WO2017051610A1 - Moteur à combustion interne - Google Patents

Moteur à combustion interne Download PDF

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Publication number
WO2017051610A1
WO2017051610A1 PCT/JP2016/072581 JP2016072581W WO2017051610A1 WO 2017051610 A1 WO2017051610 A1 WO 2017051610A1 JP 2016072581 W JP2016072581 W JP 2016072581W WO 2017051610 A1 WO2017051610 A1 WO 2017051610A1
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Prior art keywords
internal combustion
combustion engine
fuel
gas
catalyst
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PCT/JP2016/072581
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English (en)
Japanese (ja)
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金枝　雅人
助川　義寛
重雄 幡宮
久幸 折田
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株式会社日立製作所
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Publication of WO2017051610A1 publication Critical patent/WO2017051610A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N5/00—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy
    • F01N5/02—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
    • F02M27/02—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like by catalysts
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a CO 2 recovery device and a recovery method for an internal combustion engine that reduce CO 2 emitted from an internal combustion engine represented by a passenger car or a diesel engine.
  • Patent Documents 1 and 2 As a method for reducing CO 2 emitted from the internal combustion engine, an attempt has been made to reduce CO 2 generated by improving the fuel consumption of the internal combustion engine. Furthermore, techniques for synthesizing fuel using a CO 2 obtained by separation and recovery of CO 2 generated is disclosed (Patent Documents 1 and 2).
  • Patent Document 1 describes that a CO 2 recovery means and a hydrogen supply means are provided, and fuel is synthesized using the recovered CO 2 as a raw material. Furthermore, the use of a CO 2 separation membrane as a CO 2 recovery means is also described. However, it is necessary to create a pressure difference on both sides of the membrane using a blower for CO 2 separation, and the required blower power is considered large.
  • Patent Document 2 describes a technology that includes a CO 2 separation unit and an H 2 supply unit and synthesizes methane using CO 2 discharged from a power generation facility. It is also described that a CO 2 separation membrane can be used as a CO 2 separation method. However, a specific CO 2 separation method using a separation membrane is not clearly described.
  • An object of the present invention can reduce the energy at the time of recovering the CO 2 discharged from the internal combustion engine, and more can be enhanced synthesis efficiency of the fuel with CO 2, the internal combustion engine the CO 2 recovery apparatus, the recovery It is to provide a method.
  • CO 2 emitted from an internal combustion engine can be recovered with low energy. Furthermore, it is possible to synthesize fuel using recovered CO 2 as a raw material and use it as fuel for internal combustion engines, so that it is possible to highly reduce fuel consumption and reduce CO 2 emissions associated with fuel consumption. Is possible.
  • a diagram showing the installation of a CO 2 separation membrane and a methanation catalyst to capture and methanate CO 2 in engine exhaust gas It is the figure which installed the heat exchanger in the engine exhaust gas flow path. It is the figure which installed the thermoelectric conversion element in the engine exhaust gas flow path. It is the figure which showed introducing into the engine the gas obtained by the modification
  • CO 2 of several percent to several tens percent in the exhaust gas discharged from an internal combustion engine typified by a car or a diesel engine are contained, it is global warming to reduce the amount of CO 2 discharged from these internal combustion engine This is thought to lead to the prevention of transformation.
  • CO 2 in the atmosphere contains about 400 ppm, to reduce the CO 2 in the atmosphere leads to the prevention of global warming.
  • the present inventors have The flow path of the gas containing CO 2, arranged CO 2 separation membrane separating CO 2 in the gas, and the CO 2 and CO 2 separated from the separation layer, H 2 obtained from H 2 supply source
  • the internal combustion engine provided with a fuel synthesis catalyst for synthesizing a fuel containing carbon and hydrogen in the molecular structure by using the H 2 as a carrier gas for the CO 2 separation membrane
  • the exhaust gas is discharged from the internal combustion engine. It was clarified that CO 2 in the atmosphere and CO 2 in the atmosphere can be recovered with high efficiency.
