WO2017173731A1 - 基于甲醇水重整制氢发电系统的热泵空调及制热制冷方法 - Google Patents

基于甲醇水重整制氢发电系统的热泵空调及制热制冷方法 Download PDF

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WO2017173731A1
WO2017173731A1 PCT/CN2016/085897 CN2016085897W WO2017173731A1 WO 2017173731 A1 WO2017173731 A1 WO 2017173731A1 CN 2016085897 W CN2016085897 W CN 2016085897W WO 2017173731 A1 WO2017173731 A1 WO 2017173731A1
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Prior art keywords
air
hydrogen
temperature
heat exchanger
residual gas
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PCT/CN2016/085897
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English (en)
French (fr)
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向华
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广东合即得能源科技有限公司
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Publication of WO2017173731A1 publication Critical patent/WO2017173731A1/zh

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B29/00—Combined heating and refrigeration systems, e.g. operating alternately or simultaneously
    • F25B29/003—Combined heating and refrigeration systems, e.g. operating alternately or simultaneously of the compression type system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B13/00—Compression machines, plants or systems, with reversible cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B27/00—Machines, plants or systems, using particular sources of energy
    • F25B27/02—Machines, plants or systems, using particular sources of energy using waste heat, e.g. from internal-combustion engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B29/00—Combined heating and refrigeration systems, e.g. operating alternately or simultaneously
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B49/00—Arrangement or mounting of control or safety devices
    • F25B49/02—Arrangement or mounting of control or safety devices for compression type machines, plants or systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2313/00—Compression machines, plants or systems with reversible cycle not otherwise provided for
    • F25B2313/027—Compression machines, plants or systems with reversible cycle not otherwise provided for characterised by the reversing means
    • F25B2313/02741—Compression machines, plants or systems with reversible cycle not otherwise provided for characterised by the reversing means using one four-way valve
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2700/00—Sensing or detecting of parameters; Sensors therefor
    • F25B2700/21—Temperatures
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/27—Relating to heating, ventilation or air conditioning [HVAC] technologies
    • Y02A30/274—Relating to heating, ventilation or air conditioning [HVAC] technologies using waste energy, e.g. from internal combustion engine
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
    • Y02B30/52—Heat recovery pumps, i.e. heat pump based systems or units able to transfer the thermal energy from one area of the premises or part of the facilities to a different one, improving the overall efficiency
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to the field of heat pump air conditioner technology, and in particular, to a heat pump air conditioner and a heating and cooling method based on a methanol water reforming hydrogen generation power generation system.
  • the indoor heat exchanger is a condenser
  • the outdoor heat exchanger is an evaporator.
  • the evaporator absorbs heat from the ambient heat energy in the outdoor air to evaporate heat.
  • Working medium the pressure and temperature of the working fluid vapor are compressed by the compressor, and the high temperature vapor is condensed into a liquid helium through the condenser, and the released heat is transferred to the hot indoor space, and the condensed heat transfer medium is returned to the expansion valve through the expansion valve.
  • the outdoor heat exchanger is a condenser
  • the indoor heat exchanger is an evaporator.
  • the evaporator absorbs heat from the heat energy in the indoor space air to evaporate the heat transfer medium, and the working fluid vapor is compressed by the compressor. And the temperature rises, the high-temperature vapor is condensed into a liquid helium through the condenser, and the released heat is transferred to the outside, and the condensed heat transfer medium is returned to the evaporator through the expansion valve, and then evaporated, and thus reciprocated.
  • the disadvantage of the air source heat pump is that the lower the outdoor air temperature, the smaller the heat supply, especially when the outdoor air temperature is lower than -5 ° C, the heat pump is difficult to work normally, and electricity or other auxiliary heat source is needed.
  • the efficiency of the heat pump is greatly reduced. Under the heating condition of the air source heat pump, the evaporator will be frosted and need regular defrosting.
  • the defrosting module technology can refer to the Chinese patent application 201210152219.4 for the defrosting method of the air source heat pump system, 201410108455.5 - heat pump air conditioning defrosting Control method and heat pump air conditioning system, after the air source heat pump increases the defrost module, not only the stability is reduced, the maintenance cost is increased, but also a considerable part of the energy is lost.
  • the power supply source of the existing heat pump air conditioner is usually the commercial power, so the use of the existing heat pump air conditioner is subject to a large geographical restriction.
  • the technical problem to be solved by the present invention is to provide a methanol-based water solution against the above-mentioned deficiencies in the prior art.
  • the heat pump air conditioner of the hydrogen production system is reformed. Under the heating condition, the outdoor air is lower than -5 °C, and the air can still work normally and efficiently, and the evaporator does not frost, and no regular defrosting is required. And the use of the heat pump air conditioner is not limited by geography. To this end, the present invention also provides a solution to the problem of the heating and cooling method of the heat pump air conditioner.
