WO2010119972A1

WO2010119972A1 - Btl fuel production system and method for producing btl fuel

Info

Publication number: WO2010119972A1
Application number: PCT/JP2010/056897
Authority: WO
Inventors: 直彌吉川; 二郎及川; 浩康中村
Original assignee: Ｇｇｉジャパン株式会社
Priority date: 2009-04-14
Filing date: 2010-04-13
Publication date: 2010-10-21
Also published as: WO2010119973A1; JPWO2010119972A1; JPWO2010119973A1

Abstract

A target BTL (Biomass-to-Liquid) fuel is efficiently produced from a biomass material. A system for producing a BTL fuel, which comprises: a pretreatment device for pretreating a biomass material to give a material in a definite size and definite form; a heat decomposition device for thermally decomposing the biomass material to give a dry distillation gas; a purification device for purifying the dry distillation gas; and a hydrocarbon-synthesizing device for converting the thus purified gas into a hydrocarbon oil in the presence of a hydrocarbon-synthesizing catalyst. This system is provided with a hydrogen-supply unit, whereby hydrogen gas is measured and fed, and a control device, whereby the dry distillation gas and hydrogen are mixed in a controlled manner so as to give a definite carbon/hydrogen molar ratio, between the purification device and the hydrocarbon-synthesizing device.

Description

BTL manufacturing system and BTL manufacturing method

The present invention relates to a BTL production system and a BTL production method for producing hydrocarbon oil from biomass raw materials. More specifically, the present invention relates to a system and method for producing a hydrocarbon oil typified by jet fuel from a biomass feedstock.

Various attempts have been made to pyrolyze biomass to generate dry distillation gas and to convert the generated dry distillation gas into liquid fuel (BTL: Biomass to Liquid) using a Fischer-Tropsch synthesis catalyst.
Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-205135) discloses a methane fermentation tank for methane fermentation treatment of low-calorie waste, a carbonization furnace for burning carbonization by burning high-calorie waste, and the carbonization furnace. A gasification furnace for introducing and burning the generated carbide to gasify, a gas purification device for purifying the gas generated in the gasification furnace, and liquid fuel from the purified gas mainly containing the purified CO and H2 A composite waste treatment system including a liquid fuel synthesizing apparatus that performs FT synthesis (Fischer-Tropsch synthesis) and that supplies biogas generated in a methane fermentation tank to a gasification furnace as a combustor is disclosed.
Patent Document 2 (Japanese Patent Application Laid-Open No. 2007-204558) includes a gasification unit that holds a certain amount of biomass and heats it with a heating body to gasify it, and a particulate material, tar, A gas refining unit that removes at least one substance selected from sulfur compounds and nitrogen compounds and purifies biomass gas, and a liquid fuel manufacturing unit that liquefies the purified biomass refining gas to produce a biomass liquid fuel stock solution A gas-liquid separator that separates the biomass liquid fuel stock solution into biomass liquid fuel, water, and light hydrocarbons, a vacuum recovery unit that recovers the biomass liquid fuel separated by the gas-liquid separator by reducing the pressure, and Combusting the unreacted material that is not gasified in the gasification unit, and supplying the generated heat to the gasification unit, liquid combustion from biomass comprising Manufacturing apparatus is disclosed.
These techniques are in the design stage or the experimental stage, and a technique for producing BTL oil in a high yield from a biomass raw material that can be continuously operated on an industrial scale has not been established.
That is, in the prior art, only a small amount of hydrocarbons can be obtained as compared with the amount of carbon contained in the biomass material as a raw material.

JP 2006-205135 A JP 2007-204558 A

Another object of the present invention is to provide a BTL manufacturing system and a BTL manufacturing method capable of obtaining a target industrially valuable BTL in a high yield.

