WO2020008622A1 - Method for producing hydrogen using biomass as raw material - Google Patents
Method for producing hydrogen using biomass as raw material Download PDFInfo
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- WO2020008622A1 WO2020008622A1 PCT/JP2018/025703 JP2018025703W WO2020008622A1 WO 2020008622 A1 WO2020008622 A1 WO 2020008622A1 JP 2018025703 W JP2018025703 W JP 2018025703W WO 2020008622 A1 WO2020008622 A1 WO 2020008622A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
Definitions
- the present invention relates to a method for producing hydrogen using biomass as a raw material.
- hydrogen When hydrogen is used as a fuel, it does not emit carbon dioxide and is regarded as an environmentally friendly material.
- hydrogen is supplied to a fuel cell to realize its use as a fuel cell vehicle or fuel cell power plant As the power generation efficiency is expected to improve dramatically, the demand is expected to increase further in the future.
- Patent Document 1 A method for producing a product gas having a high calorific value from an organic substance and a substance mixture,
- the circulating heat-carrying medium passes through a heating zone, a reaction zone, a pyrolysis zone and a separation step and subsequently returns to the heating zone, Separating the organic substance or substance mixture into a pyrolysis gas as a solid carbon-containing residue and a volatile phase by contacting the organic substance or substance mixture in a pyrolysis zone with a heated heat carrying medium; After passing through the pyrolysis zone, the solid carbon-containing residue is separated from the heat-carrying medium in a separation step, Mixing the pyrolysis gas with steam as the reaction medium and further heating to exchange a portion of the heat contained in the heated heat carrying medium in the reaction zone to produce a product gas having a high calorific value,
- the steam is mixed with the pyrolysis gas in the pyr
- Patent Document 2 The organic waste is heated at 500 to 600 ° C. in a non-oxidizing atmosphere using a heat carrier medium, and the generated pyrolysis gas is mixed with steam at 900 to 1000 ° C. Then, the obtained reformed gas is purified. To recover hydrogen.
- a method for producing hydrogen using biomass as a raw material includes a pyrolysis step of supplying a heat carrier medium to obtain a pyrolysis gas from a biomass raw material, and increasing the temperature of the pyrolysis gas to be rich in hydrogen.
- the thermal decomposition reaction temperature is 640 to 740 ° C., and steam and oxygen gas are simultaneously supplied in the reforming step, and the heat carrying medium is not supplied to the reforming step.
- tar generated by the thermal decomposition reaction is completely decomposed, and hydrogen gas can be stably produced over a long period of time.
- FIG. 1 is a schematic diagram illustrating an example of an apparatus (equipment) for implementing one embodiment of the present invention.
- a method for producing hydrogen using biomass as a raw material includes a pyrolysis step of supplying a heat carrier medium to obtain a pyrolysis gas from a biomass raw material, and increasing the temperature of the pyrolysis gas.
- a reforming step for obtaining a hydrogen-rich reformed gas wherein the heat-carrying medium in the pyrolysis step is heated to 680 to 740 ° C .;
- the thermal decomposition reaction temperature is set to 640 to 740 ° C. to supply steam and oxygen gas simultaneously in the reforming step, and the heat carrier medium is not supplied to the reforming step.
- This hydrogen production method completely decomposes the generated tar and can stably obtain hydrogen gas for a long period of time.
- the biomass raw material may contain diphosphorus pentoxide (P 2 O 5 ).
- the thermal decomposition reaction temperature can be easily adjusted to 640 to 740 ° C.
- the thermal decomposition temperature of the thermal decomposition step in each of the hydrogen production methods is 660 to 700 ° C. As a result, the generation of tar is further suppressed, and hydrogen gas can be stably obtained over a long period of time.
- the present inventor studied the hydrogen production methods described in Patent Documents 1 and 2 above, and found that the reason why tar did not decompose was that a temperature of 640 ° C. or more described later could not be secured as a temperature in the pyrolyzer. I found something. Therefore, in order to raise the temperature in the pyrolyzer, in the hydrogen production methods described in Patent Documents 1 and 2 described above, it was examined to increase the temperature of the heat-carrying medium to be preheated. In the case, the preheated heat carrier medium is supplied to the pyrolyzer through the reformer, and the heat held by the heat carrier medium is first used as a heat source of the reformer.
- the preheater In order to raise the pyrolysis temperature for tar decomposition, the preheater requires a further increase in the preheating temperature of the heat carrying medium, that is, a preheating exceeding 1050 ° C. It was not realistic from the point of view, and it was found that it was difficult to raise the temperature of the reformer to 1000 ° C. by the heat carrying medium.
- the “heating zone”, “reaction zone”, and “pyrolysis zone” in Patent Document 1 are respectively referred to as “preheater”, “reformer”, and “pyrolyzer” in the present invention. You are.
- the present inventor further studied, (1) In order to suppress the generation of tar to a level that does not hinder the production of hydrogen, it is necessary to set the thermal decomposition reaction temperature to 640 ° C. or higher, and it is difficult to raise the temperature to 1000 ° C. in the reformer. The reason was that the heat transfer coefficient between the heat carrying medium and the reformed gas was small, and based on this finding, (2)
- the heat source of the thermal decomposer is not limited to the heat carrying medium, and the idea is to supplement the lack of heat from the heat carrying medium with the other heat sources.
- the pre-heated heat carrier medium is not charged into the reformer but is used only as a thermal decomposer and used as heat for elevating the temperature to the thermal decomposition temperature of the thermal decomposer and evaporating moisture, That the preheating temperature of the carrier medium can be lowered, (4)
- the temperature can be easily raised to a predetermined thermal decomposition reaction temperature, and At the same time, by simultaneously injecting steam, the sensitivity of the reaction temperature due to insufficient oxygen is eased and the temperature control becomes easy, (5)
- oxygen gas is supplied in place of the supply of the heat carrying medium, the temperature can be easily raised to the reforming reaction temperature of 1000 ° C.
- Heat carrying medium (1) Shape and material of the heat carrying medium
- the shape of the heat carrying medium is preferably a sphere, and the material is preferably ceramic such as alumina or steel. That is, alumina balls, ceramic balls, and steel balls can be used, and the diameter is preferably 10 to 30 mm.
- (2) Preheating temperature The heat carrying medium is preheated by a preheater, and the preheating temperature range is 680 to 740 ° C. This preheating temperature range is much lower than 1050 ° C. shown in Patent Documents 1 and 2, so that the energy required for preheating can be saved, the thermal efficiency is improved, and an expensive refractory material is used for the preheater. This has the advantage of not having to do so.
- the heat carrying medium 24 is heated in the preheater 3, serves as a heat carrying medium for thermal decomposition in the pyrolyzer 4, and supplies heat to the reaction for thermal decomposition, and the char separating device 6 separates the char and the heat medium. It is circulated and used in the circulating device 27.
- Pyrolysis reaction process in pyrolyzer The pyrolysis reaction in the pyrolyzer will be described in detail.
- Biomass raw material The raw material used in one embodiment of the present invention is biomass, sewage sludge, thinned wood, driftwood, wood pellets, straw pellets, paper sludge, garbage compost sludge, food waste, sludge, etc. Any type may be used as long as it contains hydrogen and oxygen, but sewage sludge is preferred from the viewpoint of availability. Further, the raw material may be a mixture of plural types of biomass.
- the size of the biomass may be any size as long as it has undergone coarse pulverization. For example, a solid shape such as a plate having a length of 15 mm or less and a granular shape are preferable. Although the amount of water contained varies depending on the shape, it is preferably pre-dried before being supplied to the pyrolyzer at 30 to 20% by mass.
- the pyrolysis temperature for obtaining the pyrolysis gas is 640 to 740 ° C.
- the reason for setting this temperature range is that if the temperature is lower than 640 ° C., it is difficult to completely decompose tar generated by thermal decomposition, and if it exceeds 740 ° C., an excessive heat source is required to completely decompose the tar. That's why.
- the thermal decomposition temperature is more preferably 660 to 700 ° C.
- phosphorus pentoxide (P 2 O 5 ) is contained in the organic raw material.
- P 2 O 5 evaporation is reduced. inhibition can, for volatilization vapor P 2 O 5 which may cause clogging trouble pyrolysis gas does not exist, has the advantage that it is possible to an organic material sewage sludge containing P 2 O 5.
- the heat source of the thermal decomposition is provided by the heat-carrying medium, but is not sufficient, and the temperature range is set by blowing and supplying oxygen gas.
- the heat transfer by the supply of steam and oxygen gas is much more efficient than the heat transfer of the heat carrier medium which is a solid phase.
- the supply of water vapor suppresses the generation of heat spots, alleviates rapid changes in temperature, and controls the thermal decomposition reaction in response to short-term disturbances such as changes in the amount of organic raw material supplied. It has the advantage of being easy.
- the respective supply ratios of steam and oxygen gas are preferably 1 to 4 in terms of a steam / oxygen gas molar ratio (mol of steam / mol of oxygen gas).
- the reason for this range is that if it is less than 1, the temperature fluctuation may increase, and if it exceeds 4, the steam becomes oxidizing at 600 ° C. or higher, and the CO 2 concentration increases, which is not preferable for hydrogen recovery.
- the temperature of steam is not limited, a temperature of 140 ° C. can be mentioned as an example.
- the oxygen gas is not particularly limited, and is, for example, 40% manufactured by an industrial oxygen gas generator. C. can be used. And, when the molar ratio represented by water vapor / oxygen gas becomes higher, it becomes easier to control the thermal decomposition reaction with respect to disturbance caused by slight fluctuation of the oxygen flow rate.
- the pyrolysis gas is a gas mainly composed of CH 4 , CO, CO 2 , and H 2 .
- blowing steam as described above, it is possible to obtain a H 2, because the content of H 2 is small and 10% by volume, in order to increase the content of H 2, modification in the next step I do.
- Reforming process in reformer The reformer is installed downstream of the pyrolyzer, and without using a heat carrier medium as a heat source, simultaneously supplies steam and oxygen gas, raises the temperature to 1000 ° C or higher, and performs the pyrolysis on the pyrolysis gas to obtain a hydrogen-rich crude gas. Obtain reformed gas. Then, the temperature can be easily raised to 1000 ° C. by simultaneously supplying steam and oxygen gas instead of supplying the heat carrying medium.
- the steam may be, for example, 100 to 150 ° C.
- the oxygen gas may be, for example, 40 ° C. produced by an industrial oxygen gas generator.
- a steam reforming reaction proceeds, and a hydrocarbon gas such as CH 4 gas is converted into a hydrogen gas, and the content ratio of the hydrogen gas increases.
- CH 4 + H 2 O ⁇ CO + 3H 2 can be mentioned.
- the next shift reaction proceeds, and the content ratio of hydrogen gas increases.
- the crude reformed gas thus obtained has a H 2 gas content of 50 to 54% by volume (dry basis).
- the supply of steam is not only performed to advance the steam reforming reaction, but also to ease temperature sensitivity (rapid change).
- the steam and the oxygen gas supplied to the reformer are preferably simultaneously supplied so that the molar ratio of steam / oxygen gas (mol of steam / mol of oxygen gas) becomes 1 to 4.
- H 2 gas purification process The gas that has undergone the reforming step (coarse reformed gas) is cooled and dust-removed to remove trace amounts of harmful components such as HCl, CN, and NH 3 .
- the removal can be performed by appropriately combining conventionally known means.
- the purification of H 2 gas Thereafter, the purification of H 2 gas.
- a known means may be appropriately used, and for example, a PSA means and a membrane separation means can be used.
- the heat carrying medium 24 is heated (preheated) to 680 to 740 ° C. by the preheater 3, and after heating, is fed into the thermal decomposer 4 via the valve 25.
- the heat source for preheating the heat carrier medium in the preheater 3 is a flue gas 19 of about 800 ° C. obtained by burning part of the char 18 and part of the pyrolysis gas 11 in the combustion furnace 23 as described later.