  • a heat pump air conditioner based on a methanol water reforming hydrogen generation power generation system including a compressor, a four-way reversing valve, an indoor heat exchanger, and a section Flow valve, outdoor heat exchanger, methanol water storage container, transfer pump, reformer, fuel cell, power conversion device and air residual gas mixer; the compressor, four-way reversing valve, indoor heat exchanger, section a working medium conveying circuit of the heat pump air conditioner is formed between the flow valve and the outdoor heat exchanger; the methanol water storage container stores a liquid methanol water raw material; and the transfer pump is used for conveying the methanol water raw material in the methanol water storage container The pipeline is pumped to the reforming chamber of the reformer; the reformer is provided with a reforming chamber, a hydrogen purifying device, a combustion chamber and a fleshing port, and the reforming chamber is used for reforming hydrogen production of methanol and steam A
  • the combustion of oxygen provides heat for the operation of the reformer; the carbon dioxide after separation of the hydrogen purification device, the water vapor generated by the combustion of hydrogen and oxygen in the combustion chamber, and the unburned gas in the outside air are mixed into a high temperature residual gas, from the exhaust
  • the meat mouth is discharged to the air residual gas mixer or the outside; the air residual gas mixer is used for mixing the outside air and the high temperature residual gas into a medium temperature mixed gas, and is sent to the outdoor heat exchanger; the fuel battery is used for hydrogen and air.
  • the oxygen reacts electrochemically to generate an electrical energy output; the power conversion device is configured to convert electrical energy output by the fuel cell into electricity required by the load to supply power to the compressor and the delivery pump.
  • the working fluid transport circuit is provided with a check valve for transporting a working medium in a cooling condition
  • the throttle valve includes a main capillary and a secondary capillary, wherein the secondary capillary is connected in parallel with the check valve.
  • the filter and the muffler are also disposed on the working medium conveying circuit.
  • a reversing valve is disposed between the exhaust gas mouth and the air residual gas mixer, and the high temperature residual gas discharged from the exhaust meat port is rearward through the reversing valve under the heating condition In the air residual gas mixer, under the cooling condition, the high temperature residual gas discharged from the exhaust gas vent is discharged to the outside through the reversing valve.
  • the air residual gas mixer is provided with a fan and a temperature sensor, the fan is used to fan the outside air into the air residual gas mixer, and the temperature sensor is used to detect the temperature of the mixed gas in the air residual gas mixer.
  • the mixed gas temperature ranges from 25 to 70 °C.
  • a heat exchanger is disposed on the conveying pipeline between the conveying pump and the reformer, and the low-temperature methanol and water raw materials are exchanged in the heat exchanger with the high-temperature hydrogen outputted from the reforming chamber. Methanol and water feedstocks rise in temperature
  • the hydrogen purification device is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface
  • the coating layer is a palladium-silver alloy
  • the palladium-silver alloy has a mass percentage of palladium of 75%-78 ⁇ 3 ⁇ 4, and silver accounts for 22%-25%.
  • the heating and cooling method of the heat pump air conditioner based on the methanol water reforming hydrogen production system includes the following steps:
  • a reformer in the process of operation methanol water reforming hydrogen production reaction
  • the hydrogen produced is sent to the fuel cell, in the fuel cell, hydrogen and the oxygen in the air electrochemical reaction, generating electrical energy output
  • the high temperature residual gas is discharged from the exhaust gas chute of the reformer
  • the indoor heat exchanger becomes a condenser
  • the outdoor heat exchanger becomes an evaporator
  • the high temperature residual gas is discharged to the air residual gas mixer, and is mixed with the outside air to form a medium temperature mixed gas output
  • the indoor heat exchanger becomes the evaporator
  • the outdoor heat exchanger becomes the condenser
  • the high temperature residual gas is discharged to the outside
  • the electric energy outputted by the fuel cell is converted by the power conversion device, and is the compressor and Delivery pump power supply, residual power output;
  • the temperature sensor detects the temperature of the mixed gas in the air residual gas mixer, and feeds back the temperature information to the control device, and the control device adjusts the amount of the outside air through the fan.
  • the temperature of the mixed gas is controlled to be in the range of 25 to 70 °C.
  • the beneficial effects of the invention are as follows: 1.
