention, a heating element is added in order to improve microwave absorption efficiency. As long as the heat generating material used in the present invention does not interfere with the gist of the present invention, any material can be used as long as it can generate heat by absorbing microwaves.
The second feature of the present invention is that a carbon material is used as the heat generating material. A carbon material has the advantage that it efficiently absorbs microwaves and generates heat, and itself reacts with water to generate carbon monoxide and hydrogen gas. Furthermore, according to the present invention, the carbon material 20 recovered from the previous production can be reused as the carbon material.

  The method for producing biomass pyrolysis oil according to the second embodiment of the present invention is a pretreatment in which a solid acid catalyst using a carbon material is added to a mixture of biomass and carbon material, and the mixture of biomass and carbon material is heated. It comprises a part. By pretreating the slurry of the mixture of biomass and carbon material, the viscosity of the slurry can be lowered, the heating temperature can be lowered, the heating time can be shortened, and the yield can be improved.

(Gasification of biomass pyrolysis oil)
Next, gasification of biomass pyrolysis oil will be described.
The reaction for producing hydrogen gas and carbon monoxide from the condensed aromatic ring compound is a gas reaction in which a biomass decomposition product contained in biomass pyrolysis oil is decomposed with superheated steam.
The main reaction of the gasification reaction of biomass pyrolysis oil can be expressed as shown in Equation (3).

When the weight of (C _x H _y ) in the above formula [3] is 1, the weight of water vapor necessary to decompose (C _x H _y ) into carbon monoxide and hydrogen gas is (C _x H _y ). 1.3 to 1.5 times the weight. Therefore, if high-concentration biomass pyrolysis oil is produced, the solvent water is consumed by the decomposition reaction of the biomass pyrolysis oil. That is, this reaction is a reaction in water, and water contained in the solvent water and raw material biomass is taken into the biomass pyrolysis oil. It can be used as a raw material for water gas. Therefore, there is no need to dry the raw material biomass, and energy efficiency is improved.

  A method for producing a biomass pyrolysis oil according to a third embodiment of the present invention is a pyrolysis oil comprising a high-temperature and high-pressure biomass pyrolysis oil immediately after production, comprising a hydrogen permeable membrane, a sensitized thermal catalyst, a high-frequency electromagnetic heating device, and a heating element. By supplying to a gasifier and heating, water gas containing carbon monoxide and hydrogen gas is produced continuously. For the gasification reaction, a perovskite oxide catalyst doped with nickel is preferably used.

  The method for producing biomass pyrolysis oil according to the fourth embodiment of the present invention is characterized in that, in the pyrolysis oil gasifier, a hydrogen permeable metal film is used as a hydrogen permeable film and the function of a heating element is provided. To do.

  Embodiments of a biomass pyrolysis oil production apparatus of the present invention will be described in detail with reference to the accompanying drawings. In the description of the device and the drawings, the same reference numerals are given to the components common to the respective devices, and repeated description may be omitted.

FIG. 1 is a schematic diagram showing the configuration of the biomass pyrolysis oil production apparatus according to the first embodiment of the present invention.
As shown in FIG. 1, the biomass pyrolysis oil production apparatus 100 according to this embodiment includes a wet pulverizer 111, a biomass pyrolysis oil production apparatus main body 120, and a pyrolysis oil receiver 190. The
The wet pulverizer 111 kneads the biomass 10, the carbon material 20, and the water 15 to produce a slurry-like biomass material 12 in which the biomass and the carbon material 20 are dispersed in water.

Each of the biomass 10 and the carbon material 20 is preferably pulverized to a particle size of 10 to 200 mesh, more preferably 30 to 100 mesh. The finer the particle size of the biomass 10 and the carbon material 20, the better. However, in this embodiment, even if the particle size is reduced to 200 mesh or more, there is no further effect, so it is not economical. This is not preferable because a dispersion having s is not formed.
The amount of the carbon material 20 to be added is preferably in the range of 5% by weight to 50% by weight when the sum of the dry weight of the biomass 10 and the weight of the carbon material 20 is 100% by weight. A range of 40% by weight is more preferred. If the carbon material 20 is 5% by weight or less, the effect of generating heat by absorbing microwaves cannot be sufficiently obtained, and if it is 50% by weight or more, no further heat generation effect can be obtained.

  In the present invention, it is preferable to supply the biomass and the heat generating material to the biomass pyrolysis oil production apparatus main body 120 using as little water as possible. In the wet pulverizer 111, the amount of water 15 added to the biomass 10 and the carbon material 20 is determined by the properties of the biomass used and the moisture content of the biomass. For example, when using biomass with a high water content such as seaweed, it is preferable to adjust the water content by adding biomass with a low water content.

  In this example, when the weight of all components is 100% by weight, the sum of water, water vapor, and moisture contained in biomass is preferably in the range of 25% to 60% by weight. If the amount of water is 25% by weight or less, it is difficult to supply the biomass raw material 12 to the biomass pyrolysis oil production apparatus main body. If the amount of water is 60% by weight or more, the biomass content is too low and economical. It is disadvantageous. However, when the biomass to be used is waste and the main purpose is disposal, it is possible to operate with a moisture content of 60% by weight or more.

  It is preferable to supply steam 30 to the wet pulverizer 111 to preheat the biomass material 12. The heating temperature is preferably in the range of 60 ° C to 100 ° C, more preferably in the range of 80 ° C to 98 ° C. By preheating the biomass material 12, the viscosity of the biomass material 12 in a slurry state can be reduced, and the load on the biomass pyrolysis oil production apparatus main body 120 can be reduced.

  The biomass raw material 12 supplied from the wet pulverizer 111 preferably has a viscosity in the range of 5000 cP to 50000 cP, more preferably 10000 cP to 30000 cP at the supply temperature. A low viscosity does not hinder the reaction, but for example, in the case of 5000 cP or less, it is economically advantageous to reduce the moisture and increase the amount of biomass. Moreover, when the viscosity is higher than 50000 cP, the pressure inside the biomass pyrolysis oil production apparatus main body 120 is excessively increased, which is not preferable.

  The biomass pyrolysis oil production apparatus main body 120 includes a pressure feeder 121 connected to the wet pulverizer 111, a microwave reaction tube 130 connected to the pressure feeder 121, and a pressure control valve 132 provided at the other end of the reaction tube. And a microwave heating device 122 that heats the microwave reaction tube 130.

  The form of the pressure feeder 121 is not limited as long as it is a device that can pressure-feed the slurry-like biomass raw material 12 to the microwave reaction tube 130. Examples of the preferred pressure feeder 121 include, but are not limited to, screw feeders, gear pumps, tocolloid pumps, and piston pumps.

  The microwave reaction tube 130 is connected to the pressure feeder 121 at one end and to the pressure control valve 132 at the other end. The microwave reaction tube 130 may be made of any material that does not absorb microwaves and can be used in the present invention. Preferred examples include ceramics, quartz, sapphire, alumina, silicon nitride and the like. As a more preferable example, ceramics can be shown.

  The type of the microwave heating device 122 is not limited as long as it can irradiate the microwave reaction tube 130 with the microwave and heat the biomass raw material 12 inside the microwave reaction tube 130. In order to increase the reaction efficiency, a microwave heating device 122 including a microwave oscillator 123 and a microwave resonator 129 is preferable.

  As a more preferable example, the microwave oscillator 123 shown in FIG. 1 and a cylindrical space 126 made of metal are provided on the inner surface, and the magnetic field is directed to the central axis 128 of the cylindrical space 126 inside the cylindrical space 126. A microwave resonator 129 that generates an axisymmetric microwave electromagnetic field that is parallel and has a constant magnetic field magnitude in the central axis direction and the circumferential direction of the cylindrical space 126, and shares the central axis with the microwave resonator 129. A biomass pyrolysis oil production apparatus main body 120 having a microwave reaction tube 130 installed as described above can be given.