- the combustion exhaust gas 20 is discharged from the preheater 3.
- the pyrolysis step is performed by the pyrolyzer 4, and the biomass raw material 1 is supplied to the pyrolyzer 4 by the biomass raw material transporting device 2 such as a screw conveyor.
- the temperature of the biomass raw material 1 is increased by the heat from the heat carrier medium 24 and the steam 8 and the oxygen gas 7 which are blown and supplied from the lower part of the pyrolyzer 4 at a temperature of 640 to 720 ° C. It is decomposed to generate pyrolysis gas 11.
- the reforming step is performed in the reformer 5. Most of the pyrolysis gas 11 obtained by the pyrolysis reaction is sent to the reformer 5. In the reformer 5, steam 10 and oxygen gas 9 are simultaneously blown and supplied from the lower part thereof, and the temperature of the pyrolysis gas 11 is raised to 1000 ° C., and the steam reforming reaction proceeds, and the crude reforming gas 13 Get.
- the purification process of the H 2 gas is performed in the crude reformed gas cooling / purifying device 21, and the crude reformed gas 13 that has passed through the reformer 5 is introduced into the crude reformed gas cooling / refining device 21, Although not shown, cooling, dust removal, and removal of trace amounts of harmful components are performed, and the purified reformed gas 14 is introduced into the hydrogen separator 22 to obtain pure hydrogen gas 15.
- the off-gas 16 is discharged from the hydrogen separator 22.
- the char of the heat carrier medium 24 and the biomass raw material 1 at about 640 ° C. are discharged from the bottom of the pyrolyzer 4, and are introduced into the char separation device 6 via the valve 26.
- the char separation device 6 the char 17 and the heat carrying medium 24 are separated, and the heat carrying medium 24 is sent to the heat carrying medium circulating device 27, and is returned to the preheater 3 by the device for circulating use.
- the char 17, except for a part 18 of the char, is used as an alternative fuel in a cement manufacturing facility or a coal-fired power plant.
- As the char separation device 6, a known device such as a device capable of separating the heat carrying medium 24 and the char 17 by a sieve can be used.
- the part 12 of the pyrolysis gas and the part 18 of the char are introduced into the combustion furnace 23 and burned, and serve as a heat source for the flue gas 19 at about 800 ° C. It serves as a heat source for preheating the heat carrying medium 24 by the preheater.
- an external fuel such as LNG or LPG is used to supplement the heat source. It is not necessary to use a special furnace for the combustion furnace 23.
- steam is produced using waste heat of the combustion exhaust gas 20 of the preheater, and the steam is supplied to the pyrolyzer and supplied to the reformer. It is also possible to use steam 10 that is generated.
- the organic raw material commonly used in each example and each comparative example is sewage sludge, which is as follows.
- Example 1> The preheating temperature of the heat carrying medium was set at 700 ° C.
- the temperature of the pyrolyzer pyrolysis reaction temperature
- steam at 140 ° C. and oxygen gas at 40 ° C. were blown.
- the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 1.71 Nm 3 / h and 2.75 kg / h, respectively
- the flow rates of oxygen gas and steam to the reformer were 2.3 Nm 3 / h and 3.7 kg / h, respectively.
- composition of the pyrolysis gas The composition of the pyrolysis gas, the amount of tar, and the composition of the gas leaving the reformer were measured. Table 4 shows the results. In the display of the composition of the pyrolysis gas, all hydrocarbon gases were represented by CH 4 . Hereinafter, the same notation is used.
- Example 1 the temperature of the pyrolyzer was 690 ° C. and the temperature range was 650 to 740 ° C., and the steam / oxygen gas molar ratio was 2.0 and the molar ratio range was 1.0 to 4.0. Therefore, the content ratio of CH 4 gas contained in the pyrolysis gas was low, and the generation of tar could be completely suppressed. Further, the temperature of the reformer could be set to 1000 ° C. On the other hand, in Comparative Example 1, the pyrolysis temperature was 600 ° C. and was not in the above temperature range, so that the content ratio of the CH 4 gas contained in the pyrolysis gas was high, tar was generated, and The temperature was 937 ° C.
- Example 2 in order to confirm that the evaporation of P 2 O 5 contained in the sewage sludge is suppressed, in Example 2 and Comparative Example 2, P 2 deposited on the crude reformed gas cooling / purifying device 22 in FIG. the amount of O 5 was measured.
- Example 2 With the preheating temperature of the heat carrying medium set at 700 ° C. and the temperature of the pyrolyzer at 690 ° C., steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 1.71 Nm 3 / h and 2.75 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0. The amount of P 2 O 5 deposited on the crude reforming gas cooling / refining device 22 of FIG. 1 was measured. Table 5 shows the results.
- the estimated P 2 O 5 vapor concentration was estimated based on the amount of clogs that blocked the crude reformed gas cooling / refining device 22 and the analysis results.
- Example 2 the temperature of the pyrolyzer was 690 ° C. and the temperature range was 650 to 740 ° C., and the steam / oxygen gas molar ratio was 2.0 and the molar ratio range was 1.0 to 4.0. Therefore, the amount of P 2 O 5 deposited in the crude reforming gas cooling / refining apparatus is as small as 0.02 kg, and it can be said that the evaporation of P 2 O 5 contained in the sewage sludge is almost completely suppressed. .
- the thermal decomposition temperature was 780 ° C., which was higher than the above temperature range, and the evaporation of P 2 O 5 was not suppressed.
- Example 3 In order to confirm the influence of the steam / oxygen gas molar ratio on the yield of H 2 and the stability of temperature fluctuation, a comparison is made between Example 3 and Example 2.
- Example 2 was performed as described above, but the amount of the pyrolysis gas was 16.64 Nm 3 / h, and the amount of the oxygen gas blown was ⁇ 0.30 Nm 3 / h. The variation in the temperature of the decomposer was ⁇ 60 ° C. Table 6 shows the composition of the resulting crude reformed gas.
- Example 3 With the preheating temperature of the heat carrying medium set to 700 ° C. and the temperature of the pyrolyzer set to 690 ° C., 140 ° C. steam and 40 ° C. oxygen gas were blown. At this time, the flow rates of oxygen gas and steam to the pyrolyzer were 1.71 Nm 3 / h and 5.49 kg / h, respectively, and the molar ratio of steam / oxygen gas was 4.0. Table 6 shows the composition of the obtained pyrolysis gas.
- Example 2 Comparing Example 2 with Example 3, the higher the molar ratio of water vapor / oxygen gas, the more the fluctuation of the pyrolysis reaction temperature can be suppressed with respect to the fluctuation of the oxygen gas flow rate. It can be said that the sensitivity of the resulting temperature change is improved.
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Abstract
A method for producing hydrogen using a biomass as a raw material, the method having having a pyrolysis step for supplying a heat carrier medium to obtain a pyrolysis gas from a biomass raw material, and a reforming step for raising the temperature of the pyrolysis gas to obtain a reformed gas rich in hydrogen, the method being such that: the heat carrier medium in the pyrolysis step is heated to 680-740°C; in the pyrolysis step, water vapor and oxygen gas are also supplied simultaneously to set the pyrolysis reaction temperature to 640-740°C; and in the reforming step, water vapor and oxygen gas are supplied simultaneously and the heat carrier medium is not supplied in the reforming step.
Description
本発明は、バイオマスを原料とする水素製造方法に関する。
The present invention relates to a method for producing hydrogen using biomass as a raw material.
水素は、燃料として使用された場合、二酸化炭素を排出せず、環境に優しい材料として重要視されており、例えば、燃料電池に供給されて、燃料電池車としての利用や燃料電池発電所を実現して発電効率の飛躍的な向上が見込めるため、今後、ますますその需要が増加すると予想される。
When hydrogen is used as a fuel, it does not emit carbon dioxide and is regarded as an environmentally friendly material.For example, hydrogen is supplied to a fuel cell to realize its use as a fuel cell vehicle or fuel cell power plant As the power generation efficiency is expected to improve dramatically, the demand is expected to increase further in the future.
一方、水素の原料として石油、天然ガス等の化石燃料でなく、バイオマスからの製造について提案がなされている。
On the other hand, proposals have been made for the production of hydrogen from biomass instead of fossil fuels such as oil and natural gas.
例えば、特許文献１には、
有機物質および物質混合物から高い発熱量を有する生成物ガスを製造する方法であり、
循環する熱担持媒体が、加熱帯域、反応帯域、熱分解帯域および分離工程を通過し、引き続き加熱帯域に戻り、その際、
有機物質または物質混合物を熱分解帯域中で加熱した熱担持媒体と接触することにより固体の炭素含有残留物および揮発性相として熱分解ガスに分離し、
熱分解帯域を通過後、固体の炭素含有残留物を分離工程で熱担持媒体から分離し、
熱分解ガスを反応媒体としての水蒸気と混合し、反応帯域中で加熱した熱担持媒体に含まれる熱の一部を交換することにより高い発熱量を有する生成物ガスが生じるように更に加熱する、有機物質および物質混合物から高い発熱量を有する生成物ガスを製造する方法において、
水蒸気を熱分解帯域で熱分解ガスと混合し、
全部の固体の炭素含有残留物を別の燃焼装置に供給し、ここで燃焼し、
この燃焼装置の熱い排ガスを、加熱帯域に存在する熱担持媒体の堆積を通過させ、その際大部分の顕熱を熱担持媒体に与えることを特徴とする、有機物質および物質混合物から高い発熱量を有する生成物ガスを製造する方法が、記載されている。 For example, in Patent Document 1,
A method for producing a product gas having a high calorific value from an organic substance and a substance mixture,
The circulating heat-carrying medium passes through a heating zone, a reaction zone, a pyrolysis zone and a separation step and subsequently returns to the heating zone,
Separating the organic substance or substance mixture into a pyrolysis gas as a solid carbon-containing residue and a volatile phase by contacting the organic substance or substance mixture in a pyrolysis zone with a heated heat carrying medium;
After passing through the pyrolysis zone, the solid carbon-containing residue is separated from the heat-carrying medium in a separation step,
Mixing the pyrolysis gas with steam as the reaction medium and further heating to exchange a portion of the heat contained in the heated heat carrying medium in the reaction zone to produce a product gas having a high calorific value, In a method for producing a product gas having a high calorific value from an organic substance and a substance mixture,
The steam is mixed with the pyrolysis gas in the pyrolysis zone,
All solid carbon-containing residues are fed to a separate combustion device, where they are burned,
A high calorific value from organic substances and substance mixtures, characterized in that the hot exhaust gas of this combustion device is passed through a deposition of a heat-carrying medium present in a heating zone, whereby most of the sensible heat is given to the heat-carrying medium. A method for producing a product gas having the formula:
有機物質および物質混合物から高い発熱量を有する生成物ガスを製造する方法であり、
循環する熱担持媒体が、加熱帯域、反応帯域、熱分解帯域および分離工程を通過し、引き続き加熱帯域に戻り、その際、
有機物質または物質混合物を熱分解帯域中で加熱した熱担持媒体と接触することにより固体の炭素含有残留物および揮発性相として熱分解ガスに分離し、
熱分解帯域を通過後、固体の炭素含有残留物を分離工程で熱担持媒体から分離し、
熱分解ガスを反応媒体としての水蒸気と混合し、反応帯域中で加熱した熱担持媒体に含まれる熱の一部を交換することにより高い発熱量を有する生成物ガスが生じるように更に加熱する、有機物質および物質混合物から高い発熱量を有する生成物ガスを製造する方法において、
水蒸気を熱分解帯域で熱分解ガスと混合し、
全部の固体の炭素含有残留物を別の燃焼装置に供給し、ここで燃焼し、
この燃焼装置の熱い排ガスを、加熱帯域に存在する熱担持媒体の堆積を通過させ、その際大部分の顕熱を熱担持媒体に与えることを特徴とする、有機物質および物質混合物から高い発熱量を有する生成物ガスを製造する方法が、記載されている。 For example, in Patent Document 1,
A method for producing a product gas having a high calorific value from an organic substance and a substance mixture,
The circulating heat-carrying medium passes through a heating zone, a reaction zone, a pyrolysis zone and a separation step and subsequently returns to the heating zone,
Separating the organic substance or substance mixture into a pyrolysis gas as a solid carbon-containing residue and a volatile phase by contacting the organic substance or substance mixture in a pyrolysis zone with a heated heat carrying medium;
After passing through the pyrolysis zone, the solid carbon-containing residue is separated from the heat-carrying medium in a separation step,
Mixing the pyrolysis gas with steam as the reaction medium and further heating to exchange a portion of the heat contained in the heated heat carrying medium in the reaction zone to produce a product gas having a high calorific value, In a method for producing a product gas having a high calorific value from an organic substance and a substance mixture,
The steam is mixed with the pyrolysis gas in the pyrolysis zone,
All solid carbon-containing residues are fed to a separate combustion device, where they are burned,
A high calorific value from organic substances and substance mixtures, characterized in that the hot exhaust gas of this combustion device is passed through a deposition of a heat-carrying medium present in a heating zone, whereby most of the sensible heat is given to the heat-carrying medium. A method for producing a product gas having the formula:
また、例えば、特許文献２には、
有機廃棄物を熱担持媒体を用いて、非酸化性雰囲気下において５００～６００℃で加熱し、発生した熱分解ガスを９００～１０００℃でスチームと混合せしめ、次いで、得た改質ガスを精製して水素を回収する方法が記載されている。 Also, for example, inPatent Document 2,
The organic waste is heated at 500 to 600 ° C. in a non-oxidizing atmosphere using a heat carrier medium, and the generated pyrolysis gas is mixed with steam at 900 to 1000 ° C. Then, the obtained reformed gas is purified. To recover hydrogen.