  • the invention adopts methanol and water as raw materials for reforming hydrogen production, and then uses fuel cells to generate electricity, no waste and harmful exhaust gas pollution, clean, does not affect human health, methanol source Wide range, is renewable energy, and heat pump air conditioners do not need to be powered by the mains, no geographical restrictions, can be in the absence of electricity Used in the network area, for example, a communication base station;
  • the medium-temperature mixed gas exchanges heat with the working medium, and is converted into a low-temperature mixed gas and then discharged. Therefore, in any low-temperature air environment (for example, an air environment below -5 ° C),
  • the heat pump air conditioner can work normally and efficiently;
  • the invention utilizes the heat of the high temperature residual gas of the reformer, thereby improving the utilization efficiency of the methanol water raw material.
  • the heat pump air conditioner can utilize the high temperature residual gas and the outside air at the same time. The heat makes the heat pump air conditioner more energy efficient.
  • FIG. 1 is a block diagram showing the overall structure of the present invention.
  • a heat pump air conditioner based on a methanol water reforming hydrogen generation power generation system including a compressor 1, a four-way reversing valve 2, an indoor heat exchanger 3, a throttle valve 4, and an outdoor heat exchange 5, methanol water storage container 6, transfer pump 7, reformer 8, fuel cell 9, power conversion device 10 and air residual gas mixer 11; the compressor 1, four-way reversing valve 2, indoor heat exchange a working medium conveying circuit of the heat pump air conditioner is formed between the throttle valve 4 and the outdoor heat exchanger 5.
  • the methanol water storage container 6 stores a liquid methanol water raw material; the transfer pump 7 is used to send the methanol water raw material in the methanol water storage container 6 to the reforming chamber of the reformer 8 through the transfer pipeline pump 7;
  • the whole device 8 is provided with a reforming chamber, a hydrogen purifying device, a combustion chamber and a venting port.
  • the structure of the reformer can be referred to the Chinese patent applications 201410311217.4, 201410621689.X and 201510 476342.5 which the applicant has previously applied for. Reforming chamber for hydrogen production from methanol and steam reforming A mixed gas of hydrogen and carbon dioxide should be prepared.
  • the temperature in the reforming chamber is 300-570 ° C.
  • the reforming chamber is provided with a catalyst.
  • methanol and water vapor pass through the catalyst at a pressure of 1-5 M Pa.
  • the methanol cracking reaction and the carbon monoxide shift reaction generate hydrogen and carbon dioxide, which is more than one.
  • the reaction equation is: (l) CH 3 OH ⁇ CO+2H 2 , (2)H 2 0+CO ⁇ CO 2+H 2, (3)CH 3OH+H 2 0 ⁇ CO 2 +3H 2 , H 2 and CO 2 generated by the reforming reaction, the hydrogen purifying device is used for separating the produced hydrogen gas, and the hydrogen gas is sent to the fuel cell 9, and the combustion chamber is used for partial production.
  • the obtained hydrogen gas is combusted with oxygen in the outside air to provide heat for the operation of the reformer 8; the carbon dioxide after the separation of the hydrogen purification device, the water vapor generated by the combustion of hydrogen and oxygen in the combustion chamber, and the unburned gas in the outside air are mixed.
  • the high temperature residual gas is discharged from the exhaust meat port to the air residual gas mixer 11 or the outside; the air residual gas mixer 11 is used for mixing the outside air and the high temperature residual gas into a medium temperature mixed gas, and is sent to the outdoor heat exchanger 5
  • the fuel cell 9 is used for electrochemical reaction between hydrogen and oxygen in the air to generate electrical energy output, at the anode of the fuel cell 9: 2H 2 ⁇ 4H ++ 4e -, H 2 splits into two protons and two electrons , protons pass through the proton exchange membrane (PEM), electrons pass through the anode plate, Through an external load, and into the cathode bipolar plate; the cathode of the fuel cell 9: 0 2 + 4e - + 4H + ⁇ 2H 2 0, protons, electrons and recombine to form 02 1120; the power conversion means 10 is for converting electric energy output from the fuel cell 9 into electric power required by the load, and supplies power to the compressor 1 and the transfer pump 7.
  • the working medium conveying circuit is provided with a check valve 12 for conveying a working medium in a cooling condition
  • the throttle valve 4 includes a main capillary 41 and a sub capillary 42, wherein The sub-capillary 42 is connected in parallel with the check valve 12; the filter 13 and the muffler 14 are further provided on the working medium conveying circuit.
  • a reversing valve 15 is disposed between the exhaust gas bunker and the air residual gas mixer 11 , and the high temperature residual gas discharged from the exhaust gas bunker is under the heating condition.
  • the heat pump air conditioner can utilize the high temperature residual gas and the heat of the outside air, so that the heat pump air conditioner is more energy-saving and energy-saving, generally, the heat pump Among the heat used by air conditioners, the external air heat accounts for 30 ⁇ 3 ⁇ 4-80 ⁇ 3 ⁇ 4, and the high temperature residual gas accounts for 20 ⁇ 3 ⁇ 4-70 ⁇ 3 ⁇ 4.
