JP6044236B2 - Water heater - Google Patents
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- JP6044236B2 JP6044236B2 JP2012218224A JP2012218224A JP6044236B2 JP 6044236 B2 JP6044236 B2 JP 6044236B2 JP 2012218224 A JP2012218224 A JP 2012218224A JP 2012218224 A JP2012218224 A JP 2012218224A JP 6044236 B2 JP6044236 B2 JP 6044236B2
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- hot water
- water supply
- adsorber
- heat storage
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 329
- 238000005338 heat storage Methods 0.000 claims description 181
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 239000011232 storage material Substances 0.000 claims description 59
- 239000000126 substance Substances 0.000 claims description 59
- 238000001179 sorption measurement Methods 0.000 claims description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 239000003463 adsorbent Substances 0.000 claims description 38
- 238000009833 condensation Methods 0.000 claims description 33
- 230000005494 condensation Effects 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 15
- 229910001510 metal chloride Inorganic materials 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 239000002734 clay mineral Substances 0.000 claims description 9
- 150000001805 chlorine compounds Chemical class 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 230000003100 immobilizing effect Effects 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000003795 desorption Methods 0.000 description 14
- 230000020169 heat generation Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000002803 fossil fuel Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000003021 water soluble solvent Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- -1 lithium oxide oxide Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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]
-
- 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
- Y02E60/14—Thermal energy storage
Landscapes
- Heat-Pump Type And Storage Water Heaters (AREA)
- Sorption Type Refrigeration Machines (AREA)
Description
本発明は、化学蓄熱材を利用した給湯装置に関する。 The present invention relates to a hot water supply apparatus using a chemical heat storage material.
化学反応を利用して熱の吸収、放出を行なうことのできる物質である化学蓄熱材は、従来より広く知られており、種々の分野で利用が検討されている。例えば、水酸化カルシウム（Ｃａ（ＯＨ）２）は、脱水に伴なって蓄熱（吸熱）し、水和（水酸化カルシウムへの復原）に伴なって放熱（発熱）する性質がある。また、アルカリ土類金属に属するカルシウムやマグネシウム等は、アンモニアとの反応で、アンモニアが固定化されるときは放熱し、アンモニアが脱離するときに蓄熱する性質がある。 A chemical heat storage material, which is a substance that can absorb and release heat by using a chemical reaction, has been widely known, and its use is being studied in various fields. For example, calcium hydroxide (Ca (OH) 2 ) has the property of storing heat (absorbing heat) with dehydration and radiating heat (generating heat) with hydration (restoration to calcium hydroxide). In addition, calcium, magnesium, and the like belonging to alkaline earth metals have a property of radiating heat when ammonia is immobilized and storing heat when ammonia is desorbed by reaction with ammonia.
給湯システムは、従来から化石燃料を使用したタイプが広く利用されている。このようなシステムは、化石燃料の燃焼により得られた顕熱を給湯に利用するため、熱の利用効率が１００％を超えることはなく、１００％の利用効率を実現することも難しいというのが実情である。例えば、灯油式やガス式の給湯システムでは、一般にエネルギーの消費効率を示すＣＯＰ（Coefficient Of Performance）値が１を上回ることはない。 Conventionally, hot water supply systems using fossil fuels have been widely used. Since such a system uses the sensible heat obtained by burning fossil fuel for hot water supply, the heat utilization efficiency does not exceed 100%, and it is difficult to realize the utilization efficiency of 100%. It is a fact. For example, in a kerosene type or gas type hot water supply system, a COP (Coefficient Of Performance) value indicating energy consumption efficiency generally does not exceed 1.
ＣＯＰ値は、与えられるエネルギー（例えば熱量）により、どの程度のエネルギー（熱量）の出力が可能であるかを表す成績係数のことである。燃焼して熱エネルギーを得る化石燃料を用いたシステムは、顕熱ロスが著しく大きく、ＣＯＰ値は一般的に低い値となる。 The COP value is a coefficient of performance representing how much energy (heat amount) can be output by given energy (for example, heat amount). A system using fossil fuel that obtains thermal energy through combustion has a significantly large sensible heat loss, and the COP value is generally low.
ＣＯＰを高める技術の一つとして、一対の吸着器、凝縮器及び蒸発器を備えた吸着式ヒートポンプが提案されている（例えば、特許文献１参照）。このようなヒートポンプを利用した給湯技術としては、近年、ＣＯＰが１を超える熱駆動式の給湯システムが提案されている。 As one of techniques for increasing COP, an adsorption heat pump including a pair of adsorbers, a condenser, and an evaporator has been proposed (see, for example, Patent Document 1). As a hot water supply technique using such a heat pump, in recent years, a heat-driven hot water supply system having a COP exceeding 1 has been proposed.
しかしながら、従来から提案されている吸着式ヒートポンプでは、吸着器における吸着時と脱着時の温度差が大きい等の場合、顕熱ロスが大きくなり、熱の利用効率としては高くない。しかも、一対の吸着器における吸着、脱着のタイミングが別々に決定されるため、連続的な熱生成が行なえない。 However, in the conventionally proposed adsorption heat pump, when the temperature difference between adsorption and desorption in the adsorber is large, the sensible heat loss increases, and the heat utilization efficiency is not high. In addition, since the adsorption and desorption timings in the pair of adsorbers are determined separately, continuous heat generation cannot be performed.
また、近年報告されている給湯システムは、ガス等の化石燃料を利用したものであり、化石燃料基準の効率からみると必ずしも高効率なシステム構成とは言い難い。また、ヒートポンプタイプでも、電気エネルギーを利用するため、一次エネルギー換算では効率がよいとは言い難い。 In addition, hot water supply systems reported in recent years use fossil fuels such as gas, and are not necessarily highly efficient system configurations from the viewpoint of the efficiency of fossil fuel standards. Even in the heat pump type, since electric energy is used, it is difficult to say that the efficiency is high in terms of primary energy.
本発明は、上記に鑑みなされたものであり、顕熱ロスが少なく熱の利用効率に優れており、給湯温度に応じて効率良く給湯する給湯装置を提供することを目的とし、該目的を達成することを課題とする。 The present invention has been made in view of the above, and has an object of providing a hot water supply apparatus that has low sensible heat loss and excellent heat utilization efficiency and efficiently supplies hot water according to the hot water supply temperature, and achieves the object. The task is to do.
本発明は、以下の知見に基づいて達成されたものである。即ち、
従来から提案されている一対の吸着器、凝縮器、及び蒸発器を備えたシステム構成において、吸着器に代えて化学蓄熱器を利用した構成にすると、化学蓄熱器の化学蓄熱材において発現する多大な吸発熱の利用が可能になるため、給湯温度に応じた給湯効率の改善が図れると共に、外部から供給しなければならない熱エネルギー（顕熱）を軽減することができるとの知見である。
The present invention has been achieved based on the following findings. That is,
In a system configuration including a pair of adsorbers, condensers, and evaporators that have been proposed in the past, if a configuration using a chemical heat accumulator instead of an adsorber is used, a large amount that is expressed in the chemical heat storage material of the chemical heat accumulator It is a knowledge that since it is possible to use heat absorption and heat generation, it is possible to improve the efficiency of hot water supply according to the hot water supply temperature and to reduce the heat energy (sensible heat) that must be supplied from the outside.
前記目的を達成するために、本発明の給湯装置は、
熱媒を蒸発させる蒸発器と、蒸発器から熱媒が供給され、供給された熱媒を吸着する吸着器と、蒸発器から熱媒が供給され、供給された熱媒が固定化されるときに該熱媒の蒸発潜熱以上の反応熱を放出し、該熱媒が脱離するときに蓄熱する化学蓄熱材を備え、吸着器の再生温度以上の熱を吸着器に放熱可能な蓄熱反応器と、吸着器から熱媒が供給され、供給された熱媒を凝縮する凝縮器と、吸着器、蓄熱反応器、及び凝縮器の少なくとも１つと熱的に接続されて熱交換することで給湯する給湯部と、を設けて構成されたものである。
In order to achieve the above object, the hot water supply apparatus of the present invention comprises:
When an evaporator that evaporates the heating medium, a heating medium is supplied from the evaporator, an adsorber that adsorbs the supplied heating medium, a heating medium is supplied from the evaporator, and the supplied heating medium is fixed The heat storage reactor is equipped with a chemical heat storage material that releases reaction heat equal to or greater than the latent heat of evaporation of the heat medium and stores heat when the heat medium is desorbed, and is capable of dissipating heat above the regeneration temperature of the adsorber to the adsorber Then, a heat medium is supplied from the adsorber, and the hot water is supplied by exchanging heat with at least one of the condenser that condenses the supplied heat medium, the adsorber, the heat storage reactor, and the condenser. And a hot water supply section.
本発明においては、蓄熱反応器において熱媒を反応させて反応熱を生成し、この反応熱を吸着器の再生に利用する。このとき、蒸発器では熱媒の蒸発潜熱分の吸熱作用が生じる。例えば酸化カルシウムを用いた蓄熱反応系では、ＣａＯ＋Ｈ２Ｏ（熱媒）→Ｃａ（ＯＨ）２＋Ｑ［反応熱］の反応により得られる反応熱Ｑは大きく、「（反応熱Ｑ）＞＞（蒸発器の吸熱）」となる（例えば、蒸発器の吸熱量の２．５倍）。
吸着器は凝縮器と接続され、吸着器に蓄熱反応器での反応熱が加えられると、吸着器に吸着されている熱媒が脱離する。脱離した熱媒は凝縮器で凝縮され、その凝縮熱は温水として回収される。さらに、吸着器において熱媒脱離が終了し完全に再生すると、吸着器は蒸発器と接続される。蒸発器において反応熱を利用して気化した熱媒が吸着器に供給され吸着されると、その吸着熱（温熱）は、温水として回収される。すなわち、例えば蓄熱反応器で１００の反応熱を得た場合を考えると、例えば１００の反応熱を吸着器に与えて熱媒を脱離、凝縮させることで凝縮熱を得て１００の温水が生成される。さらに、蒸発器と吸着器とを接続し、吸着器に気化した熱媒を供給して吸着熱を得ることで、１００の温水が生成される。このように、熱と熱媒のやり取りを繰り返し行なうことで、化学蓄熱材の反応で蓄熱反応器に生成される熱エネルギー（反応熱Ｑ）から（顕熱を無視した場合）温水を従来の２倍量取り出すことが可能になる。
なお、吸着器の再生とは、吸着器の吸着材に吸着している熱媒を、熱の付与により吸着材から脱離（脱着）することをいい、再生温度は、吸着材から脱離が起きる温度である。
In the present invention, the heat medium is reacted in the heat storage reactor to generate reaction heat, and this reaction heat is used for regeneration of the adsorber. At this time, in the evaporator, an endothermic action corresponding to the latent heat of evaporation of the heat medium occurs. For example, in a heat storage reaction system using calcium oxide, the reaction heat Q obtained by the reaction CaO + H 2 O (heat medium) → Ca (OH) 2 + Q [reaction heat] is large, and “(reaction heat Q) >> (evaporation) (For example, 2.5 times the endothermic amount of the evaporator).