有機廃棄物を熱担持媒体を用いて、非酸化性雰囲気下において５００～６００℃で加熱し、発生した熱分解ガスを９００～１０００℃でスチームと混合せしめ、次いで、得た改質ガスを精製して水素を回収する方法が記載されている。 Also, for example, in
The organic waste is heated at 500 to 600 ° C. in a non-oxidizing atmosphere using a heat carrier medium, and the generated pyrolysis gas is mixed with steam at 900 to 1000 ° C. Then, the obtained reformed gas is purified. To recover hydrogen.
上記各特許文献に記載された方法では、水素ガスを得ることを目的としているものの、熱分解反応によりタールが発生しタールによる管路の閉塞が生じるため、長期にわたって安定的に水素ガスを得ることが難しいという課題を有している。
Although the method described in each of the above patent documents aims at obtaining hydrogen gas, tar is generated by the thermal decomposition reaction and blockage of the pipeline is caused by the tar, so that hydrogen gas can be stably obtained over a long period of time. Is difficult.
本発明は、この課題を解決するものであって、次のとおりのものである。
本発明の一態様に係るバイオマスを原料とする水素製造方法は、熱担持媒体を供給してバイオマス原料から熱分解ガスを得る熱分解工程、及び、該熱分解ガスを昇温させて水素に富む改質ガスを得る改質工程、を有し、前記熱分解工程における前記熱担持媒体は６８０～７４０℃に加熱されており、前記熱分解工程では、さらに、水蒸気と酸素ガスを同時供給して熱分解反応温度を６４０～７４０℃とし、前記改質工程では、水蒸気と酸素ガスを同時供給し、前記熱担持媒体は前記改質工程には供給されないこと、を特徴とする。 The present invention solves this problem, and is as follows.
A method for producing hydrogen using biomass as a raw material according to one embodiment of the present invention includes a pyrolysis step of supplying a heat carrier medium to obtain a pyrolysis gas from a biomass raw material, and increasing the temperature of the pyrolysis gas to be rich in hydrogen. A reforming step of obtaining a reformed gas, wherein the heat carrying medium in the pyrolysis step is heated to 680 to 740 ° C., and in the pyrolysis step, steam and oxygen gas are further supplied simultaneously. The thermal decomposition reaction temperature is 640 to 740 ° C., and steam and oxygen gas are simultaneously supplied in the reforming step, and the heat carrying medium is not supplied to the reforming step.
本発明の一態様に係るバイオマスを原料とする水素製造方法は、熱担持媒体を供給してバイオマス原料から熱分解ガスを得る熱分解工程、及び、該熱分解ガスを昇温させて水素に富む改質ガスを得る改質工程、を有し、前記熱分解工程における前記熱担持媒体は６８０～７４０℃に加熱されており、前記熱分解工程では、さらに、水蒸気と酸素ガスを同時供給して熱分解反応温度を６４０～７４０℃とし、前記改質工程では、水蒸気と酸素ガスを同時供給し、前記熱担持媒体は前記改質工程には供給されないこと、を特徴とする。 The present invention solves this problem, and is as follows.
A method for producing hydrogen using biomass as a raw material according to one embodiment of the present invention includes a pyrolysis step of supplying a heat carrier medium to obtain a pyrolysis gas from a biomass raw material, and increasing the temperature of the pyrolysis gas to be rich in hydrogen. A reforming step of obtaining a reformed gas, wherein the heat carrying medium in the pyrolysis step is heated to 680 to 740 ° C., and in the pyrolysis step, steam and oxygen gas are further supplied simultaneously. The thermal decomposition reaction temperature is 640 to 740 ° C., and steam and oxygen gas are simultaneously supplied in the reforming step, and the heat carrying medium is not supplied to the reforming step.
上記によれば、熱分解反応により発生したタールの完全な分解がなされ、長期にわたって安定的に水素ガスを製造することができる。
According to the above, tar generated by the thermal decomposition reaction is completely decomposed, and hydrogen gas can be stably produced over a long period of time.
＜本発明の実施形態の説明＞
最初に本発明の実施態様を列記して説明する。
なお、本明細書及び特許請求の範囲において数値範囲を「～」で表現するとき、その範囲は上限及び下限の数値を含んでいる。また、「／」は、除算を表す。 <Description of Embodiment of the Present Invention>
First, embodiments of the present invention will be listed and described.
In the present specification and claims, when a numerical range is expressed by "-", the range includes upper and lower numerical values. “/” Represents division.
最初に本発明の実施態様を列記して説明する。
なお、本明細書及び特許請求の範囲において数値範囲を「～」で表現するとき、その範囲は上限及び下限の数値を含んでいる。また、「／」は、除算を表す。 <Description of Embodiment of the Present Invention>
First, embodiments of the present invention will be listed and described.
In the present specification and claims, when a numerical range is expressed by "-", the range includes upper and lower numerical values. “/” Represents division.
（１）本発明の一態様に係るバイオマスを原料とする水素製造方法は、熱担持媒体を供給してバイオマス原料から熱分解ガスを得る熱分解工程、及び、該熱分解ガスを昇温させて水素に富む改質ガスを得る改質工程、を有し、前記熱分解工程における前記熱担持媒体は６８０～７４０℃に加熱されており、前記熱分解工程では、さらに、水蒸気と酸素ガスを同時供給して熱分解反応温度を６４０～７４０℃とし、前記改質工程では、水蒸気と酸素ガスを同時供給し、前記熱担持媒体は前記改質工程には供給されない。この水素製造方法は、発生したタールを完全に分解し、長期にわたって安定的に水素ガスを得ることができる。また、バイオマス原料に五酸化二リン（Ｐ２Ｏ５）が含まれることがあるが、熱分解の温度を６４０～７２０℃とすることによりＰ２Ｏ５蒸発が抑制できる。
(1) A method for producing hydrogen using biomass as a raw material according to one embodiment of the present invention includes a pyrolysis step of supplying a heat carrier medium to obtain a pyrolysis gas from a biomass raw material, and increasing the temperature of the pyrolysis gas. A reforming step for obtaining a hydrogen-rich reformed gas, wherein the heat-carrying medium in the pyrolysis step is heated to 680 to 740 ° C .; The thermal decomposition reaction temperature is set to 640 to 740 ° C. to supply steam and oxygen gas simultaneously in the reforming step, and the heat carrier medium is not supplied to the reforming step. This hydrogen production method completely decomposes the generated tar and can stably obtain hydrogen gas for a long period of time. In addition, the biomass raw material may contain diphosphorus pentoxide (P 2 O 5 ). By setting the thermal decomposition temperature to 640 to 720 ° C., the evaporation of P 2 O 5 can be suppressed.
（２）前記水素製造法の前記熱分解工程において、同時供給する水蒸気と酸素ガスの水蒸気のモル／酸素ガスのモルが１～４である。これにより、熱分解反応温度を６４０～７４０℃とすることが容易にできる。
(2) In the thermal decomposition step of the hydrogen production method, the molar ratio of water vapor / oxygen gas / oxygen gas to steam supplied simultaneously is 1 to 4. Thereby, the thermal decomposition reaction temperature can be easily adjusted to 640 to 740 ° C.
（３）前記各水素製造法の前記熱分解工程の熱分解温度が６６０～７００℃である。これにより、より一層、タールの発生が抑えられ、長期にわたって安定的に水素ガスを得ることができる。
(3) The thermal decomposition temperature of the thermal decomposition step in each of the hydrogen production methods is 660 to 700 ° C. As a result, the generation of tar is further suppressed, and hydrogen gas can be stably obtained over a long period of time.
＜本発明の実施形態の詳細＞
本発明を実施するための一態様について、以下に詳述するが、まず、該態様を導出した知見及び着想について述べる。 <Details of Embodiment of the Present Invention>
One embodiment for carrying out the present invention will be described in detail below. First, knowledge and ideas derived from the embodiment will be described.
本発明を実施するための一態様について、以下に詳述するが、まず、該態様を導出した知見及び着想について述べる。 <Details of Embodiment of the Present Invention>
One embodiment for carrying out the present invention will be described in detail below. First, knowledge and ideas derived from the embodiment will be described.
本発明者は、前述の特許文献１および２に記載された水素製造方法について検討したところ、タールが分解しない原因について、熱分解器における温度として、後述する６４０℃以上の温度を確保できないためであることを発見した。
そこで、熱分解器における温度を上昇させるために、前述の特許文献１および２に記載された水素製造方法において、予熱される熱担持媒体の温度を上昇させることを検討したところ、これら水素製造方法では、予熱された熱担持媒体が改質器を経由して熱分解器に投入されており、熱担持媒体が保有する熱が改質器の熱源としてまず利用されてしまうため、熱分解器におけるタール分解のための熱分解温度を上昇させるためには、予熱器において、さらなる熱担持媒体の予熱温度の上昇、すなわち、１０５０℃を超える予熱が必要になるものの、この予熱温度のさらなる上昇は工業的にみると現実的でなく、しかも、熱担持媒体による改質器の温度を１０００℃に昇温は困難であることがわかった。
なお、前記特許文献１でいう「加熱帯域」、「反応帯域」、「熱分解帯域」は、それぞれ、本発明でいう「予熱器」、「改質器」、「熱分解器」として前記議論をしている。 The present inventor studied the hydrogen production methods described inPatent Documents 1 and 2 above, and found that the reason why tar did not decompose was that a temperature of 640 ° C. or more described later could not be secured as a temperature in the pyrolyzer. I found something.
Therefore, in order to raise the temperature in the pyrolyzer, in the hydrogen production methods described inPatent Documents 1 and 2 described above, it was examined to increase the temperature of the heat-carrying medium to be preheated. In the case, the preheated heat carrier medium is supplied to the pyrolyzer through the reformer, and the heat held by the heat carrier medium is first used as a heat source of the reformer. In order to raise the pyrolysis temperature for tar decomposition, the preheater requires a further increase in the preheating temperature of the heat carrying medium, that is, a preheating exceeding 1050 ° C. It was not realistic from the point of view, and it was found that it was difficult to raise the temperature of the reformer to 1000 ° C. by the heat carrying medium.
