WO2020008621A1 - Méthode de production d'hydrogène à l'aide de biomasse en tant que matière première - Google Patents

Méthode de production d'hydrogène à l'aide de biomasse en tant que matière première Download PDF

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WO2020008621A1
WO2020008621A1 PCT/JP2018/025701 JP2018025701W WO2020008621A1 WO 2020008621 A1 WO2020008621 A1 WO 2020008621A1 JP 2018025701 W JP2018025701 W JP 2018025701W WO 2020008621 A1 WO2020008621 A1 WO 2020008621A1
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gas
raw material
outer cylinder
combustion
pyrolysis gas
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English (en)
Japanese (ja)
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俊一 内藤
白水　渡
和幸 原田
後藤　賢一
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株式会社 翼エンジニアリングサービス
俊一 内藤
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Priority to PCT/JP2018/025701 priority Critical patent/WO2020008621A1/fr
Priority to CN201880095346.0A priority patent/CN112368236B/zh
Priority to JP2019513470A priority patent/JP6590359B1/ja
Publication of WO2020008621A1 publication Critical patent/WO2020008621A1/fr

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    • C—CHEMISTRY; METALLURGY
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    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/28—Other processes
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    • 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
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    • 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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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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
    • C10K3/001—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 by thermal treatment
    • C10K3/003—Reducing the tar content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10K3/001—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 by thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/006—Reducing the tar content by steam reforming
    • 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
    • C10K3/001—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 by thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/008—Reducing the tar content by cracking
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/0465—Composition of the impurity
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/0465—Composition of the impurity
    • C01B2203/049—Composition of the impurity the impurity being carbon
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    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
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    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
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    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C10B57/10—Drying
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to a method for producing hydrogen using biomass as a raw material.
  • Biomass combustion power generation Biomass is directly burned, and steam is generated using this combustion heat, and power is generated by this steam.
  • Biomass gasification power generation Combustible pyrolysis gas is generated from biomass raw material, and power is generated using this gas as fuel.
  • This method has advantages such as low generation of greenhouse gas (N 2 O: nitrous oxide and the like) and low generation of DXN (dioxin), (1) Tar generated during thermal decomposition causes blockage of downstream piping, making it difficult to continue continuous operation (Global Environmental Symposium Proceedings, 13 (2005), 225), (2) It requires a lot of energy to dry the biomass raw material, (3) In the power generation by the gas engine, maintenance is complicated due to the presence of tar, and the recovery of hydrogen cannot be stably performed due to the clogging of equipment due to tar and the trouble of cleaning. And there was a problem.
  • the first problem is a technical problem that must be solved, but the second problem is an economic problem, and it is preferable to solve it.
  • First problem When pyrolyzing a biomass raw material, tar is contained in a pyrolysis gas, and this tar blocks a pipe of a downstream (backstream) plant, so that the plant cannot be operated stably.
  • Second problem The cost for drying the biomass raw material is high, and commercial application is difficult.
  • Patent Document 1 In order to solve the first problem, when the removal of tar from biomass raw materials described in Patent Documents 1 to 4 is examined, there are the following problems.
  • the tar removal method described in Patent Document 1 requires a new vertical shaft furnace separately, and since only oxidizing gas is blown, hydrogen is burned, so that only a small amount of hydrogen can be recovered, and a large amount of hydrogen can be recovered. Had the problem of being difficult.
  • the temperature inside the retort is set to a temperature (600 ° C.) required to exceed the normal operating temperature and to remove tar in order to suppress the volatilization and disappearance of organic combustible components.
  • the purpose is to temporarily raise the tar several times a day until the tar is peeled off from the inner wall of the inner cylinder to reduce the tar discharging work.
  • the present invention generates a pyrolysis gas having a first tar in an inner cylinder, guides the gas to an outer cylinder, and regulates the outer cylinder temperature by blowing a specified amount of steam and oxygen. It controls the temperature within the temperature, produces a second pyrolysis gas without tar, prevents clogging in the latter stage, and enables stable recovery of hydrogen gas. to differ greatly.
  • the method for removing tar from organic raw materials described in Patent Documents 1 to 4 does not solve the first problem, and removes tar from a pyrolysis gas. It is difficult to stably recover the purpose of collecting hydrogen gas.
  • the second object of the present invention is to improve the economic efficiency by a method in which a part of the second pyrolysis gas is introduced into a combustion chamber and the produced combustion exhaust gas is directly or indirectly used as a heat source for drying the raw material.
  • a raw material drying step of drying the raw material by a raw material dryer (2) a raw material drying step of drying the raw material by a raw material dryer; A material supply step of supplying a raw material having passed through the raw material drying step to the inner cylinder of an external combustion rotary kiln having an inner cylinder and an outer cylinder, A step of thermally decomposing the raw material supplied to the inner cylinder in the inner cylinder by heat of the outer cylinder to generate a first pyrolysis gas; A step of introducing the first pyrolysis gas into the outer cylinder to introduce the first pyrolysis gas into the outer cylinder; A step of decomposing tar in the first pyrolysis gas with the outer cylinder to obtain a second pyrolysis gas; Removing the second pyrolysis gas from the outer cylinder and introducing it to a reforming furnace and a combustion furnace; A reforming step of increasing the gas temperature of the reforming furnace to obtain a crude reformed gas having an increased hydrogen content from the second pyrolysis gas; A hydrogen recovery
  • a raw material drying step of drying the raw material by a raw material dryer A raw material supply step of supplying a dry raw material having passed through the raw material drying step to the inner cylinder of an external combustion type rotary kiln;
  • a first outer cylinder is provided on an inlet side of the inner cylinder and an at least one second outer cylinder is provided on an outlet side of the inner cylinder outside the inner cylinder of the external combustion rotary kiln, and the dry raw material supplied to the inner cylinder is provided.