The adsorber is connected to a condenser, and when heat of reaction in the heat storage reactor is applied to the adsorber, the heat medium adsorbed on the adsorber is desorbed. The desorbed heat medium is condensed in a condenser, and the heat of condensation is recovered as hot water. Further, when the heat medium desorption in the adsorber is completed and completely regenerated, the adsorber is connected to the evaporator. When the heat medium vaporized using reaction heat in the evaporator is supplied to the adsorber and adsorbed, the heat of adsorption (warm heat) is recovered as hot water. That is, for example, when the reaction heat of 100 is obtained by the heat storage reactor, for example, the heat of reaction is given to the adsorber and the heat medium is desorbed and condensed to obtain the heat of condensation and 100 hot water is generated. Is done. Furthermore, 100 warm water is produced | generated by connecting an evaporator and an adsorber and supplying the heat medium vaporized to the adsorber and obtaining adsorption heat. In this way, by repeating the exchange of heat and heat medium, the hot water is converted from the heat energy (reaction heat Q) generated in the heat storage reactor by the reaction of the chemical heat storage material (when sensible heat is ignored) to the conventional 2 Double amount can be taken out.
The regeneration of the adsorber means that the heat medium adsorbed on the adsorbent of the adsorber is desorbed (desorbed) from the adsorbent by applying heat, and the regeneration temperature is the desorption from the adsorbent. This is the temperature at which it will occur.
本発明に係る給湯装置では、更に、蓄熱反応器の化学蓄熱材を加熱する熱源が設けられた構成が好ましい。発熱反応を繰り返した化学蓄熱材を再生するため、外部から加熱するための熱源を設けることで、化学蓄熱材の発熱反応を継続的に維持することができる。 In the hot water supply apparatus according to the present invention, a configuration in which a heat source for heating the chemical heat storage material of the heat storage reactor is further provided is preferable. In order to regenerate the chemical heat storage material having repeated the exothermic reaction, the heat generation reaction for the chemical heat storage material can be continuously maintained by providing a heat source for heating from the outside.
本発明に係る給湯装置において、吸着器は、蒸発器から蓄熱反応器に熱媒が供給されて蓄熱反応器から放出された反応熱で加熱されたときには、熱媒を脱離し、かつ蒸発器から供給された熱媒を吸着したときは、給湯部は、前記吸着器の吸着熱を水と熱交換することで給湯する。さらに加えて、凝縮器は、吸着器から脱離した熱媒を凝縮し、かつ凝縮時の凝縮熱を利用し、給湯部は、凝縮器での凝縮熱を水と熱交換することで給湯する態様に構成することができる。
このような態様によると、蒸発器での蒸発潜熱を利用して、その反応熱分に相当する吸着熱で温水を生成し、反応熱の一部を利用して吸着材の再生を行ない、脱着熱に相当する凝縮熱でその反応熱分に相当する凝縮熱で温水を生成するので、蓄熱反応器で得られた反応熱Ｑの無駄を省き、所望の給湯温度に対応する必要な熱量での給湯が行なえる。したがって、蓄熱反応器での反応熱より低い所望温度の給湯に必要な熱量を多く確保できる効果（増熱効果）があり、給湯量が増す。
In the hot water supply apparatus according to the present invention, when the heat medium is supplied from the evaporator to the heat storage reactor and heated by the reaction heat released from the heat storage reactor, the adsorber desorbs the heat medium and from the evaporator. When the supplied heat medium is adsorbed, the hot water supply unit supplies hot water by exchanging the adsorption heat of the adsorber with water. In addition, the condenser condenses the heat medium desorbed from the adsorber and uses the condensation heat at the time of condensation, and the hot water supply unit supplies hot water by exchanging heat of condensation in the condenser with water. It can be configured in an embodiment.
According to such an embodiment, the latent heat of vaporization in the evaporator is used to generate hot water with the heat of adsorption corresponding to the heat of reaction, and the adsorbent is regenerated using part of the heat of reaction. Since the hot water is generated with the condensation heat corresponding to the heat of the reaction with the heat of condensation corresponding to the heat, the waste of the reaction heat Q obtained in the heat storage reactor is eliminated, and the required amount of heat corresponding to the desired hot water supply temperature is saved. Hot water can be supplied. Therefore, there is an effect (heat increase effect) that can secure a large amount of heat necessary for hot water supply at a desired temperature lower than the reaction heat in the heat storage reactor, and the hot water supply amount increases.
一方、本発明に係る給湯装置では、蒸発器から蓄熱反応器に熱媒が供給されたときに、給湯部は、蓄熱反応器から放出された反応熱を水と熱交換することで給湯してもよい。これにより、高温の給湯需要が生じた場合に迅速に給湯することが可能になる。 On the other hand, in the hot water supply apparatus according to the present invention, when the heat medium is supplied from the evaporator to the heat storage reactor, the hot water supply section supplies hot water by exchanging the reaction heat released from the heat storage reactor with water. Also good. Thereby, when a hot water supply demand arises, it becomes possible to supply hot water quickly.
本発明に係る給湯装置は、蓄熱反応器の化学蓄熱材が外部の熱源（ヒータ等）により直接加熱されたときに、給湯部は、加熱された蓄熱反応器の顕熱の一部を前記吸着器に付与し吸着器から脱離した熱媒を凝縮したときの凝縮熱を水と熱交換することで給湯することができる。すなわち、外部熱源により直接加熱された蓄熱反応器の顕熱の一部が吸着器に与えられると、吸着器では熱媒が脱離し、脱離した熱媒が供給された凝縮器において熱媒が凝縮され凝縮熱が生じると、給湯部はこの凝縮熱を水と熱交換して温水を給湯する。
化学蓄熱材を再生するときには、外部熱源により高温で加熱されるため（例えばＣａ（ＯＨ）２の脱水反応では約４００℃程度）、顕熱ロスが生じやすいが、この顕熱を有効に利用することで熱効率が向上し、給湯効率（ＣＯＰ）の点で有利である。
In the hot water supply apparatus according to the present invention, when the chemical heat storage material of the heat storage reactor is directly heated by an external heat source (such as a heater), the hot water supply unit adsorbs part of the sensible heat of the heated heat storage reactor. Hot water can be supplied by exchanging heat of condensation with water when the heat medium applied to the vessel and desorbed from the adsorber is condensed. That is, when a part of the sensible heat of the heat storage reactor heated directly by the external heat source is given to the adsorber, the heat medium is desorbed in the adsorber, and the heat medium is depleted in the condenser supplied with the desorbed heat medium. When condensed and condensed heat is generated, the hot water supply unit exchanges this condensed heat with water to supply hot water.
When regenerating a chemical heat storage material, since it is heated at a high temperature by an external heat source (for example, about 400 ° C. in the dehydration reaction of Ca (OH) 2 ), sensible heat loss is likely to occur, but this sensible heat is used effectively. This improves the thermal efficiency, which is advantageous in terms of hot water supply efficiency (COP).
本発明に係る給湯装置は、蒸発器から吸着器に熱媒が供給されたときに、給湯部は、吸着器から放出された吸着熱を水と熱交換することで給湯することができる。吸着器の放出熱は化学蓄熱材の反応熱に比べて大きくないが、給湯需要の給湯温度が比較的低いときには吸着熱で温水を給湯することができる。 In the hot water supply apparatus according to the present invention, when a heat medium is supplied from the evaporator to the adsorber, the hot water supply unit can supply hot water by exchanging heat of adsorption released from the adsorber with water. Although the heat released from the adsorber is not large compared to the reaction heat of the chemical heat storage material, hot water can be supplied with adsorption heat when the hot water supply temperature for hot water supply is relatively low.
本発明に係る給湯装置では、蓄熱反応器の化学蓄熱材を外部の熱源により直接加熱した場合は、加熱によって蓄熱反応器から脱離した熱媒が凝縮器に送られて凝縮されることで、給湯部は、凝縮器から放出された凝縮熱を水と熱交換することで給湯することができる。この場合、凝縮器では、外部より化学蓄熱材を加熱した際の顕熱の一部に対応した凝縮熱が得られ、顕熱を有効利用できるので、所望とする温水を迅速に供給することが可能になる。 In the hot water supply apparatus according to the present invention, when the chemical heat storage material of the heat storage reactor is directly heated by an external heat source, the heat medium desorbed from the heat storage reactor by heating is sent to the condenser and condensed, The hot water supply unit can supply hot water by exchanging heat of condensation emitted from the condenser with water. In this case, in the condenser, condensation heat corresponding to a part of the sensible heat when the chemical heat storage material is heated from the outside can be obtained, and the sensible heat can be effectively used. It becomes possible.