The “heating zone”, “reaction zone”, and “pyrolysis zone” in Patent Document 1 are respectively referred to as “preheater”, “reformer”, and “pyrolyzer” in the present invention. You are.
そこで、熱分解器における温度を上昇させるために、前述の特許文献１および２に記載された水素製造方法において、予熱される熱担持媒体の温度を上昇させることを検討したところ、これら水素製造方法では、予熱された熱担持媒体が改質器を経由して熱分解器に投入されており、熱担持媒体が保有する熱が改質器の熱源としてまず利用されてしまうため、熱分解器におけるタール分解のための熱分解温度を上昇させるためには、予熱器において、さらなる熱担持媒体の予熱温度の上昇、すなわち、１０５０℃を超える予熱が必要になるものの、この予熱温度のさらなる上昇は工業的にみると現実的でなく、しかも、熱担持媒体による改質器の温度を１０００℃に昇温は困難であることがわかった。
なお、前記特許文献１でいう「加熱帯域」、「反応帯域」、「熱分解帯域」は、それぞれ、本発明でいう「予熱器」、「改質器」、「熱分解器」として前記議論をしている。 The present inventor studied the hydrogen production methods described in
Therefore, in order to raise the temperature in the pyrolyzer, in the hydrogen production methods described in
The “heating zone”, “reaction zone”, and “pyrolysis zone” in Patent Document 1 are respectively referred to as “preheater”, “reformer”, and “pyrolyzer” in the present invention. You are.
そこで、本発明者は、さらに検討を行ったところ、
（１）タールの発生を水素の製造に当たって支障がない程度に抑制するためには、熱分解反応温度を６４０℃以上にすることが必要であり、改質器において１０００℃への昇温が困難な理由は熱担持媒体と改質ガス間の伝熱係数が小さいためであるとの知見を得て、この知見のもとに、
（２）熱分解器の熱源を熱担持媒体のみにはせず、熱担持媒体のみからもたらされる熱量不足する熱量を他の熱源で補うことを着想し、
（３）予熱した熱担持媒体の投入は改質器には行わず熱分解器のみとして、熱分解器の熱分解温度までの昇温と水分の蒸発のための熱として利用させれば、熱担持媒体の予熱温度を低くすることができること、
（４）熱分解器の熱分解反応のための他の熱源として酸素ガスを吹き込むことによって発生する部分酸化反応熱を利用すれば、容易に所定の熱分解反応温度まで昇温でき、かつ、この際、水蒸気を同時に吹き込むことによって、酸素の過少による反応温度の敏感性を緩和して温度制御が容易になること、
（５）改質器では、熱担持媒体の供給に替えて酸素ガスを供給すれば、部分酸化反応熱により、容易に１０００℃の改質反応温度まで昇温でき、かつ、この際、水蒸気を同時に吹き込むことによって、酸素の過少による反応温度の敏感性を緩和して温度制御が容易になること、
の新規な知見と着想を得たのである。
次に、この知見と着想に係る事項を踏まえて、本発明を実施するための形態を説明する。まず、各工程について説明する。 Therefore, the present inventor further studied,
(1) In order to suppress the generation of tar to a level that does not hinder the production of hydrogen, it is necessary to set the thermal decomposition reaction temperature to 640 ° C. or higher, and it is difficult to raise the temperature to 1000 ° C. in the reformer. The reason was that the heat transfer coefficient between the heat carrying medium and the reformed gas was small, and based on this finding,
(2) The heat source of the thermal decomposer is not limited to the heat carrying medium, and the idea is to supplement the lack of heat from the heat carrying medium with the other heat sources.
(3) If the pre-heated heat carrier medium is not charged into the reformer but is used only as a thermal decomposer and used as heat for elevating the temperature to the thermal decomposition temperature of the thermal decomposer and evaporating moisture, That the preheating temperature of the carrier medium can be lowered,
(4) By utilizing the partial oxidation reaction heat generated by blowing oxygen gas as another heat source for the thermal decomposition reaction of the thermal cracker, the temperature can be easily raised to a predetermined thermal decomposition reaction temperature, and At the same time, by simultaneously injecting steam, the sensitivity of the reaction temperature due to insufficient oxygen is eased and the temperature control becomes easy,
(5) In the reformer, if oxygen gas is supplied in place of the supply of the heat carrying medium, the temperature can be easily raised to the reforming reaction temperature of 1000 ° C. due to the heat of the partial oxidation reaction. Simultaneous blowing eases the sensitivity of the reaction temperature due to insufficient oxygen and facilitates temperature control.
He gained new insights and ideas.
Next, an embodiment for carrying out the present invention will be described based on the findings and ideas. First, each step will be described.
（１）タールの発生を水素の製造に当たって支障がない程度に抑制するためには、熱分解反応温度を６４０℃以上にすることが必要であり、改質器において１０００℃への昇温が困難な理由は熱担持媒体と改質ガス間の伝熱係数が小さいためであるとの知見を得て、この知見のもとに、
（２）熱分解器の熱源を熱担持媒体のみにはせず、熱担持媒体のみからもたらされる熱量不足する熱量を他の熱源で補うことを着想し、
（３）予熱した熱担持媒体の投入は改質器には行わず熱分解器のみとして、熱分解器の熱分解温度までの昇温と水分の蒸発のための熱として利用させれば、熱担持媒体の予熱温度を低くすることができること、
（４）熱分解器の熱分解反応のための他の熱源として酸素ガスを吹き込むことによって発生する部分酸化反応熱を利用すれば、容易に所定の熱分解反応温度まで昇温でき、かつ、この際、水蒸気を同時に吹き込むことによって、酸素の過少による反応温度の敏感性を緩和して温度制御が容易になること、
（５）改質器では、熱担持媒体の供給に替えて酸素ガスを供給すれば、部分酸化反応熱により、容易に１０００℃の改質反応温度まで昇温でき、かつ、この際、水蒸気を同時に吹き込むことによって、酸素の過少による反応温度の敏感性を緩和して温度制御が容易になること、
の新規な知見と着想を得たのである。
次に、この知見と着想に係る事項を踏まえて、本発明を実施するための形態を説明する。まず、各工程について説明する。 Therefore, the present inventor further studied,
(1) In order to suppress the generation of tar to a level that does not hinder the production of hydrogen, it is necessary to set the thermal decomposition reaction temperature to 640 ° C. or higher, and it is difficult to raise the temperature to 1000 ° C. in the reformer. The reason was that the heat transfer coefficient between the heat carrying medium and the reformed gas was small, and based on this finding,
(2) The heat source of the thermal decomposer is not limited to the heat carrying medium, and the idea is to supplement the lack of heat from the heat carrying medium with the other heat sources.
(3) If the pre-heated heat carrier medium is not charged into the reformer but is used only as a thermal decomposer and used as heat for elevating the temperature to the thermal decomposition temperature of the thermal decomposer and evaporating moisture, That the preheating temperature of the carrier medium can be lowered,
(4) By utilizing the partial oxidation reaction heat generated by blowing oxygen gas as another heat source for the thermal decomposition reaction of the thermal cracker, the temperature can be easily raised to a predetermined thermal decomposition reaction temperature, and At the same time, by simultaneously injecting steam, the sensitivity of the reaction temperature due to insufficient oxygen is eased and the temperature control becomes easy,
(5) In the reformer, if oxygen gas is supplied in place of the supply of the heat carrying medium, the temperature can be easily raised to the reforming reaction temperature of 1000 ° C. due to the heat of the partial oxidation reaction. Simultaneous blowing eases the sensitivity of the reaction temperature due to insufficient oxygen and facilitates temperature control.
He gained new insights and ideas.
Next, an embodiment for carrying out the present invention will be described based on the findings and ideas. First, each step will be described.
熱担持媒体
（１）熱担持媒体の形状・材質
熱担持媒体の形状は球が好ましく、材質としては、アルミナ等のセラミック、鋼が望ましい。すなわち、アルミナボール、セラミックボール、鋼球が使用でき、その径は、１０～３０ｍｍが好適である。
（２）予熱温度
熱担持媒体は予熱器で予熱され、予熱温度範囲は、６８０～７４０℃とする。この予熱温度範囲は、特許文献１、２で示された１０５０℃よりも遙かに低く、予熱に必要とするエネルギーを節約することができ熱効率がよくなる上、予熱器に高価な耐火材を使用しなくてもすむという利点をもたらす。
熱担持媒体２４は、予熱器３で昇温され熱分解器４で熱分解の熱担持媒体として熱分解に反応に熱を供し、チャー分離装置６でチャーと熱媒体を分離後、熱担持媒体循環装置２７にて循環使用される。 Heat carrying medium (1) Shape and material of the heat carrying medium The shape of the heat carrying medium is preferably a sphere, and the material is preferably ceramic such as alumina or steel. That is, alumina balls, ceramic balls, and steel balls can be used, and the diameter is preferably 10 to 30 mm.
(2) Preheating temperature The heat carrying medium is preheated by a preheater, and the preheating temperature range is 680 to 740 ° C. This preheating temperature range is much lower than 1050 ° C. shown inPatent Documents 1 and 2, so that the energy required for preheating can be saved, the thermal efficiency is improved, and an expensive refractory material is used for the preheater. This has the advantage of not having to do so.
Theheat carrying medium 24 is heated in the preheater 3, serves as a heat carrying medium for thermal decomposition in the pyrolyzer 4, and supplies heat to the reaction for thermal decomposition, and the char separating device 6 separates the char and the heat medium. It is circulated and used in the circulating device 27.
（１）熱担持媒体の形状・材質
熱担持媒体の形状は球が好ましく、材質としては、アルミナ等のセラミック、鋼が望ましい。すなわち、アルミナボール、セラミックボール、鋼球が使用でき、その径は、１０～３０ｍｍが好適である。
（２）予熱温度
熱担持媒体は予熱器で予熱され、予熱温度範囲は、６８０～７４０℃とする。この予熱温度範囲は、特許文献１、２で示された１０５０℃よりも遙かに低く、予熱に必要とするエネルギーを節約することができ熱効率がよくなる上、予熱器に高価な耐火材を使用しなくてもすむという利点をもたらす。
熱担持媒体２４は、予熱器３で昇温され熱分解器４で熱分解の熱担持媒体として熱分解に反応に熱を供し、チャー分離装置６でチャーと熱媒体を分離後、熱担持媒体循環装置２７にて循環使用される。 Heat carrying medium (1) Shape and material of the heat carrying medium The shape of the heat carrying medium is preferably a sphere, and the material is preferably ceramic such as alumina or steel. That is, alumina balls, ceramic balls, and steel balls can be used, and the diameter is preferably 10 to 30 mm.
(2) Preheating temperature The heat carrying medium is preheated by a preheater, and the preheating temperature range is 680 to 740 ° C. This preheating temperature range is much lower than 1050 ° C. shown in
The
熱分解器における熱分解反応工程：
熱分解器における熱分解反応について詳述する。 Pyrolysis reaction process in pyrolyzer:
The pyrolysis reaction in the pyrolyzer will be described in detail.
熱分解器における熱分解反応について詳述する。 Pyrolysis reaction process in pyrolyzer:
The pyrolysis reaction in the pyrolyzer will be described in detail.