  • the type of CO 2 separation membrane is not particularly limited.
  • inorganic membranes using zeolite, mesoporous silica, etc., organic membranes using dendrimers, cardo polymers, and ionic liquids can be used. Since the CO 2 separation performance varies depending on the CO 2 separation membrane used, the amount of CO 2 separation can be optimized by changing the flow rate and pressure of the CO 2 -containing gas and carrier gas.
  • the ratio of the obtained mixed gas of CO 2 and H 2 may change.
  • the flow rate and concentration of the gas containing CO 2 are measured in advance, and the obtained CO 2 and H 2 are obtained by changing the flow rate and pressure of the H 2 gas used as the carrier gas based on the measured value.
  • the ratio of the mixed gas can be controlled.
  • CO 2 concentration of the CO 2 containing gas flowing into the CO 2 separation membrane depends on the type of CO 2 containing gas. In the case of exhaust gas from an internal combustion engine, the gas type may be 10% or more. When the gas type is air, it is expected to be around 400 ppm. And it flows into the CO 2 separation membrane, CO 2 amount, the CO 2 concentration, it is necessary to select the CO 2 separation membrane.
  • the fuel synthesized from CO 2 and H 2 is not particularly limited as long as it contains hydrogen and carbon in the molecular structure.
  • alkanes such as methane, ethane and propane, alkenes such as ethylene and propylene, and alkynes such as acetylene are conceivable.
  • fuels containing oxygen in the molecular structure in addition to hydrogen and carbon such as alcohols such as methanol and ethanol, and dimethyl ether are also conceivable.
  • the fuel obtained depends on the composition of the fuel synthesis catalyst and the temperature and pressure of the gas flowing into the catalyst.
  • the internal combustion engine targeted by the present invention is not particularly limited as long as it generates CO 2 .
  • an internal combustion engine such as a gasoline vehicle, a diesel vehicle, or a natural gas vehicle, an internal combustion engine used for a construction machine, an agricultural machine, or a ship can be considered. It can also be a stationary engine.
  • An internal combustion engine that uses natural gas mainly composed of methane as fuel is preferable from the viewpoint of reducing CO 2 emissions.
  • ships loaded with diesel engines and diesel generators are also targeted. In this case, it is also conceivable to use the electricity generated from the diesel generator for water electrolysis. Or it can also be used as electricity used for lighting and air conditioning in a ship by using together electricity obtained by converting exhaust heat.
  • the fuel synthesis catalyst is not particularly limited as long as it is a catalyst that can react with CO 2 and hydrogen to accelerate the fuel synthesis reaction including hydrogen and carbon in the molecular structure.
  • the methanation catalyst when a methanation catalyst is applied, is composed of a porous carrier of an inorganic compound and Rh, Pt, Pd, Ir, Ni supported on the porous carrier as a catalytically active component. , Mn, and Cu, and the porous carrier is a catalyst containing at least one selected from Al, Ce, La, Ti, and Zr, so that the methanation performance is improved. . Rh, Pt, Pd, Ir, Ni, Mn, and Cu are highly dispersed by using an oxide having a high specific surface area as a porous support for the methanation catalyst, and the methanation performance is enhanced.
  • the specific surface area of the porous carrier used in the present invention is preferably in the range of 30 to 800 m 2 / g, particularly preferably in the range of 50 to 400 m 2 / g.
  • Rh, Pt, Pd, Ir, Ni, Mn, and Cu may be included as catalytic active components.
  • the total supported amount of the catalytically active components Rh, Pt, Pd, Ir, Ni, Mn and Cu is preferably 0.0003 mol parts to 1.0 mol parts in terms of elements with respect to 2 mol parts of the porous carrier. If the total supported amount of Rh, Pt, Pd, Ir, Ni, Mn and Cu is less than 0.0003 mol part, the loading effect is insufficient, while if it exceeds 1.0 mol part, the specific surface area of the active ingredient itself decreases. In addition, the catalyst cost is increased.