本発明に係る給湯装置の蓄熱反応器は、化学蓄熱材の少なくとも一種として、金属酸化物及び金属塩化物から選択される化合物を用いて構成された態様が好ましく、アルカリ金属の水酸化物及び塩化物、アルカリ土類金属の水酸化物及び塩化物、並びに遷移金属の水酸化物及び塩化物からなる群から選択される化合物を有している態様がより好ましい。 The heat storage reactor of the hot water supply apparatus according to the present invention is preferably an embodiment configured using a compound selected from metal oxides and metal chlorides as at least one kind of chemical heat storage material, alkali metal hydroxides and chlorides More preferred is an embodiment having a compound selected from the group consisting of a metal oxide, an alkaline earth metal hydroxide and chloride, and a transition metal hydroxide and chloride.
金属酸化物及び金属塩化物は、高い蓄熱密度（ｋＪ／ｋｇ）が得られる点で好適であり、熱の有効利用に適している。アルカリ金属の水酸化物及び塩化物、アルカリ土類金属の水酸化物及び塩化物、及び遷移金属の水酸化物及び塩化物は、温熱及び冷熱の生成効率をより高める点で有用である。 Metal oxides and metal chlorides are suitable in that a high heat storage density (kJ / kg) is obtained, and are suitable for effective use of heat. Alkali metal hydroxides and chlorides, alkaline earth metal hydroxides and chlorides, and transition metal hydroxides and chlorides are useful in terms of further increasing the efficiency of producing hot and cold heat.
なお、蓄熱密度は、水やアンモニア等の熱媒の脱離により水酸化物又は金属塩化物１ｋｇあたりに蓄熱される熱量（ｋＪ）を示す。 The heat storage density indicates the amount of heat (kJ) stored per kg of hydroxide or metal chloride due to desorption of a heat medium such as water or ammonia.
本発明においては、熱媒として水を用い、水の授受により蓄熱、放熱を行なう場合、化学蓄熱材としては、酸化カルシウム（ＣａＯ）、酸化マグネシウム（ＭｇＯ）、及び酸化バリウム（ＢａＯ）から選択されるものが好ましい。 In the present invention, when water is used as a heat medium and heat is stored and released by transferring water, the chemical heat storage material is selected from calcium oxide (CaO), magnesium oxide (MgO), and barium oxide (BaO). Those are preferred.
本発明においては、熱媒としてアンモニアを用い、アンモニアの授受により蓄熱、放熱を行なう場合、化学蓄熱材としては、塩化リチウム（ＬｉＣｌ）、塩化マグネシウム（ＭｇＣｌ２）、塩化カルシウム（ＣａＣｌ２）、塩化ストロンチウム（ＳｒＣｌ２）、塩化バリウム（ＢａＣｌ２）、塩化マンガン（ＭｎＣｌ２）、塩化コバルト（ＣｏＣｌ２）、及び塩化ニッケル（ＮｉＣｌ２）から選択されるものが好ましい。 In the present invention, when ammonia is used as a heating medium and heat is stored and released by transferring ammonia, the chemical heat storage material is lithium chloride (LiCl), magnesium chloride (MgCl 2 ), calcium chloride (CaCl 2 ), chloride. Those selected from strontium (SrCl 2 ), barium chloride (BaCl 2 ), manganese chloride (MnCl 2 ), cobalt chloride (CoCl 2 ), and nickel chloride (NiCl 2 ) are preferred.
本発明における吸着器は、熱媒を吸着する吸着材を設けて構成されていることが好ましい。吸着材としては、熱媒を物理吸着する物理吸着材を設けて構成された態様が好ましく、活性炭、メソポーラスシリカ、ゼオライト、シリカゲル、及び粘土鉱物からなる群から選択される物理吸着材を設けた構成がより好ましい。特に物理吸着材である活性炭、メソポーラスシリカ、ゼオライト、シリカゲル、及び粘土鉱物は、熱媒脱離しあるいは脱離した熱媒を再吸着する場合に、熱媒１ｍｏｌの脱離あるいは吸着に要する熱量が化学吸着材に比べて小さく、少ない熱量で熱媒の授受を行なうことができる。
また、従来は熱の利用効率を高めるため貯湯槽を設けた例があるが、貯湯槽では放熱による顕熱ロス（熱エネルギー損失）が大きいのに対し、化学蓄熱材を利用した蓄熱では、バルブ等で熱媒移動が遮断される限り、半永久的に熱エネルギーを保持することが可能である。例えば一般に使用される貯湯槽に比べて約１５０倍の蓄熱密度を達成することができる。
The adsorber in the present invention is preferably configured by providing an adsorbent that adsorbs the heat medium. The adsorbent preferably has a physical adsorbent that physically adsorbs the heat medium, and is provided with a physical adsorbent selected from the group consisting of activated carbon, mesoporous silica, zeolite, silica gel, and clay mineral. Is more preferable. In particular, activated carbon, mesoporous silica, zeolite, silica gel, and clay minerals, which are physical adsorbents, have a chemical amount of heat required for desorption or adsorption of 1 mol of the heat medium when the heat medium is desorbed or resorbed. It is smaller than the adsorbent and can transfer the heat medium with a small amount of heat.
Conventionally, there is an example in which a hot water storage tank is provided in order to increase the heat utilization efficiency, but in the hot water storage tank, sensible heat loss (heat energy loss) due to heat radiation is large, whereas in heat storage using a chemical heat storage material, a valve is used. As long as the transfer of the heat medium is interrupted by, for example, the heat energy can be held semipermanently. For example, a heat storage density about 150 times that of a commonly used hot water storage tank can be achieved.
本発明において、蓄熱反応器の熱媒固定化時に放出される反応熱の熱量が、吸着器の熱媒吸着時に放出される吸着熱の熱量の２倍以上である場合が好ましい。単に外部熱源を用いた加熱によるのではなく、化学蓄熱材の反応熱が吸着器の吸着時における熱量より２倍以上であることで、蓄熱反応器の反応熱の一部で吸着器を加熱して熱媒を脱離させ、さらに他の一部で吸着器に蒸発器から熱媒を供給、吸着させることができる。これにより、２倍以上の増熱効果が期待される。 In the present invention, it is preferable that the amount of heat of reaction released when the heat storage reactor is fixed to the heat medium is twice or more than the amount of heat of adsorption released when the adsorber adsorbs the heat medium. Rather than simply heating using an external heat source, the heat of reaction of the chemical heat storage material is more than twice the amount of heat generated during the adsorption of the adsorber, so that the adsorber is heated with a part of the heat of reaction of the heat storage reactor. Thus, the heat medium can be desorbed, and the heat medium can be supplied and adsorbed from the evaporator to the adsorber by another part. Thereby, the heat increase effect of 2 times or more is expected.
本発明に係る給湯装置には、給湯部から所定の閾値温度以上（例えば５０℃以上）の給湯温度で給湯するときには、蒸発器から蓄熱反応器に熱媒を供給し、給湯部は、蓄熱反応器の反応熱を水と熱交換することで給湯すると共に、給湯部から所定の閾値温度未満（例えば５０℃未満）の給湯温度で給湯するときには、給湯部は、吸着器において熱媒が吸着するときの吸着熱を水と熱交換し、かつ凝縮器において熱媒を凝縮させるときの凝縮熱を水と熱交換することで給湯する構成とすることができる。 In the hot water supply apparatus according to the present invention, when hot water is supplied from a hot water supply portion at a hot water supply temperature that is equal to or higher than a predetermined threshold temperature (for example, 50 ° C. or higher), a heat medium is supplied from the evaporator to the heat storage reactor. When hot water is supplied by exchanging the reaction heat of the heat exchanger with water and hot water is supplied at a hot water supply temperature lower than a predetermined threshold temperature (for example, lower than 50 ° C.) from the hot water supply portion, the hot water adsorbs the heat medium in the adsorber. It is possible to supply hot water by exchanging heat of the heat with water and exchanging the heat of condensation with water when the heat medium is condensed in the condenser.
本発明では、化学蓄熱材を用いた蓄熱反応器と吸着器とを配設することによって、例えば５０℃以上の比較的温度の高い給湯需要があるときには、蓄熱反応器の反応熱を直接熱交換することで、高温の給湯を迅速に行なうことができる。逆に、給湯需要の給湯温度が例えば５０℃未満の比較的低い温度域であるときには、蓄熱反応器での反応熱の一部を吸着器に与えて熱媒を脱離させ、凝縮器での熱媒凝縮時の凝縮熱で比較低温の温水を給湯することができる。このとき、温水の温度は化学蓄熱材の反応熱に比べて低いため、この低い温度の温水を多量に給湯することが可能であり、吸着器の再生が完了したときは蒸発器からの熱媒供給が可能で吸着器の吸着熱による温水の給湯も行なえる利点がある。 In the present invention, by arranging a heat storage reactor and an adsorber using a chemical heat storage material, when there is a demand for hot water supply with a relatively high temperature of, for example, 50 ° C. or higher, the reaction heat of the heat storage reactor is directly exchanged. By doing so, a hot water supply can be performed rapidly. Conversely, when the hot water supply temperature for hot water supply is in a relatively low temperature range of, for example, less than 50 ° C., a part of the reaction heat in the heat storage reactor is given to the adsorber to desorb the heat medium, and in the condenser Hot water of comparatively low temperature can be supplied with the heat of condensation during heat medium condensation. At this time, since the temperature of the hot water is lower than the reaction heat of the chemical heat storage material, it is possible to supply a large amount of hot water at this low temperature, and when regeneration of the adsorber is completed, the heat medium from the evaporator There is an advantage that hot water can be supplied by the heat of adsorption of the adsorber.
本発明によれば、顕熱ロスが少なく熱の利用効率に優れており、給湯温度に応じて効率良く給湯する給湯装置が提供される。 ADVANTAGE OF THE INVENTION According to this invention, there is little sensible heat loss and it is excellent in the utilization efficiency of heat, and the hot water supply apparatus which supplies hot water efficiently according to hot water supply temperature is provided.
以下、図１〜図９を参照して、本発明の給湯装置の実施形態について具体的に説明する。但し、本発明においては、以下に示す実施形態に制限されるものではない。 Hereinafter, with reference to FIGS. 1-9, embodiment of the hot water supply apparatus of this invention is described concretely. However, the present invention is not limited to the embodiments shown below.