（１）バイオマス原料：
本発明の一態様において用いられる原料はバイオマスであり、下水汚泥、間伐材、流木材、木質ペレット、ストローペレット、製紙スラッジ、生ごみコンポストスラッジ、食品廃棄物、汚泥等、生物体由来の炭素、水素および酸素を含むものであれば種類を問わないが、入手のしやすさから下水汚泥が好適である。また、原料は、複数種類のバイオマスの混合物であってもよい。
バイオマスの大きさは、粗粉砕処理を経た程度の大きさであればよい。例えば長さが１５ｍｍ以下の大きさの板状などの個体形状、粒状が好ましい。含有する水分量は、その形状によって異なるが、３０～２０質量％に熱分解器に供給する前に予備乾燥されていることが好ましい。 (1) Biomass raw material:
The raw material used in one embodiment of the present invention is biomass, sewage sludge, thinned wood, driftwood, wood pellets, straw pellets, paper sludge, garbage compost sludge, food waste, sludge, etc. Any type may be used as long as it contains hydrogen and oxygen, but sewage sludge is preferred from the viewpoint of availability. Further, the raw material may be a mixture of plural types of biomass.
The size of the biomass may be any size as long as it has undergone coarse pulverization. For example, a solid shape such as a plate having a length of 15 mm or less and a granular shape are preferable. Although the amount of water contained varies depending on the shape, it is preferably pre-dried before being supplied to the pyrolyzer at 30 to 20% by mass.
本発明の一態様において用いられる原料はバイオマスであり、下水汚泥、間伐材、流木材、木質ペレット、ストローペレット、製紙スラッジ、生ごみコンポストスラッジ、食品廃棄物、汚泥等、生物体由来の炭素、水素および酸素を含むものであれば種類を問わないが、入手のしやすさから下水汚泥が好適である。また、原料は、複数種類のバイオマスの混合物であってもよい。
バイオマスの大きさは、粗粉砕処理を経た程度の大きさであればよい。例えば長さが１５ｍｍ以下の大きさの板状などの個体形状、粒状が好ましい。含有する水分量は、その形状によって異なるが、３０～２０質量％に熱分解器に供給する前に予備乾燥されていることが好ましい。 (1) Biomass raw material:
The raw material used in one embodiment of the present invention is biomass, sewage sludge, thinned wood, driftwood, wood pellets, straw pellets, paper sludge, garbage compost sludge, food waste, sludge, etc. Any type may be used as long as it contains hydrogen and oxygen, but sewage sludge is preferred from the viewpoint of availability. Further, the raw material may be a mixture of plural types of biomass.
The size of the biomass may be any size as long as it has undergone coarse pulverization. For example, a solid shape such as a plate having a length of 15 mm or less and a granular shape are preferable. Although the amount of water contained varies depending on the shape, it is preferably pre-dried before being supplied to the pyrolyzer at 30 to 20% by mass.
（２）熱分解ガスを得る熱分解：
熱分解ガスを得る熱分解の温度は、６４０～７４０℃とする。この温度範囲とした理由は、６４０℃未満であると熱分解によって発生したタールを完全に分解することが難しく、７４０℃を超えると同タール完全に分解するために必要以上の熱源が必要になるためである。熱分解温度は６６０～７００℃がより好ましい。 (2) Pyrolysis to obtain pyrolysis gas:
The pyrolysis temperature for obtaining the pyrolysis gas is 640 to 740 ° C. The reason for setting this temperature range is that if the temperature is lower than 640 ° C., it is difficult to completely decompose tar generated by thermal decomposition, and if it exceeds 740 ° C., an excessive heat source is required to completely decompose the tar. That's why. The thermal decomposition temperature is more preferably 660 to 700 ° C.
熱分解ガスを得る熱分解の温度は、６４０～７４０℃とする。この温度範囲とした理由は、６４０℃未満であると熱分解によって発生したタールを完全に分解することが難しく、７４０℃を超えると同タール完全に分解するために必要以上の熱源が必要になるためである。熱分解温度は６６０～７００℃がより好ましい。 (2) Pyrolysis to obtain pyrolysis gas:
The pyrolysis temperature for obtaining the pyrolysis gas is 640 to 740 ° C. The reason for setting this temperature range is that if the temperature is lower than 640 ° C., it is difficult to completely decompose tar generated by thermal decomposition, and if it exceeds 740 ° C., an excessive heat source is required to completely decompose the tar. That's why. The thermal decomposition temperature is more preferably 660 to 700 ° C.
また、有機原料として下水汚泥等を用いると、有機原料中に五酸化二リン（Ｐ２Ｏ５）が含まれるが、熱分解の温度を６４０～７４０℃とすることによりＰ２Ｏ５蒸発が抑制でき、熱分解ガスに閉塞トラブルを起こす恐れのあるＰ２Ｏ５の揮散蒸気が存在しないため、Ｐ２Ｏ５を含む下水汚泥を有機原料とすることが可能となる利点を有する。
熱分解の熱源は熱担持媒体がもたらすが、それだけでは十分でなく、酸素ガスを吹込み供給することによって、前記温度範囲とする。 Further, when sewage sludge or the like is used as an organic raw material, phosphorus pentoxide (P 2 O 5 ) is contained in the organic raw material. However, by setting the thermal decomposition temperature to 640 to 740 ° C., P 2 O 5 evaporation is reduced. inhibition can, for volatilization vapor P 2 O 5 which may cause clogging trouble pyrolysis gas does not exist, has the advantage that it is possible to an organic material sewage sludge containing P 2 O 5.
The heat source of the thermal decomposition is provided by the heat-carrying medium, but is not sufficient, and the temperature range is set by blowing and supplying oxygen gas.
熱分解の熱源は熱担持媒体がもたらすが、それだけでは十分でなく、酸素ガスを吹込み供給することによって、前記温度範囲とする。 Further, when sewage sludge or the like is used as an organic raw material, phosphorus pentoxide (P 2 O 5 ) is contained in the organic raw material. However, by setting the thermal decomposition temperature to 640 to 740 ° C., P 2 O 5 evaporation is reduced. inhibition can, for volatilization vapor P 2 O 5 which may cause clogging trouble pyrolysis gas does not exist, has the advantage that it is possible to an organic material sewage sludge containing P 2 O 5.
The heat source of the thermal decomposition is provided by the heat-carrying medium, but is not sufficient, and the temperature range is set by blowing and supplying oxygen gas.
水蒸気と酸素ガスを同時吹込み供給することによる熱源の確保により、水蒸気と酸素ガスの供給による熱伝達が、固相である熱担持媒体の熱伝達に比して遙かに効率がよい上に、供給される水蒸気によって、ヒートスポットの生成を抑制し、温度の急激な変化が緩和でき、しかも、有機原料供給量などの変化等の短時間で変化する外乱に応じて熱分解反応の制御が容易である利点を有している。
By securing a heat source by simultaneously injecting and supplying steam and oxygen gas, the heat transfer by the supply of steam and oxygen gas is much more efficient than the heat transfer of the heat carrier medium which is a solid phase. The supply of water vapor suppresses the generation of heat spots, alleviates rapid changes in temperature, and controls the thermal decomposition reaction in response to short-term disturbances such as changes in the amount of organic raw material supplied. It has the advantage of being easy.
ここで、水蒸気と酸素ガスのそれぞれの供給比は、水蒸気／酸素ガスのモル比（水蒸気のモル／酸素ガスのモル）で１～４が好ましい。この範囲とする理由は、１未満であると温度変動が大きくなることがあり、４を超えると、水蒸気が６００℃以上で酸化性となり、ＣＯ２濃度が大きくなって水素回収には好ましくなくなってしまうためである。
そして、水蒸気は、温度に制約はないものの、一例として、１４０℃の温度のものを挙げることができ、酸素ガスは、特に制約はなく、例えば、工業用の酸素ガス発生器で製造した、４０℃程度のものを用いることができる。そして、水蒸気／酸素ガスで表されるモル比が高くなると、酸素流量のわずかな変動によりもたらされる外乱に対して熱分解反応の制御がより容易となる。 Here, the respective supply ratios of steam and oxygen gas are preferably 1 to 4 in terms of a steam / oxygen gas molar ratio (mol of steam / mol of oxygen gas). The reason for this range is that if it is less than 1, the temperature fluctuation may increase, and if it exceeds 4, the steam becomes oxidizing at 600 ° C. or higher, and the CO 2 concentration increases, which is not preferable for hydrogen recovery. This is because
Although the temperature of steam is not limited, a temperature of 140 ° C. can be mentioned as an example. The oxygen gas is not particularly limited, and is, for example, 40% manufactured by an industrial oxygen gas generator. C. can be used. And, when the molar ratio represented by water vapor / oxygen gas becomes higher, it becomes easier to control the thermal decomposition reaction with respect to disturbance caused by slight fluctuation of the oxygen flow rate.
そして、水蒸気は、温度に制約はないものの、一例として、１４０℃の温度のものを挙げることができ、酸素ガスは、特に制約はなく、例えば、工業用の酸素ガス発生器で製造した、４０℃程度のものを用いることができる。そして、水蒸気／酸素ガスで表されるモル比が高くなると、酸素流量のわずかな変動によりもたらされる外乱に対して熱分解反応の制御がより容易となる。 Here, the respective supply ratios of steam and oxygen gas are preferably 1 to 4 in terms of a steam / oxygen gas molar ratio (mol of steam / mol of oxygen gas). The reason for this range is that if it is less than 1, the temperature fluctuation may increase, and if it exceeds 4, the steam becomes oxidizing at 600 ° C. or higher, and the CO 2 concentration increases, which is not preferable for hydrogen recovery. This is because
Although the temperature of steam is not limited, a temperature of 140 ° C. can be mentioned as an example. The oxygen gas is not particularly limited, and is, for example, 40% manufactured by an industrial oxygen gas generator. C. can be used. And, when the molar ratio represented by water vapor / oxygen gas becomes higher, it becomes easier to control the thermal decomposition reaction with respect to disturbance caused by slight fluctuation of the oxygen flow rate.
ここで、熱分解ガスは、ＣＨ４、ＣＯ、ＣＯ２、Ｈ２が主成分のガスである。そして、前記のように水蒸気を吹込むことにより、Ｈ２を得ることができるが、Ｈ２の含有割合は１０体積％と少ないため、Ｈ２の含有割合を上昇させるべく、次工程で改質を行う。
Here, the pyrolysis gas is a gas mainly composed of CH 4 , CO, CO 2 , and H 2 . By blowing steam, as described above, it is possible to obtain a H 2, because the content of H 2 is small and 10% by volume, in order to increase the content of H 2, modification in the next step I do.
改質器における改質工程：
改質器は熱分解器の下流に設け、熱源として熱担持媒体を用いず水蒸気と酸素ガスを同時供給して１０００℃以上に昇温して熱分解ガスに対して行い、水素に富んだ粗改質ガスを得る。そして、熱担持媒体の供給に替え、水蒸気と酸素ガスを同時供給することにより１０００℃へ容易に昇温することができる。
ここで、水蒸気は、一例として、１００～１５０℃のものを挙げることができ、酸素ガスは、例えば、工業用の酸素ガス発生器で製造した４０℃のものを用いることができる。 Reforming process in reformer:
The reformer is installed downstream of the pyrolyzer, and without using a heat carrier medium as a heat source, simultaneously supplies steam and oxygen gas, raises the temperature to 1000 ° C or higher, and performs the pyrolysis on the pyrolysis gas to obtain a hydrogen-rich crude gas. Obtain reformed gas. Then, the temperature can be easily raised to 1000 ° C. by simultaneously supplying steam and oxygen gas instead of supplying the heat carrying medium.
Here, the steam may be, for example, 100 to 150 ° C., and the oxygen gas may be, for example, 40 ° C. produced by an industrial oxygen gas generator.
改質器は熱分解器の下流に設け、熱源として熱担持媒体を用いず水蒸気と酸素ガスを同時供給して１０００℃以上に昇温して熱分解ガスに対して行い、水素に富んだ粗改質ガスを得る。そして、熱担持媒体の供給に替え、水蒸気と酸素ガスを同時供給することにより１０００℃へ容易に昇温することができる。
ここで、水蒸気は、一例として、１００～１５０℃のものを挙げることができ、酸素ガスは、例えば、工業用の酸素ガス発生器で製造した４０℃のものを用いることができる。 Reforming process in reformer:
The reformer is installed downstream of the pyrolyzer, and without using a heat carrier medium as a heat source, simultaneously supplies steam and oxygen gas, raises the temperature to 1000 ° C or higher, and performs the pyrolysis on the pyrolysis gas to obtain a hydrogen-rich crude gas. Obtain reformed gas. Then, the temperature can be easily raised to 1000 ° C. by simultaneously supplying steam and oxygen gas instead of supplying the heat carrying medium.