  • Combustion process to obtain combustion exhaust gas by burning in Has, Part of the combustion exhaust gas is introduced into the first outer cylinder, Heating the kiln inner cylinder, After the other part of the combustion exhaust gas is heated to the remaining part of the drying circulating gas, which is charged into the raw material dryer and used for circulation, Gather with a part of the combustion gas, Surplus flue gas boilers produce steam for power generation by steam turbine generators, which are released to the atmosphere, A method for producing hydrogen using biomass as a raw material.
  • a raw material drying step of drying the raw material by a raw material dryer A raw material supply step of supplying a dry raw material having passed through the raw material drying step to the inner cylinder of an external combustion type rotary kiln;
  • a first outer cylinder is provided on an inlet side of the inner cylinder and an at least one second outer cylinder is provided on an outlet side of the inner cylinder outside the inner cylinder of the external combustion rotary kiln, and the dry raw material supplied to the inner cylinder is provided.
  • Combustion process to obtain combustion exhaust gas by combustion, Has, Part of the combustion exhaust gas is introduced into the first outer cylinder, The kiln inner wall is heated, and the remaining portion of the combustion exhaust gas that is introduced into the exhaust gas side pipe of the raw material dryer is partially charged into the raw material dryer, The remainder is used in a surplus flue gas boiler to use steam for power generation by a steam turbine generator for production, and then discharged to the atmosphere to discharge the humidifier of the dryer to the outside of the system.
  • a raw material drying step of drying the raw material A material supply step of supplying a dried raw material having passed through the raw material drying step to the inner cylinder of an external combustion type rotary kiln;
  • a first outer cylinder is provided on an inlet side of the inner cylinder and an at least one second outer cylinder is provided on an outlet side of the inner cylinder outside the inner cylinder of the external combustion rotary kiln, and the dry raw material supplied to the inner cylinder is provided.
  • the tar contained in the first pyrolysis gas can be completely decomposed in the nearest outer cylinder, and the second pyrolysis gas obtained by decomposing the tar, that is, no tar is obtained from the biomass raw material. Since the pyrolysis gas can be obtained stably and efficiently over a long period of time, stable recovery of hydrogen can be realized in a reforming furnace in which the temperature is increased and the amount of hydrogen is increased. Further, regarding the second problem, efficient drying of the raw material having a high moisture content can be achieved by utilizing waste heat of the combustion exhaust gas 90 obtained by burning the second pyrolysis gas in the combustion furnace 8.
  • biomass raw material 30 used in one embodiment of the present invention is derived from living organisms such as sewage sludge, thinned wood, driftwood, wood pellets, straw pellets, paper sludge, garbage compost sludge, food waste, and sludge. Any type may be used as long as it contains carbon, hydrogen, and oxygen, but sewage sludge is more preferable because of availability and ease of securing the amount. Further, the raw material may be a mixture of plural types of biomass. Also, waste plastics may be included in biomass as a raw material (a biomass mixture or waste plastic 95 can be supplied together with the biomass raw material 30 as shown in FIG.
  • the size of the raw material may be a size that has undergone coarse pulverization.
  • the shape may be an individual shape such as a plate shape or a rod shape, or may be a granular shape or a sludge shape.
  • the amount of water contained may vary depending on the shape, but may be up to 85% by mass.
  • the external-combustion rotary kiln 1 used in one embodiment of the present invention is provided with, for example, as shown in FIG.
  • the inner cylinder 2 rotates around its axis, and is provided with a plurality of discharge pipes 21B for discharging the pyrolysis gas to the outer cylinder 3 except for the central portion in the longitudinal direction of the inner cylinder 2;
  • Injection port 9 for injecting a combination of at least one of oxygen or air and water vapor into the outer sheath 3 made of coated steel sheet, and a pyrolysis gas (first pyrolysis gas) discharged through a discharge pipe 21B. Is further thermally decomposed to discharge the outer cylinder 3 to the outside.
  • the outer cylinder 3 may be divided into a plurality of parts (FIGS. 2, 3, and 4).
  • the material of the discharge pipe 21B and the inner cylinder is desirably made of a heat-resistant steel plate in terms of tar thermal decomposition and heat transfer performance, but other materials producing the same effect are also possible.
  • the exhaust pipe 21 ⁇ / b> B is for discharging the pyrolysis gas (first pyrolysis gas) generated in the inner cylinder 2 to the outer cylinder 3 immediately.
  • the shape may be such that only the pyrolysis gas (first pyrolysis gas) can be discharged to the outer cylinder 3 without the biomass itself, which is a biomass raw material, being discharged to the outer cylinder 3 as a solid.
  • powdered biomass powder accompanying the gas is allowed.
  • the raw material moves toward the outlet of the inner cylinder 2 according to the rotation of the inner cylinder 2, and the temperature gradually rises in this moving process to generate a pyrolysis gas (first pyrolysis gas).