本実施形態では、蓄熱反応器の化学蓄熱材として酸化カルシウム（ＣａＯ）を、吸着器の吸着材としてシリカゲルを用い、熱媒として水を用いた蓄熱型吸着式ヒートポンプ給湯システム（以下、単に「給湯システム」又は「本実施形態の給湯システム」ともいう。）を一例に詳細に説明する。 In this embodiment, calcium oxide (CaO) is used as the chemical heat storage material of the heat storage reactor, silica gel is used as the adsorbent of the adsorber, and water is used as a heat medium. The system "or" the hot water supply system of the present embodiment ") will be described in detail as an example.
本実施形態の給湯システム１００は、図１に示すように、蓄熱反応器１０と、蓄熱反応器と熱的に接続されている吸着器２０と、蓄熱反応器及び吸着器への熱媒供給が可能なように接続された蒸発器３０、蓄熱反応器及び吸着器からの熱媒供給が可能なように接続された凝縮器４０と、蓄熱反応器、吸着器、及び凝縮器とそれぞれ熱的に接続された給湯部５０とを備えている。 As shown in FIG. 1, the hot water supply system 100 of the present embodiment includes a heat storage reactor 10, an adsorber 20 that is thermally connected to the heat storage reactor, and a heat medium supply to the heat storage reactor and the adsorber. The evaporator 30 connected as possible, the condenser 40 connected so as to be able to supply the heat medium from the heat storage reactor and the adsorber, and the heat storage reactor, the adsorber and the condenser thermally And a hot water supply unit 50 connected thereto.
本実施形態の蓄熱反応器１０は、化学蓄熱材として、酸化カルシウム（ＣａＯ）を備えており、熱媒である水が供給されることで、下記の反応を起こして反応熱を生じる。化学蓄熱材は、化学反応を利用して熱の吸収、放出を行なうことのできる物質であり、粉体を成形した成形物として反応器内に設けられていてもよい。 The heat storage reactor 10 of the present embodiment includes calcium oxide (CaO) as a chemical heat storage material, and is supplied with water as a heat medium, thereby causing the following reaction to generate reaction heat. The chemical heat storage material is a substance that can absorb and release heat using a chemical reaction, and may be provided in the reactor as a molded product obtained by molding powder.
化学蓄熱材であるＣａＯは、水和により放熱（発熱）し、脱水を伴なって蓄熱（吸熱）する構成となる。すなわち、ＣａＯは、以下に示す反応により蓄熱、放熱を可逆的に繰り返することができる。
ＣａＯ ＋ Ｈ２Ｏ ⇔ Ｃａ（ＯＨ）２ ・・・(a)
またこれに、蓄熱量、発熱量Ｑを併せて示すと、以下のようになる。
ＣａＯ ＋ Ｈ２Ｏ → Ｃａ（ＯＨ）２ ＋ Ｑ ・・・(b)
Ｃａ（ＯＨ）２ ＋ Ｑ → ＣａＯ ＋ Ｈ２Ｏ ・・・(c)
CaO which is a chemical heat storage material is configured to radiate heat (heat generation) by hydration and to store heat (heat absorption) with dehydration. That is, CaO can reversibly repeat heat storage and heat dissipation by the reactions shown below.
CaO + H 2 O Ｃａ Ca (OH) 2 (a)
In addition, when the heat storage amount and the heat generation amount Q are also shown, this is as follows.
CaO + H 2 O → Ca (OH) 2 + Q (b)
Ca (OH) 2 + Q → CaO + H 2 O (c)
本実施形態では、図１に示されるように、蒸発器３０から水蒸気（Ｈ２Ｏ）が供給されると、上記反応を起こして反応熱Ｑを生成する。生成した反応熱Ｑは、図２に示されるように、吸着器２０との間の熱交換により、吸着器２０に与えることができるようになっている。また、図４に示されるように、反応熱を直接給湯用の水と熱交換することで、高温の給湯が可能になる。 In the present embodiment, as shown in FIG. 1, when steam (H 2 O) is supplied from the evaporator 30, the above reaction occurs to generate reaction heat Q. The generated reaction heat Q can be given to the adsorber 20 by heat exchange with the adsorber 20, as shown in FIG. Further, as shown in FIG. 4, hot water supply can be performed by exchanging heat of reaction directly with water for hot water supply.
化学蓄熱材としては、酸化物系の材料として、ＣａＯのほか、例えば、酸化マグネシウム（ＭｇＯ）、酸化バリウム（ＢａＯ）などのアルカリ土類金属の無機酸化物や、酸化リチウムなどのアルカリ金属の無機酸化物、酸化アルミニウム（Ａｌ２Ｏ３）、等の無機酸化物などが挙げられる。金属酸化物は、一種単独で用いるほか、二種以上を併用してもよい。 As the chemical heat storage material, as an oxide-based material, in addition to CaO, for example, an inorganic oxide of an alkaline earth metal such as magnesium oxide (MgO) or barium oxide (BaO), or an inorganic of an alkali metal such as lithium oxide oxide, aluminum oxide (Al 2 O 3), and the like inorganic oxides like. A metal oxide may be used individually by 1 type, and may use 2 or more types together.
上記以外の化学蓄熱材としては、蓄熱密度をより高める観点から、金属塩化物も好適である。金属塩化物は、熱媒としてアンモニア等を使用する場合に好適に用いられ、アンモニアの吸着時に発熱反応を生じる化合物を適用することができる。金属塩化物では、アンモニアが蓄熱材に固定化（吸着）されるとき（例えばＭｇＣｌ２の場合、下記の可逆反応(1)において右方向に進む反応時）に放熱し、アンモニアが蓄熱材から脱離するとき（例えばＭｇＣｌ２の場合、下記の可逆反応(1)において左方向に進め反応時）に蓄熱する。
ＭｇＣｌ２・２ＮＨ３＋ ４ＮＨ３ ⇔ ＭｇＣｌ２・６ＮＨ３ ＋ Ｑ１［ｋＪ］ …(1)
As the chemical heat storage material other than the above, metal chloride is also preferable from the viewpoint of further increasing the heat storage density. The metal chloride is suitably used when ammonia or the like is used as a heating medium, and a compound that generates an exothermic reaction upon adsorption of ammonia can be applied. Metal chloride dissipates heat when ammonia is immobilized (adsorbed) on the heat storage material (for example, in the case of MgCl 2 , the reaction proceeds to the right in the following reversible reaction (1)), and ammonia is desorbed from the heat storage material. When it is released (for example, in the case of MgCl 2 , heat is stored in the following reversible reaction (1), proceeding leftward).
MgCl 2 · 2NH 3 + 4NH 3 ＭｇMgCl 2 · 6NH 3 + Q 1 [kJ] (1)
金属塩化物としては、例えば、アルカリ金属の塩化物、アルカリ土類金属の塩化物、及び遷移金属の塩化物などが好適であり、塩化リチウム（ＬｉＣｌ）、塩化マグネシウム（ＭｇＣｌ２）、塩化カルシウム（ＣａＣｌ２）、塩化ストロンチウム（ＳｒＣｌ２）、塩化バリウム（ＢａＣｌ２）、塩化マンガン（ＭｎＣｌ２）、塩化コバルト（ＣｏＣｌ２）、及び塩化ニッケル（ＮｉＣｌ２）がより好ましい。金属塩化物は、一種単独で用いるほか、二種以上を併用してもよい。
金属塩化物の種類は、アンモニア圧や温度に合わせて適宜選定することができる。したがって、熱利用の対象に合わせ、アンモニア圧や温度を選定できる幅が広がる。
As the metal chloride, for example, an alkali metal chloride, an alkaline earth metal chloride, and a transition metal chloride are preferable, and lithium chloride (LiCl), magnesium chloride (MgCl 2 ), calcium chloride ( More preferred are CaCl 2 ), strontium chloride (SrCl 2 ), barium chloride (BaCl 2 ), manganese chloride (MnCl 2 ), cobalt chloride (CoCl 2 ), and nickel chloride (NiCl 2 ). A metal chloride may be used alone or in combination of two or more.
The kind of metal chloride can be appropriately selected according to the ammonia pressure and temperature. Therefore, the range in which the ammonia pressure and temperature can be selected in accordance with the heat utilization target is expanded.
上記の中では、水を熱媒とする系では、水和反応に伴なって放熱し、脱水反応に伴なって吸熱する水和反応性蓄熱材が好ましく、特に酸化カルシウム（ＣａＯ）好ましい。
また、アンモニアを熱媒とする系は、氷点下での運転が可能である。この場合、アンモニアの吸着温度が低い場合は、ＢａＣｌ２、ＣａＣｌ２、ＳｒＣｌ２を選択することができ、アンモニアの吸着温度が比較的高い場合は、ＭｇＣｌ２、ＭｎＣｌ２、ＣｏＣｌ２、ＮｉＣｌ２を選択することができる。
Among the above, in a system using water as a heat medium, a hydration reactive heat storage material that dissipates heat with a hydration reaction and absorbs heat with a dehydration reaction is preferable, and calcium oxide (CaO) is particularly preferable.
In addition, a system using ammonia as a heat medium can be operated below freezing point. In this case, when the ammonia adsorption temperature is low, BaCl 2 , CaCl 2 , and SrCl 2 can be selected. When the ammonia adsorption temperature is relatively high, MgCl 2 , MnCl 2 , CoCl 2 , and NiCl 2 can be selected. You can choose.
化学蓄熱材は、ＣａＯ等の例えば粒状物をプレス成形して得られた成形体として設けることができる。
成形方法については、特に限定はなく、例えば、化学蓄熱材及び必要に応じてバインダー等の他の成分を含む蓄熱材（又は蓄熱材を含むスラリー）を、加圧成形、押出成形等の公知の成形方法を適用することができる。成形時の圧力は、例えば２０〜１００ＭＰａとすることができ、２０〜４０ＭＰａが好ましい。
The chemical heat storage material can be provided as a molded body obtained by press molding, for example, a granular material such as CaO.