  When the microwave reaction tube 130 is irradiated with microwaves from the microwave heating device 122, the carbon material contained in the biomass raw material 12 absorbs the microwave and generates heat, thereby heating the biomass raw material 12. The heating temperature of the biomass raw material 12 is preferably in the temperature range of 120 ° C to 347 ° C, more preferably in the range of 150 ° C to 347 ° C, and still more preferably in the temperature range of 200 ° C to 347 ° C. .

The biomass raw material 12 is converted into the crude biomass pyrolysis oil 59 by being heated to a temperature range of 120 ° C. to 347 ° C. Since the biomass 10 contains water, the water boils and the microwave reaction tube 130 is pressurized. The pressure is preferably in the range of 2 to 22 MPa.
Since the microwave oscillator 123 can rapidly heat the irradiated object, the reaction time can be in the range of 10 seconds to 600 seconds.
The generated high-temperature and high-pressure crude biomass pyrolysis oil 59 is discharged from the pressure control valve 132 to a normal-pressure pyrolysis oil receiver 190.

The pyrolysis oil receiver 190 is connected to the pressure control valve 132, the pyrolysis oil discharge part 185 from which the high-temperature and high-pressure crude biomass pyrolysis oil 59 is discharged, and the heat provided at the bottom of the pyrolysis oil discharge part 185. It is preferable to provide a cracked oil outlet 188, a filter 189, a condenser 186 for condensing pressurized water vapor, and a non-condensed component outlet 187.
In the high-temperature and high-pressure crude biomass pyrolysis oil 59 released from the pressure control valve 132 to the pyrolysis oil discharge section 185, the non-volatile component moves to the lower part of the pyrolysis oil discharge section 185, and the condensed component 61 that has been vaporized is condensed. Condensed in the vessel 186 and refluxed to the pyrolysis oil discharge unit 185, the non-condensed component 62 passes through the non-condensed component outlet 187 and is discharged. The non-volatile component and the condensed component 61 pass through the filter 189 from the pyrolysis oil outlet 188 and are separated into the biomass pyrolysis oil 60 and the recovered carbon material 20.

FIG. 2 is a schematic diagram showing the configuration of the biomass pyrolysis oil production apparatus according to the second embodiment of the present invention.
In the second embodiment of the present invention, a part of the carbon material is used in place of the solid acid catalyst 22.
The type of the solid acid catalyst is not particularly limited as long as it meets the gist of the present invention. A preferable example is a solid acid catalyst obtained by sulfonating a carbon material. A sulfonated solid acid catalyst is also a raw material for this reaction.

  As the sulfonated solid acid catalyst, for example, the solid acid catalyst described in Patent Document 6 can be shown as a more preferable example. Further, the recovered carbon material can be used by sulfonation by the method described in Patent Document 6, for example.

As shown in FIG. 2, the biomass pyrolysis oil production apparatus 100 according to this embodiment includes a biomass pretreatment unit 110, a biomass pyrolysis oil production apparatus main body 120, and a pyrolysis oil receiver 190. Is done.
The biomass pretreatment unit 110 includes a wet pulverizer 111 and a pretreatment unit 112.
The wet pulverizer 111 kneads the biomass 10, the carbon material 20, the solid acid catalyst 22, and the water 15 to produce the biomass raw material 12 that is a dispersion system in which the biomass and the carbon material are dispersed in water, and the pretreatment unit 112. Manufactures the pretreated biomass 13 which is a high-viscosity fluid in which the biomass and the heat generating material are dispersed in water by heating the biomass raw material 12 and partially hydrolyzing the biomass.

  The carbon material 20 absorbs microwaves and generates heat, and is added to heat the reaction mixture. The carbon material 20 has the advantage that it efficiently absorbs microwaves and generates heat, and it itself becomes a reaction raw material and does not generate impurities. Furthermore, in the present invention, the carbon material 20 can be reused from the carbon material 20 collected in the previous production.

  Each of the biomass 10, the carbon material 20, and the solid acid catalyst 22 is preferably pulverized to a particle size of 10 to 200 mesh, more preferably 30 to 100 mesh. The finer the particle sizes of the biomass 10, the carbon material 20, and the solid acid catalyst 22, the better. However, in this embodiment, even if the particle size is reduced to 200 mesh or more, there is no further effect. The following particle sizes are not preferable because a fluid dispersion is not formed.

Since the solid acid catalyst 22 used in the present embodiment is obtained by introducing a sulfonic acid group into the carbon material 20, when both are used, the total amount of the carbon material 20 and the solid acid catalyst 22 is set as the amount of the carbon material. Is preferred. That is, when the sum of the dry weight of the biomass, the weight of the carbon material, and the weight of the solid acid catalyst is 100% by weight, the sum of the weight of the carbon material and the weight of the solid acid catalyst is 5% by weight to The range is preferably 50% by weight, and more preferably 10% to 40% by weight.
If the sum of the carbon material 20 and the solid acid catalyst 22 is 5% by weight or less, the action of absorbing microwaves and generating heat cannot be sufficiently obtained, and if it is 50% by weight or more, no further heat generation effect can be obtained.
Among these, the weight of the solid acid catalyst 22 is preferably in the range of 0.5% by weight to 40% by weight, and more preferably in the range of 1% by weight to 30% by weight. If the weight of the solid acid catalyst 22 is 0.50.5% by weight, sufficient catalytic action cannot be obtained, and if it is 40% by weight or more, no further catalytic effect can be obtained.

  In the present invention, it is preferable to supply the biomass 10, the carbon material 20, and the solid acid catalyst 22 to the biomass pyrolysis oil production apparatus main body 120 using as little water as possible. In the wet pulverizer 111, the amount of water 15 added to the biomass 10, the carbon material 20, and the solid acid catalyst 22 is determined by the properties of the biomass used and the moisture content of the biomass. For example, when using biomass with a high water content such as seaweed, it is preferable to adjust the water content by adding biomass with a low water content.

  In this example, when the weight of all the components charged in the reaction is 100% by weight, the sum of water, water vapor, and water contained in the biomass is in the range of 25% to 60% by weight. preferable. If the amount of water is 25% by weight or less, it is difficult to supply the biomass raw material 12 to the biomass pyrolysis oil production apparatus main body. If the amount of water is 60% by weight or more, the biomass content is too low and economical. It is disadvantageous. However, when the biomass to be used is waste and the main purpose is disposal, it is possible to operate with a moisture content of 60% by weight or more.

  It is preferable to supply the superheated steam 32 to the wet pulverizer 111 to preheat the biomass raw material 12. The heating temperature is preferably in the range of 60 ° C to 100 ° C, more preferably in the range of 80 ° C to 98 ° C. By preheating the biomass material 12, the viscosity of the biomass material 12 in a slurry state can be reduced, and the difference between the temperature of the biomass material 12 and the temperature of the pretreatment unit 112 can be reduced.

The pretreatment unit 112 heats the biomass raw material 12 supplied from the wet pulverizer 111 to a predetermined temperature using the superheated steam 32 for a predetermined time, and partially hydrolyzes the biomass raw material 12 to produce the pretreated biomass 13. It is preferable that the reaction apparatus.
The supplied steam is preferably superheated steam in the range of 90 ° C. to 150 ° C. (4.7 MPa). If the heating temperature is 90 ° C. or lower, hydrolysis does not proceed, and if it is 150 ° C. or higher, hydrolysis proceeds too much, so that many low-boiling components and non-condensed components are produced, and the yield of the target product may be reduced.