  • the thermal decomposition temperature in the inner cylinder 2 is desirably 300 to less than 640 ° C. More preferably, the temperature is 300 to 590 ° C. The reason is that if the temperature is lower than 300 ° C., a large amount of carbide residue is generated and the amount of volatile gas is reduced from about 20% to about 40%. If the temperature exceeds 640 ° C., a large increase in pyrolysis gas cannot be expected, and the temperature exceeds 740 ° C. This is because the thermal decomposition gas does not increase while the heat load increases.
  • a plurality of discharge conduits 21B are provided at locations where the inner cylinder thermal decomposition temperature is in the range of 300 to less than 640 ° C., and when the outer cylinder 3 is divided into plural parts. (FIGS. 3 and 4) are provided at locations corresponding to the respective outer cylinders 5, at locations where the thermal decomposition temperature of the inner cylinder 2 is in the range of 300 ° C. to less than 640 ° C., respectively.
  • the outer cylinder 3 at least one of air and oxygen gas and steam are supplied in combination from the inlet 9 so that the temperature in the outer cylinder becomes 640 to 740 ° C., and the pyrolysis gas introduced from the discharge pipe 21 B is introduced.
  • the (first pyrolysis gas) is partially oxidized to decompose the tar component to obtain a pyrolysis gas (second pyrolysis gas).
  • the reason for setting the thermal decomposition temperature range is that if the temperature is lower than 640 ° C, tar cannot be decomposed. If the temperature is higher than 740 ° C, an excessive heat source is supplied for decomposing the tar component.
  • the temperature outside the inner cylinder 2 becomes extremely high, and the heat resistance required for the steel sheet constituting the inner cylinder 2 becomes excessive.
  • the upper limit of 740 ° C. it goes without saying that if the development of the heat-resistant temperature of general-purpose materials proceeds in the future, it can be raised to a higher temperature (around 790 ° C.).
  • FIGS. As the form in which the outer cylinder is divided into a plurality of parts, those shown in FIGS.
  • FIGS. As a typical example, in the form shown in FIG. 2, at least one of air or oxygen gas and steam is supplied to only the second outer cylinder 5 in combination, and the second outer cylinder 4 is supplied with the second outer cylinder 4.
  • a combustion exhaust gas (outlet gas of the combustion furnace) 90 obtained by burning the pyrolysis gas (second pyrolysis gas) taken out of the cylinder 5 in the combustion furnace, and a part of the combustion exhaust gas 93 are supplied from the branch 39 to the inner cylinder 2.
  • the amount of oxidizing agent used in the outer cylinder 5 can be reduced and the efficiency of hydrogen production can be increased. is there. This has the attendant effect of increasing the temperature in the low temperature region (such as the portion at 200 ° C. or lower) before the temperature of the raw material of the inner cylinder 2 is increased to the dew condensation temperature or higher, thereby preventing dew condensation corrosion.
  • the molar ratio of the water vapor and the oxygen gas component supplied to the outer cylinder 3 of FIG. 1 and the second outer cylinder 5 of FIGS. is preferably 0.4 to 4.
  • the reason for the lower limit of the molar ratio of the steam / oxygen gas component to be blown is that if the ratio is less than 0.4, the temperature of the blown oxygen is so high that the oxygen blowing portion is locally heated to a high temperature. This is because a uniform temperature rise over the entire outer cylinder 5 cannot be achieved.
  • the reason for the upper limit of 4 is that if it exceeds 4, steam becomes oxidizable at 600 ° C. or higher, and the CO 2 concentration increases, which is not preferable for hydrogen recovery.
  • the first pyrolysis gas containing tar generated in the inner cylinder 2 immediately moves to the outer cylinder 3 or the second outer cylinder 5 via the discharge pipe 21B, and 3 or the second outer cylinder 5 converts the gas into a second pyrolysis gas without tar.
  • the steam is desirably a high temperature steam.
  • Examples thereof include a steam having a temperature of 150 to 200 ° C. and superheated steam.
  • the oxygen gas is produced by, for example, room temperature air or an industrial oxygen generator. At least one of oxygen (for example, around 40 ° C.) can be used. In normal operation, it is preferable to use oxygen produced by a membrane or an oxygen generator using an adsorbent method.
  • one or more thermometers are installed in the inner cylinder 2 and the outer cylinder 3 in order to check temperature uniformity for use in temperature control.
  • a chamber 6 is provided at an outlet end of the inner cylinder 2, and a carbide residue 24 exposed to a temperature of 300 ° C. to less than 640 ° C. is collected from a lower portion thereof.
  • the temperature in the chamber 6 is supplied by combining at least one of air or oxygen gas and water vapor, and supplied from the nozzle 11 so that the molar number of water vapor / the molar number of oxygen gas component is 0.4 to 4. Can be.
  • the temperature in the chamber 6 can be controlled in a temperature range from 300 to less than 640 ° C.
  • the reason for the lower limit of the molar ratio of the steam / oxygen gas component to be blown is that if the ratio is less than 0.4, the temperature of the blown oxygen is so high that the oxygen blowing portion is locally heated to a high temperature. A uniform temperature rise over the entire outer cylinder 5 cannot be achieved.
  • the reason for the upper limit of 4 is that if it exceeds 4, steam becomes oxidizable at 600 ° C. or higher, and the CO 2 concentration increases, which is not preferable for hydrogen recovery.
  • the balance between the recovery of the carbide residue 24 and the gas recovery from the outer cylinder 3 and the second outer cylinder 5 via the discharge pipe 21B for the volatile gas should be adjusted. Can be.