  • the high temperature residual gas discharged from the exhaust port is discharged to the outside through the reversing valve 15.
  • the air residual gas mixer 11 is provided with a fan and a temperature sensor, the fan is used to fan the outside air into the air residual gas mixer 11, and the temperature sensor is used to detect the air residual gas mixer.
  • the mixed gas temperature in the range of the mixed gas is 25 to 70 °C.
  • a heat exchanger 16 is disposed on a conveying pipe between the transfer pump 7 and the reformer 8, and a low-temperature methanol and water raw material is disposed in the heat exchanger 16 and outputted from the reforming chamber.
  • the high temperature hydrogen gas is exchanged, the temperature of the methanol and water feedstock is raised, and the hydrogen temperature is lowered.
  • the hydrogen purification device is a membrane separation device for vacuum-plating palladium-silver alloy on a porous ceramic surface, and the coating layer is a palladium-silver alloy, and the palladium-silver alloy has a mass percentage of palladium of 75%-78 ⁇ 3 ⁇ 4, and silver accounts for 22 ⁇ 3 ⁇ 4. -25%.
  • the heating and cooling method of the heat pump air conditioner based on the methanol water reforming hydrogen generation power generation system includes the following steps
  • the indoor heat exchanger becomes a condenser
  • the outdoor heat exchanger becomes an evaporator
  • the high temperature residual gas is discharged to the air residual gas mixer, and is mixed with the outside air to form a medium temperature mixed gas output
  • the indoor heat exchanger becomes the evaporator
  • the outdoor heat exchanger becomes the condenser
  • the high temperature residual gas is discharged to the outside
  • the electric energy outputted by the fuel cell is converted by the power conversion device, and is the compressor and Delivery pump power supply, residual power output;
  • the temperature sensor detects the temperature of the mixed gas in the air residual gas mixer, and feeds the temperature information to the control device, and the control device adjusts the amount of the outside air through the fan.