The present invention that solves the above-described problems includes a pretreatment device for pretreating a biomass raw material to a predetermined size, a predetermined moisture content, and a predetermined range of carbon content and hydrogen content per unit mass, BTL production comprising a pyrolysis device that decomposes into dry distillation gas, a purification device that purifies the dry distillation gas, and a hydrocarbon synthesis device that uses the purified gas as hydrocarbon oil in the presence of a hydrocarbon synthesis catalyst A hydrogen supply system for metering and adding hydrogen gas between the purification device and the hydrocarbon synthesis device, a dry distillation gas purified by the purification device, and hydrogen metered from the hydrogen supply system And adjusting the mixed gas so that the carbon: hydrogen molar ratio is 1: 2 to 1: 6 in the dry distillation gas based on the content of the carbon component and the hydrogen component contained in the biomass raw material About BTL manufacturing system characterized by comprising a location.
The present invention further includes a pretreatment step of pretreating the biomass raw material so as to have a predetermined size, a predetermined moisture content, a predetermined range of carbon content and hydrogen content per unit mass, and a heat treatment of the pretreated biomass raw material. A carbonization gas generation step for generating a carbonization gas by introducing it into a cracking device, a purification step for purifying the generated carbonization gas, and synthesis by adding hydrogen to the purified carbonization gas at a predetermined carbon: hydrogen molar ratio. A mixed gas preparation step for preparing a mixed gas, a hydrocarbon oil production step for converting the prepared mixed gas into a hydrocarbon, and a mixed gas obtained in the hydrocarbon production step into a hydrocarbon oil and an unreacted component The manufacturing method of BTL characterized by including the separation process of separating.

FIG. 1 is a diagram showing a basic configuration of a BTL manufacturing system according to an embodiment of the present invention.
FIG. 2 is a drawing showing an example of a thermal decomposition apparatus in the BTL manufacturing system of the present invention.
FIG. 3 is a drawing showing an example of a carrier gas supply system that supplies the thermal decomposition apparatus.
FIG. 4 is a drawing showing an example of a purification apparatus in the BTL manufacturing system of the present invention.
FIG. 5 is a drawing showing an example of a hydrogen supply system in the BTL production system of the present invention.
FIG. 6 is a drawing showing an example of an adjusting device in the BTL manufacturing system of the present invention.
FIG. 7 is a flowchart showing an example of calculation of the hydrogen addition amount in the BTL production system of the present invention.
FIG. 8 is a flowchart showing the method for manufacturing the BTL of the present invention.