  • the collected carbide residue 24 is used as a fuel for power generation outside, a fuel for the combustion furnace 8, an auxiliary fuel for the hot blast stove (auxiliary fuel or a second thermal decomposition gas blowing point 38), and a combustion gas waste heat boiler 51B (FIG.
  • the fuel of 4) can be used as fuel for the surplus flue gas boiler 110 (FIGS. 1, 2, and 3).
  • the pyrolysis gas in this chamber is exhausted to the outer cylinder 3 or the outer cylinder 5 via the discharge pipe 21B. 39C in the figure shows the outlet of the carbide residue.
  • the pyrolysis gas (second pyrolysis gas) pyrolyzed in the outer cylinder 3 of the external combustion type rotary kiln 1 is as follows: 1) new air from the combustion furnace air inlet 13 introduced into the combustion furnace in the second system; 2) A part or all of the humidified exhaust gas from the dryer for drying the raw material is mixed and burned to produce a combustion exhaust gas 90.
  • the illustrated gas inlet 92 to the combustion furnace indicates the inlet of the second pyrolysis gas to the combustion furnace 8. 3)
  • fresh air can be blown into the air that has been heat-exchanged and preheated by the combustion exhaust gas 93.
  • This combustion exhaust gas 93 can be used in the following 1) to 4), can be used as a drying heat source for each raw material, and can generate electric power using surplus combustion exhaust gas.
  • 1) Heat source for drying raw materials (Figs. 1, 2, 3, 4) 2) Steam is produced by the surplus flue gas boiler 110 (FIGS. 1, 2 and 3) or the combustion gas waste heat boiler 51B (FIG. 4) and supplied to the steam generator 111. (FIGS. 1, 2, 3, 4). 3) ⁇ Explanation of power generation using combustion exhaust gas>
  • Reference numeral 20 indicates water-steam which is a working fluid of the boiler.
  • FIGS. 1, 2, and 3 show steam which is a working fluid of the surplus flue gas boiler 110, and FIG.
  • Reference numeral 21 denotes a combustion exhaust gas inducing fan, which regulates and controls the pressure of the combustion furnace 8 by a valve not provided with an upstream number.
  • the surplus flue gas boiler 110 and the steam power generator 111 are not shown in FIGS. 1, 2, and 3, but may be installed by branching downstream of the cyclone 15. 4) As shown in FIG. 4, a part of the combustion exhaust gas 93 is branched at the branch 39, the temperature of the outer cylinder 4 is raised, and then connected to a line in front of the drying exhaust gas fan 42 of the dryer exhaust gas discharging line.
  • this connection point may be re-injected into the flue gas pipe 36C on the upstream side of the combustion gas exhaust heat boiler 51B.
  • the other portion of the flue gas which is obtained by branching the flue gas at the branch 39, produces steam using a 51B combustion gas waste heat boiler, and the dried raw material is dried using the steam 102.
  • the steam 102 obtained by indirectly drying the raw material 30 becomes drain and returns from the steam return line 103 to the drain recovery device 104.
  • the steam 102 may be partially blown directly into the raw material dryer 32 to loosen the raw material.
  • reference numeral 106 denotes an air blowing port for the dryer, which blows an amount determined in consideration of the amount of the exhaust pipe 23 and the set moisture at the dryer outlet.
  • the air preheated by the combustion exhaust gas can be used.
  • the pyrolysis gas (second pyrolysis gas) is sent from the outer cylinder 3 (FIG. 1) or the second outer cylinder 5 (FIGS. 2, 3, and 4) to the reforming furnace 7 and the combustion furnace 8, 2, 3 and 4, when there are two outer cylinders, a part of the combustion exhaust gas 93 of the combustion furnace is passed through the branch 39 as shown in FIGS.
  • the inner cylinder 2 is supplied to the outer cylinder (first outer cylinder) 4 on the inlet side of the inner cylinder, and the temperature of the inner cylinder 2 and the low-temperature region raw material are constantly raised to reduce the amount of oxygen used in the outer cylinder 5.
  • the combustion exhaust gas (* 5) after heating the outer cylinder 4 is returned to the combustion exhaust gas conduit 112. 3 and 4, it is returned to the upstream of the drying exhaust gas fan 42.
  • it may be returned to the flue gas conduit 88, and in FIG. 4, it may be returned to the line 36C (FIGS. 1, 2). , 3, 4).
  • the steam generated from the combustion exhaust gas allows excess steam that is used for drying to flow to the steam generator 111 to generate power.
  • FIG. 1 the combustion exhaust gas
  • the flue gas 93 can be exhausted by raising the temperature of the flue gas (B) 83 in the flue gas-dry circulation gas (B) heat exchanger 18.
  • the flue gas may be directly circulated from the conduit 88 to the raw material dryer 32 without passing through the flue gas-drying circulating gas (B) heat exchanger 18 (18 shown in FIG. 2).
  • the drying circulation exhaust gas 83 heated by the combustion exhaust gas-drying circulation gas (B) heat exchanger 18 is recycled to the raw material dryer 32 via a pipe 88 in each case. It is circulated and used for drying raw materials.
  • the gas temperature of the reforming furnace 7 is desirably 900 to 1100 ° C.
  • oxygen gas and steam are supplied into the reforming furnace 7 from below the reforming furnace 7.
  • the steam and oxygen gas supplied to the reforming furnace 7 preferably have a molar ratio of steam / oxygen gas (mol number of steam / mol number of oxygen gas component) of 0.4 to 4. .