Here, the steam may be, for example, 100 to 150 ° C., and the oxygen gas may be, for example, 40 ° C. produced by an industrial oxygen gas generator.
改質により、水蒸気改質反応が進行して、ＣＨ４ガス等の炭化水素ガスが水素ガスに転化し、水素ガスの含有割合が増大する。ここで、代表的な水蒸気改質反応として、
ＣＨ４ ＋ Ｈ２Ｏ → ＣＯ ＋ ３Ｈ２
を挙げることができる。
また、次のシフト反応も進行して、水素ガスの含有割合が増大する。
ＣＯ ＋ Ｈ２Ｏ → ＣＯ２ ＋ Ｈ２
このようにして得た粗改質ガスは、Ｈ２ガスの含有割合が５０～５４体積％（ドライベース）となっている。
なお、水蒸気の供給は、前記水蒸気改質反応を進行させるためだけになされるのではなく、温度の過敏性（急激な変化）の緩和のためにもなされる。
改質器に供給される水蒸気と酸素ガスは、一例として、水蒸気／酸素ガスのモル比（水蒸気のモル／酸素ガスのモル）で１～４となるように同時供給されることが好ましい。 By the reforming, a steam reforming reaction proceeds, and a hydrocarbon gas such as CH 4 gas is converted into a hydrogen gas, and the content ratio of the hydrogen gas increases. Here, as a typical steam reforming reaction,
CH 4 + H 2 O → CO + 3H 2
Can be mentioned.
Further, the next shift reaction proceeds, and the content ratio of hydrogen gas increases.
CO + H 2 O → CO 2 + H 2
The crude reformed gas thus obtained has a H 2 gas content of 50 to 54% by volume (dry basis).
Note that the supply of steam is not only performed to advance the steam reforming reaction, but also to ease temperature sensitivity (rapid change).
As an example, the steam and the oxygen gas supplied to the reformer are preferably simultaneously supplied so that the molar ratio of steam / oxygen gas (mol of steam / mol of oxygen gas) becomes 1 to 4.
ＣＨ４ ＋ Ｈ２Ｏ → ＣＯ ＋ ３Ｈ２
を挙げることができる。
また、次のシフト反応も進行して、水素ガスの含有割合が増大する。
ＣＯ ＋ Ｈ２Ｏ → ＣＯ２ ＋ Ｈ２
このようにして得た粗改質ガスは、Ｈ２ガスの含有割合が５０～５４体積％（ドライベース）となっている。
なお、水蒸気の供給は、前記水蒸気改質反応を進行させるためだけになされるのではなく、温度の過敏性（急激な変化）の緩和のためにもなされる。
改質器に供給される水蒸気と酸素ガスは、一例として、水蒸気／酸素ガスのモル比（水蒸気のモル／酸素ガスのモル）で１～４となるように同時供給されることが好ましい。 By the reforming, a steam reforming reaction proceeds, and a hydrocarbon gas such as CH 4 gas is converted into a hydrogen gas, and the content ratio of the hydrogen gas increases. Here, as a typical steam reforming reaction,
CH 4 + H 2 O → CO + 3H 2
Can be mentioned.
Further, the next shift reaction proceeds, and the content ratio of hydrogen gas increases.
CO + H 2 O → CO 2 + H 2
The crude reformed gas thus obtained has a H 2 gas content of 50 to 54% by volume (dry basis).
Note that the supply of steam is not only performed to advance the steam reforming reaction, but also to ease temperature sensitivity (rapid change).
As an example, the steam and the oxygen gas supplied to the reformer are preferably simultaneously supplied so that the molar ratio of steam / oxygen gas (mol of steam / mol of oxygen gas) becomes 1 to 4.
Ｈ２ガスの精製工程：
改質工程を経たガス（粗改質ガス）は、冷却され除塵されて、ＨＣｌ、ＣＮ、ＮＨ３等の微量の有害成分を除去する。ここで除去は、従来公知の手段を適宜組み合わせて行うことができる。その後、Ｈ２ガスの精製を行う。Ｈ２ガスの精製は、公知の手段を適宜使用すればよく、例えば、ＰＳＡ手段、膜分離手段が使用できる。 H 2 gas purification process:
The gas that has undergone the reforming step (coarse reformed gas) is cooled and dust-removed to remove trace amounts of harmful components such as HCl, CN, and NH 3 . Here, the removal can be performed by appropriately combining conventionally known means. Thereafter, the purification of H 2 gas. For the purification of the H 2 gas, a known means may be appropriately used, and for example, a PSA means and a membrane separation means can be used.
改質工程を経たガス（粗改質ガス）は、冷却され除塵されて、ＨＣｌ、ＣＮ、ＮＨ３等の微量の有害成分を除去する。ここで除去は、従来公知の手段を適宜組み合わせて行うことができる。その後、Ｈ２ガスの精製を行う。Ｈ２ガスの精製は、公知の手段を適宜使用すればよく、例えば、ＰＳＡ手段、膜分離手段が使用できる。 H 2 gas purification process:
The gas that has undergone the reforming step (coarse reformed gas) is cooled and dust-removed to remove trace amounts of harmful components such as HCl, CN, and NH 3 . Here, the removal can be performed by appropriately combining conventionally known means. Thereafter, the purification of H 2 gas. For the purification of the H 2 gas, a known means may be appropriately used, and for example, a PSA means and a membrane separation means can be used.
次に、実施例について説明するが、本発明は、これら実施例に限定されるものではなく、その趣旨を逸脱しない範囲で適宜変更可能であることは言うまでもない。
Next, examples will be described. However, it is needless to say that the present invention is not limited to these examples and can be appropriately changed without departing from the gist of the present invention.
図１に示す装置（設備）を用いて、以下に記載する各実施例および各比較例を実施した。以下、図１に示されている本発明を実施するための装置の一例である概略図を参照して前記各工程を説明する。
各 Using the apparatus (equipment) shown in FIG. 1, each Example and each Comparative Example described below were implemented. Hereinafter, each of the above steps will be described with reference to a schematic diagram showing an example of an apparatus for carrying out the present invention shown in FIG.
熱担持媒体２４は、６８０～７４０℃に予熱器３で加熱（予熱）されて、加熱後、弁２５を経由して熱分解器４に投入される。ここで、予熱器３で熱担持媒体を予熱する熱源は、後述するように、チャーの一部１８や熱分解ガス１１の一部を燃焼炉２３で燃焼させた約８００℃の燃焼排ガス１９であり、予熱器３からは燃焼排ガス２０が排出される。
(4) The heat carrying medium 24 is heated (preheated) to 680 to 740 ° C. by the preheater 3, and after heating, is fed into the thermal decomposer 4 via the valve 25. Here, the heat source for preheating the heat carrier medium in the preheater 3 is a flue gas 19 of about 800 ° C. obtained by burning part of the char 18 and part of the pyrolysis gas 11 in the combustion furnace 23 as described later. Thus, the combustion exhaust gas 20 is discharged from the preheater 3.
熱分解工程は、熱分解器４によってなされ、バイオマス原料１は、スクリューコンベア等のバイオマス原料搬送装置２により熱分解器４へ供給される。このバイオマス原料１は、投入された熱担持媒体２４からの熱および熱分解器４の下部から同時に吹込み供給される水蒸気８と酸素ガス７とにより昇温され、６４０～７２０℃の温度で熱分解され熱分解ガス１１が発生する。
The pyrolysis step is performed by the pyrolyzer 4, and the biomass raw material 1 is supplied to the pyrolyzer 4 by the biomass raw material transporting device 2 such as a screw conveyor. The temperature of the biomass raw material 1 is increased by the heat from the heat carrier medium 24 and the steam 8 and the oxygen gas 7 which are blown and supplied from the lower part of the pyrolyzer 4 at a temperature of 640 to 720 ° C. It is decomposed to generate pyrolysis gas 11.
改質工程は、改質器５でなされる。熱分解反応によって得られた熱分解ガス１１は、その大部分が改質器５へ送られる。改質器５では、その下部から水蒸気１０と酸素ガス９が同時に吹込み供給され、熱分解ガス１１を１０００℃まで昇温し、前述の水蒸気改質反応を進行させて、粗改質ガス１３を得る。
The reforming step is performed in the reformer 5. Most of the pyrolysis gas 11 obtained by the pyrolysis reaction is sent to the reformer 5. In the reformer 5, steam 10 and oxygen gas 9 are simultaneously blown and supplied from the lower part thereof, and the temperature of the pyrolysis gas 11 is raised to 1000 ° C., and the steam reforming reaction proceeds, and the crude reforming gas 13 Get.
Ｈ２ガスの精製工程は、粗改質ガス冷却・精製装置２１でなされ、改質器５を経た粗改質ガス１３は、粗改質ガス冷却・精製装置２１へ導入されて、各手段の図示はされていないが、冷却、除塵、微量の有害成分の除去がそれぞれなされ、精製改質ガス１４となり、水素分離装置２２へ導入され、純水素ガス１５を得る。なお、水素分離装置２２からはオフガス１６が排出される。
The purification process of the H 2 gas is performed in the crude reformed gas cooling / purifying device 21, and the crude reformed gas 13 that has passed through the reformer 5 is introduced into the crude reformed gas cooling / refining device 21, Although not shown, cooling, dust removal, and removal of trace amounts of harmful components are performed, and the purified reformed gas 14 is introduced into the hydrogen separator 22 to obtain pure hydrogen gas 15. The off-gas 16 is discharged from the hydrogen separator 22.
また、熱分解器４の底からは、６４０℃程度となった熱担持媒体２４とバイオマス原料１のチャーが排出され、これらはチャー分離装置６へ弁２６を経由して導入される。チャー分離装置６では、チャー１７と熱担持媒体２４とが分離され、熱担持媒体２４は熱担持媒体循環装置２７へ送られて、該装置によって予熱器３へ戻され循環使用される。また、チャー１７は、そのチャーの一部１８を除き、セメント製造施設や石炭火力発電所での代替燃料などに使用される。なお、チャー分離装置６は、例えば、篩によって熱担持媒体２４とチャー１７を分離できるものなど、公知のものが使用できる。
{Circle around (4)} The char of the heat carrier medium 24 and the biomass raw material 1 at about 640 ° C. are discharged from the bottom of the pyrolyzer 4, and are introduced into the char separation device 6 via the valve 26. In the char separation device 6, the char 17 and the heat carrying medium 24 are separated, and the heat carrying medium 24 is sent to the heat carrying medium circulating device 27, and is returned to the preheater 3 by the device for circulating use. The char 17, except for a part 18 of the char, is used as an alternative fuel in a cement manufacturing facility or a coal-fired power plant. As the char separation device 6, a known device such as a device capable of separating the heat carrying medium 24 and the char 17 by a sieve can be used.
ここで、前述のとおり、熱分解ガスの一部１２とチャーの一部１８は、燃焼炉２３に導入されて燃焼し、約８００℃の燃焼排ガス１９のための熱源となり、該燃焼排ガス１９は予熱器で熱担持媒体２４を予熱する熱源となる。熱分解ガスの一部１２とチャーの一部１８のみでは、この予熱のための熱源として不足するときは、ＬＮＧ、ＬＰＧ等の外部燃料を使用して熱源を補う。なお、燃焼炉２３は、特別なものを使用する必要はない。
Here, as described above, the part 12 of the pyrolysis gas and the part 18 of the char are introduced into the combustion furnace 23 and burned, and serve as a heat source for the flue gas 19 at about 800 ° C. It serves as a heat source for preheating the heat carrying medium 24 by the preheater. When only a part 12 of the pyrolysis gas and a part 18 of the char are insufficient as a heat source for the preheating, an external fuel such as LNG or LPG is used to supplement the heat source. It is not necessary to use a special furnace for the combustion furnace 23.