(Basic configuration)
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. First, the basic configuration of the BTL manufacturing system of the present invention will be described with reference to FIG.
As shown in FIG. 1, the hydrocarbon production system of the present invention heats a biomass raw material pretreated by the pretreatment device 10 for pretreating the biomass raw material to a predetermined size and moisture content, and the pretreatment treatment device 10. FT synthesis tower 70, which is a thermal decomposition apparatus 20 that decomposes into a dry distillation gas, a purification apparatus 40 that purifies the dry distillation gas, and a hydrocarbon synthesis apparatus that uses the purified gas as hydrocarbon oil in the presence of a hydrocarbon synthesis catalyst. And a hydrogen supply device 60 for supplying the dry distillation gas with a shortage of hydrogen for hydrocarbon synthesis, and the BTL production system of the present invention includes an adjusting device 50 for mixing the purified dry distillation gas and hydrogen, have. More preferably, in the BTL production system of the present invention, the adjusting device 50 has a configuration for returning unreacted gas to the adjusting device 50 in the FT synthesis tower.
As will be described later, the pyrolysis apparatus 20 replaces the inlet 21 for introducing biomass as a raw material and the atmosphere in the pyrolysis apparatus 20, and sends the generated dry distillation gas to the subsequent purification apparatus 40. A gas supply system 30 is provided.
The BTL production apparatus of the present invention purifies a dry distillation gas generated by thermally decomposing a predetermined pretreated biomass with a thermal decomposition apparatus 20 with a purification apparatus 40, and adds hydrogen to the purified dry distillation gas to form a mixed gas. The mixed gas is converted into hydrocarbon oil by the FT synthesis tower. At this time, since the shortage of hydrogen is supplied from the hydrogen supply system 50 based on the carbon content and hydrogen content of the biomass raw material, the yield of BTL oil in the BTL production apparatus of the present invention increases.
(Raw material and pretreatment)
The biomass that can be used in the present invention is not particularly limited as long as it has a carbon source that generates dry distillation gas by thermal decomposition treatment, and can be appropriately used from a wide range of biomass.
Biomass materials applicable in the present invention include marine product-derived materials (seaweed, processed fishery product residues, etc.), forestry-derived materials (wood chips, pruning residue, bark, etc.), and agricultural-derived materials (biomass plants, crop residues, vegetation) , Waste after crop harvesting, residues after bioethanol extraction such as corn core), livestock-derived materials (livestock and poultry manure, food processing residues), sludge-derived materials, sludge, and mixtures thereof. It is not limited to.
In the present invention, a mixture of biomass derived from different sources can be used as a starting material, but a single product is preferable in order to obtain a raw material having a predetermined raw material standard by a pretreatment described later. In particular, it is preferable to use a single product having relatively stable component contents such as seaweed and wood chips.
These biomass raw materials have different carbon contents and hydrogen contents depending on the origin. For example, in the case of wood chips, about 50 to 60% by mass of carbon and 4 to 8% by mass of hydrogen are contained on a dry basis, and in the case of sludge, about 40 to 50% by mass of carbon and 10 to 20% by mass of hydrogen are contained. Thus, the biomass raw material has an excessive carbon content relative to the hydrogen content.
In the present invention, hydrogen is added based on such carbon content and hydrogen content so as to obtain an optimal carbon: hydrogen molar ratio (C: H). Generally, C: H = 1: 1. The hydrogen content is adjusted to be from 5 to 1: 6, preferably from 1: 2 to 1: 5, more preferably from 1: 2 to 1: 4.
At this time, the biomass material is provided in various forms as a crude material. Therefore, in the present invention, two viewpoints are used for pretreatment for using such a crude material as a production material.
In the pretreatment in the present invention, (1) sufficient moisture adjustment to be within a predetermined carbon hydrogen molar ratio range (moisture adjustment is important from the viewpoint of energy reduction in thermal decomposition); (2) It is important to pulverize to a predetermined size in advance so as to efficiently thermally decompose.
However, pretreatment of these biomass raw materials is appropriately selected from the viewpoints of introduction of a pretreatment device, energy required for moisture adjustment, introduction of a pulverizer, efficiency of the pulverizer, and the like. What is important in the present invention is that the biomass raw material satisfies predetermined raw material standards (carbon and hydrogen content, water content, and size).
For biomass raw materials, for example, when the moisture content is sufficiently low, such as wood chips, moisture adjustment may be omitted, and when pulverization after drying is not required, such as sludge, grinding is omitted. May be.