The residence time of the biomass raw material 12 is inversely proportional to the reaction temperature. A relatively short time is required if the reaction temperature is high, and a long time is required if the reaction temperature is low. The reaction time is preferably in the range of 3 minutes to 300 minutes, more preferably in the range of 10 minutes to 150 minutes. If the residence time is 3 minutes or less, the hydrolysis reaction does not proceed sufficiently. If the residence time is 300 minutes or more, the hydrolysis reaction proceeds excessively, so that a large amount of non-condensed components are produced and the carbon yield is lowered.
The pretreated biomass 13 supplied from the pretreatment unit 112 preferably has a viscosity in the range of 50000 cP or less, more preferably 30000 cP at the supply temperature.

The pretreated biomass 13 is supplied from the pretreatment unit 112 to the biomass pyrolysis oil production apparatus main body 120.
As shown in FIG. 2, the biomass pyrolysis oil production apparatus main body 120 includes a pressure feeder 121 connected to the pretreatment unit 112, a microwave reaction tube 130 connected to the pressure feeder 121, and the other end of the reaction tube. It is preferable to include a pressure control valve 132 provided and a microwave heating device 122 that heats the microwave reaction tube 130.

It is preferable that the pressurized feeder 121 pressurizes and supplies superheated steam to the pretreated biomass 13 and feeds a predetermined amount of the pretreated biomass 13 to the microwave reaction tube 130. The temperature of the superheated steam is preferably in the range of 120 ° C. (2.0 MPa) to 180 ° C. (10 MPa), and more preferably in the range of 120 ° C. to 150 ° C.
When the temperature of the superheated steam is lower than 2.0 MPa (120 ° C.), the pressure may be insufficient to transport the pretreated biomass 13. When the temperature of the superheated steam is higher than 10 MPa (180 ° C.), the decomposition reaction of the pretreated biomass 13 may occur. It progresses too much and a decomposition product may be generated, resulting in a decrease in yield.

  The microwave reaction tube 130 is connected to the pressure feeder 121 at one end and to the pressure control valve 132 at the other end. The microwave reaction tube 130 may be made of any material that does not absorb microwaves and can be used in the present invention. Preferred examples include ceramics, quartz, sapphire, alumina, and silicon nitride. As a more preferable example, ceramics can be shown.

The type of the microwave heating device 122 is not limited as long as it can irradiate the microwave reaction tube 130 with microwaves and heat the microwave reaction tube 130. In order to increase the reaction efficiency, a microwave heating device 122 including a microwave oscillator 123 and a microwave resonator 129 is preferable.
As a more preferable example, the microwave oscillator 123 shown in FIG. 1 and a cylindrical space 126 made of metal are provided on the inner surface, and the direction of the magnetic field is in the central axis 128 of the cylindrical space 126 inside the cylindrical space 126. A microwave resonator 129 that generates an axisymmetric microwave electromagnetic field that is parallel and has a constant magnetic field in the cylindrical axial direction of the cylindrical space 126 in the central axis direction and the circumferential direction, and the microwave resonator 129 and the central axis. The biomass pyrolysis oil manufacturing apparatus main body 120 which has the microwave reaction tube 130 installed so that it may share can be mentioned.

When the microwave reaction tube 130 is irradiated with microwaves from the microwave heating device 122, the carbon material contained in the pretreated biomass 13 absorbs microwaves and generates heat to heat the pretreated biomass 13. The heating temperature of the pretreated biomass 13 is preferably in the temperature range of 120 ° C to 347 ° C, more preferably in the range of 150 ° C to 347 ° C, and still more preferably in the temperature range of 200 ° C to 347 ° C. Can do.
The pretreated biomass 13 is converted into the crude biomass pyrolysis oil 59 by being heated to a temperature range of 120 ° C to 347 ° C. Since the biomass 10 contains water, the water boils and the microwave reaction tube 130 is pressurized. The pressure is preferably in the range of 2 to 22 MPa.
Since the microwave oscillator 123 can rapidly heat the irradiated object, the reaction time can be in the range of 10 seconds to 600 seconds.
The generated high-temperature and high-pressure crude biomass pyrolysis oil 59 is discharged from the pressure control valve 132 to a normal-pressure pyrolysis oil receiver 190.

The pyrolysis oil receiver 190 is connected to the pressure control valve 132, the pyrolysis oil discharge part 185 from which the high-temperature and high-pressure crude biomass pyrolysis oil 59 is discharged, and the heat provided at the bottom of the pyrolysis oil discharge part 185. It is preferable to provide a cracked oil outlet 188, a filter 189, a condenser 186 for condensing pressurized water vapor, and a non-condensed component outlet 187.
In the high-temperature and high-pressure crude biomass pyrolysis oil 59 released from the pressure control valve 132 to the pyrolysis oil discharge section 185, the non-volatile component moves to the lower part of the pyrolysis oil discharge section 185, and the condensed component 61 that has been vaporized is condensed. Condensed in the vessel 186 and refluxed to the pyrolysis oil discharge unit 185, the non-condensed component 62 passes through the non-condensed component outlet 187 and is discharged. The non-volatile component and the condensed component 61 pass through the filter 189 from the pyrolysis oil outlet 188 and are separated into the biomass pyrolysis oil 60 and the recovered carbon material 20.

Since the hydrolysis reaction in the biomass pretreatment unit 110 and the biomass decomposition reaction in the biomass pyrolysis oil production apparatus main body 120 can be promoted by adding the solid acid catalyst 22, the biomass pretreatment unit 110 and the biomass heat The reaction temperature of the cracked oil production apparatus main body 120 can be lowered, the amount of carbon material and non-condensed components produced can be reduced, and the yield can be improved.
However, the solid acid catalyst 22 is a substance containing sulfonic acid and contains sulfur element as a constituent element. In this example, the sulfonic acid did not have a catalyst poison, and the activity of the hydrogen permeable metal membrane and the perovskite catalyst was not reduced in the test production. However, care must be taken to prevent the generation of catalyst poisons due to the decomposition of the solid acid catalyst 22 and the contamination of the catalyst poisons by impurities.

(Third embodiment)
FIG. 3 is a schematic view showing a biomass pyrolysis oil production apparatus according to the third embodiment of the present invention. The third embodiment of the present invention is characterized in that the produced biomass pyrolysis oil is continuously supplied to the pyrolysis oil gasifier.
As shown in FIG. 3, the biomass pyrolysis oil production apparatus 100 used in the third embodiment of the present invention includes a biomass pretreatment unit 110, a biomass pyrolysis oil production apparatus main body 120, and a pyrolysis oil gasification apparatus 150. The separation and purification device 160 is preferably included.
The biomass pretreatment unit 110 and the biomass pyrolysis oil production apparatus main body 120 are the same as the apparatus of the first embodiment or the second embodiment shown in FIG.

  The pyrolysis oil gasification apparatus 150 heats the biomass pyrolysis oil 60 produced by the biomass pyrolysis oil production apparatus main body 120 in superheated steam to form a water gas 52 containing hydrogen gas 40 and carbon monoxide 50. Preferably, the separation and purification device 160 is a device that separates and purifies the gas generated in the biomass pyrolysis oil production device main body 120 and the recovered carbon material 20.

FIG. 4 is a diagram of a pyrolysis oil gasification device of a biomass pyrolysis oil production device according to a third embodiment of the present invention.
As shown in FIG. 4, the pyrolysis oil gasifier 151 according to the third embodiment of the present invention is an inline high-frequency induction heating device having an outer tube 157 and an inner tube 159 communicating with the pressure control valve 132. Is preferred. If desired, a filtration device can be provided between the pressure control valve 132 and the pyrolysis oil gasifier 150.