なお、図示はしていないが、本装置（設備）において、予熱器の燃焼排ガス２０の廃熱を利用して水蒸気を作製し、これを熱分解器に供給する水蒸気８、改質器に供給する水蒸気１０とすることも可能である。
Although not shown, in the present apparatus (equipment), steam is produced using waste heat of the combustion exhaust gas 20 of the preheater, and the steam is supplied to the pyrolyzer and supplied to the reformer. It is also possible to use steam 10 that is generated.
各実施例および各比較例に共通して使用した有機原料は下水汚泥であって、以下のとおりのものである。
有機 The organic raw material commonly used in each example and each comparative example is sewage sludge, which is as follows.
供給量 ２７．２ｋｇ／ｈ
水分含有量 ２０質量％
灰分、揮発分および固定炭素の割合、ならびに、元素分析の結果を、それぞれ、表１、表２に示す。
Supply amount 27.2kg / h
Water content 20% by mass
Tables 1 and 2 show the proportions of ash, volatiles and fixed carbon, and the results of elemental analysis, respectively.
水分含有量 ２０質量％
灰分、揮発分および固定炭素の割合、ならびに、元素分析の結果を、それぞれ、表１、表２に示す。
Supply amount 27.2kg / h
Tables 1 and 2 show the proportions of ash, volatiles and fixed carbon, and the results of elemental analysis, respectively.
各実施例および各比較例に共通して、熱担持媒体として、表３に示すアルミナボールを使用した。
ア ル ミ ナ Alumina balls shown in Table 3 were used as a heat-carrying medium in each of Examples and Comparative Examples.
＜実施例１＞
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度（熱分解反応温度）を６９０℃として、１４０℃の水蒸気と４０℃の酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、水蒸気流量は、それぞれ、１．７１Ｎｍ3／ｈ、 ２．７５ｋｇ／ｈで、水蒸気／酸素ガスのモル比は２．０（＝（２．７５×１０３／１８）／（１．７１×１０３／２２．４））、改質器へ酸素ガス流量、水蒸気流量は、それぞれ、２．３Ｎｍ3／ｈ、３．７ｋｇ／ｈであった。
また、熱分解ガス組成、タール量、および、改質器を出たガス組成を測定した。その結果を表４に示す。
なお、熱分解ガス組成の表示において、ＣＨ４により全ての炭化水素ガスを表現した。以下、同様の表記をしている。 <Example 1>
The preheating temperature of the heat carrying medium was set at 700 ° C., the temperature of the pyrolyzer (pyrolysis reaction temperature) was set at 690 ° C., and steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 1.71 Nm 3 / h and 2.75 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0 (= (2.75 × 10 3 /18)/(1.71×10 3 /22.4)), the flow rates of oxygen gas and steam to the reformer were 2.3 Nm 3 / h and 3.7 kg / h, respectively.
The composition of the pyrolysis gas, the amount of tar, and the composition of the gas leaving the reformer were measured. Table 4 shows the results.
In the display of the composition of the pyrolysis gas, all hydrocarbon gases were represented by CH 4 . Hereinafter, the same notation is used.
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度（熱分解反応温度）を６９０℃として、１４０℃の水蒸気と４０℃の酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、水蒸気流量は、それぞれ、１．７１Ｎｍ3／ｈ、 ２．７５ｋｇ／ｈで、水蒸気／酸素ガスのモル比は２．０（＝（２．７５×１０３／１８）／（１．７１×１０３／２２．４））、改質器へ酸素ガス流量、水蒸気流量は、それぞれ、２．３Ｎｍ3／ｈ、３．７ｋｇ／ｈであった。
また、熱分解ガス組成、タール量、および、改質器を出たガス組成を測定した。その結果を表４に示す。
なお、熱分解ガス組成の表示において、ＣＨ４により全ての炭化水素ガスを表現した。以下、同様の表記をしている。 <Example 1>
The preheating temperature of the heat carrying medium was set at 700 ° C., the temperature of the pyrolyzer (pyrolysis reaction temperature) was set at 690 ° C., and steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 1.71 Nm 3 / h and 2.75 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0 (= (2.75 × 10 3 /18)/(1.71×10 3 /22.4)), the flow rates of oxygen gas and steam to the reformer were 2.3 Nm 3 / h and 3.7 kg / h, respectively.
The composition of the pyrolysis gas, the amount of tar, and the composition of the gas leaving the reformer were measured. Table 4 shows the results.
In the display of the composition of the pyrolysis gas, all hydrocarbon gases were represented by CH 4 . Hereinafter, the same notation is used.
＜比較例１＞
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度を６００℃としてして、１４０℃の水蒸気と４０℃酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、蒸気流量は、それぞれ、０．７６Ｎｍ3／ｈ、１．２１ｋｇ／ｈで、水蒸気／酸素ガスのモル比は２．０、改質器へ酸素ガス流量、水蒸気流量は、それぞれ、２．３Ｎｍ3／ｈ、３．７ｋｇ／ｈであった。熱分解ガス組成とタール量を測定した。その結果を表４に示す。 <Comparative Example 1>
With the preheating temperature of the heat carrying medium set to 700 ° C. and the temperature of the pyrolyzer set to 600 ° C., 140 ° C. steam and 40 ° C. oxygen gas were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 0.76 Nm 3 / h and 1.21 kg / h, respectively, the steam / oxygen gas molar ratio was 2.0, and the oxygen gas flow to the reformer was The flow rate and the steam flow rate were 2.3 Nm 3 / h and 3.7 kg / h, respectively. The composition of the pyrolysis gas and the amount of tar were measured. Table 4 shows the results.
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度を６００℃としてして、１４０℃の水蒸気と４０℃酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、蒸気流量は、それぞれ、０．７６Ｎｍ3／ｈ、１．２１ｋｇ／ｈで、水蒸気／酸素ガスのモル比は２．０、改質器へ酸素ガス流量、水蒸気流量は、それぞれ、２．３Ｎｍ3／ｈ、３．７ｋｇ／ｈであった。熱分解ガス組成とタール量を測定した。その結果を表４に示す。 <Comparative Example 1>
With the preheating temperature of the heat carrying medium set to 700 ° C. and the temperature of the pyrolyzer set to 600 ° C., 140 ° C. steam and 40 ° C. oxygen gas were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 0.76 Nm 3 / h and 1.21 kg / h, respectively, the steam / oxygen gas molar ratio was 2.0, and the oxygen gas flow to the reformer was The flow rate and the steam flow rate were 2.3 Nm 3 / h and 3.7 kg / h, respectively. The composition of the pyrolysis gas and the amount of tar were measured. Table 4 shows the results.
実施例１は、熱分解器の温度が６９０℃で、６５０～７４０℃の温度範囲にあり、また、水蒸気／酸素ガスのモル比が２．０で１．０～４．０のモル比範囲にあるため、熱分解ガスに含まれるＣＨ４ガスの含有割合が低く、タールの発生を完全に抑えることができた。また、改質器の温度を１０００℃にすることができた。
これに対して、比較例１は、熱分解温度が６００℃で、前記温度範囲にないため、熱分解ガスに含まれるＣＨ４ガスの含有割合が高く、タールの発生が生じ、改質器の温度は９３７℃であった。 In Example 1, the temperature of the pyrolyzer was 690 ° C. and the temperature range was 650 to 740 ° C., and the steam / oxygen gas molar ratio was 2.0 and the molar ratio range was 1.0 to 4.0. Therefore, the content ratio of CH 4 gas contained in the pyrolysis gas was low, and the generation of tar could be completely suppressed. Further, the temperature of the reformer could be set to 1000 ° C.
On the other hand, in Comparative Example 1, the pyrolysis temperature was 600 ° C. and was not in the above temperature range, so that the content ratio of the CH 4 gas contained in the pyrolysis gas was high, tar was generated, and The temperature was 937 ° C.
これに対して、比較例１は、熱分解温度が６００℃で、前記温度範囲にないため、熱分解ガスに含まれるＣＨ４ガスの含有割合が高く、タールの発生が生じ、改質器の温度は９３７℃であった。 In Example 1, the temperature of the pyrolyzer was 690 ° C. and the temperature range was 650 to 740 ° C., and the steam / oxygen gas molar ratio was 2.0 and the molar ratio range was 1.0 to 4.0. Therefore, the content ratio of CH 4 gas contained in the pyrolysis gas was low, and the generation of tar could be completely suppressed. Further, the temperature of the reformer could be set to 1000 ° C.
On the other hand, in Comparative Example 1, the pyrolysis temperature was 600 ° C. and was not in the above temperature range, so that the content ratio of the CH 4 gas contained in the pyrolysis gas was high, tar was generated, and The temperature was 937 ° C.
次に、下水汚泥に含まれるＰ２Ｏ５の蒸発が抑制されること確認するために、実施例２と比較例２において、図１の粗改質ガス冷却・精製装置２２に堆積したＰ２Ｏ５の量を計測した。
Next, in order to confirm that the evaporation of P 2 O 5 contained in the sewage sludge is suppressed, in Example 2 and Comparative Example 2, P 2 deposited on the crude reformed gas cooling / purifying device 22 in FIG. the amount of O 5 was measured.
＜実施例２＞
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度を６９０℃として、１４０℃の水蒸気と４０℃の酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、水蒸気流量は、それぞれ、１．７１Ｎｍ3／ｈ、２．７５ｋｇ／ｈで水蒸気／酸素ガスのモル比は２．０であり、５時間の運転し、図１の粗改質ガス冷却・精製装置２２に堆積したＰ２Ｏ５の量を計測した。結果を表５に示す。 <Example 2>
With the preheating temperature of the heat carrying medium set at 700 ° C. and the temperature of the pyrolyzer at 690 ° C., steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 1.71 Nm 3 / h and 2.75 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0. The amount of P 2 O 5 deposited on the crude reforming gas cooling /refining device 22 of FIG. 1 was measured. Table 5 shows the results.
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度を６９０℃として、１４０℃の水蒸気と４０℃の酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、水蒸気流量は、それぞれ、１．７１Ｎｍ3／ｈ、２．７５ｋｇ／ｈで水蒸気／酸素ガスのモル比は２．０であり、５時間の運転し、図１の粗改質ガス冷却・精製装置２２に堆積したＰ２Ｏ５の量を計測した。結果を表５に示す。 <Example 2>
With the preheating temperature of the heat carrying medium set at 700 ° C. and the temperature of the pyrolyzer at 690 ° C., steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 1.71 Nm 3 / h and 2.75 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0. The amount of P 2 O 5 deposited on the crude reforming gas cooling /
＜比較例２＞
熱担持媒体の予熱温度を８００℃とし、熱分解器の温度を７８０℃として、１４０℃の水蒸気と４０℃酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、蒸気流量は、それぞれ、３．１４Ｎｍ3／ｈ、５．０ｋｇ／ｈで水蒸気／酸素ガスのモル比は２．０であり、５時間の運転し、図１の粗改質ガス冷却・精製装置２２に堆積したＰ２Ｏ５の量を計測した。結果を表５に示す。 <Comparative Example 2>
With the preheating temperature of the heat carrying medium set to 800 ° C. and the temperature of the pyrolyzer set to 780 ° C., steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 3.14 Nm 3 / h and 5.0 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0. The amount of P 2 O 5 deposited on the crude reforming gas cooling /refining device 22 of FIG. 1 was measured. Table 5 shows the results.