The pretreatment in the present invention is appropriately selected according to the carbon source (biomass raw material) to be used and its situation. What is important in the pretreatment is removal of impurities as much as possible, moisture adjustment, and size adjustment.
The target moisture content is less than 60%, preferably less than 30%, more preferably less than 10%. If the water content is too high, energy consumption due to excessive evaporation in the thermal decomposition apparatus becomes too large.
The size of biomass is preferably as fine as possible from the viewpoint of efficient thermal decomposition. By pretreating in this way, the carbon content and hydrogen content per unit weight can be assumed. In other words, in the present invention, the biomass raw material pretreated in this way is used as a raw material reference for the starting raw material, and is used as a reference for calculating the amount of hydrogen to be described later based on the carbon and hydrogen content per unit weight.
In the specific embodiment of the present invention, it is preferable to crush and pulverize the biomass raw material while adjusting the water content.
The pretreatment device can be appropriately selected from known devices according to the purpose and the status of biomass. When wood chips are used as a biomass raw material, the pretreatment device finely pulverizes with a primary pulverizer for coarse pulverization. A secondary pulverizing apparatus. Thus, by combining the primary pulverizer and the secondary pulverizer to make the wood chip a predetermined size, the thermal decomposition efficiency in the thermal decomposition apparatus 20 to be used is determined, and the wood chip is determined according to the origin (for example, The carbon content and the hydrogen content are determined within a certain range.
When seaweed or the like is used as a raw material, it may be dried in advance. However, a moisture content adjusting device such as a dehydrating device or a drying device for adjusting the moisture content, and a pulverizing device (primary Use a pre-treatment device combined with the following grinding).
By performing the pretreatment in this way, the carbon content and the hydrogen content are determined within a certain range as in the case of wood chips.
In the present invention, one of the characteristics is that a biomass raw material having such a clear raw material standard is used as a starting raw material.
Note that the pretreatment device 10, the thermal decomposition device 20, and the subsequent device may be separated. That is, it is also within the scope of the present invention to perform a pretreatment or a part of the pretreatment at the raw material supplier and produce a desired BTL oil in the BTL production system.
(Thermal decomposition)
The biomass raw material pretreated in the present invention is then thermally decomposed into crude dry distillation gas by the thermal decomposition apparatus 20. The pyrolysis apparatus 20 applicable in the present invention includes, for example, an inlet 21 for charging a biomass raw material that has been pretreated as shown in FIG. 2, a function of replacing the atmosphere in the pyrolysis apparatus 20, and the generated dry distillation gas. It has a carrier gas introduction port 23 having a carrier gas function to be transferred to the process, and a discharge port 22 for discharging the generated dry distillation gas (crude dry distillation gas), and pyrolyzes the biomass material input from the input port 21 It is a device having a heat source (not shown), and is not particularly limited as long as it is a pyrolysis device having such a function, and can be applied to a continuous type such as a rotary kiln type or a batch type. .
The pyrolysis apparatus 20 shown in FIG. 2 has a configuration in which a biomass raw material charged from the charging port 21 is pushed by a raw material pushing device 21a. At this time, air contained in the raw material is removed from the lower side of the inlet 21 and a substantial amount of oxygen is removed when entering the inside of the thermal decomposition apparatus 20.
Therefore, a considerable amount of air is replaced by the introduction of the carrier gas. The introduced biomass raw material is heated to a pyrolysis temperature in a carrier gas atmosphere by a heating means (not shown) and pyrolyzed to become a dry distillation gas containing impurities and a remaining solid component.
The heat source of the thermal decomposition apparatus can be oil as in the past, but those using electric energy or a hybrid with an oil type are preferred from the viewpoint of easy temperature control in the heat separator.
When electric energy is used, the hydrocarbon (gas and / or oil) obtained by the present invention is used as a heat source, or the mixture of hydrogen and hydrocarbons generated by the present invention is used as an energy source. It is preferable to do. The thermal decomposition apparatus using electric energy may be a conventional electric furnace, but may be a heating method using microwaves or a heating method using a ceramic heating element.