  The outer tube 157 is a cylindrical container formed of a non-magnetic material, and is provided at one end of the outer tube 157 and is gasified to communicate with a pressure control valve 132 that is an outlet of the biomass pyrolysis oil production apparatus main body 120. A device inlet 154, an expansion part 141 for vaporizing biomass pyrolysis oil at normal pressure, a heating element 156 provided inside the outer tube 157 and formed of a magnetic material, and provided at the other end of the outer tube 157 A gasifier outlet 155 communicated with the gas separator 162 and a high-frequency electromagnetic induction coil 158 wound around the outer circumference of the outer pipe 157, and the sensitized heat catalyst 142 is filled between the outer pipe and the inner pipe. It is preferable.

The inner tube 159 is one or more tubes provided inside the outer tube, and is preferably formed of the hydrogen permeable membrane 222 and penetrates the side wall of the outer tube 157 and communicates with the hydrogen gas outlet 218.
The hydrogen permeable membrane 222 that forms the inner tube 159 may include a zeolite membrane 226 having hydrogen permeability and a support 220 formed of a porous material. The zeolite membrane 226 is preferably SOD zeolite.

  The sensitized heat catalyst 142 is a catalyst for decomposing solid components such as the carbon material 20 contained in the vaporized biomass pyrolysis oil. Any sensitizing heat catalyst 142 may be used as long as it meets the object of the present invention, and a nickel-doped perovskite catalyst can be cited as a particularly preferred example.

The sensitizing heat catalyst 142 is preferably a catalyst containing a transition metal such as iron, manganese, zinc, copper, or nickel. Of these, nickel-doped perovskite oxide catalysts are particularly preferred.
The perovskite oxide is a transition metal oxide having the same crystal structure as that of perovskite (apatite, CaTiO3).

  Since the SOD zeolite passes both the hydrogen gas 40 and the water vapor 30, when using the inner tube 159 formed of the hydrogen permeable membrane 222 having the SOD zeolite membrane 226, the hydrogen gas 40 and the water vapor 30 are further It is preferable to provide a water vapor separator 170 that allows only one of them to pass.

The heating element 156 formed of a magnetic material may be any magnetic material that generates heat by generating an induction current with a high frequency transmitted from the high frequency electromagnetic induction coil 158 wound around the outer periphery of the outer tube 157. In order to make the temperature distribution inside the outer tube uniform, it is preferably arranged uniformly, it is desirable that the pressure loss inside the outer tube is small, and in order to increase the heat transfer effect, those having a large surface area are preferable.
The high frequency electromagnetic induction coil 158 used in the present example used an in-line heater manufactured by Daiichi High Frequency Industrial Co., Ltd. as a basic structure.

  The high-temperature and high-pressure biomass pyrolysis oil produced by the biomass pyrolysis oil production apparatus main body 120 is vaporized by being discharged from the pressure control valve 132 to the normal-pressure expansion part 141. At this time, 500 to 1000 ° C. superheated steam 32 can be supplied in order to compensate for a decrease in reaction temperature due to vaporization heat and adiabatic expansion.

  Biomass pyrolysis oil self-decomposes while generating heat when heated to 380 ° C or higher. Therefore, heating is performed with a high-frequency induction heating device at the start of the reaction, and temperature control may be performed after the reaction reaches a steady state. The reaction temperature is preferably in the range of 380 to 850 ° C, more preferably in the range of 500 to 800 ° C. At 380 ° C. or lower, spontaneous decomposition does not proceed, and at 450 ° C. or lower, the reverse shift reaction shown in the following (1) proceeds and the carbon monoxide content decreases. At temperatures higher than 850 ° C., the self-decomposition reaction proceeds too rapidly.

FIG. 5 is a diagram showing a separation and purification device of the biomass pyrolysis oil production device according to the third embodiment of the present invention.
As shown in FIG. 5, the separation and purification device 160 preferably includes a cyclone solid / gas separator 162 communicating with the gasifier outlet 155 and a water vapor separator 170 connected to the hydrogen gas outlet 218.

  The water vapor separation membrane applied to the water vapor separator 170 is not particularly limited as long as it meets the object of the present invention, but preferred examples include an SOD type zeolite membrane and a hydrogen permeable metal membrane mainly composed of platinum or niobium. Can be mentioned. The hydrogen gas 40 is obtained through the steam separator 170. In order to obtain pure hydrogen, the water vapor separator 170 having a hydrogen permeable metal membrane is preferable. The SOD type zeolite membrane in this case acts as a hydrogen permeable membrane, but also partially passes water vapor.

The cyclone solid / gas separator 162 separates the carbon material 20 and the gas component. The carbon material 20 obtained from the carbon material outlet 164 is recovered and reused.
A water vapor separator 170 having a water vapor passage membrane is connected to the gas component outlet 166 of the solid / gas separator 162. As the water vapor passing membrane, an SOD type zeolite membrane is preferable. The SOD type zeolite membrane in this case acts as a water vapor permeable membrane, separates water vapor and carbon monoxide, and is obtained from a carbon monoxide outlet 177, which is an outlet for gas that did not pass through the water vapor permeable membrane. It is done.

  A dust remover 180 for removing fine particles and a desulfurizer 181 for removing sulfur can be connected between the gas component outlet 166 of the cyclone-type solid / gas separator 162 and the water vapor separator 170. Further, a carbon dioxide separator 184 having an SOD type zeolite membrane can be connected to the carbon monoxide outlet 177.

  The water gas used to produce dimethyl ether has a 2: 1 ratio of hydrogen gas to carbon monoxide gas. On the other hand, when water gas is produced from carbon, the ratio of the generated hydrogen gas to carbon monoxide gas is stoichiometrically 1: 1, and the ratio when water gas is produced from hydrocarbon is 2: 1. Water gas generally has a hydrogen gas ratio that is often too low.

  FIG. 6 is a view of the water gas component adjusting device of the biomass pyrolysis oil production device according to the fourth embodiment of the present invention. As shown in FIG. 6, in this embodiment, the water gas component adjusting device 192 is provided with a branch pipe 195 in a pipe line 194 that connects the desulfurizer 181 and the water vapor separator 170, and the gas component 70 that passes through the pipe line 194. A part of is diverted to the branch 195. The carbon monoxide 50 in the diverted gas component 70 is converted into hydrogen gas using a reverse shift reactor 183, and the generated hydrogen gas is separated using a hydrogen separator 196 having a hydrogen-selective metal membrane. Hydrogen gas 40 is produced. Thereby, the ratio of hydrogen gas can be increased, and the component ratio of the produced water gas can be adjusted.

FIG. 7 shows a pyrolysis oil gasifier according to the fourth embodiment of the present invention.
In the fourth embodiment of the present invention, in the schematic diagram showing the biomass pyrolysis oil production apparatus shown in FIG. 3, the inner pipe 159 of the pyrolysis oil gasification apparatus 150 is formed including a metal film having hydrogen permeability. It is characterized by that.

  As shown in FIG. 7, the pyrolysis oil gasifier 152 is preferably an inline high-frequency induction heating device having an outer tube 157 and an inner tube 159 communicating with the pressure control valve 132. If desired, a filtration device can be provided between the pressure control valve 132 and the pyrolysis oil gasifier 150.