  • the present invention is a heat pump air conditioner and a heating and cooling method based on a methanol water reforming hydrogen generation power generation system.
  • the outdoor air is lower than -5 ° C, and can still be normally efficient.
  • there is no frost on the evaporator no regular defrosting is required, and the use of the heat pump air conditioner is not limited by geography. Therefore, it has industrial applicability.

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  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
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Abstract

一种基于甲醇水重整制氢发电系统的热泵空调，包括压缩机（1）、四通换向阀（2）、室内换热器（3）、节流阀（4）、室外换热器（5）、甲醇水储存容器（6）、输送泵（7）、重整器（8）、燃料电池（9）、电力转换装置（10）及空气余气混合器（11）；重整器（8）产生的高温余气，从排气囱口排向空气余气混合器（11）或外界；空气余气混合器（11）用于将外界空气与高温余气混合成中温混合气体，输向室外换热器（5）；燃料电池（9）用于氢气与空气中的氧气发生电化学反应，产生电能输出；电力转换装置（10）用于将燃料电池（9）输出的电能转换为负载所需求的电，为压缩机（1）及输送泵（7）供电。该热泵空调在制热工况下，室外空气低于-5℃时，仍能正常高效工作，蒸发器上也不会结霜，无需定期除霜，且其使用不受地域限制。

Description

说明书
发明名称：基于甲醇水重整制氢发电系统的热泵空调及制热制冷方 法
技术领域
[0001] 本发明涉及热泵空调技术领域， 特别涉及一种基于甲醇水重整制氢发电系统的 热泵空调及制热制冷方法。
背景技术
[0002] 随着不可再生能源如煤、 石油、 天然气等越来越少， 耗电量非常小的空气能热 泵空调应运而生。 空气源热泵原理就是利用逆卡诺原理， 在制热工况下， 室内 换热器为冷凝器， 室外换热器为蒸发器， 蒸发器从室外空气中的环境热能中吸 取热量以蒸发传热工质， 工质蒸气经压缩机压缩后压力和温度上升， 高温蒸气 通过冷凝器冷凝成液体吋， 释放出的热量传递给用热的室内空间， 冷凝后的传 热工质通过膨胀阀返回到蒸发器， 然后再被蒸发， 如此循环往复。 在制冷工况 下， 室外换热器为冷凝器， 室内换热器为蒸发器， 蒸发器从室内空间空气中的 热能中吸取热量以蒸发传热工质， 工质蒸气经压缩机压缩后压力和温度上升， 高温蒸气通过冷凝器冷凝成液体吋， 释放出的热量传递至室外， 冷凝后的传热 工质通过膨胀阀返回到蒸发器， 然后再被蒸发， 如此循环往复。
[0003] 然而， 空气源热泵的缺点是室外空气温度越低吋供热量越小， 特别是当室外空 气温度低于 -5°C吋， 热泵就难以正常工作， 需要用电或其他辅助热源对空气进行 加热， 热泵的效率大大降低。 空气源热泵在制热工况下， 蒸发器上会结霜， 需 要定期除霜， 除霜模块技术可参照中国专利申请 201210152219.4用于空气源热泵 系统的除霜方法、 201410108455.5—种热泵空调除霜控制方法及热泵空调系统， 空气源热泵增加除霜模块之后， 不但稳定性降低、 维护成本增加， 而且也损失 相当大一部分能量。 此外， 现有热泵空调的供电来源通常为市电， 因此现有热 泵空调的使用受到较大的地域限制。
技术问题
[0004] 本发明要解决的技术问题是针对上述现有技术中的不足， 提供一种基于甲醇水 重整制氢发电系统的热泵空调， 该热泵空调在制热工况下， 室外空气低于 -5°C吋 ， 仍能正常高效工作， 蒸发器上也不会结霜， 无需定期除霜， 并且该热泵空调 的使用不受地域限制。 为此， 本发明还要提供一种该热泵空调的制热制冷方法 问题的解决方案
技术解决方案