  • mol part means the content ratio of each component in terms of mol number.
  • the loading amount of B component is 1 mol part with respect to 2 mol part of A component, regardless of the absolute amount of A component.
  • the amount of fuel used in the internal combustion engine can be reduced by introducing the fuel obtained by the fuel synthesis reaction into the engine that drives the internal combustion engine as a fuel source for the internal combustion engine.
  • a water electrolysis device is installed in an internal combustion engine and hydrogen is generated by electrolysis of water, it is possible to use water generated during fuel synthesis as a water supply source.
  • the method for generating H 2 is not particularly concerned.
  • a hydrogen tank in the internal combustion engine and supply H 2 from the tank to the methanation catalyst.
  • the tank can be loaded with H 2 by compressing or liquefying hydrogen as a gas.
  • an H 2 carrier such as an organic hydride or a hydrogen storage alloy can be used.
  • organic hydride or hydrogen storage alloy When organic hydride or hydrogen storage alloy is used, a storage tank is required, but it is thought that H 2 can be transported with lower energy than transporting H 2 itself. Heat is required when taking out H 2 from these H 2 carriers, but if exhaust heat from the engine is used, the temperature of the H 2 carrier can be increased efficiently.
  • Ammonia can also be used as the H 2 carrier, but when H 2 is extracted from NH 3 , N 2 is also generated at the same time, so when using it as a carrier gas for a CO 2 separation membrane, the carrier gas A step of removing N 2 is required before use as a substrate.
  • the method for electrolyzing water is not particularly concerned. Any method may be used as long as H 2 is obtained by the following reaction.
  • a method for electrolyzing 2H 2 O ⁇ 2H 2 + O 2 water for example, an alkaline water electrolysis type, a solid polymer type, or the like can be considered. Electricity is needed to electrolyze water. In that case, for example, it is conceivable that the heat of engine exhaust gas from the internal combustion engine is recovered to generate electricity, and the obtained electricity is used for water electrolysis.
  • the exhaust gas discharged from the internal combustion engine can be over 400 ° C. Therefore, it is also effective to obtain electricity using the heat of exhaust gas.
  • One possible method is to use a combination of a heat exchanger, an expander and a working medium.
  • the working medium is circulated in advance in the heat exchanger.
  • the working medium changes from liquid to gas by the heat of the exhaust gas.
  • the working medium converted into gas can be sent to the expander to generate electricity.
  • the working medium is then sent back to the liquid by being sent to the condenser.
  • electricity can be generated by circulating the working medium and recovering the heat of the exhaust gas.
  • the obtained electricity can be used for water electrolysis.
  • the working medium to be used is not particularly limited as long as it meets the above purpose.
  • ethylene glycol, water, etc. can be considered.
  • thermoelectric conversion element As one method for obtaining electricity using the heat of exhaust gas, the use of a thermoelectric conversion element is also conceivable. By installing a thermoelectric conversion element in the exhaust gas passage and bringing the exhaust gas into contact with the thermoelectric conversion element, the heat of the exhaust gas is converted into electricity, and electricity can be obtained. The obtained electricity can be used as electricity during water electrolysis.
  • thermoelectric conversion element used is not particularly limited.
  • an element made of bismuth and tellurium, an element containing lead, an element made of silicon and germanium, and the like are conceivable.
  • Any catalyst that can burn H 2 , CO, hydrocarbons, etc. is not particularly limited.
  • a catalyst in which at least one selected from Pt, Pd, and Rh as a catalyst active component is supported on a porous carrier containing alumina can be considered.
  • the following can be considered as a reaction for reforming methane with steam.
  • the 2CH 4 + 2H 2 O ⁇ 2CO + 3H 2 reaction is an endothermic reaction, and combustion heat is higher when CO and H 2 obtained by the above reaction are combusted than when CH 4 is combusted. Therefore, the fuel efficiency of the internal combustion engine is improved when CO, H 2 obtained as the fuel is used as the fuel of the internal combustion engine, compared with the case where CH 4 is used as the fuel. Therefore, it is considered that this method of once reforming the fuel is effective as a measure for improving the fuel consumption of the internal combustion engine.