  The outer tube 157 is a cylindrical container formed of a non-magnetic material, and is provided at one end of the outer tube 157 and is gasified to communicate with a pressure control valve 132 that is an outlet of the biomass pyrolysis oil production apparatus main body 120. An apparatus inlet 154, an expansion part 141 for vaporizing biomass pyrolysis oil at normal pressure, a gasifier outlet 155 provided at the other end of the outer pipe 157 and communicating with the solid / gas separator 160, and an outer pipe 157 A high-frequency electromagnetic induction coil 158 wound around the outer periphery.

The inner pipe 159 is one or more pipes provided inside the outer pipe, and is preferably formed of the hydrogen permeable membrane 223 and penetrates the side wall of the outer pipe 157 and communicates with the hydrogen gas outlet.
The hydrogen permeable membrane 223 forming the inner tube 159 is characterized by including a hydrogen permeable metal membrane 224 and a support 220 formed of a porous body.

A hydrogen permeable metal film 224 mainly composed of platinum or niobium can be given. The hydrogen permeable metal film 224 is preferably a metal film containing one or more metal elements selected from platinum, palladium, vanadium, niobium, tungsten, and molybdenum. More preferably, the film 224 is a metal film selected from platinum, palladium, and an alloy obtained by adding tungsten or molybdenum to niobium.
Since the hydrogen permeable metal film 224 also serves as a heating element of the high frequency electromagnetic induction heating device, the pyrolysis oil gasifier 152 of this embodiment does not require a separate heating element.

  It is preferable to fill the sensitized heat catalyst 142 between the outer tube and the inner tube. The sensitized heat catalyst 142 is a catalyst for decomposing solid components such as the carbon material 20 contained in the vaporized biomass pyrolysis oil. Any sensitizing heat catalyst 142 may be used as long as it meets the object of the present invention, and a particularly preferred example is a perovskite catalyst doped with nickel.

The heating element 156 formed of a magnetic material may be any magnetic material that generates heat by generating an induction current with a high frequency transmitted from the high frequency electromagnetic induction coil 158 wound around the outer periphery of the outer tube 157. In order to make the temperature distribution inside the outer tube uniform, it is preferably arranged uniformly, it is desirable that the pressure loss inside the outer tube is small, and in order to increase the heat transfer effect, those having a large surface area are preferable.
The high frequency electromagnetic induction coil 158 used in the present example used an in-line heater manufactured by Daiichi High Frequency Industrial Co., Ltd. as a basic structure.

  The high-temperature and high-pressure biomass pyrolysis oil produced by the biomass pyrolysis oil production apparatus main body 120 is vaporized by being discharged from the pressure control valve 132 to the normal-pressure expansion part 141. At this time, 500 to 1000 ° C. superheated steam 32 can be supplied in order to compensate for a decrease in reaction temperature due to vaporization heat and adiabatic expansion.

FIG. 8 is a diagram showing a separation and purification device of the biomass pyrolysis oil production device according to the fifth embodiment of the present invention.
As shown in FIG. 8, the separation and purification device 160 preferably includes a cyclone solid / gas separator 162 communicating with the gasifier outlet 155. Since the biomass pyrolysis oil production apparatus 152 according to the fifth embodiment includes the hydrogen permeable metal membrane 224 in the inner pipe, a high-purity hydrogen gas is obtained from the hydrogen gas outlet 218, and thus a separate hydrogen gas purification facility is provided. Is often unnecessary.

The cyclone solid / gas separator 162 separates the carbon material 20 and the gas component. The carbon material 20 obtained from the carbon material outlet 164 is recovered and reused.
A water vapor separator 170 having a water vapor passage membrane is connected to the gas component outlet 166 of the solid / gas separator 162. As the water vapor passing membrane, an SOD type zeolite membrane is preferable. The SOD type zeolite membrane in this case acts as a water vapor permeable membrane, separates water vapor and carbon monoxide, and is obtained from a carbon monoxide outlet 177, which is an outlet for gas that did not pass through the water vapor permeable membrane. It is done.

  A dust remover 180 for removing fine particles and a desulfurizer 181 for removing sulfur can be connected between the gas component outlet 166 of the cyclone-type solid / gas separator 162 and the water vapor separator 170. Further, a carbon dioxide separator 184 having an SOD type zeolite membrane can be connected to the carbon monoxide outlet 177.

  The water gas used to produce dimethyl ether has a 2: 1 ratio of hydrogen gas to carbon monoxide gas. On the other hand, when water gas is produced from carbon, the ratio of the generated hydrogen gas to carbon monoxide gas is stoichiometrically 1: 1, and the ratio when water gas is produced from hydrocarbon is 2: 1. Water gas generally has a hydrogen gas ratio that is often too low.

  FIG. 6 is a view of the water gas component adjusting device of the biomass pyrolysis oil production device according to the third embodiment of the present invention. As shown in FIG. 6, in this embodiment, the water gas component adjusting device 192 is provided with a branch pipe 195 in a pipe line 194 that connects the desulfurizer 181 and the water vapor separator 170, and the gas component 70 that passes through the pipe line 194. A part of is diverted to the branch 195. The carbon monoxide 50 in the diverted gas component 70 is converted into hydrogen gas using a reverse shift reactor 183, and the generated hydrogen gas is separated using a hydrogen separator 196 having a hydrogen-selective metal membrane. Hydrogen gas 40 is produced. Thereby, the ratio of hydrogen gas can be increased, and the component ratio of the produced water gas can be adjusted.

FIG. 9 is a schematic view of a dimethyl ether production apparatus.
As shown in FIG. 9, the dimethyl ether production apparatus 300 mixes hydrogen gas 40 and carbon monoxide 50 to produce an aqueous gas 52 and supplies it to the methanol production apparatus 302 to obtain Cu, Zn, Cr, Al, Au. , Or a catalyst containing one or more elements of Zr is heated at 120 to 300 ° C. by microwave heating to produce methanol, and a known dehydration catalyst such as methanol or alumina is used. It can be used to produce dimethyl ether by heating to 200-350 ° C. in an etherification device 303 equipped with a microwave heating device.

(Production Example 1)
Production of Nickel-Doped Perovskite Oxide Catalyst 63 g of citric acid and 56 ml of ethylene glycol were dissolved in about 350 ml of water, 10 g of calcium carbonate was gradually dissolved in this aqueous solution, and a total solution of 500 ml of water was used as a calcium stock solution. 63 g of citric acid and 56 ml of ethylene glycol were dissolved in about 350 ml of water, 14.8 g of strontium carbonate was gradually dissolved in this aqueous solution, and then a total solution of 500 ml with water was used as the strontium stock solution. 105 g of citric acid and 112 ml of ethylene glycol are dissolved in about 350 ml of water, and 28.4 g of tetraisopropyl orthotitanate is added to this aqueous solution. When the solution is stirred vigorously, the resulting white precipitate dissolves and becomes a clear solution. Water was added to this to make a total volume of 500 ml to obtain a titanium stock solution. 42 g of citric acid and 56 ml of ethylene glycol are dissolved in about 250 ml of water, and 29.1 g of nickel nitrate hexahydrate is added thereto and stirred at 90 ° C. in a rotary evaporator. Several hours later, a yellowish brown gas was generated. When the generation of this gas stopped, water was added to the liquid to make a total volume of 250 ml, which was used as a nickel stock solution.
40 ml of calcium stock solution, 10 ml of strontium stock solution, 50 ml of titanium stock solution and 5 ml of nickel stock solution were mixed, concentrated under reduced pressure, and then dried on a hot plate. This was put in an electric furnace and heated to 300 ° C. in the air. When the generation of white smoke stopped, the temperature was raised to 500 ° C. and baked for 5 hours. The solid obtained here was powdered in a mortar and mixed well. It was again fired at 850 ° C. for 10 hours in air to obtain a nickel-doped perovskite oxide catalyst.