The molding method is not particularly limited. For example, a heat storage material (or a slurry containing a heat storage material) containing a chemical heat storage material and other components such as a binder as necessary is formed by a known method such as pressure molding or extrusion molding. A molding method can be applied. The pressure at the time of shaping | molding can be 20-100 Mpa, for example, and 20-40 Mpa is preferable.
蓄熱反応器１０には、化学蓄熱材を加熱して脱水反応させて再生するための加熱手段として外部熱源６０が熱交換管１６を介して熱的に接続されている。外部熱源６０により化学蓄熱材を加熱することで、化学蓄熱材の水（熱媒）との反応性が改善される。
外部熱源６０としては、燃料を燃焼して加熱する燃焼器、電気ヒータ等のヒータ類などを使用することができる。
An external heat source 60 is thermally connected to the heat storage reactor 10 via a heat exchange pipe 16 as a heating means for heating and regenerating the chemical heat storage material by dehydration reaction. By reacting the chemical heat storage material with the external heat source 60, the reactivity of the chemical heat storage material with water (heat medium) is improved.
As the external heat source 60, a combustor that burns and heats fuel, a heater such as an electric heater, or the like can be used.
熱交換管１６は、無端の配管と、この配管内を流通する熱交換用流体とで構成されている。配管に取り付けられた図示しない循環用ポンプによって、配管中を熱交換用流体（例えば水又は水と水溶性溶剤（エタノール等のアルコールやエチレングリコール等のグリコールなど）との混合溶媒）が循環して流通することで、熱源６０の熱を蓄熱反応器１０に付与して加熱できるようになっている。 The heat exchange pipe 16 is composed of an endless pipe and a heat exchange fluid that circulates in the pipe. A circulation pump (not shown) attached to the pipe circulates the heat exchange fluid (for example, water or a mixed solvent of water and a water-soluble solvent (alcohol such as ethanol or glycol such as ethylene glycol)) in the pipe. By circulating, the heat of the heat source 60 can be applied to the heat storage reactor 10 and heated.
吸着器２０は、水（熱媒）を吸着する吸着材としてシリカゲル（物理吸着材）が配設されており、熱交換管１２を介して蓄熱反応器１０と熱的に接続されている。吸着器２０は、蓄熱反応器１０からの熱で吸着材が加熱されると、吸着材であるシリカゲルに吸着されている水（熱媒）を脱離し、脱離した水を凝縮器４０に供給することができる。 The adsorber 20 is provided with silica gel (physical adsorbent) as an adsorbent that adsorbs water (heat medium), and is thermally connected to the heat storage reactor 10 via the heat exchange pipe 12. When the adsorbent is heated by the heat from the heat storage reactor 10, the adsorber 20 desorbs water (heat medium) adsorbed on the silica gel as the adsorbent and supplies the desorbed water to the condenser 40. can do.
吸着材が用いられることにより、化学蓄熱材に比べて、熱媒の吸着（固定化）及び脱離に要する熱量をより小さくすることができ、低エネルギーでも熱媒の着脱が容易に行なえる。熱媒にアンモニアを用いた場合、アンモニア１ｍｏｌの吸着及び脱離に要する熱量は、化学蓄熱材（例えば、ＬｉＣｌ、ＭｇＣｌ２、ＣａＣｌ２、ＳｒＣｌ２、ＢａＣｌ２、ＭｎＣｌ２、ＣｏＣｌ２、ＮｉＣｌ２等）では４０〜６０ｋＪ／ｍｏｌであるのに対し、物理吸着材では２０〜３０ｋＪ／ｍｏｌに抑えることができる。 By using the adsorbent, the amount of heat required for adsorption (immobilization) and desorption of the heat medium can be further reduced as compared with the chemical heat storage material, and the heat medium can be easily attached and detached even with low energy. When ammonia is used as the heat medium, the amount of heat required for adsorption and desorption of 1 mol of ammonia is a chemical heat storage material (for example, LiCl, MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , MnCl 2 , CoCl 2 , NiCl 2, etc.). ) Is 40 to 60 kJ / mol, while it can be suppressed to 20 to 30 kJ / mol with the physical adsorbent.
吸着材としては、多孔体を用いることができる。多孔体としては、吸着（好ましくは物理吸着）によるアンモニアの固定化及び脱離の反応性をより向上させる観点から、細孔径が１０ｎｍ以下の孔を有する多孔体が好ましい。細孔径の下限は、製造適性等の観点から、０．５ｎｍが好ましい。多孔体としては、前記同様の観点から、平均１次粒子径が５０μｍ以下の１次粒子が凝集して得られた１次粒子凝集体である多孔体が好ましい。平均１次粒子径の下限は、製造適性等の観点から１μｍが好ましい。 A porous material can be used as the adsorbent. The porous body is preferably a porous body having pores having a pore diameter of 10 nm or less from the viewpoint of further improving the reactivity of immobilization and desorption of ammonia by adsorption (preferably physical adsorption). The lower limit of the pore diameter is preferably 0.5 nm from the viewpoint of production suitability and the like. As the porous body, from the same viewpoint as described above, a porous body which is a primary particle aggregate obtained by aggregating primary particles having an average primary particle diameter of 50 μm or less is preferable. The lower limit of the average primary particle diameter is preferably 1 μm from the viewpoint of production suitability and the like.
吸着材の例としては、本実施形態で用いられているシリカゲルのほか、例えば、活性炭、メソポーラスシリカ、ゼオライト、粘土鉱物等が挙げられる。前記粘土鉱物としては、非架橋の粘土鉱物であっても、架橋された粘土鉱物（架橋粘土鉱物）であってもよい。粘土鉱物の例として、セピオライト等が挙げられる。
吸着材の比表面積は、ＢＥＴ法による比表面積で５００ｍ２／ｇ以上２５００ｍ２／ｇ以下（より好ましくは１０００ｍ２／ｇ以上２５００ｍ２／ｇ以下）であることが好ましい。
Examples of the adsorbent include activated carbon, mesoporous silica, zeolite, clay mineral and the like in addition to the silica gel used in the present embodiment. The clay mineral may be an uncrosslinked clay mineral or a crosslinked clay mineral (crosslinked clay mineral). Examples of clay minerals include sepiolite.
The specific surface area of the adsorbent is preferably 500 m 2 / g or more and 2500 m 2 / g or less (more preferably 1000 m 2 / g or more and 2500 m 2 / g or less) as a specific surface area according to the BET method.
本発明においては、熱媒の圧力や温度に合わせて、吸着材（好ましくは多孔体）の種類を適宜選定することができる。吸着による水の固定化及び脱離の反応性をより向上させる観点からは、シリカゲルを少なくとも含む態様が好ましい。また、吸着によるアンモニアの固定化及び脱離の反応性をより向上させる観点からは、活性炭を少なくとも含む態様が好ましい。 In the present invention, the type of adsorbent (preferably a porous body) can be appropriately selected according to the pressure and temperature of the heat medium. From the viewpoint of further improving the reactivity of water immobilization and desorption by adsorption, an embodiment containing at least silica gel is preferable. Further, from the viewpoint of further improving the reactivity of immobilization and desorption of ammonia by adsorption, an embodiment including at least activated carbon is preferable.
吸着材（好ましくは物理吸着材）を用いた熱媒の授受により吸発熱する構成の場合、吸着材量中に占める吸着材の含有比率は、熱媒の固定化及び脱離の反応性をより高く維持する観点から、８０体積％以上が好ましく、９０体積％以上がより好ましい。 In the case of a structure that absorbs and generates heat by transferring a heat medium using an adsorbent (preferably a physical adsorbent), the content ratio of the adsorbent in the amount of adsorbent increases the reactivity of fixing and desorption of the heat medium From the viewpoint of maintaining high, 80% by volume or more is preferable, and 90% by volume or more is more preferable.
吸着材を成形体にして利用する場合、吸着材と共にバインダーを含有してもよい。バインダーを含有することで、成形体の形状がより維持され易くなるので、吸着による熱媒の固定化及び脱離の反応性がより向上する。バインダーとしては、水溶性バインダーが好ましい。水溶性バインダーとしては、ポリビニルアルコール、トリメチルセルロース等が挙げられる。
また、吸着材及びバインダーに加えて、必要に応じて、他の成分を含有していてもよい。他の成分の例として、カーボンファイバーや金属繊維等の熱伝導性無機材料等が挙げられる。
When the adsorbent is used as a molded body, a binder may be contained together with the adsorbent. By containing the binder, the shape of the molded body is more easily maintained, so that the heat medium fixation and desorption reactivity by adsorption is further improved. As the binder, a water-soluble binder is preferable. Examples of the water-soluble binder include polyvinyl alcohol and trimethyl cellulose.
Moreover, in addition to the adsorbent and the binder, other components may be contained as necessary. Examples of other components include thermally conductive inorganic materials such as carbon fibers and metal fibers.
吸着材及びバインダーを用いて成形する場合、バインダーの含有比率は、成形体の形状をより効果的に維持する観点から、５体積％以上が好ましく、１０体積％以上がより好ましい。成形方法については、特に限定はなく、例えば、吸着材（及び必要に応じバインダー等の他の成分）を加圧成形、押し出し成形等の公知の成形手段により成形する方法が挙げられる。成形時の圧力は、例えば２０〜１００ＭＰａとすることができ、２０〜４０ＭＰａが好ましい。 When molding using an adsorbent and a binder, the content ratio of the binder is preferably 5% by volume or more and more preferably 10% by volume or more from the viewpoint of more effectively maintaining the shape of the molded body. The molding method is not particularly limited, and examples thereof include a method in which an adsorbent (and other components such as a binder as necessary) is molded by known molding means such as pressure molding and extrusion molding. The pressure at the time of shaping | molding can be 20-100 Mpa, for example, and 20-40 Mpa is preferable.