  • the reason for this is that if it is less than 0.4, the temperature of the oxygen blowing portion becomes locally high due to the temperature sensitivity due to the oxygen being blown, and the uniform temperature increase over the entire reforming furnace 7 cannot be achieved.
  • the temperature of the reforming furnace 7 is preferably from 900 ° C. to 1100 ° C. More preferably, it is 1000 to 1050 ° C.
  • the reason why the temperature is more preferably 1000 ° C. or more is that the steam reforming reaction and the shift reaction below become dominant at 1000 ° C. or more and the amount of CO increases, and the upper limit of 1100 ° C. is that the heat load is too high. This is because the amount of oxygen blown for increasing the temperature increases, and the amount of recovered hydrogen decreases.
  • the concentration of H 2 gas increases.
  • Typical steam reforming reaction CH 4 + H 2 O ⁇ CO + 3H 2 Shift reaction: CO + H 2 O ⁇ CO 2 + H 2
  • the typical steam reforming reaction proceeds when the residence time in the reforming furnace 7 is 2 seconds or more, for example, 2.5 to 3 seconds.
  • the crude reformed gas 50 thus obtained has a H 2 gas content of 50 to 54% by volume (dry basis). It is to be noted that the supply of steam is performed not only to advance the steam reforming reaction, but also to alleviate the above-mentioned temperature sensitivity (rapid rise in temperature due to oxygen injection).
  • the reformed gas cooler 53 to the activated carbon adsorption treatment device 56B, 81 and 80 are collectively referred to as a reformed gas gas treatment device 53B.
  • the reformed gas processing apparatus 53B will be described in detail with reference to FIG. 1, but the same applies to other drawings.
  • the reformed gas processing device 53B can be configured by a conventionally known technique, and after being subjected to water spray cooling 84 by the reformed gas cooler 53 and dust removal by the reformed gas bag filter 54, each device (the acid gas processing device 55, In the alkaline gas treatment device 56 and the activated carbon adsorption treatment device 56B), removal processing of trace harmful components such as HCl, CN, and NH 3 is performed.
  • each removal process is illustrated only briefly, it can be performed by appropriately combining conventionally known techniques.
  • water containing a small amount of tar is separated by a separation water pot 80 and transferred to a wastewater treatment 81 in case of emergency.
  • the crude reformed gas that has passed through the reformed gas processing device 53B is first heated by the reformed gas heater 57 by the steam 58. This has a function of preventing naphthalene and the like from being deposited in the gas due to a pressure drop and a temperature drop downstream of the CO 2 recovery device 60, the crude hydrogen gas compressor 61, the hydrogen separation device 70, and the like. Then, the pressure of the reforming furnace 7 and the outer cylinder 3 (or the second outer cylinder 5 in FIGS. 2, 3 and 4) is increased by the crude reforming gas inducing fan 59 by the pressure control valve 59B.
  • the crude reformed gas is sent to the hydrogen separator 70 side while controlling based on the detection data of the control detector.
  • CO 2 when the S content in the raw material is 0.2% by mass or less (dry base), CO 2 can be economically recovered from the crude reformed gas by the CO 2 recovery device 60 before hydrogen recovery. It is possible. However, when the S content exceeds 0.2% by mass (dry basis), it is preferable not to perform CO 2 recovery in consideration of economy.
  • the recovered CO 2 may be used for promoting plant growth.
  • the CO 2 recovery from the crude reformed gas can be achieved by a well-known technique, such as an amine absorption method or PSA (using an adsorbent such as zeolite), although not shown in detail.
  • the hydrogen separator 57B 1, 2, 3, and 4 from the reformed gas heater 57 to the point before the product pure hydrogen 77 are collectively referred to as a hydrogen separator 57B.
  • the crude reformed gas is compressed by the crude hydrogen gas compressor 61, and is introduced into the hydrogen separator 70, where the offgas 71 is separated to obtain the product pure hydrogen 77.
  • the hydrogen separation device 70 may employ a known technique, for example, a hydrogen PSA.
  • the entire device from the off-gas storage tank 72 for storing the off-gas 71 in the gas engine / off-gas device 72B to the flare stack 74 is shown.
  • the off-gas 71 from which hydrogen has been recovered by the hydrogen separator 70 contains a CO component and the remaining hydrogen component of the recovered hydrogen component, and thus can be used as fuel for a gas engine.
  • the fuel was able to generate 94-167 kW / 206 kg of raw material / hr-DRY.
  • the auxiliary fuel 38 is supplied to the auxiliary fuel 38 for direct heating and indirect heating for drying the raw material, the auxiliary burner fuel 14 of the combustion furnace 8, and the hot blast furnace 35.
  • the auxiliary fuel 38 can be used when the raw material to be dried and dried has a large amount of water.
  • the off-gas 71 is temporarily stored in an off-gas storage tank 72, and is boosted in pressure by an off-gas high-pressure compressor 73 to be supplied to a gas engine generator 75 to generate electric power in preparation for the average use of production off-gas.
  • the case where the off-gas 76 is used in an auxiliary burner or the like is also exemplified by the off-gas 76 in the figure.
  • the flare stack 74 is for combustion exhaust when off-gas is not used.
  • the temperature of the combustion furnace 8 is more preferably 850 to 900 ° C., and the residence time is more preferably 2.5 seconds or more. At this time, since the second pyrolysis gas that has been pyrolyzed at 740 ° C.