[0005] 为解决上述第一个技术问题， 本发明的技术方案是： 一种基于甲醇水重整制氢 发电系统的热泵空调， 包括压缩机、 四通换向阀、 室内换热器、 节流阀、 室外 换热器、 甲醇水储存容器、 输送泵、 重整器、 燃料电池、 电力转换装置及空气 余气混合器； 所述压缩机、 四通换向阀、 室内换热器、 节流阀与室外换热器之 间形成热泵空调的工质输送回路； 所述甲醇水储存容器储存有液态的甲醇水原 料； 所述输送泵用于将甲醇水储存容器中的甲醇水原料通过输送管道泵送至重 整器的重整室； 重整器设有重整室、 氢气纯化装置、 燃烧腔及排气肉口， 所述 重整室用于甲醇与水蒸汽发生重整制氢反应制得氢气和二氧化碳的混合气体， 所述氢气纯化装置用于分离出制得的氢气， 该氢气输向燃料电池， 所述燃烧腔 用于部分制得的氢气与外界空气中的氧气燃烧， 为重整器的运行提供热量； 所 述氢气纯化装置分离之后的二氧化碳、 燃烧腔内氢气氧气燃烧产生的水汽以及 外界空气中的未燃烧气体混合成高温余气， 从排气肉口排向空气余气混合器或 外界； 所述空气余气混合器用于将外界空气与高温余气混合成中温混合气体， 输向室外换热器； 所述燃料电池用于氢气与空气中的氧气发生电化学反应， 产 生电能输出； 所述电力转换装置用于将燃料电池输出的电能转换为负载所需求 的电， 为压缩机及输送泵供电。
[0006] 优选地， 所述工质输送回路设有用于输送制冷工况状态下的工质的止回阀， 所 述节流阀包括主毛细管和副毛细管， 其中副毛细管与止回阀相并联； 所述工质 输送回路上还设有过滤器及消声器。
[0007] 优选地， 所述排气肉口与空气余气混合器之间设有换向阀， 在制热工况状态下 ， 从排气肉口排出的高温余气经换向阀后排向空气余气混合器， 在制冷工况状 态下， 从排气囱口排出的高温余气经换向阀后排向外界。 [0008] 优选地， 所述空气余气混合器设有风扇及温度感应器， 风扇用于将外界空气扇 入空气余气混合器， 温度感应器用于检测空气余气混合器内的混合气体温度， 该混合气体温度范围为 25〜70°C。
[0009] 优选地， 所述输送泵与重整器之间的输送管道上设有换热器， 低温的甲醇和水 原料在换热器中， 与重整室输出的高温氢气进行换热， 甲醇和水原料温度升高
， 氢气温度降低。
[0010] 优选地， 所述氢气纯化装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置， 镀膜层为钯银合金， 钯银合金的质量百分比钯占 75%-78<¾， 银占 22%-25%。
[0011] 为解决上述第二个技术问题， 本发明的技术方案是： 所述基于甲醇水重整制氢 发电系统的热泵空调的制热制冷方法， 包括以下步骤：
[0012] a.重整器在运行过程中， 发生甲醇水重整制氢反应， 制得的氢气输向燃料电池 ， 在燃料电池内， 氢气与空气中的氧气发生电化学反应， 产生电能输出， 与此 同吋， 从重整器的排气囱口排出高温余气；
[0013] b.在制热工况下， 室内换热器成为冷凝器， 室外换热器成为蒸发器， 高温余气 排向空气余气混合器， 并与外界空气混合成中温混合气体输向室外换热器， 在 室外换热器中， 中温混合气体与工质换热， 转化成低温混合气体后排出； 燃料 电池输出的电能经电力转换装置转换后， 为压缩机及输送泵供电， 余电输出；
[0014] c.在制冷工况下， 室内换热器成为蒸发器， 室外换热器成为冷凝器， 高温余气 排向外界； 燃料电池输出的电能经电力转换装置转换后， 为压缩机及输送泵供 电， 余电输出；
[0015] 优选地， 在制热工况下， 温度传感器实吋检测空气余气混合器中的混合气体温 度， 并将温度信息反馈给控制装置， 控制装置通过风扇调整外界空气的送入量 ， 以控制混合气体的温度范围在 25〜70°C内。
发明的有益效果
有益效果
[0016] 本发明的有益效果是： 其一、 本发明采用甲醇和水作为原料进行重整制氢， 再 利用燃料电池发电， 无废澄和有害废气污染,清洁， 不影响人体健康， 甲醇来源 广泛， 是可再生能源， 并且热泵空调无需市电供电， 不受地域限制， 可在无电 网区域使用， 例如通讯基站； 其二、 在制热工况下， 由于高温余气排向空气余 气混合器， 并与外界空气混合成中温混合气体输向室外换热器， 此吋， 室外换 热器为蒸发器， 在室外换热器中， 中温混合气体与工质换热， 转化成低温混合 气体后排出， 因此， 在任何低温空气环境 （例如 -5°C以下的空气环境） ， 热泵空 调均能正常高效工作； 其三、 在制热工况下， 由于室外换热器 （即蒸发器） 输 入的是中温混合气体， 因此也不会结霜， 无需定期除霜； 其四、 本发明使重整 器的高温余气热量得到利用， 从而提高了甲醇水原料的利用效率， 与此同吋， 高温余气与外界空气混合后， 热泵空调能同吋利用高温余气及外界空气的热量 ， 使得热泵空调更节能省电。
对附图的简要说明
附图说明
[0017] 图 1为本发明的整体结构方框示意图。
本发明的实施方式
[0018] 下面结合附图对本发明的结构原理和工作原理作进一步详细说明。