熱交換管１２は、無端の配管と、この配管内を流通する熱交換用流体とで構成されている。配管に取り付けられた図示しない循環用ポンプによって、配管中を熱交換用流体（例えば水又は水と水溶性溶剤（エタノール等のアルコールやエチレングリコール等のグリコールなど）との混合溶媒）が循環して流通することで、吸着器２０より熱量の高い蓄熱反応器の熱を吸着器２０に付与できるようになっている。 The heat exchange pipe 12 is composed of an endless pipe and a heat exchange fluid that circulates in the pipe. A circulation pump (not shown) attached to the pipe circulates the heat exchange fluid (for example, water or a mixed solvent of water and a water-soluble solvent (alcohol such as ethanol or glycol such as ethylene glycol)) in the pipe. By circulating, the heat of the heat storage reactor having a higher heat quantity than the adsorber 20 can be applied to the adsorber 20.
蒸発器３０は、熱媒を気化し、気化した熱媒を供給可能に蓄熱反応器１０及び吸着器２０と接続されている。具体的には、蒸発器３０には、バルブＶ１を有する熱媒供給管３２の一端と、バルブＶ３を有する熱媒供給管３４の一端とがそれぞれ接続されており、蒸発器３０は熱媒供給管３２、３４を介して蓄熱反応器１０、吸着器２０と連通されている。 The evaporator 30 is connected to the heat storage reactor 10 and the adsorber 20 so as to vaporize the heat medium and supply the vaporized heat medium. Specifically, one end of a heat medium supply pipe 32 having a valve V1 and one end of a heat medium supply pipe 34 having a valve V3 are respectively connected to the evaporator 30, and the evaporator 30 is supplied with a heat medium. The heat storage reactor 10 and the adsorber 20 are communicated with each other through pipes 32 and 34.
熱媒供給管３２の他端は、蓄熱反応器１０と接続されており、バルブＶ１を開くことで、水蒸気（熱媒）は、熱媒供給管３２を通じて蓄熱反応器１０に供給される。このとき、蒸発器での蒸気圧が蓄熱反応器より高いため、バルブを開くことで熱媒の供給が可能である。また、熱媒供給により化学蓄熱材は発熱反応を起こして反応熱を生成するが、バルブＶ１を閉じておくことで、半永久的に熱エネルギーを蓄えておくことが可能である。 The other end of the heat medium supply pipe 32 is connected to the heat storage reactor 10, and steam (heat medium) is supplied to the heat storage reactor 10 through the heat medium supply pipe 32 by opening the valve V <b> 1. At this time, since the vapor pressure in the evaporator is higher than that in the heat storage reactor, the heating medium can be supplied by opening the valve. Further, the chemical heat storage material causes an exothermic reaction to generate reaction heat by supplying the heat medium, but it is possible to store heat energy semipermanently by closing the valve V1.
熱媒供給管３４の他端は、吸着器２０と接続されており、バルブＶ３を開くことで、水蒸気（熱媒）は、熱媒供給管３４を通じて吸着器２０に供給される。このとき、蒸発器での蒸気圧が吸着器より高いため、バルブを開くことで熱媒の供給が可能である。また、熱媒の供給により、熱媒が吸着材に吸着されると発熱反応が生じて吸着熱を生成するが、バルブＶ３を閉じておくことで、半永久的に熱エネルギーを蓄えておくことが可能である。 The other end of the heat medium supply pipe 34 is connected to the adsorber 20, and water vapor (heat medium) is supplied to the adsorber 20 through the heat medium supply pipe 34 by opening the valve V <b> 3. At this time, since the vapor pressure in the evaporator is higher than that in the adsorber, the heating medium can be supplied by opening the valve. Further, when the heat medium is adsorbed by the adsorbent by supplying the heat medium, an exothermic reaction occurs to generate heat of adsorption, but heat energy can be stored semipermanently by closing the valve V3. Is possible.
また、蒸発器３０は、熱交換管３６を介して冷熱需要の例であるエアコン室外機などの冷熱機器７０と熱的に接続されている。蒸発器３０では、熱媒の気化のために冷熱が生成されるため、熱交換管３６を通じて熱交換することで、冷熱需要のある機器との間で熱の有効利用が図れる。 In addition, the evaporator 30 is thermally connected to a cooling device 70 such as an air conditioner outdoor unit that is an example of cooling demand through a heat exchange pipe 36. In the evaporator 30, since cold heat is generated for vaporizing the heat medium, heat can be effectively used with equipment having cold demand by exchanging heat through the heat exchange pipe 36.
熱交換管３６は、熱交換管１２と同様に、無端の配管とこの配管内を流通する熱交換用流体とで構成されている。配管に取り付けられた図示しない循環用ポンプによって、配管中を熱交換用流体（例えば上記同様に水又は水と水溶性溶剤との混合溶媒）が循環して流通することで、冷熱を冷熱機器７０に供給することができる。 Similar to the heat exchange pipe 12, the heat exchange pipe 36 is composed of an endless pipe and a heat exchange fluid flowing through the pipe. A heat exchange fluid (for example, water or a mixed solvent of water and a water-soluble solvent) circulates and circulates in the pipe by a circulation pump (not shown) attached to the pipe, so that the cold heat is supplied to the refrigeration equipment 70. Can be supplied to.
凝縮器４０は、熱媒供給管４２、４４により蓄熱反応器１０及び吸着器２０と熱媒供給が可能に接続されており、蓄熱反応器１０及び吸着器２０から供給された水蒸気（熱媒）を凝縮する。具体的には、凝縮器４０には、バルブＶ２を有する熱媒供給管４２の一端と、バルブＶ４を有する熱媒供給管４４の一端とがそれぞれ接続されており、凝縮器４０は熱媒供給管４２、４４を介して蓄熱反応器１０、吸着器２０と連通されている。 The condenser 40 is connected to the heat storage reactor 10 and the adsorber 20 through the heat medium supply pipes 42 and 44 so as to be able to supply the heat medium, and water vapor (heat medium) supplied from the heat storage reactor 10 and the adsorber 20. To condense. Specifically, one end of a heat medium supply pipe 42 having a valve V2 and one end of a heat medium supply pipe 44 having a valve V4 are connected to the condenser 40, and the condenser 40 supplies the heat medium. The heat storage reactor 10 and the adsorber 20 are communicated with each other through pipes 42 and 44.
熱媒供給管４２の他端は、蓄熱反応器１０と接続されており、バルブＶ２を開くことで、水蒸気（熱媒）が熱媒供給管４２を通じて凝縮器４０に送られる。このとき、凝縮器での蒸気圧が蓄熱反応器より低いため、バルブを開くことで熱媒の供給が可能である。凝縮器では、水蒸気を凝縮して水に戻す際に凝縮熱を生成し、この凝縮熱を熱交換することで温水の給湯が可能である。 The other end of the heat medium supply pipe 42 is connected to the heat storage reactor 10, and steam (heat medium) is sent to the condenser 40 through the heat medium supply pipe 42 by opening the valve V <b> 2. At this time, since the vapor pressure in the condenser is lower than that in the heat storage reactor, the heating medium can be supplied by opening the valve. In the condenser, when the water vapor is condensed and returned to the water, condensation heat is generated, and hot water can be supplied by exchanging heat of the condensation heat.
熱媒供給管４４の他端は、吸着器２０と接続されており、バルブＶ４を開くことで、水蒸気（熱媒）が熱媒供給管４４を通じて凝縮器４０に送られる。このとき、凝縮器での蒸気圧が吸着器より低いため、バルブを開くことで熱媒の供給が可能である。凝縮器では、上記のように凝縮熱を生成し、この凝縮熱を熱交換することで温水の給湯が可能である。 The other end of the heat medium supply pipe 44 is connected to the adsorber 20, and steam (heat medium) is sent to the condenser 40 through the heat medium supply pipe 44 by opening the valve V <b> 4. At this time, since the vapor pressure in the condenser is lower than that in the adsorber, the heating medium can be supplied by opening the valve. In the condenser, hot water can be supplied by generating condensation heat as described above and exchanging heat of the condensation heat.
凝縮器４０には、バルブＶ５を有する熱媒流通管４８の一端が接続されており、熱媒流通管４８の他端は蒸発器３０と接続されている。このように、凝縮器４０と蒸発器３０とは、熱媒流通管４８により互いに連通されており、凝縮器４０で凝縮し生成された水（熱媒）は熱媒流通管４８を流通して蒸発器３０に戻されるようになっている。 One end of a heat medium circulation pipe 48 having a valve V <b> 5 is connected to the condenser 40, and the other end of the heat medium circulation pipe 48 is connected to the evaporator 30. Thus, the condenser 40 and the evaporator 30 are connected to each other by the heat medium flow pipe 48, and water (heat medium) condensed and generated by the condenser 40 flows through the heat medium flow pipe 48. It is returned to the evaporator 30.
給湯部５０は、熱交換管を介して蓄熱反応器１０、吸着器２０、及び凝縮器３０とそれぞれ熱的に接続されている。
蓄熱反応器１０と給湯部５０とは、熱交換管１４を介して熱的に接続されている。蓄熱反応器１０の化学蓄熱材が熱媒と発熱反応を起こすと、その反応熱を熱交換管１４を介して直接熱交換に利用し、給湯部において高温の給湯を迅速に行なえるようになっている。
吸着器２０と給湯部５０とは、熱交換管２２を介して熱的に接続されている。吸着器２０に熱媒が吸着すると、その吸着熱を熱交換管２２を介して水と熱交換し、給湯部において温水を給湯できるようになっている。
また、凝縮器３０と給湯部５０とは、熱交換管４６を介して熱的に接続されている。凝縮器３０に熱媒が供給されて凝縮されると、その凝縮熱を熱交換管４６を介して水と熱交換し、給湯部において温水を給湯することができる。
The hot water supply unit 50 is thermally connected to the heat storage reactor 10, the adsorber 20, and the condenser 30 through heat exchange tubes.
The heat storage reactor 10 and the hot water supply unit 50 are thermally connected via the heat exchange pipe 14. When the chemical heat storage material of the heat storage reactor 10 causes an exothermic reaction with the heat medium, the reaction heat can be used directly for heat exchange through the heat exchange pipe 14 so that high-temperature hot water supply can be performed quickly in the hot water supply section. ing.