In a preferred embodiment of the present invention, the pyrolysis apparatus includes an input amount measuring device (for example, a weight sensor) for measuring the input amount of biomass raw material, a flow rate sensor for measuring the flow rate of the carrier gas, and the inside of the furnace It is preferable to provide a known sensor such as a temperature sensor for measuring the temperature, a pressure sensor for measuring the pressure in the apparatus, and a flow rate sensor for measuring the discharge amount and discharge pressure of the dry distillation gas.
In particular, the pyrolysis apparatus is composed of a weight sensor for measuring the input amount of biomass raw material, a flow sensor for measuring the flow rate of the carrier gas, a flow sensor and a temperature sensor for measuring the discharge amount and discharge temperature of the dry distillation gas. This information is important for calculating the carbon content and the hydrogen content (and hence the molar ratio of carbon to hydrogen).
The electric heating method is easy to control based on information from these sensors, and is preferable in terms of energy cost reduction, quick start-up, and ease of maintenance and operation. In particular, in the case of the micro-wave type, the energy cost is about 1/10 compared to an electric furnace (an additional half by inserting an inverter circuit), the start-up is faster (about 5 minutes), and higher-temperature pyrolysis is possible. There is an advantage that downsizing is possible and maintenance and operation are easy.
In this way, the predetermined biomass material is generally pyrolyzed at a high temperature of 700 ° C. or higher, so that water gas is mainly formed at a predetermined pyrolysis rate depending on the type of biomass material to be pyrolyzed and the degree of pretreatment. A dry distillation gas is produced (crude dry distillation gas).
In the present invention, a biomass raw material obtained by subjecting a certain raw material to a certain treatment is used as a starting raw material, so that the pyrolysis apparatus 20 can generate dry distillation gas with stable efficiency.
The carrier gas supply system 30 is mainly composed of a water tank 31 for storing water for generating water vapor and an induction heating line 32 for overheating the generated water vapor. Since the superheated steam can be heated to a temperature of about 600 ° C. to 900 ° C., it can also be used as a heat source for the thermal decomposition apparatus 20.
In the embodiment shown in FIG. 3, superheated steam can be sent to a hydrogen supply system 60 to be described later and used for generating hydrogen by catalytic reaction, and water from a purification device 50 such as an ion exchange scrubber can be used. It is also possible to have a configuration in which the water is sent to the hot water tank 31.
This configuration has an advantage that the apparatus configuration is simplified and energy consumption is reduced.
(Purification equipment)
The purification device 40 is a device that removes impurities from the generated crude dry distillation gas, and can be configured by combining devices well known in the art. In a preferred embodiment of the present invention, as shown in FIG. 4, a dry distillation in which a combination of a desulfurization / detarring device 41 and an ion exchange scrubber 43 or a combination of a desulfurization / detarging device 41, an ion exchange scrubber 43 and a cyclone 42 is purified. It is preferable in that the gas is purer and the hydrocarbon oil as the final product does not contain ionic components such as chlorine.
In other words, the ion exchange scrubber is a scrubber having both an anion exchange resin layer and a cation exchange resin layer, and is removed at an efficiency of 98% or more during gas treatment of HCl, HCN, Cl ₂ , NO ₂ , SO _2, etc. Is possible. Further, it is possible to simultaneously perform the adsorption treatment of the contaminated gas and the regeneration of the ion exchange fiber in one chamber.
Conventionally, the gas generated by this type of pyrolysis has been treated with a normal scrubber. However, depending on the origin of biomass raw materials, ordinary scrubbers may not sufficiently remove halogens and metal ions such as chlorine and iodine, and may remain in the purified gas, adversely affecting the hydrocarbon oil that is the final product. There was a case. Therefore, in the present invention, it is preferable to employ an ion exchange scrubber.
In addition, the crude water gas often contains a sulfur component, a tar component, and the like, which may adversely affect the hydrocarbon oil that is the final product. Therefore, in the present invention, these components are removed by a desulfurization / detar apparatus. Such an apparatus is not particularly limited as long as it achieves the object of the present invention, but can be composed of activated carbon that becomes denser from upstream to downstream, and is configured to switch a plurality of activated carbon layers in terms of maintenance. It is also possible to do.
The desulfurization / detar apparatus 41 is a known apparatus as described in, for example, Patent Document 2, and the cyclone 42 is also a known apparatus.