[0019] 如图 1所示， 一种基于甲醇水重整制氢发电系统的热泵空调， 包括压缩机 1、 四 通换向阀 2、 室内换热器 3、 节流阀 4、 室外换热器 5、 甲醇水储存容器 6、 输送泵 7、 重整器 8、 燃料电池 9、 电力转换装置 10及空气余气混合器 11 ; 所述压缩机 1 、 四通换向阀 2、 室内换热器 3、 节流阀 4与室外换热器 5之间形成热泵空调的工 质输送回路， 在图 1的工质输送回路中， 虚线箭头表示制热工况， 实线箭头表示 制冷工况； 所述甲醇水储存容器 6储存有液态的甲醇水原料； 所述输送泵 7用于 将甲醇水储存容器 6中的甲醇水原料通过输送管道泵 7送至重整器 8的重整室； 重 整器 8设有重整室、 氢气纯化装置、 燃烧腔及排气肉口， 重整器的结构可参照本 申请人在此之前申请的中国专利申请 201410311217.4、 201410621689.X及 201510 476342.5 , 所述重整室用于甲醇与水蒸汽发生重整制氢反应制得氢气和二氧化碳 的混合气体， 重整室内的温度为 300-570°C温度， 重整室内设有催化剂， 在重整 室内， 甲醇与水蒸气在 1-5M Pa的压力条件下通过催化剂， 在催化剂的作用下， 发生甲醇裂解反应和一氧化碳的变换反应， 生成氢气和二氧化碳， 这是一个多 组份、 多反应的气固催化反应系统， 反应方程为： （l)CH 3OH→CO+2H 2、 (2)H 2 0+CO→CO 2+H 2、 (3)CH 3OH+H 20→CO 2+3H 2， 重整反应生成的 H 2和 CO 2， 所述氢气纯化装置用于分离出制得的氢气， 该氢气输向燃料电池 9， 所述燃烧腔 用于部分制得的氢气与外界空气中的氧气燃烧， 为重整器 8的运行提供热量； 所 述氢气纯化装置分离之后的二氧化碳、 燃烧腔内氢气氧气燃烧产生的水汽以及 外界空气中的未燃烧气体混合成高温余气， 从排气肉口排向空气余气混合器 11 或外界； 所述空气余气混合器 11用于将外界空气与高温余气混合成中温混合气 体， 输向室外换热器 5; 所述燃料电池 9用于氢气与空气中的氧气发生电化学反 应， 产生电能输出， 在燃料电池 9的阳极： 2H 2→4H ++4e -， H 2分裂成两个质子 和两个电子， 质子穿过质子交换膜 （PEM) ， 电子通过阳极板， 通过外部负载 ， 并进入阴极双极板； 在燃料电池 9的阴极： 0 2+4e -+4H +→2H 20， 质子、 电子 和 0 2重新结合以形成11 20; 所述电力转换装置 10用于将燃料电池 9输出的电能转 换为负载所需求的电， 为压缩机 1及输送泵 7供电。
[0020] 如图 1所示， 所述工质输送回路设有用于输送制冷工况状态下的工质的止回阀 1 2, 所述节流阀 4包括主毛细管 41和副毛细管 42， 其中副毛细管 42与止回阀 12相 并联； 所述工质输送回路上还设有过滤器 13及消声器 14。
[0021] 如图 1所示， 所述排气囱口与空气余气混合器 11之间设有换向阀 15， 在制热工 况状态下， 从排气囱口排出的高温余气经换向阀 15后排向空气余气混合器 11， 高温余气与外界空气混合后， 热泵空调能同吋利用高温余气及外界空气的热量 ， 使得热泵空调更节能省电， 一般地， 热泵空调利用的热量中， 外界空气热量 占比 30<¾-80<¾， 高温余气占比 20<¾-70<¾。 在制冷工况状态下， 从排气囱口排出 的高温余气经换向阀 15后排向外界。
[0022] 如图 1所示， 所述空气余气混合器 11设有风扇及温度感应器， 风扇用于将外界 空气扇入空气余气混合器 11， 温度感应器用于检测空气余气混合器 11内的混合 气体温度， 该混合气体温度范围为 25〜70°C。
[0023] 如图 1所示， 所述输送泵 7与重整器 8之间的输送管道上设有换热器 16， 低温的 甲醇和水原料在换热器 16中， 与重整室输出的高温氢气进行换热， 甲醇和水原 料温度升高， 氢气温度降低。 [0024] 所述氢气纯化装置为在多孔陶瓷表面真空镀钯银合金的膜分离装置， 镀膜层为 钯银合金， 钯银合金的质量百分比钯占 75%-78<¾， 银占 22<¾-25%。
[0025] 上述基于甲醇水重整制氢发电系统的热泵空调的制热制冷方法， 包括以下步骤
[0026] a.重整器在运行过程中， 发生甲醇水重整制氢反应， 制得的氢气输向燃料电池 ， 在燃料电池内， 氢气与空气中的氧气发生电化学反应， 产生电能输出， 与此 同吋， 从重整器的排气囱口排出高温余气；
[0027] b.在制热工况下， 室内换热器成为冷凝器， 室外换热器成为蒸发器， 高温余气 排向空气余气混合器， 并与外界空气混合成中温混合气体输向室外换热器， 在 室外换热器中， 中温混合气体与工质换热， 转化成低温混合气体后排出； 燃料 电池输出的电能经电力转换装置转换后， 为压缩机及输送泵供电， 余电输出 （ 可为其他设备或负载供电） ；
[0028] c.在制冷工况下， 室内换热器成为蒸发器， 室外换热器成为冷凝器， 高温余气 排向外界； 燃料电池输出的电能经电力转换装置转换后， 为压缩机及输送泵供 电， 余电输出；
[0029] 优选地， 在制热工况下， 温度传感器实吋检测空气余气混合器中的混合气体温 度， 并将温度信息反馈给控制装置， 控制装置通过风扇调整外界空气的送入量
， 以控制混合气体的温度范围在 25〜70°C内。