  • the catalyst temperature needs to be 700 ° C. or higher although it depends on the catalyst composition and gas conditions used. Therefore, it is conceivable to use alcohol, for example, as a means for advancing the reaction for reforming the fuel using lower temperature exhaust heat.
  • alcohol for example, as a means for advancing the reaction for reforming the fuel using lower temperature exhaust heat.
  • the steam reforming reaction of ethanol is described by the following reaction formula. C 2 H 5 OH + H 2 O ⁇ 2CO + 4H
  • the two reactions are also endothermic. Combustion heat is better when the CO and H 2 obtained by the above reaction are burned than when C 2 H 5 OH is burned. high.
  • the reforming catalyst is not particularly limited as long as it can reform the fuel.
  • the reforming catalyst has a porous carrier of an inorganic compound and at least one selected from Pt, Pd, Rh, Ni, and Co supported as a catalytically active component on the porous carrier,
  • the reforming performance is enhanced when the porous support is a catalyst containing at least one selected from Al, Ce, La, Ti, Zr and Zn.
  • the porous carrier used for the methanation catalyst or the active ingredient may be supported on a substrate.
  • the base material cordierite that has been used conventionally, ceramics made of Si-Al-O, or heat-resistant metal substrates such as stainless steel are suitable.
  • the loading amount of the material is 10 g or more and 300 g or less with respect to 1 L of the base material in order to improve the CO 2 capture performance and methanation performance. If it is 10 g or less, the CO 2 capture performance and methanation performance will deteriorate.
  • the weight is 300 g or more, when the substrate has a honeycomb shape, problems such as clogging of the gas flow path are likely to occur.
  • a preparation method of the methanation catalyst for example, a physical preparation method such as an impregnation method, a kneading method, a coprecipitation method, a sol-gel method, an ion exchange method, a vapor deposition method, a preparation method using a chemical reaction, or the like may be used. it can.
  • the methanation catalyst As a starting material for the methanation catalyst, various compounds such as nitric acid compounds, chlorides, acetic acid compounds, complex compounds, hydroxides, carbonate compounds, organic compounds, metals, and metal oxides can be used.
  • the catalyst component when two or more elements are combined as a catalyst active component, the catalyst component is uniformly supported by preparing it by a co-impregnation method using an impregnating solution in which the active component is present in the same solution. Can do.
  • the shape of the methanation catalyst can be appropriately adjusted according to the application.
  • a honeycomb structure obtained by coating the purification catalyst of the present invention on a honeycomb structure made of various base materials such as cordierite, Si-Al-O, SiC, stainless steel, pellets, plates, granules, Examples include powder.
  • a honeycomb shape it is preferable to use a structure made of cordierite or Si—Al—O as the base material, but a honeycomb may be formed only with a porous carrier and a catalytically active component.
  • FIG. 1 shows an embodiment in which a CO 2 separation membrane and a methanation catalyst are combined.
  • CO 2 separation by CO 2 separation membrane is caused by both sides of the CO 2 partial pressure difference CO 2 separation membrane.
  • exhaust gas discharged from the engine 26 is introduced into one side of the CO 2 separation membrane 25. Further, H 2 obtained by electrolyzing water obtained from the water tank 27 using the water electrolysis device 28 is introduced as a carrier gas to the other side of the CO 2 separation membrane 25. The CO 2 in the exhaust gas passes through the membrane due to the CO 2 partial pressure difference on both sides of the CO 2 separation membrane and mixes with the carrier gas H 2 .
  • the obtained mixed gas of CO 2 and H 2 is introduced into the methanation catalyst 29.
  • CO 2 and H 2 react on the methanation catalyst 29 to obtain a gas containing CH 4 and water.
  • this gas By introducing this gas into the condenser 30, water is separated and only CH 4 is obtained.