The adsorber 20 and the hot water supply unit 50 are thermally connected via the heat exchange pipe 22. When the heat medium is adsorbed on the adsorber 20, the heat of adsorption is exchanged with water through the heat exchange pipe 22, and hot water can be supplied in the hot water supply section.
Further, the condenser 30 and the hot water supply unit 50 are thermally connected via a heat exchange pipe 46. When the heat medium is supplied to the condenser 30 and condensed, the heat of condensation is exchanged with water via the heat exchange pipe 46, and hot water can be supplied in the hot water supply section.
熱交換管１４、２２、４６は、いずれも、無端の配管と、この配管内を流通する熱交換用流体とで構成されている。配管に取り付けられた図示しない循環用ポンプによって、配管中を熱交換用流体が循環流通することで、蓄熱反応器、吸着器、凝縮器の熱を給湯部５０に供給できるようになっている。熱交換用流体には、例えば、水、又は水と水溶性溶剤（エタノール等のアルコールやエチレングリコール等のグリコールなど）との混合溶媒を用いることができる。 Each of the heat exchange tubes 14, 22, and 46 is composed of an endless pipe and a heat exchange fluid that circulates in the pipe. The heat exchange fluid circulating in the pipe is circulated by a circulation pump (not shown) attached to the pipe, so that the heat of the heat storage reactor, the adsorber, and the condenser can be supplied to the hot water supply unit 50. As the heat exchange fluid, for example, water or a mixed solvent of water and a water-soluble solvent (alcohol such as ethanol or glycol such as ethylene glycol) can be used.
本実施形態の蓄熱型吸着式ヒートポンプ給湯システム１００は、蒸発器３０から蓄熱反応器１０に水蒸気(熱媒)を供給し、蓄熱反応器１０において化学蓄熱材と水（熱媒）とを反応させて反応熱を生成する。この反応熱を吸着器２０の再生に利用する。このとき、蒸発器３０では、熱媒の蒸発潜熱分の吸熱作用が生じ、「（反応熱）＞＞（蒸発器３０の吸熱）」となる。酸化カルシウムを用いた本実施形態の蓄熱反応は、下記の通りである。
ＣａＯ ＋ Ｈ２Ｏ（熱媒） → Ｃａ（ＯＨ）２＋ Ｑ［反応熱］
反応熱Ｑ＞＞（蒸発器３０の吸熱）
本実施形態では、蓄熱反応器１０と蒸発器３０とを接続し、吸着器２０と凝縮器４０とを接続する。蒸発器３０では、熱媒である水を蒸発させて水蒸気を生成すると、吸熱が生じる。生成した水蒸気(熱媒)が供給されると、蓄熱反応器１０では反応熱Ｑを生成する。蓄熱反応器１０での反応熱Ｑが吸着器２０に加えられると、吸着器２０に吸着されている熱媒が脱離する。脱離した熱媒は、凝縮器４０に送られ、凝縮器で凝縮される。この凝縮熱は、熱交換管４６を介して水と熱交換し、給湯部５０において温水として回収される。凝縮器で凝縮された熱媒は、凝縮器４０から熱媒流通管４８を流通して、蒸発器３０に戻される。
次いて、吸着器２０に吸着している熱媒が完全に脱離し吸着器２０の再生が完了すると、吸着器２０と蒸発器３０とを接続し、蒸発器３０から吸着器２０に水蒸気（熱媒）が供給される。吸着器２０では、供給された水蒸気が吸着すると、吸着熱（温熱）を生成し、生成した吸着熱は熱交換管２２を介して水と熱交換し、給湯部５０において温水として回収される。
本実施形態では、例えば蓄熱反応器１０で１００の反応熱Ｑを生成した場合を考えると、上記のように、例えば１００の反応熱Ｑを吸着器２０に与え、熱媒を脱離させ、脱離した熱媒を凝縮器４０で凝縮させることで、１００の凝縮熱を得て温水を生成する。さらに、蒸発器３０から水蒸気（熱媒）を吸着器２０に供給することで、１００の吸着熱を得て温水を生成する。このようにして、化学蓄熱材１０での発熱反応で蓄熱反応器に生成される熱エネルギー（反応熱Ｑ）から、従来の２倍量の温水を取り出すことが可能になる。
以上のように、本実施形態の給湯システムでは、顕熱ロスが少なく熱の利用効率に優れており、給湯温度に応じて効率の良い給湯が行なえる。
The heat storage type adsorption heat pump hot water supply system 100 of this embodiment supplies water vapor (heat medium) from the evaporator 30 to the heat storage reactor 10, and causes the chemical heat storage material and water (heat medium) to react in the heat storage reactor 10. To generate heat of reaction. This reaction heat is used for the regeneration of the adsorber 20. At this time, in the evaporator 30, an endothermic action corresponding to the latent heat of evaporation of the heat medium occurs, and “(reaction heat) >> (endotherm of the evaporator 30)” is obtained. The heat storage reaction of this embodiment using calcium oxide is as follows.
CaO + H 2 O (heat medium) → Ca (OH) 2 + Q [heat of reaction]
Heat of reaction Q >> (endotherm of evaporator 30)
In the present embodiment, the heat storage reactor 10 and the evaporator 30 are connected, and the adsorber 20 and the condenser 40 are connected. In the evaporator 30, when water as a heat medium is evaporated to generate water vapor, heat is absorbed. When the generated water vapor (heat medium) is supplied, the heat storage reactor 10 generates reaction heat Q. When the reaction heat Q in the heat storage reactor 10 is applied to the adsorber 20, the heat medium adsorbed on the adsorber 20 is desorbed. The desorbed heat medium is sent to the condenser 40 and condensed by the condenser. This condensed heat exchanges heat with water via the heat exchange pipe 46 and is recovered as hot water in the hot water supply unit 50. The heat medium condensed by the condenser flows through the heat medium flow pipe 48 from the condenser 40 and is returned to the evaporator 30.
Next, when the heat medium adsorbed on the adsorber 20 is completely desorbed and the regeneration of the adsorber 20 is completed, the adsorber 20 and the evaporator 30 are connected, and water vapor (heat Medium) is supplied. In the adsorber 20, when the supplied water vapor is adsorbed, heat of adsorption (hot heat) is generated, and the generated heat of heat is exchanged with water through the heat exchange pipe 22, and is collected as hot water in the hot water supply unit 50.
In this embodiment, for example, when considering the case where 100 heats of reaction Q are generated in the heat storage reactor 10, as described above, for example, 100 heats of reaction Q are given to the adsorber 20, the heat medium is desorbed, and desorption is performed. The separated heat medium is condensed by the condenser 40 to obtain 100 heat of condensation and generate hot water. Furthermore, by supplying water vapor (heat medium) from the evaporator 30 to the adsorber 20, 100 heat of adsorption is obtained to generate hot water. In this way, it is possible to extract twice as much hot water as conventional from the heat energy (reaction heat Q) generated in the heat storage reactor by the exothermic reaction in the chemical heat storage material 10.
As described above, the hot water supply system of this embodiment has little sensible heat loss and excellent heat utilization efficiency, and can perform efficient hot water supply according to the hot water supply temperature.
制御装置９０は、給湯システムの全制御を担う制御手段であり、バルブＶ１〜Ｖ４、及び外部熱源などと電気的に接続されており、バルブや熱源、熱交換を制御して熱利用をコントロールできるように構成されている。 The control device 90 is a control means responsible for the overall control of the hot water supply system, and is electrically connected to the valves V1 to V4 and an external heat source, and can control the use of heat by controlling the valves, the heat source, and the heat exchange. It is configured as follows.
次に、本実施形態の給湯システムを制御する制御手段である制御装置９０による制御ルーチンのうち、給湯需要における給湯温度に合わせて給湯の仕方（給湯ルート）を選択する給湯制御ルーチンを中心に図７を参照して説明する。 Next, among the control routines by the control device 90 which is a control means for controlling the hot water supply system of the present embodiment, the figure mainly focuses on the hot water supply control routine for selecting the hot water supply method (hot water supply route) according to the hot water supply temperature in the hot water supply demand. This will be described with reference to FIG.
本実施形態の給湯システムの起動スイッチのオンにより制御装置９０の電源がオンされると、システムが起動され、給湯ルートを制御するための給湯制御ルーチンが実行される。なお、システムの起動は、自動で行なう以外に手動で行なうようにしてもよい。 When the power supply of the control device 90 is turned on by turning on the start switch of the hot water supply system of the present embodiment, the system is started and a hot water supply control routine for controlling the hot water supply route is executed. The system may be started manually instead of automatically.
本ルーチンが実行されると、まず給湯需要における給湯温度又は給湯量を判断するため、ステップ１００において、要求されている給湯温度が所定の閾値温度Ｔ［℃］以上であるか否かが判定される。 When this routine is executed, first, in order to determine the hot water supply temperature or the amount of hot water supply in the hot water supply demand, it is determined in step 100 whether or not the requested hot water supply temperature is equal to or higher than a predetermined threshold temperature T [° C.]. The
ステップ１００において、給湯温度が閾値温度Ｔ以上であると判定されたときには、高温給湯を賄う必要があるため、ステップ１２０において、バルブＶ１を開き、蓄熱反応器１０に蒸発器３０により水蒸気（熱媒）を供給して発熱反応を開始することで、蓄熱反応器１０において反応熱Ｑを得る。一方、ステップ１００において、給湯温度が閾値温度Ｔ未満であると判定されたときには、ステップ２２０において、吸着器２０の再生が必要であるか否かが判定される。 When it is determined in step 100 that the hot water supply temperature is equal to or higher than the threshold temperature T, it is necessary to cover the high temperature hot water supply. Therefore, in step 120, the valve V1 is opened, and the steam storage (heat medium) is added to the heat storage reactor 10 by the evaporator 30. ) To start the exothermic reaction, the reaction heat Q is obtained in the heat storage reactor 10. On the other hand, when it is determined in step 100 that the hot water supply temperature is lower than the threshold temperature T, it is determined in step 220 whether or not the adsorber 20 needs to be regenerated.