熱担持媒体の予熱温度を８００℃とし、熱分解器の温度を７８０℃として、１４０℃の水蒸気と４０℃酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス流量、蒸気流量は、それぞれ、３．１４Ｎｍ3／ｈ、５．０ｋｇ／ｈで水蒸気／酸素ガスのモル比は２．０であり、５時間の運転し、図１の粗改質ガス冷却・精製装置２２に堆積したＰ２Ｏ５の量を計測した。結果を表５に示す。 <Comparative Example 2>
With the preheating temperature of the heat carrying medium set to 800 ° C. and the temperature of the pyrolyzer set to 780 ° C., steam at 140 ° C. and oxygen gas at 40 ° C. were blown. At this time, the oxygen gas flow rate and the steam flow rate to the pyrolyzer were 3.14 Nm 3 / h and 5.0 kg / h, respectively, and the steam / oxygen gas molar ratio was 2.0. The amount of P 2 O 5 deposited on the crude reforming gas cooling /
推定Ｐ２Ｏ５蒸気濃度は、粗改質ガス冷却・精製装置２２を閉塞した閉塞物の量とその分析結果によって推定した。
The estimated P 2 O 5 vapor concentration was estimated based on the amount of clogs that blocked the crude reformed gas cooling / refining device 22 and the analysis results.
実施例２は、熱分解器の温度が６９０℃で、６５０～７４０℃の温度範囲にあり、また、水蒸気／酸素ガスのモル比が２．０で１．０～４．０のモル比範囲にあるため、粗改質ガス冷却・精製装置に堆積したＰ２Ｏ５の量が０．０２ｋｇと少なく、下水汚泥に含まれているＰ２Ｏ５の蒸発をほぼ完全に抑えているといえる。
これに対して、比較例２は、熱分解温度が７８０℃で、前記温度範囲よりも高く、Ｐ２Ｏ５の蒸発は抑えられていない。 In Example 2, the temperature of the pyrolyzer was 690 ° C. and the temperature range was 650 to 740 ° C., and the steam / oxygen gas molar ratio was 2.0 and the molar ratio range was 1.0 to 4.0. Therefore, the amount of P 2 O 5 deposited in the crude reforming gas cooling / refining apparatus is as small as 0.02 kg, and it can be said that the evaporation of P 2 O 5 contained in the sewage sludge is almost completely suppressed. .
On the other hand, in Comparative Example 2, the thermal decomposition temperature was 780 ° C., which was higher than the above temperature range, and the evaporation of P 2 O 5 was not suppressed.
これに対して、比較例２は、熱分解温度が７８０℃で、前記温度範囲よりも高く、Ｐ２Ｏ５の蒸発は抑えられていない。 In Example 2, the temperature of the pyrolyzer was 690 ° C. and the temperature range was 650 to 740 ° C., and the steam / oxygen gas molar ratio was 2.0 and the molar ratio range was 1.0 to 4.0. Therefore, the amount of P 2 O 5 deposited in the crude reforming gas cooling / refining apparatus is as small as 0.02 kg, and it can be said that the evaporation of P 2 O 5 contained in the sewage sludge is almost completely suppressed. .
On the other hand, in Comparative Example 2, the thermal decomposition temperature was 780 ° C., which was higher than the above temperature range, and the evaporation of P 2 O 5 was not suppressed.
次に、水蒸気／酸素ガスのモル比が、Ｈ２の収量や温度変動の安定性に与える影響を確認するために、実施例３と実施例２と比較する。
Next, in order to confirm the influence of the steam / oxygen gas molar ratio on the yield of H 2 and the stability of temperature fluctuation, a comparison is made between Example 3 and Example 2.
＜実施例２＞
実施例２は、前記のとおり行ったものであるが、熱分解ガス量は、１６．６４Ｎｍ3／ｈであり、酸素ガス吹込み量が±０．３０Ｎｍ3／ｈの変動に対して、熱分解器の温度の変動は±６０℃であった。得られた粗改質ガスの組成を表６に示す。 <Example 2>
Example 2 was performed as described above, but the amount of the pyrolysis gas was 16.64 Nm 3 / h, and the amount of the oxygen gas blown was ± 0.30 Nm 3 / h. The variation in the temperature of the decomposer was ± 60 ° C. Table 6 shows the composition of the resulting crude reformed gas.
実施例２は、前記のとおり行ったものであるが、熱分解ガス量は、１６．６４Ｎｍ3／ｈであり、酸素ガス吹込み量が±０．３０Ｎｍ3／ｈの変動に対して、熱分解器の温度の変動は±６０℃であった。得られた粗改質ガスの組成を表６に示す。 <Example 2>
Example 2 was performed as described above, but the amount of the pyrolysis gas was 16.64 Nm 3 / h, and the amount of the oxygen gas blown was ± 0.30 Nm 3 / h. The variation in the temperature of the decomposer was ± 60 ° C. Table 6 shows the composition of the resulting crude reformed gas.
＜実施例３＞
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度を６９０℃として、１４０℃の水蒸気と４０℃酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス、蒸気流量は、それぞれ、１．７１Ｎｍ3／ｈ、５．４９ｋｇ／ｈであり、水蒸気／酸素ガスのモル比は、４．０であった。得られた熱分解ガスの組成を表６に示す。 <Example 3>
With the preheating temperature of the heat carrying medium set to 700 ° C. and the temperature of the pyrolyzer set to 690 ° C., 140 ° C. steam and 40 ° C. oxygen gas were blown. At this time, the flow rates of oxygen gas and steam to the pyrolyzer were 1.71 Nm 3 / h and 5.49 kg / h, respectively, and the molar ratio of steam / oxygen gas was 4.0. Table 6 shows the composition of the obtained pyrolysis gas.
熱担持媒体の予熱温度を７００℃とし、熱分解器の温度を６９０℃として、１４０℃の水蒸気と４０℃酸素ガスを吹込んだ。このとき、熱分解器への酸素ガス、蒸気流量は、それぞれ、１．７１Ｎｍ3／ｈ、５．４９ｋｇ／ｈであり、水蒸気／酸素ガスのモル比は、４．０であった。得られた熱分解ガスの組成を表６に示す。 <Example 3>
With the preheating temperature of the heat carrying medium set to 700 ° C. and the temperature of the pyrolyzer set to 690 ° C., 140 ° C. steam and 40 ° C. oxygen gas were blown. At this time, the flow rates of oxygen gas and steam to the pyrolyzer were 1.71 Nm 3 / h and 5.49 kg / h, respectively, and the molar ratio of steam / oxygen gas was 4.0. Table 6 shows the composition of the obtained pyrolysis gas.
実施例２と実施例３とを比較すると、水蒸気／酸素ガスのモル比が高い方が、酸素ガス流量の変動に対して熱分解反応温度の変動を抑えることができ、酸素ガス流量の変動に起因する温度変化の過敏性が改善されるといえる。
Comparing Example 2 with Example 3, the higher the molar ratio of water vapor / oxygen gas, the more the fluctuation of the pyrolysis reaction temperature can be suppressed with respect to the fluctuation of the oxygen gas flow rate. It can be said that the sensitivity of the resulting temperature change is improved.
今回開示された実施の形態はあらゆる点で例示であって、制限的なものではないと考えるべきである。本発明の範囲は前記した実施の形態ではなく、特許請求の範囲によって示され、特許請求の範囲に記載された事項の均等の範囲の全ての変更が含まれる。
実 施 The embodiments disclosed this time are illustrative in all aspects and should not be considered as restrictive. The scope of the present invention is defined by the terms of the claims, rather than the embodiments described above, and includes all modifications within the scope of equivalents of the subject matter recited in the claims.
１ バイオマス原料
２ バイオマス原料搬送装置
３ 予熱器
４ 熱分解器
５ 改質器
６ チャー分離装置
７ 酸素ガス
８ 水蒸気
９ 酸素ガス
１０ 水蒸気
１１ 熱分解ガス
１２ 熱分解ガスの一部
１３ 粗改質ガス
１４ 精製改質ガス
１５ 製品純水素ガス
１６ オフガス
１７ チャー
１８ チャーの一部
１９ 燃焼排ガス
２０ 燃焼排ガス
２１ 粗改質ガス冷却・精製装置
２２ 水素分離装置
２３ 燃焼炉
２４ 熱担持媒体
２５ 弁
２６ 弁
２７ 熱担持媒体循環装置 DESCRIPTION OF SYMBOLS 1 Biomassraw material 2 Biomass raw material transport apparatus 3 Preheater 4 Thermal decomposer 5 Reformer 6 Char separation device 7 Oxygen gas 8 Steam 9 Oxygen gas 10 Steam 11 Pyrolysis gas 12 Part of pyrolysis gas 13 Crude reformed gas 14 Refined reformed gas 15 Product pure hydrogen gas 16 Offgas 17 Char 18 Part of char 19 Combustion exhaust gas 20 Combustion exhaust gas 21 Crude reformed gas cooling / refining device 22 Hydrogen separator 23 Combustion furnace 24 Heat carrier medium 25 Valve 26 Valve 27 Heat Carrying medium circulation device
２ バイオマス原料搬送装置
３ 予熱器
４ 熱分解器
５ 改質器
６ チャー分離装置
７ 酸素ガス
８ 水蒸気
９ 酸素ガス
１０ 水蒸気
１１ 熱分解ガス
１２ 熱分解ガスの一部
１３ 粗改質ガス
１４ 精製改質ガス
１５ 製品純水素ガス
１６ オフガス
１７ チャー
１８ チャーの一部
１９ 燃焼排ガス
２０ 燃焼排ガス
２１ 粗改質ガス冷却・精製装置
２２ 水素分離装置
２３ 燃焼炉
２４ 熱担持媒体
２５ 弁
２６ 弁
２７ 熱担持媒体循環装置 DESCRIPTION OF SYMBOLS 1 Biomass
Claims (3)
- 熱担持媒体を供給してバイオマス原料から熱分解ガスを得る熱分解工程、及び、
該熱分解ガスを昇温させて水素に富む改質ガスを得る改質工程、
を有し、
前記熱分解工程における前記熱担持媒体は６８０～７４０℃に加熱されており、
前記熱分解工程では、さらに、水蒸気と酸素ガスを同時供給して熱分解反応温度を６４０～７４０℃とし、
前記改質工程では、水蒸気と酸素ガスを同時供給し、
前記熱担持媒体は前記改質工程には供給されないこと、
を特徴とするバイオマスを原料とする水素製造方法。 A pyrolysis step of supplying a heat-carrying medium to obtain a pyrolysis gas from the biomass raw material, and
A reforming step of raising the temperature of the pyrolysis gas to obtain a hydrogen-rich reformed gas,
Has,
The heat carrying medium in the pyrolysis step is heated to 680 to 740 ° C.,
In the pyrolysis step, steam and oxygen gas are supplied simultaneously to set the pyrolysis reaction temperature to 640 to 740 ° C.
In the reforming step, steam and oxygen gas are simultaneously supplied,
The heat carrying medium is not supplied to the reforming step,
A method for producing hydrogen using biomass as a raw material. - 前記熱分解工程において、同時供給する水蒸気と酸素ガスの水蒸気のモル／酸素ガスのモルが１～４であることを特徴とする請求項１に記載のバイオマスを原料とする水素製造方法。 (4) The method for producing hydrogen using biomass as a raw material according to (1), wherein in the thermal decomposition step, moles of steam and oxygen gas of steam and oxygen gas supplied simultaneously are 1 to 4.
- 前記熱分解工程の熱分解反応温度が６６０～７００℃であることを特徴とする請求項１または請求項２に記載のバイオマスを原料とする水素製造方法。
The method for producing hydrogen using biomass as a raw material according to claim 1, wherein the pyrolysis reaction temperature in the pyrolysis step is 660 to 700 ° C.
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| WO2021221164A1 (en) * | 2020-04-30 | 2021-11-04 | 株式会社ジャパンブルーエナジー | Biomass gasification device |
| US20220002152A1 (en) * | 2020-07-01 | 2022-01-06 | James E. Klepper | System and method for making syngas |
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