By comprising in this way, the refinement | purification recirculation | reflux gas which has a fixed property irrespective of the origin of biomass raw material can be obtained combining with the pretreatment of this invention. That is, it is preferable to use a reflux gas substantially free of ionic components, particularly halogen components and sulfur components. Such purified carbonization gas is extremely advantageous for providing the desired hydrocarbon oil containing no chlorine or the like.
(Hydrogen supply system)
In the present invention, purified water gas is mixed with hydrogen in order to make up for the lack of hydrogen compared to carbon. That is, the hydrogen required to produce hydrocarbon oils according to the present invention is deficient compared to carbon from purified water gas. Therefore, in order to produce hydrocarbon oil with a good yield (yield) by the system and method of the present invention, hydrogen is supplied from the hydrogen supply system to the purified water gas. In the present invention, it is preferable to synthesize hydrogen on-site and use the synthesized hydrogen according to the required amount, more preferably to use superheated steam used as a carrier gas and hydrogen generated by a hydrogen generation catalyst. .
More specifically, as shown in FIG. 5, by bringing a CaBr / FeO catalyst into contact with the superheated steam shown in FIG. 3, the steam is decomposed into oxygen and hydrogen. The resulting hydrogen is taken into a hydrogen tank and used to mix with purified water gas as necessary.
In this way, hydrogen can be produced in the system. By arranging a hydrogen supply system 60 capable of producing hydrogen in the system, a large amount of hydrogen can be supplied to the purified water gas. This makes it possible to obtain hydrocarbons with a good yield in the system of the present invention. It is also possible to use the obtained hydrogen for power generation.
(Hydrogen addition to dry distillation gas)
In the present invention, hydrogen from such a hydrogen supply system is added to the purified dry distillation gas. Hydrogen may be added in advance to the carrier gas or added to the water source of superheated steam as microbubbles. However, it is preferable to provide an adjusting device as shown in FIG.
(Adjustment device)
The adjustment device 50 shown in FIG. 6 mixes a dry distillation gas purified by the purification device 40, hydrogen from the hydrogen supply system 60, and preferably an unreacted gas from the FT synthesis tower 80 described later in a predetermined amount, It is a device that adjusts the mixed gas sent to the FT synthesis tower, and temporarily mixes the gas mixed with the gas mixer 51 provided with control valves 52a, 52b, 52c such as electromagnetic valves for adjusting the gas pressure of each gas. It comprises a buffer tank 53 for storage. The gas mixer 51 preferably includes gas compression means (not shown). As such a gas compression means, for example, by arranging a heat exchange tube using superheated steam as a heat medium in the gas mixer 51, the mixed gas in the gas mixer 51 is expanded and pressurized.
The amount of hydrogen added at this time is determined, for example, as shown in FIG.
That is, in the present invention, the raw material standard is determined in advance by pretreatment (hydrogen content and carbon content), and the hydrogen content and carbon content of the dry distillation gas are determined by this raw material standard.
Then, the amount of dry distillation gas generated per unit time is calculated by measuring the amount of gas generated by the actual operation of the thermal decomposition apparatus 20 and discharged from the thermal decomposition apparatus 20. The gas generation amount of the dry distillation gas can be approximately determined as a value obtained by subtracting the flow rate of the carrier gas introduced per unit time from the flow rate of the gas discharged from the discharge port 21 per unit time.
Then, the amount of hydrogen shortage is calculated from the composition of carbonized gas (carbon and hydrogen content) and the flow rate.
Further, in the specific embodiment of the present invention, when the unreacted gas from the FT synthesis tower 80 is mixed, the component of the unreacted gas is generally a lower hydrocarbon. The amount of hydrogen to be actually introduced is calculated by correcting the above.
Based on the hydrogen addition amount calculated in this way, the adjustment device 50 supplies a predetermined amount of hydrogen gas from the hydrogen supply system 50 via the control valve 52c and the dry distillation gas purified from the purification device 40 via the control valve 52a. If necessary, the flow rate of the off-gas is controlled through the control valve 52b and sent to the gas mixer 41, and the mixed gas of these gases is temporarily stored in the buffer tank 43.
In this way, it is possible to prepare a mixed gas in which the carbon: hydrogen molar ratio is optimized in the adjusting device 40.
In this way, the mixed gas in which the ratio of carbon and hydrogen is optimized is sent to the subsequent FT synthesis tower.
(FT synthesis)
In the present invention, a mixed gas in which the ratio of carbon and hydrogen is optimized is sent to the FT synthesis tower 70 and subjected to the FT synthesis reaction until it becomes a hydrocarbon having a predetermined molecular weight range. The FT synthesis tower itself is composed of an FT synthesis tower in which a Fischer-Tropsch catalyst known in the art is packed by a known method.