(Production Example 2)
(1) Production of sulfonic acid group-introduced amorphous carbon from glucose 10 g of D-glucose is heated at 250 ° C. for 15 hours in an inert gas stream, and brown organic powder [half-value width (2θ) is 30 ° A diffraction peak on the (002) plane is observed. ] Was obtained. 5 g of this powder was added to 200 mL of 96% sulfuric acid, and heated at 150 ° C. for 15 hours while blowing nitrogen gas at 30 ml / min to obtain a black solid. This black solid was washed with 300 mL of distilled water, and this operation was repeated until the sulfuric acid in the distilled water after washing was below the detection limit of elemental analysis to obtain sulfonic acid group-introduced amorphous carbon. The resulting sulfonic acid group-introduced amorphous carbon powder has a chemical shift due to a condensed aromatic carbon 6-membered ring in the vicinity of 130 ppm of the 13C nuclear magnetic resonance spectrum, and a condensed aromatic carbon 6 to which a sulfonic acid group is bonded in the vicinity of 140 ppm. A chemical shift due to the member ring appeared. In the powder X-ray diffraction pattern of the obtained sulfonic acid group-introduced amorphous carbon powder, a diffraction peak on the carbon (002) plane was confirmed. The half width (2θ) of the diffraction peak on the (002) plane was 20 °. The sulfonic acid density of the amorphous carbon introduced with sulfonic acid residues was 4.5 mmol / g.

Example 1
1563.8 kg of sawdust 10, 250 kg of the solid acid catalyst 22, and 210 kg of the carbon material 20 were uniformly mixed by the mixer 111 to produce the biomass raw material 12.
The biomass raw material 12 was supplied with 163.3 kg of 500 ° C. superheated steam 32 using the flow mixer 112 to heat the biomass raw material 12 and transport it to the pressurized feeder 121 as a carrier gas.
The biomass raw material 12 is added to a microwave reaction tube 130 which is a ceramic tube having an inner diameter of 20 mm and a length of 1000 mm by adding 268.7 kg of 500 ° C. heated steam 32 using a pressure feeder 121 and pressurizing to 3.0 MPa. The amount was supplied at a rate of 25 kg / hr in terms of dry biomass supply. A microwave was applied to the biomass material 12 in the microwave reaction tube 130 using a microwave heating device 122.
The carbon material 20 and the solid acid catalyst 22 absorb microwaves and generate heat, the biomass raw material 12 is heated to 200 ° C., the biomass is decomposed into heavy tar components, and a crude biomass pyrolysis oil 59 is generated.
As the microwave heating device 122, a continuous microwave processing device (manufactured by Nippon Chemical Machinery Co., Ltd., microwave output 5.0 kW) was used.
From the pressure control valve 132 provided at the outlet of the biomass pyrolysis oil production apparatus, the high-temperature and high-pressure crude biomass pyrolysis oil 59 is discharged to the biomass pyrolysis oil discharge section 185, and 2022 kg of biomass pyrolysis oils 60 and 306 are discharged. 2 kg of non-condensable component 62 was obtained. The non-condensed components included 153.1 kg carbon monoxide, 43.7 kg methane, and 109.4 kg carbon dioxide.
The elemental analysis of the raw material biomass and the produced biomass pyrolysis oil 60 was performed, and the combustion heat quantity was calculated from the elemental analysis values, which were 16.7 MJ / kg (Dry) and 15.0 MJ / kg (Dry), respectively. Therefore, the energy recovery rate of the biomass pyrolysis oil 60 with respect to the biomass raw material 12 was 69.7%.

(Example 2)
The biomass raw material 12 was manufactured by uniformly mixing 1563.8 kg of sawdust 10, 250 kg of the solid acid catalyst 22, and 210 kg of the carbon material 20 with the wet pulverizer 111.
The biomass raw material 12 was supplied with 163.3 kg of 500 ° C. superheated steam 32 at the pretreatment unit 112 and heated at 95 to 98 ° C. for 1 hour to obtain pretreated biomass 13.
The microwave reactor tube which is a ceramic tube having an inner diameter of 20 mm and a length of 1000 mm by adding 268.7 kg of 500 ° C. heated steam 32 to the pretreated biomass 13 using a pressure feeder 121 and pressurizing to 3.0 MPa. 130 was supplied at a rate of 25 kg / hr in terms of dry biomass supply. A microwave was applied to the biomass material 12 in the microwave reaction tube 130 using a microwave heating device 122. The carbon material 20 and the solid acid catalyst absorbed microwaves to generate heat, the biomass raw material 12 was heated to 190 to 200 ° C., the biomass was decomposed into heavy tar components, and a crude biomass pyrolysis oil 59 was generated.
As the microwave heating device 122, a continuous microwave processing device (manufactured by Nippon Chemical Machinery Co., Ltd., microwave output 5.0 kW) was used.
From the pressure control valve 132 provided at the outlet of the biomass pyrolysis oil production apparatus, high-temperature and high-pressure crude biomass pyrolysis oil 59 is discharged to the pyrolysis oil receiver 185, and 2149.6 kg of biomass pyrolysis oil 60, and 306.2 kg of non-condensable component 62 was obtained. The non-condensed components included 153.1 kg carbon monoxide, 43.7 kg methane, and 109.4 kg carbon dioxide.
The elemental analysis of the raw material biomass and the produced biomass pyrolysis oil 60 was performed, and the combustion heat quantity was calculated from the elemental analysis values, which were 16.7 MJ / kg (Dry) and 15.0 MJ / kg (Dry), respectively. Therefore, the energy recovery rate of the biomass pyrolysis oil 60 with respect to the biomass raw material 12 was 74.1%.

(Example 3)
Similarly to Example 1, the biomass raw material 12 was prepared by uniformly mixing 1500 kg of sawdust 10, 250 kg of the solid acid catalyst 22, and 210 kg of the carbon material 20 with a wet pulverizer 111. The biomass raw material 12 was decomposed using the biomass pyrolysis oil production leaving main body 202 shown in FIG. 3 in the same manner as in Example 1 to obtain 1580.3 kg of crude biomass pyrolysis oil 59.
Next, as shown in FIG. 4, the pressure control valve 132 of the biomass pyrolysis oil production apparatus main body 202 is connected to the biomass pyrolysis oil reformer inlet 154 of the biomass pyrolysis oil reformer 152, so Biomass pyrolysis oil was discharged into the expansion section 141 and vaporized at normal pressure. The crude biomass pyrolysis oil 59 became an aerosol in which moisture was vaporized and the biomass decomposition product powder floated in the superheated steam 32 in the steam.
A high frequency is applied from a high frequency electromagnetic induction coil 158 wound around the outer periphery of the outer tube 157 of the pyrolysis oil gasifier 152, and the hydrogen permeable metal film 224 containing niobium as a main component forming the inner tube 159 is high frequency induction. The biomass decomposition product was heated to 700 ° C. The heavy tar component in the biomass decomposition product contained in the crude biomass pyrolysis oil 59 is decomposed into carbon monoxide 50 and hydrogen gas 40 in contact with the perovskite-supported Ni catalyst while being transported in powder form by superheated steam 32. It was done.
The hydrogen gas 40 permeated the hydrogen permeable metal film 224 of the inner tube 159 and was discharged from the hydrogen gas outlet 143 which is the outlet of the inner tube 159. The yield of hydrogen gas was 135.9 kg, and the yield of hydrogen gas 30 was 53.6% by weight, assuming that the raw material biomass was cellulose.
The product obtained from the gasifier outlet 155 which is the outlet of the outer tube 157 was sent to the separation and purification apparatus 160 shown in FIG.
In the solid / gas separator 162, 183.7 kg of the carbon material 20 and 1810 kg of the gas component 70 were obtained.
The gas component is passed through the dust remover 180 to recover 175.7 kg of the carbon material, and after passing through the desulfurizer 181, the sulfur component is removed, and then passed through the steam separator 170 having a steam permeable membrane, It separated into water vapor that passed through and gas components that did not pass through the water vapor permeable membrane.
The gas that did not pass through the water vapor permeable membrane contained 1281.3 kg of carbon monoxide, 402.8 kg of carbon dioxide, and 39.7 kg of methane according to gas chromatography analysis.
The gas that did not pass through the water vapor permeable membrane was passed through a carbon dioxide separator 184 to obtain 1360.20 kg of carbon monoxide having a purity of 94.2% by weight. The yield of carbon monoxide after conversion to purity was 1281.3 kg, and the main impurity was 4.4% by weight of methane. The yield of carbon monoxide was 72.2% by weight.