[0030] 以上所述， 仅是本发明较佳实施方式， 凡是依据本发明的技术方案对以上的实 施方式所作的任何细微修改、 等同变化与修饰， 均属于本发明技术方案的范围 内。
工业实用性
[0031] 本发明为一种基于甲醇水重整制氢发电系统的热泵空调及制热制冷方法， 该热 泵空调在制热工况下， 室外空气低于 -5°C吋， 仍能正常高效工作， 蒸发器上也不 会结霜， 无需定期除霜， 并且该热泵空调的使用不受地域限制。 因此， 具有工 业实用性。

Claims

权利要求书
[权利要求 1] 基于甲醇水重整制氢发电系统的热泵空调， 其特征在于： 包括压缩机
、 四通换向阀、 室内换热器、 节流阀、 室外换热器、 甲醇水储存容器 、 输送泵、 重整器、 燃料电池、 电力转换装置及空气余气混合器； 所 述压缩机、 四通换向阀、 室内换热器、 节流阀与室外换热器之间形成 热泵空调的工质输送回路； 所述甲醇水储存容器储存有液态的甲醇水 原料； 所述输送泵用于将甲醇水储存容器中的甲醇水原料通过输送管 道泵送至重整器的重整室； 重整器设有重整室、 氢气纯化装置、 燃烧 腔及排气肉口， 所述重整室用于甲醇与水蒸汽发生重整制氢反应制得 氢气和二氧化碳的混合气体， 所述氢气纯化装置用于分离出制得的氢 气， 该氢气输向燃料电池， 所述燃烧腔用于部分制得的氢气与外界空 气中的氧气燃烧， 为重整器的运行提供热量； 所述氢气纯化装置分离 之后的二氧化碳、 燃烧腔内氢气氧气燃烧产生的水汽以及外界空气中 的未燃烧气体混合成高温余气， 从排气 ®口排向空气余气混合器或外 界； 所述空气余气混合器用于将外界空气与高温余气混合成中温混合 气体， 输向室外换热器； 所述燃料电池用于氢气与空气中的氧气发生 电化学反应， 产生电能输出； 所述电力转换装置用于将燃料电池输出 的电能转换为负载所需求的电， 为压缩机及输送泵供电。
[权利要求 2] 根据权利要求 1所述的基于甲醇水重整制氢发电系统的热泵空调， 其 特征在于： 所述工质输送回路设有用于输送制冷工况状态下的工质的 止回阀， 所述节流阀包括主毛细管和副毛细管， 其中副毛细管与止回 阀相并联； 所述工质输送回路上还设有过滤器及消声器。
[权利要求 3] 根据权利要求 1所述的基于甲醇水重整制氢发电系统的热泵空调， 其 特征在于： 所述排气肉口与空气余气混合器之间设有换向阀， 在制热 工况状态下， 从排气肉口排出的高温余气经换向阀后排向空气余气混 合器， 在制冷工况状态下， 从排气肉口排出的高温余气经换向阀后排 向外界。
[权利要求 4] 根据权利要求 1所述的基于甲醇水重整制氢发电系统的热泵空调， 其 特征在于： 所述空气余气混合器设有风扇及温度感应器， 风扇用于将 外界空气扇入空气余气混合器， 温度感应器用于检测空气余气混合器 内的混合气体温度， 该混合气体温度范围为 25〜70°C。
[权利要求 5] 根据权利要求 1所述的基于甲醇水重整制氢发电系统的热泵空调， 其 特征在于： 所述输送泵与重整器之间的输送管道上设有换热器， 低温 的甲醇和水原料在换热器中， 与重整室输出的高温氢气进行换热， 甲 醇和水原料温度升高， 氢气温度降低。
[权利要求 6] 根据权利要求 1所述的基于甲醇水重整制氢发电系统的热泵空调， 其 特征在于： 所述氢气纯化装置为在多孔陶瓷表面真空镀钯银合金的膜 分离装置， 镀膜层为钯银合金， 钯银合金的质量百分比钯占 75%-78<¾ ， 银占 y^
[权利要求 7] 权利要求 1-6中任意一项所述基于甲醇水重整制氢发电系统的热泵空 调的制热制冷方法， 其特征在于， 包括以下步骤：
a.重整器在运行过程中， 发生甲醇水重整制氢反应， 制得的氢气输向 燃料电池， 在燃料电池内， 氢气与空气中的氧气发生电化学反应， 产 生电能输出， 与此同吋， 从重整器的排气囱口排出高温余气； b.在制热工况下， 室内换热器成为冷凝器， 室外换热器成为蒸发器， 高温余气排向空气余气混合器， 并与外界空气混合成中温混合气体输 向室外换热器， 在室外换热器中， 中温混合气体与工质换热， 转化成 低温混合气体后排出； 燃料电池输出的电能经电力转换装置转换后， 为压缩机及输送泵供电， 余电输出；
c.在制冷工况下， 室内换热器成为蒸发器， 室外换热器成为冷凝器， 高温余气排向外界； 燃料电池输出的电能经电力转换装置转换后， 为 压缩机及输送泵供电， 余电输出。
[权利要求 8] 根据权利要求 7所述基于甲醇水重整制氢发电系统的热泵空调的制热 制冷方法， 其特征在于： 在制热工况下， 温度传感器实吋检测空气余 气混合器中的混合气体温度， 并将温度信息反馈给控制装置， 控制装 置通过风扇调整外界空气的送入量， 以控制混合气体的温度范围在 25 〜70。C内。
PCT/CN2016/085897 2016-04-07 2016-06-15 基于甲醇水重整制氢发电系统的热泵空调及制热制冷方法 WO2017173731A1 (zh)

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