In the FT synthesis tower 70, a mixed gas having an optimized ratio of carbon and hydrogen is compressed by, for example, a compressor (not shown) and brought into contact with a Fischer-Tropsch catalyst at a predetermined temperature, typically 200 to 250 ° C. Conversion to the desired hydrocarbon.
The gas containing hydrocarbons thus synthesized is a separation device 80, generally a device that separates hydrocarbon oil 90 and off-gas (unreacted gas) mainly composed of lower hydrocarbons by a condenser. .
In a preferred embodiment of the present invention, the separated unreacted gas is temporarily stored in an unreacted gas tank (not shown) if desired, and then returned to the adjusting device 50 to be mixed with purified dry distillation gas and hydrogen. Then, it is again subjected to the hydrocarbon synthesis reaction in the FT synthesis tower 70. In the present invention, the unreacted gas means a gas that has not been converted to a desired molecular weight, and generally means an unreacted water gas and a lower hydrocarbon (methane, ethane, butane, propane, etc.).
Thus, the yield of BTL is increased by circulating unreacted gas.
In the BTL production system of the present invention configured as described above, the pyrolyzed gas generated by pyrolysis is purified by using the pretreated biomass material as a starting material, and purified. At this time, impurities contained in the biomass raw material are within an assumed range in advance, and substantially all impurities can be removed by a purification apparatus including a desulfurization / detarring apparatus and an ion exchange scrubber. Therefore, a dry distillation gas having a carbon: hydrogen content within a predetermined range is stably generated. By adding a predetermined amount of hydrogen to such dry distillation gas, it becomes possible to produce BTL oil with high yield. Also. Since the separated unreacted gas is circulated to the adjusting device and FT synthesis is performed together with a predetermined amount of hydrogen and dry distillation gas, the yield can be further improved.
Furthermore, since the BTL to be produced shows a stable property by constituting the biomass raw material with a single biomass, the BTL production apparatus of the present invention is a bio-material composed of hydrocarbon components within a predetermined range such as jet biofuel. The fuel can be selectively produced.
(Production method)
Next, the manufacturing method of BTL of this invention is demonstrated based on FIG.
The BTL production method of the present invention is a BTL production method in which a biomass raw material is pyrolyzed to generate dry distillation gas, and after refining the dry distillation gas, hydrocarbon oil is obtained by a hydrocarbon synthesis catalyst. A pretreatment step (A) for pretreatment so as to obtain a carbon content and hydrogen content in a predetermined range per size, a predetermined moisture content and a unit mass, and a biomass raw material which has been pretreated are put into a pyrolysis apparatus and dry-distilled For the synthesis of a carbonization gas generation step (B) for generating a gas, a purification step (C) for purifying the generated carbonization gas, and hydrogen is added to the purified carbonization gas at a predetermined carbon: hydrogen molar ratio. The mixed gas obtained in the mixed gas preparation step (D), the hydrocarbon oil production step (E) for converting the prepared mixed gas into hydrocarbons, and the hydrocarbon production step Including and Le, and a separation step of separating the unreacted fraction (F).
First, in the process A, the biomass raw material is pretreated in advance so as to have a known carbon content and hydrogen content, and in the process B, the pretreated biomass raw material is put into a thermal decomposition apparatus and thermally decomposed, and the process C To purify impurities.
The carbon content and hydrogen content in the carbonized gas thus purified are within a known range, and the amount of hydrogen necessary to obtain the optimum carbon-hydrogen molar ratio is, for example, as shown in FIG. Can be obtained by calculation. In step D, the amount of hydrogen calculated in this way is added to the refined dry distillation gas to optimize the amount of carbon and hydrogen components in the mixed gas.
The molar ratio at this time is C: H = 1: 1.5 to 1: 6, preferably 1: 2 to 1: 5, more preferably 1: 2 to 1: 4, as described above.
In this way, the mixed gas in which the molar ratio of carbon and hydrogen is adjusted is converted into a hydrocarbon by FT synthesis in Step E.
And the component obtained at the process E in the process F is isolate | separated into a hydrocarbon oil and an unreacted part, and hydrocarbon oil is collect | recovered as BTL.
The unreacted component can be returned to step D and re-synthesised as desired.
As described above, in the method of the present invention, hydrogen is added to a large number of biomass raw materials having an excess carbon content and a shortage of hydrogen content, so that the hydrocarbon oil can be converted without leaving a carbon content. Further, the yield can be further increased by returning the unreacted component to the adjustment step and performing FT synthesis again.
Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments and can be widely applied.