  • the combustion furnace uses: 1) Even when burning at a high temperature of 850 to 900 ° C., there is no volatilization of phosphorus (P 2 O 5 ) or the like, and there is no problem of blockage in the wake. 2) Since combustible gas is burned in a reducing atmosphere, DXN (dioxin) generation is small. 3) The generation of greenhouse gas (N 2 O: nitrous oxide) is low because it is pyrolyzed at low temperature and burned at high temperature after pyrolysis. This has the effect. In the combustion furnace 8, air is introduced from the combustion furnace air inlet 13 to burn the pyrolysis gas (second pyrolysis gas). The use of the combustion furnace auxiliary burner fuel 14 during startup is permitted regardless of the essence of the present invention.
  • the outlet gas (combustion exhaust gas) 90 of the combustion furnace discharged from the combustion furnace 8 is a heat source for indirectly heating the dryer circulation gas (B) 83. That is, the flue gas 90 passes through the flue gas cyclone 15, passes through the flue gas-drying circulating gas (B) heat exchanger 18, passes through the surplus flue gas boiler 110, and passes through the known environmentally harmful substance removing means 22. The exhaust gas is exhausted to the atmosphere through the exhaust pipe 23.
  • the boiler working fluid (water-steam) 20 manufactured here generates electric power in the power generation device 111.
  • the flue gas-drying circulation gas (B) heat exchanger 18 indirectly heats the dryer circulation gas (B) 83 to serve as a heat source for drying the raw material.
  • the combustion gas-air heat exchanger 16 heats the air taken in from the air inlet 17 with the gas obtained by branching the combustion exhaust gas 93 at the branch 39, and blows it into the hot stove 35 via the hot stove fan 37. .
  • heated air is blown into the hot stove 35 from the heated air blowing port 36B, but the hot stove burner 36 is used as an auxiliary only at startup and when the moisture evaporation energy in the raw material dryer 32 is insufficient. I do.
  • the auxiliary combustion fuel or the second pyrolysis gas can be supplied to the hot blast stove burner 36 by extracting a part of the auxiliary combustion fuel or the second pyrolysis gas, not shown, from the gas exhaust pipe 21C. Alternatively, it can be blown using the off gas 76.
  • a heating gas of substantially the same amount as the amount exhausted by the exhaust pipe 23 is injected into the conduit 88 of the drying circulation gas (B) 83. That is, moisture is exhausted by the exhaust pipe 23, and a heated gas with little moisture is blown into the raw material dryer 32 from the outlet 88 of the hot stove 35 from the conduit 88 of the drying circulation gas (B) 83 before the raw material dryer 32. It is also possible to supply the branch gas at the branch 39 of the combustion exhaust gas 93 introduced into the combustion gas-air heat exchanger 16 between the drying exhaust gas cyclone 40 and the drying exhaust gas bag filter 41. This is shown in FIGS.
  • the raw material dryer exhaust gas has a higher drying efficiency when the outlet temperature is low, and mixes a high-temperature gas in front of the dry exhaust gas bag filter 41 to raise the temperature of the dryer outlet gas 89, so that the dry exhaust gas Corrosion due to low-temperature condensation in the bag filter 41 can be prevented.
  • the biomass raw material 30 is supplied to the dewatering raw material hopper 31 and, via the raw material dryer 32, becomes a dry raw material 33 having a water content of, for example, 80% by mass to 20% by mass, and is supplied to the dry raw material supply hopper 34.
  • the outlet gas of the raw material dryer 32 that is, the dryer outlet gas 89 flows to the pipe 86 and is introduced into the combustion furnace at the branch point into the dryer circulation gas (A) 82 and the dryer circulation gas ( B) Branch to 83.
  • the dryer circulating gas (B) 83 is clockwise (clockwise) starting from the branch point, and in this order, the combustion gas-dry circulating gas (B) heat exchanger 18, the raw material dryer 32, the drying exhaust gas cyclone 40, The circulating gas returns to the branch point via the drying exhaust gas bag filter 41 and the drying exhaust gas fan 42.
  • the combustion exhaust gas 90 discharged from the combustion furnace 8 is used as the following heat source as the combustion exhaust gas 93 having passed through the combustion gas cyclone 15. 1) After passing through the combustion gas cyclone 15, a part of the gas is blown in a branch 39 in front of a dry exhaust gas filter 41 that takes the dust of the dry circulating gas, and the temperature of the dryer outlet gas 89 is increased to thereby increase the dry exhaust gas filter.
  • Heat source for producing steam for drying raw materials in combustion gas exhaust heat boiler 51B (FIG. 4) 7)
  • the heat source is introduced into the first outer cylinder 4 from the branch 39 to raise the temperature of the steel shell and the raw material of the inner cylinder to reduce the amount of oxygen used in the outer cylinder and improve the efficiency of hydrogen recovery (FIGS. 2, 3). 4)
  • the particles collected from the dry exhaust gas cyclone 40 and the dry exhaust gas bag filter 41 are organic substances, and thus are sent to the dewatering material hopper 31.
  • a part of the pyrolysis gas (second pyrolysis gas) generated from the outer cylinder 3 and the second outer cylinder 5 may be used as the fuel 38 of the hot stove burner 36 of the hot stove 35.
  • a part of the combustion exhaust gas 93 is branched at the branch 39, and is the same up to the combustion gas-air heat exchanger 16, but after passing through the heat exchanger, the first portion of the external combustion type rotary kiln 1.
  • the configuration is changed in such a way that it is introduced into the outer cylinder 4 and used as a heat source for the steel plate and the raw material of the inner cylinder 2 and then re-entered into the pipeline 112 in front of the combustion exhaust gas induction fan 21.