  • the separated water is returned to the water tank 27 and reused for water electrolysis.
  • the obtained CH 4 is compressed by the compressor 31 and then stored in the methane storage section 32, introduced into the engine 26 as necessary, and used as engine fuel.
  • a battery mounted on the internal combustion engine, a solar cell installed in the internal combustion engine, or the like can be considered.
  • FIG. 2 shows an embodiment in which a heat exchanger 23 is installed in front of the CO 2 separation membrane.
  • a gasoline engine was assumed as the engine 26.
  • a working medium is circulated to the heat exchanger 23.
  • the working medium is changed from liquid to gas using the heat of the exhaust gas.
  • the obtained gas is introduced into the expander 20 to generate electricity and obtain electricity.
  • the working medium gas that has passed through the expander 20 is introduced into the condenser 21, returned to the liquid, and circulated by the pump 22.
  • the electricity obtained as described above is used for electrolysis of water by the water electrolysis device 28.
  • This configuration makes it possible to obtain electricity used during water electrolysis.
  • FIG. 3 shows an example in which a thermoelectric conversion element 33 is installed in front of the CO 2 separation membrane. By letting the exhaust gas flow into the thermoelectric conversion element, the heat of the exhaust gas is converted into electricity. The obtained electricity is used for electrolysis of water by the water electrolysis device 28.
  • This configuration makes it possible to obtain electricity used during water electrolysis.
  • FIG. 4 shows an embodiment in which a heat exchanger 23 is installed in front of the CO 2 separation membrane and a fuel reformer 41 is further installed. Part of the methane obtained by the method shown in the figure is introduced into the heat exchanger 23, and the temperature of the methane is increased. Thereafter, CO and H 2 are obtained by introducing the fuel reformer together with H 2 O. H 2 O is used of H 2 O obtained in the condenser 30. CO.H 2 obtained by reforming methane is used as fuel for the engine 26. Compared to the combustion heat of methane, the combustion heat of CO and H 2 obtained by reforming methane once is larger. Therefore, by adopting this configuration, the heat of the exhaust gas can be recovered, and the fuel consumption of the internal combustion engine can be improved.
  • FIG. 5 shows an embodiment in which the hydrogen storage material 42 is used instead of the electrolysis of water as the H 2 supply method for the configuration shown in the fourth embodiment.
  • the hydrogen storage material 42 an organic hydride such as toluene can be considered.
  • exhaust heat from the engine exhaust gas is used as heat when taking out H 2 from the organic hydride.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un moteur à combustion interne qui récupère le CO2 dans un gaz de faible énergie et synthétise un combustible. Un moteur à combustion interne selon la présente invention est caractérisé en ce que : une membrane de séparation de CO2 destinée à séparer du CO2 d'un gaz contenant du CO2 est agencée dans un trajet d'écoulement destiné au gaz; et du H2 est utilisé comme gaz porteur pour la membrane de séparation de CO2.
PCT/JP2016/072581 2015-09-25 2016-08-02 Moteur à combustion interne WO2017051610A1 (fr)

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JP2015187590A JP2018204433A (ja) 2015-09-25 2015-09-25 内燃機関
JP2015-187590 2015-09-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11813562B2 (en) 2022-02-01 2023-11-14 Halliburton Energy Services, Inc. Systems and methods for capturing carbon dioxide in exhaust gas
EP4130205A4 (fr) * 2020-03-26 2024-01-17 Hitachi, Ltd. Dispositif de production de carburant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102222965B1 (ko) * 2020-10-16 2021-03-04 한국해양과학기술원 Lng 연료 추진 선박에서 배출되는 이산화탄소를 포집하여 액화하는 시스템 및 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4130205A4 (fr) * 2020-03-26 2024-01-17 Hitachi, Ltd. Dispositif de production de carburant
US11813562B2 (en) 2022-02-01 2023-11-14 Halliburton Energy Services, Inc. Systems and methods for capturing carbon dioxide in exhaust gas

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