In the BTL production system and production method of the present invention, the dry-distilled gas generated by the thermal decomposition is purified by the thermal decomposition using the pretreated biomass material as the starting material, and purified. At this time, impurities contained in the biomass raw material are within an assumed range in advance, and substantially all impurities can be removed by a purification apparatus including a desulfurization / detarring apparatus and an ion exchange scrubber. Therefore, a dry distillation gas having a carbon: hydrogen content within a predetermined range is stably generated. By adding a predetermined amount of hydrogen to such dry distillation gas, it becomes possible to produce BTL oil with high yield. Also. Since the separated unreacted gas is circulated to the adjusting device and FT synthesis is performed together with a predetermined amount of hydrogen and dry distillation gas, the yield can be further improved.
Furthermore, since the BTL to be produced shows a stable property by constituting the biomass raw material with a single biomass, the BTL production apparatus of the present invention is a bio-material composed of hydrocarbon components within a predetermined range such as jet biofuel. The fuel can be selectively produced.

DESCRIPTION OF SYMBOLS 10 Pretreatment apparatus 20 Pyrolysis apparatus 30 Carrier gas supply system 40 Refinement apparatus 50 Adjustment apparatus 60 Hydrogen supply system 70 FT synthesis tower 80 Hydrocarbon oil

Claims

A pretreatment device for pretreating a biomass raw material to a predetermined size, a predetermined moisture content, and a predetermined range of carbon content and hydrogen content per unit mass;
A pyrolysis device that pyrolyzes biomass raw material into dry distillation gas, a purification device that purifies dry distillation gas,
A hydrocarbon synthesizer that converts purified gas into hydrocarbon oil in the presence of a hydrocarbon synthesis catalyst, and a BTL production system comprising:
Hydrogen supply system for metering and adding hydrogen gas between the purification apparatus and the hydrocarbon synthesis apparatus, dry distillation gas purified by the purification apparatus and hydrogen metered and added from the hydrogen supply system, And an adjusting device for adjusting the mixed gas so that the carbon: hydrogen molar ratio is from 1: 2 to 1: 6 based on the content of the carbon component and the hydrogen component contained in the dry distillation gas. A featured BTL manufacturing system.
The pyrolysis apparatus comprises a weight sensor for measuring the input amount of biomass raw material, a flow sensor for measuring the flow rate of the carrier gas, a flow sensor and a temperature sensor for measuring the discharge amount and discharge temperature of the dry distillation gas. The system is equipped with an electronic computer for measuring the carbon content and hydrogen content in the dry distillation gas per unit time by these sensors, and based on the measurement results and the type of the biomass The BTL manufacturing system according to claim 2, wherein a hydrogen addition amount is calculated, and hydrogen is supplied from the hydrogen supply system based on the calculated hydrogen addition amount.
The gas regulator further includes a gas supply line for mixing unreacted gas from the hydrocarbon synthesizer, and the purified dry distillation gas, hydrogen from the hydrogen supplier, and the hydrocarbon synthesis The BTL manufacturing system according to claim 1, wherein unreacted gas from the apparatus is mixed.
The gas adjusting device includes a gas mixing section having a purified dry distillation gas inlet, a hydrogen gas inlet and an unreacted gas inlet each having a flow control bubble, and at least one for temporarily storing the mixed gas. The BTL manufacturing system according to claim 1, comprising a buffer tank.
The BTL manufacturing system according to claim 1, wherein superheated steam is introduced into the thermal decomposition apparatus as a carrier gas or a carrier gas and a heat source of the thermal decomposition apparatus.
The BTL production system according to claim 1, wherein the purification device is composed of a desulfurization device and an ion exchange scrubber.
2. The BTL manufacturing system according to claim 1, wherein the biomass raw material is a biomass raw material derived from wood, vegetation, agricultural products, agricultural product residues, or a mixture thereof, and the pretreatment device includes a crushing device. .
2. The BTL manufacturing system according to claim 1, wherein the biomass raw material is a biomass raw material containing a predetermined amount of moisture, and the pretreatment device is constituted by a moisture adjusting device or a moisture adjusting device and a pulverizing device. .
The BTL production system according to claim 1, wherein the hydrocarbon oil to be produced is a jet biofuel.
A pretreatment step of pretreating the biomass raw material so as to have a predetermined size, a predetermined moisture content, and a predetermined range of carbon content and hydrogen content per unit mass;
A dry distillation gas generation step in which a pretreated biomass material is introduced into a thermal decomposition apparatus to generate dry distillation gas;
A purification step for purifying the generated dry distillation gas, a mixed gas preparation step for preparing a mixed gas for synthesis by adding hydrogen to the purified dry distillation gas so as to have a predetermined carbon: hydrogen molar ratio,
A BTL comprising a hydrocarbon oil production process for converting the prepared mixed gas into hydrocarbons, and a separation process for separating the mixed gas obtained in the hydrocarbon production process into hydrocarbon oil and unreacted components Manufacturing method.
The method for producing a BTL according to claim 10, further comprising an unreacted component circulation step for returning an unreacted component generated in the separation step to the mixed gas preparation step.
Based on the ratio of carbon to hydrogen contained in the biomass raw material to be introduced, hydrogen is added so that the ratio of carbon to hydrogen in the mixed gas is 1: 2 to 1: 4 in molar ratio. The method for producing a BTL according to claim 10.