  • the discharge pipe 21B is arranged only between the inner cylinder and the second outer cylinder 5.
  • the second pyrolysis gas is generated only in the second outer cylinder 5.
  • Other configurations are the same as those in FIG.
  • the wall temperature of the inner cylinder 2 near the inner cylinder inlet and the temperature of the raw material in the inner cylinder can be increased, and the amount of oxygen used in the outer cylinder 5 can be reduced. Since it can be reduced, the efficiency of hydrogen recovery can be improved.
  • the steel sheet serving as a low-temperature portion at the beginning of the supply of the raw material of the inner cylinder 2 does not cool down, it is possible to prevent the raw material from being placed in a low temperature range (180 ° C.
  • FIG. 3 differs from FIG. 2 in the following points.
  • the dryer circulation gas is branched into two, and the dryer circulation exhaust gas B is heated by the heat exchanger 18 and circulated to the raw material dryer 32.
  • the whole is injected into the combustion furnace and the combustion exhaust gas 93 is directly injected into the raw material dryer 32.
  • Oxygen required for generating the second pyrolysis gas in the outer cylinder 5 is the temperature rise due to the partial combustion carried by oxygen, because the heat from the outer cylinder 4 heats the raw material and the inner cylinder steel plate. Therefore, the amount of oxygen used is reduced and the recovery rate of the hydrogen component is increased.
  • the steam generator 111 using the combustion exhaust gas may be provided by branching at the pipe 93 (the downstream side of the combustion exhaust gas cyclone 15) or provided after branching to the raw material dryer 32. It becomes.
  • FIG. 4 steam is produced in the combustion gas waste heat boiler 51B using the combustion exhaust gas, and the raw material is dried with the steam.
  • the surplus combustion exhaust gas boiler 110 is provided, but in the embodiment shown in FIG. 4, the function of the surplus combustion exhaust gas boiler 110 in FIG.
  • the raw material is mainly indirectly heated by steam, but a small amount of steam can be directly blown to loosen the raw material.
  • the amount of exhaust gas from the raw material dryer 32 which is dried by the steam-using method shown in FIG. 4 has the advantage of being reduced to about ⁇ , but since there is much moisture, a scrubber is used instead of the cyclone 40 and the bag filter 41 shown in the figure. You can do it. In that case, wastewater treatment occurs and joins with the wastewater treatment 81 in FIG. This scrubber can eliminate harmful gas components such as HCl, but has the disadvantage of losing the heat of the dry circulating gas and has the advantage of reducing the amount of processing gas.
  • reference numeral 111 denotes a steam generator using surplus steam.
  • the biomass raw material commonly used in Examples and Comparative Examples is sewage sludge, which is as follows. Supply amount: 1720 kg / hr Water content: 80% by mass (however, dried to 20% by mass by the raw material dryer 32) Tables 1 and 2 show the results of the raw material dewatered sludge analysis (analysis of ash, volatile matter and fixed carbon ratio) and the raw material dewatered sludge elemental analysis, respectively.
  • Example 1, 1-1 and Comparative Example 1 Temperature of outer cylinder>
  • the sewage sludge was supplied to the inner cylinder 2 of the external combustion type rotary kiln 1.
  • the case of 600 ° C. which is less than the lower limit of the specified value of one embodiment of the present invention
  • Example 1-1 shows a case where the upper limit of the specified value of one embodiment of the present invention is 740 ° C.
  • Table 3 shows the amount of water vapor and oxygen blown into the outer cylinder 3 of the external combustion type rotary kiln 1 in each of the above examples. I do.
  • Example 1 which satisfies the temperature range of the outer cylinder 3 of the external combustion type rotary kiln defined in one embodiment of the present invention, shows that the pyrolysis gas (No. The amount of tar (in the outer cylinder) in (2 pyrolysis gas) is less than the detection limit of less than 0.001 g / Nm 3 .
  • Comparative Example 1 in which the outer cylinder temperature is 600 ° C., which is less than the lower limit of 640 ° C. specified in one embodiment of the present invention, tar remains in the outer cylinder 3 remarkably.
  • Example 1-1 where the outer cylinder temperature is the upper limit of 740 ° C.
  • the tar amount in the outer cylinder is below the detection limit as in Example 1, but the creep rupture of the inner cylinder steel plate It has a strength of 20 Mpa at 740 ° C. in SUS310S (creep strength at a rupture time of 5 to 10 hours), and creep rupture strength under operating conditions at 740 ° C. even for high-grade materials such as high oxidation-resistant austenitic stainless steel ASTM NUSS 31060. Is 40 Mpa (creep strength when the rupture time is 10 5 hr), 740 ° C. is close to the boundary where long-term operation is possible from the viewpoint of high-temperature strength. In Example 1 and Example 1-1, approximately 52% by volume (dry base) of hydrogen gas was obtained in the reformed gas.
  • Example 2 a preferred example within the molar ratio regulation of the present invention, the molar ratio was 1.99, In Example 2-1, the lower limit of the molar ratio of the present invention was set to 0.4, In Example 2-2, the molar ratio of the present invention was set at 3.91, which is near the upper limit of 4; Table 4 shows the results (temperature control sensitivity (outer cylinder temperature change), pyrolysis gas component and amount in outer cylinder 3).
  • Example 2 the sewage sludge was supplied to the inner cylinder 2 of the external combustion type rotary kiln 1.