Example 4
In this embodiment, the separation and purification device 160 used in Embodiment 2 is further provided with a water gas component adjusting device 192 shown in FIG. The water gas component adjusting device 192 is a hydrogen separator having a branch pipe 195 provided in a pipe line 194 that connects the desulfurizer 181 and the steam separator 170, a component adjusting valve 193, a reverse shift reactor 183, and a hydrogen-selective metal membrane. A container 196. The hydrogen gas that has passed through the hydrogen separator 196 is merged with the hydrogen gas supplied from the hydrogen gas outlet 143 of the biomass pyrolysis oil gasifier 150, and the exhaust gas that has passed through the hydrogen separator 196 is exhausted to the atmosphere.
As in Example 2, the biomass raw material 12 prepared from 2000 kg of sawdust 10, 3000 kg of the solid acid catalyst 22, and 240 kg of the carbon material 20 is decomposed using the biomass pyrolysis oil production leaving body 202. Then, crude biomass pyrolysis oil 59 was produced, and hydrogen gas 40 and carbon monoxide 50 were produced using the biomass pyrolysis oil production apparatus 200.
In this embodiment, a branch pipe 195 is provided in a pipe line 194 communicating with the desulfurizer 181 and the water vapor separator 170, and 12.9% of the gas component 70 passing through the pipe line 194 is divided into the branch pipe 195.
The carbon monoxide 50 in the diverted gas component 70 is converted into hydrogen gas using a reverse shift reactor 183, and the generated hydrogen gas is separated using a hydrogen separator 196 having a hydrogen-selective metal membrane, A total of 212.6 kg of hydrogen gas 40 was obtained in accordance with the hydrogen gas supplied from the hydrogen gas outlet 143 of the biomass pyrolysis oil reformer 150.
The remaining gas component 70 was treated in the same manner as in Example 3 to obtain 1488.3 kg of carbon monoxide 50 in terms of pure carbon monoxide. The yield of the obtained hydrogen gas 40 and carbon monoxide 50 was 62.9%, and the molar ratio was 2: 1.

DESCRIPTION OF SYMBOLS 10 Biomass 12 Biomass raw material 13 Pretreated biomass 15 Water 20 Carbon material 22 Solid acid catalyst 25 Heat generating material 30 Water vapor 32 Superheated steam 40 Hydrogen gas 44 Carbon dioxide gas 50 Carbon monoxide 52 Water gas 59 Crude biomass pyrolysis oil 60 Biomass pyrolysis Oil 61 Condensed component 62 Non-condensed component 70 Gas component 100 Biomass pyrolysis oil production device 110 Biomass pretreatment unit 111 Wet crusher 112 Pretreatment unit 120 Biomass pyrolysis oil production device main body 121 Pressure feeder 122 Microwave heating device 123 Micro Wave oscillator 126 Cylindrical space 128 Central axis 129 Microwave resonator 130 Microwave reaction tube 132 Pressure control valve 141 Expansion part 142 Sensitization thermal catalyst 143 Hydrogen gas outlet 150 to 152 Pyrolysis oil gas Gasifier inlet 155 Gasifier outlet 156 Heating element 157 Outer tube 158 High frequency electromagnetic induction coil 159 Inner tube 160 Separation and purification device 162 Solid / gas separator 164 Carbon material outlet 166 Gas component outlet 170 Steam separator 171 Hydrogen Gas outlet 177 Carbon monoxide outlet 180 Dust remover 181 Desulfurizer 183 Reverse shift reactor 184 Carbon dioxide gas separator 185 Pyrolysis oil discharge section 186 Condenser 187 Non-condensed component outlet 188 Pyrolysis oil outlet 189 Filter 190 Pyrolysis oil receiver Vessel 192 Water gas component adjustment device 193 Component adjustment valve 194 Pipe line 195 Branch pipe 196 Hydrogen separator 218 Hydrogen gas outlet 220 Support 222 Hydrogen permeable membrane 223 Hydrogen permeable membrane 224 Hydrogen permeable metal membrane 226 Zeolite membrane 300 Made of dimethyl ether 301 dimethyl ether 302 methanol production apparatus 303 etherification device

Claims (28)

Biomass raw material production means that knead biomass, carbon material, and water into biomass raw material,
Raw material supply means for pumping the biomass raw material to a microwave reaction tube that is formed of a material that does not absorb microwaves and includes pressure control means;
Microwave heating means for producing a crude biomass pyrolysis oil by heating the biomass raw material in the microwave reaction tube to a temperature range of 120 ° C. to 347 ° C. with a microwave heating device;
Separation means for separating biomass pyrolysis oil from the crude biomass pyrolysis oil;
An apparatus for producing biomass pyrolysis oil, comprising: Biomass raw material production means for producing biomass raw material by kneading biomass, carbon material, solid acid catalyst, and water;
A raw material supply unit that is formed of a material that does not absorb microwaves and is fed to a microwave reaction tube having a pressure control unit, and a biomass material in the microwave reaction tube is heated at 120 ° C. to 347 by a microwave heating device. Microwave heating means for producing crude biomass pyrolysis oil by heating to a temperature range of ℃,
An apparatus for producing biomass pyrolysis oil, comprising:   The apparatus for producing biomass pyrolysis oil according to claim 2, wherein the solid acid catalyst is a carbon-based acid catalyst.   The biomass according to claim 2 or 3, further comprising pretreatment means for heating the biomass raw material and producing pretreated biomass between the biomass raw material production means and the raw material supply means. Pyrolysis oil production equipment. The microwave heating means includes
A microwave oscillator and a container having a cylindrical space made of metal at least on the inner surface, the direction being parallel to the central axis of the cylinder of the cylindrical space and the size of the cylindrical space being in the cylindrical space A microwave resonator having an axially symmetric microwave electromagnetic field constant in a central axis direction and a circumferential direction of the cylindrical space, and
The microwave reaction tube formed of a material that does not absorb microwaves, and
The microwave reaction tube shares the central axis with the central axis of the cylindrical space, penetrates the inside of the microwave resonator, is connected to the raw material supply means at one end, and the pressure control means is at the other end. The apparatus for producing biomass pyrolysis oil according to any one of claims 1 to 4, wherein the apparatus is provided.   The apparatus for producing biomass pyrolysis oil according to claim 4, further comprising means for removing the solid acid catalyst from the pretreated biomass. Discharge means for discharging the crude biomass pyrolysis oil from the pressure control means to a solid-liquid separator;
A condensing means that is connected to the gas outlet of the solid-liquid separator and condenses biomass pyrolysis oil;
Separation means for separating the biomass pyrolysis oil and the carbon material contained in the crude biomass pyrolysis oil;
The apparatus for producing biomass pyrolysis oil according to any one of claims 1 to 6, wherein: Discharge means for discharging the crude biomass pyrolysis oil from the pressure control means to a hydrogen permeation membrane, a high-frequency electromagnetic induction heating device, and a pyrolysis oil gasification means including a heating element;
Gasification means for heating the crude biomass pyrolysis oil by the high-frequency electromagnetic induction heating device and the heating element, and pyrolyzing the crude biomass pyrolysis oil to produce hydrogen gas and carbon monoxide;
The apparatus for producing biomass pyrolysis oil according to any one of claims 1 to 6, wherein: The gasification means is a cylindrical container formed of a non-magnetic material, provided at one end thereof, an inlet to which the crude biomass pyrolysis oil is supplied, and the crude biomass pyrolysis oil at normal pressure An outer tube having an expanded portion that is opened and vaporized; and an outlet provided at the other end of the container; and a high-frequency electromagnetic induction coil wound around the outer periphery;
One or more inner pipes provided inside the outer pipe, having a hydrogen permeable membrane and having a hydrogen gas outlet penetrating a part of the outer pipe;
A heating element that is formed of a magnetic material and heats a space between the outer tube and the inner tube;
The apparatus for producing biomass pyrolysis oil according to claim 8.   The said gasification means is further equipped with the catalyst which accelerates | stimulates decomposition | disassembly of the said crude biomass pyrolysis oil, The manufacturing method of biomass pyrolysis oil of Claim 8 or 9 characterized by the above-mentioned.   The apparatus for producing biomass pyrolysis oil according to claim 10, wherein the catalyst is a perovskite oxide catalyst doped with nickel.   The hydrogen permeable membrane is formed to include a hydrogen permeable zeolite membrane, and further includes a separation unit that allows only one of hydrogen gas and water vapor to pass therethrough. The manufacturing apparatus of biomass pyrolysis oil as described in claim | item.   The hydrogen permeable film is formed to include a hydrogen permeable metal film, and the hydrogen permeable metal film acts as a heating element of a high frequency electromagnetic induction heating device. The manufacturing apparatus of biomass pyrolysis oil as described in claim | item.   14. The hydrogen permeable metal film is a metal film containing one or more metal elements selected from platinum, palladium, vanadium, niobium, tungsten, and molybdenum. The apparatus for producing biomass pyrolysis oil as described in 1. Biomass raw material production stage to knead biomass, carbon material, and water into biomass raw material,
A raw material supply stage in which the biomass raw material is formed of a material that does not absorb microwaves and is pumped to a microwave reaction tube provided with pressure control means;
A microwave heating step of producing a crude biomass pyrolysis oil by heating the biomass raw material in the microwave reaction tube to a temperature range of 120 ° C. to 347 ° C. with a microwave heating device;
Separating the biomass pyrolysis oil from the crude biomass pyrolysis oil;
A method for producing biomass pyrolysis oil, comprising: Biomass raw material production stage of kneading biomass, carbon material, solid acid catalyst, and water to produce biomass raw material,
A raw material supply stage in which the biomass raw material is formed of a material that does not absorb microwaves and is pumped to a microwave reaction tube provided with pressure control means;
A microwave heating step of producing a crude biomass pyrolysis oil by heating the biomass raw material in the microwave reaction tube to a temperature range of 120 ° C. to 347 ° C. with a microwave heating device;
A method for producing biomass pyrolysis oil, comprising:   The method for producing biomass pyrolysis oil according to claim 16, wherein the solid acid catalyst is a carbon-based acid catalyst.   The biomass heat according to claim 16 or 17, further comprising a pretreatment stage in which the biomass raw material is heated to produce pretreated biomass between the biomass raw material production stage and the raw material supply stage. A method for producing cracked oil. The microwave heating means includes
A microwave oscillator and a container having a cylindrical space made of metal at least on the inner surface, the orientation of the cylindrical space being parallel to the central axis of the cylindrical space and the size of the cylinder of the cylindrical space being A microwave resonator having an axially symmetric microwave electromagnetic field constant in a central axis direction and a circumferential direction of the cylindrical space, and
The microwave reaction tube formed of a material that does not absorb microwaves, and
The microwave reaction tube shares the central axis with the central axis of the cylindrical space, penetrates the inside of the microwave resonator, is connected to the raw material supply means at one end, and the pressure control means is at the other end. The method for producing biomass pyrolysis oil according to any one of claims 15 to 18, wherein the biomass pyrolysis oil is provided.   The method for producing a biomass pyrolysis oil according to claim 18, further comprising the step of removing the solid acid catalyst from the pretreated biomass. A discharge stage for discharging the crude biomass pyrolysis oil from the pressure control means to a solid-liquid separator;
A condensing step for condensing biomass pyrolysis oil with a condensing means for condensing the biomass pyrolysis oil, connected to the gas outlet of the solid-liquid separator;
A separation step of separating the biomass pyrolysis oil and the carbon material contained in the crude biomass pyrolysis oil;
The method for producing biomass pyrolysis oil according to any one of claims 15 to 20, characterized by comprising: A discharge step of supplying the crude biomass pyrolysis oil from the pressure control means to a pyrolysis oil gasification means comprising a hydrogen permeable membrane, a high-frequency electromagnetic induction heating device, and a heating element;
A gasification step of heating the crude biomass pyrolysis oil by the high-frequency electromagnetic induction heating device and the heating element, and pyrolyzing the crude biomass pyrolysis oil to produce hydrogen gas and carbon monoxide;
The method for producing biomass pyrolysis oil according to any one of claims 15 to 20, characterized by comprising: The gasification step is a cylindrical container formed of a non-magnetic material, provided at one end thereof, to which the crude biomass pyrolysis oil is supplied, and the crude biomass pyrolysis oil is at normal pressure. An outer tube having an expanded portion that is opened and vaporized; and an outlet provided at the other end of the container; and a high-frequency electromagnetic induction coil wound around the outer periphery;
One or more inner pipes provided inside the outer pipe, having a hydrogen permeable membrane and having a hydrogen gas outlet penetrating a part of the outer pipe;
A heating element that is formed of a magnetic material and heats a space between the outer tube and the inner tube;
23. The method for producing biomass pyrolysis oil according to claim 22, wherein the crude biomass pyrolysis oil is heated by a pyrolysis oil gasification means having a thermal decomposition of the crude biomass pyrolysis oil. .   The said gasification means is further equipped with the catalyst which accelerates | stimulates decomposition | disassembly of the said crude biomass pyrolysis oil, The manufacturing method of biomass pyrolysis oil of Claim 22 or 23 characterized by the above-mentioned.   The method for producing biomass pyrolysis oil according to claim 24, wherein the catalyst is a nickel-doped perovskite oxide catalyst.   The hydrogen permeable membrane is formed to include a hydrogen permeable zeolite membrane, and further includes a separation unit that allows only one of hydrogen gas and water vapor to pass therethrough. The manufacturing method of biomass pyrolysis oil as described in a term.   The biomass according to claim 22 or 23, wherein the hydrogen permeable membrane includes a hydrogen permeable metal membrane, and the hydrogen permeable metal membrane functions as a heating element of a high frequency electromagnetic induction heating device. A method for producing pyrolysis oil.   28. The hydrogen permeable metal film is a metal film containing at least one metal element selected from platinum, palladium, vanadium, niobium, tungsten, and molybdenum. A method for producing a biomass pyrolysis oil as described in 1. above.

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