  • FIG. 9 is a graph showing the change in the thermal decomposition temperature of the outer cylinder 3 with respect to the change in the oxygen gas flow rate in 2-1) and 4 (Example 2-2).
  • the higher the molar ratio the more the sensitivity (temperature change of the outer cylinder) of the temperature change caused by the fluctuation of the oxygen gas flow rate is improved.
  • the sensitivity is improved, but the oxygen blowing amount is increased.
  • the lower limit of the molar ratio is 0.4 (Example 2-1), the sensitivity is deteriorated, but the oxygen blowing amount is reduced.
  • the upper and lower limits of the molar ratio were determined from these two balances.
  • Example 3 and Examples 3-1 and 3-2 Temperature of outer cylinder and control temperature of reforming furnace> Example 1 was described as Example 3, and Examples 3-1 and 3-2 were compared under the following conditions. That is, in the embodiment shown in FIG. 1, the sewage sludge was supplied to the inner cylinder 2 of the external combustion type rotary kiln 1. In Examples 3, 3-1, and 3-2, the outer cylinder 3 commonly thermally decomposes at the preferred control temperature of 650 ° C. of the present invention, but the temperature of the reforming furnace is different. In the case of the reforming furnace temperature of 1050 ° C. which is more preferable in the range specified by the present invention in Example 3, Example 3-1 is the case of the lower limit of 900 ° C. specified in the present invention, Example 3-2 is a case where the upper limit specified by the present invention is 1100 ° C., And the results are shown in Table 5.
  • the thermal decomposition temperature in the outer cylinder is 650 ° C. in Example 3 and Examples 3-1 and 3-2, the amount and composition of the thermal decomposition gas are the same.
  • the lower limit of the reforming furnace reaction temperature of one embodiment of the present invention is 900 ° C. in Example 3-1, and the upper limit of the reforming furnace reaction temperature is 1100 ° C. in Example 3-2. From this result, it was confirmed that the hydrogen component can be recovered at a reforming furnace temperature of 900 to 1100 ° C. with a yield of about 50 to 53% by volume. In addition, it was found that the vicinity of 1050 ° C. in Example 3 was desirable from both aspects of yield and energy consumption.
  • Example 4 Use of off-gas>
  • the pyrolysis gas obtained in Example 1 was supplied to the reforming furnace 7 to obtain a crude reformed gas, which was then cooled and dust-removed to remove trace harmful components such as HCl, CN, and NH 3.
  • a hydrogen separator to separate off-gas. Table 6 shows the composition of this off-gas.
  • this off-gas has a calorific value of 2,616 kcal / Nm 3 , it is possible to generate 94 to 167 kW / raw material 206 kg / hr-Dry using a gas engine (generating from raw material sewage sludge 344 kg / hr-Dry).
  • a gas engine generating from raw material sewage sludge 344 kg / hr-Dry.
  • hydrogen is produced from the reformed gas at 60% of the second pyrolysis gas and the off-gas is used).
  • it can be used as a fuel 14 for a combustion furnace auxiliary burner of the combustion furnace 8.
  • Example 5 uses the second pyrolysis gas generated in Example 1 to reduce the amount of auxiliary fuel for drying the raw material, and Comparative Example 5 (where the second pyrolysis gas is not used as a heat source). Compared. As described above, in one embodiment of the present invention, in the flue gas-drying circulating gas (B) heat exchanger 18, the flue gas 93 indirectly heats the dryer circulating gas (B) 83 to produce biomass as a raw material. Since it is a heat source for drying (water content is set to 20% by mass), the amount of auxiliary fuel in the hot blast stove 35 for this drying is reduced by an example of operating conditions (Example 1).
  • Example 5 This is compared with the case where 100% of the second pyrolysis gas generated in (2) is used (Example 5) and the comparative example 5 in which indirect heating is not performed in the flue gas-drying circulation gas (B) heat exchanger 18.
  • Table 7 shows the results.

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Abstract

L'invention concerne une méthode de production d'hydrogène à partir d'une matière première de biomasse, la méthode étant caractérisée en ce que : après la génération d'un premier gaz de pyrolyse dans un cylindre interne d'un four rotatif à combustion externe par la chaleur générée dans un cylindre externe du four rotatif à combustion externe et l'introduction d'une matière première de biomasse fournie au cylindre interne dans le cylindre externe, de la vapeur d'eau et au moins l'un parmi de l'oxygène et de l'air sont combinés dans le cylindre externe et introduits dans le cylindre externe de telle sorte que le rapport du nombre de moles de vapeur d'eau par rapport au nombre de moles de composant gazeux d'oxygène est de 0,4 à 4 ; la température à l'intérieur du cylindre externe est régulée entre 640 et 740°C pour obtenir un second gaz de pyrolyse ; une partie du second gaz de pyrolyse est introduite dans un four de reformage, la température dans le four de reformage est augmentée pour obtenir un gaz reformé brut ayant une teneur en hydrogène accrue, et l'hydrogène est récupéré ; et le reste du second gaz de pyrolyse est introduit dans un four de combustion, la matière première de biomasse est séchée à l'aide du gaz d'échappement de combustion en tant que source de chaleur, et le gaz d'échappement de combustion excédentaire est utilisé pour générer de l'énergie.
PCT/JP2018/025701 2018-07-06 2018-07-06 Méthode de production d'hydrogène à l'aide de biomasse en tant que matière première WO2020008621A1 (fr)

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