ステップ１４０では、図４に示すように、蓄熱反応器１０の反応熱Ｑを熱交換管１４を介して直接水と熱交換し、高温給湯する。その後、本ルーチンを終了する。 In step 140, as shown in FIG. 4, the reaction heat Q of the heat storage reactor 10 is directly heat-exchanged with water through the heat exchange pipe 14, and hot water is supplied. Thereafter, this routine is terminated.
ステップ２２０において、吸着器２０への熱媒吸着が不要と判定されたときには、吸着器の再生を継続できるため、図２に示されるように、バルブＶ１の開放に続いてバルブＶ４を開き、蓄熱反応器１０の反応熱を熱交換管１２を介して吸着器２０に与える。反応熱で加熱された吸着器２０では、吸着していた熱媒が脱離し、吸着材が次第に再生する。脱離した熱媒は、熱媒供給管４４を通じて凝縮器４０に送られ、次のステップ２６０において、凝縮時の凝縮熱を熱交換管４６を介して水と熱交換する。このとき、給湯部５０において、脱離した熱媒量分の温水を給湯する。その後、本ルーチンを終了する。 In step 220, when it is determined that the adsorption of the heat medium to the adsorber 20 is unnecessary, since the regeneration of the adsorber can be continued, as shown in FIG. 2, the valve V4 is opened following the opening of the valve V1 to store heat. The reaction heat of the reactor 10 is given to the adsorber 20 through the heat exchange tube 12. In the adsorber 20 heated by the reaction heat, the adsorbed heat medium is desorbed and the adsorbent is gradually regenerated. The desorbed heat medium is sent to the condenser 40 through the heat medium supply pipe 44, and in the next step 260, the heat of condensation at the time of condensation is exchanged with water via the heat exchange pipe 46. At this time, the hot water supply unit 50 supplies hot water for the amount of the desorbed heat medium. Thereafter, this routine is terminated.
次に、ステップ２２０において、吸着器２０の再生が完了し熱媒を吸着器に供給する必要があると判定されたときには、図３に示すように、次のステップ３２０でバルブＶ３を開き、蒸発器３０から水蒸気（熱媒）を吸着器に供給し、吸着材に吸着させる。このとき、吸着熱が発生するため、次のステップ３４０において、吸着器２０での吸着熱を熱交換管２２を介して水と熱交換し、吸着熱分の温水を給湯する。その後、本ルーチンを終了する。 Next, in step 220, when it is determined that the regeneration of the adsorber 20 is completed and it is necessary to supply the heat medium to the adsorber, the valve V3 is opened in the next step 320 as shown in FIG. Water vapor (heat medium) is supplied from the vessel 30 to the adsorber and is adsorbed by the adsorbent. At this time, since heat of adsorption is generated, in the next step 340, the heat of adsorption in the adsorber 20 is exchanged with water through the heat exchange pipe 22, and hot water corresponding to the heat of adsorption is supplied. Thereafter, this routine is terminated.
本実施形態の給湯システムでは、上記したように、以下に示す給湯モード（ａ）〜（ｅ）を有している。給湯温度が５０℃未満の比較的低温の給湯が要求されるときには、下記（ａ）〜（ｂ）の給湯モードが、給湯温度が５０℃以上の比較的高温の給湯が要求されるときには、下記（ｃ）〜（ｅ）の給湯モードが用いられる。また、下記のうち、蓄熱反応器から直接高温の給湯を得る給湯モード（ｃ）以外は、一旦吸着器又は凝縮器との熱交換を経ており、本実施形態の給湯システムの持つ増熱効果を利用する。
（ａ）水源→吸着器２０との熱交換→給湯（図３）
（ｂ）水源→凝縮器４０との熱交換→給湯（図２）
（ｃ）水源→蓄熱反応器１０との熱交換→給湯（図４）
（ｄ）水源→吸着器２０との熱交換（図３）→蓄熱反応器１０との熱交換→給湯（図５）
（ｅ）水源→凝縮器４０との熱交換（図６）→蓄熱反応器１０との熱交換→給湯（図５）
As described above, the hot water supply system of the present embodiment has the following hot water supply modes (a) to (e). When a relatively low temperature hot water supply with a hot water supply temperature of less than 50 ° C. is required, the following (a) to (b) hot water supply modes are required, and when a relatively high temperature hot water supply with a hot water supply temperature of 50 ° C. or higher is required: The hot water supply modes (c) to (e) are used. Of the following, except for the hot water supply mode (c) in which high-temperature hot water supply is obtained directly from the heat storage reactor, heat exchange with the adsorber or condenser is performed once, and the heat increase effect of the hot water supply system of the present embodiment is obtained. Use.
(A) Water source → Heat exchange with adsorber 20 → Hot water supply (FIG. 3)
(B) Water source → Heat exchange with condenser 40 → Hot water supply (Fig. 2)
(C) Water source → Heat exchange with the heat storage reactor 10 → Hot water supply (FIG. 4)
(D) Water source → heat exchange with the adsorber 20 (FIG. 3) → heat exchange with the heat storage reactor 10 → hot water supply (FIG. 5)
(E) Water source → Heat exchange with condenser 40 (FIG. 6) → Heat exchange with heat storage reactor 10 → Hot water supply (FIG. 5)
以下に、本実施形態の給湯システムでの給湯モードの例を図２〜図６を参照して詳述する。 Below, the example of the hot water supply mode in the hot water supply system of this embodiment is explained in full detail with reference to FIGS.
図２は、バルブＶ１、Ｖ４を開いて（バルブＶ２、Ｖ３は閉状態）、蒸発器３０と蓄熱反応器１０とを接続すると共に、吸着器２０と凝縮器４０とを接続し、蓄熱反応器と吸着器との熱交換を経て、吸着器の吸着材から脱離した熱媒の凝縮により得られる凝縮熱を利用して給湯するものである。この場合、蓄熱反応器１０で生成した反応熱Ｑで吸着器２０が加熱され、その熱量に対応した凝縮熱で給湯する。
このとき、水（熱媒）の反応量を１［ｍｏｌ］、水とＣａＯとの反応熱Ｑを１１３［ｋＪ／ｍｏｌ］、水の蒸発潜熱を４５［ｋＪ／ｍｏｌ］とすると、各器では下記の熱が生成する。
蒸発器（冷熱）：４５［ｋＪ］
蓄熱反応器（温熱）：１１３［ｋＪ］
ここで、冷熱温度を２５℃とする。ここでは、水での熱交換を想定し９０℃での取り出しを想定する。凝縮器４０と吸着器２０とを接続し、蓄熱反応器で生成した反応熱１１３［ｋＪ］と温度９０℃の温水とを吸着器２０に投入する。吸着器２０は、給湯温度４５℃から９０℃まで昇温させるものとする。凝縮器４０では、吸着器での昇温に対応する凝縮熱が発生するため、給湯部５０において給湯温度４５℃の温水を回収する。吸着熱を４５［ｋＪ／ｍｏｌ］、吸着器２０の熱容量を０．５［ｋＪ／℃］とすると、吸着器で脱離した水量は１．９５［ｍｏｌ］となる。各器での熱のやり取りは、
吸着器（吸着熱＋顕熱）：１１３［ｋＪ］
凝縮器（凝縮熱）：８８［ｋＪ］
なお、蒸発器３０では、水蒸気（熱媒）の供給に伴ない冷熱が発生するため、熱交換管３６を介して熱的に接続されているエアコン室外機等の冷熱機器（冷熱需要）に対し、冷熱の利用が可能である。
FIG. 2 shows that the valves V1 and V4 are opened (valves V2 and V3 are closed), the evaporator 30 and the heat storage reactor 10 are connected, the adsorber 20 and the condenser 40 are connected, and the heat storage reactor is connected. Hot water is supplied by utilizing the heat of condensation obtained by condensation of the heat medium desorbed from the adsorbent of the adsorber through heat exchange with the adsorber. In this case, the adsorber 20 is heated by the reaction heat Q generated in the heat storage reactor 10, and hot water is supplied with the condensation heat corresponding to the amount of heat.
At this time, if the reaction amount of water (heat medium) is 1 [mol], the reaction heat Q between water and CaO is 113 [kJ / mol], and the latent heat of evaporation of water is 45 [kJ / mol] The following heat is generated.
Evaporator (cold heat): 45 [kJ]
Thermal storage reactor (heat): 113 [kJ]
Here, the cold temperature is set to 25 ° C. Here, it is assumed that the heat exchange with water is assumed and the extraction at 90 ° C. is assumed. The condenser 40 and the adsorber 20 are connected, and the heat of reaction 113 [kJ] generated in the heat storage reactor and hot water having a temperature of 90 ° C. are charged into the adsorber 20. The adsorber 20 is assumed to raise the temperature of the hot water supply from 45 ° C. to 90 ° C. In the condenser 40, heat of condensation corresponding to the temperature rise in the adsorber is generated, so hot water having a hot water supply temperature of 45 ° C. is collected in the hot water supply section 50. When the heat of adsorption is 45 [kJ / mol] and the heat capacity of the adsorber 20 is 0.5 [kJ / ° C.], the amount of water desorbed by the adsorber is 1.95 [mol]. The heat exchange in each unit is
Adsorber (adsorption heat + sensible heat): 113 [kJ]
Condenser (condensation heat): 88 [kJ]
In the evaporator 30, cold heat is generated with the supply of water vapor (heat medium), and therefore, with respect to a cooling device (cooling demand) such as an air conditioner outdoor unit that is thermally connected via the heat exchange pipe 36. It is possible to use cold energy.
図３は、バルブＶ３を開いて（バルブＶ１、Ｖ２、Ｖ４は閉状態）、蒸発器３０と吸着器２０とを接続し、吸着器２０に水蒸気（熱媒）が吸着する際の吸着熱を利用して給湯するものである。このとき、蒸発器３０では冷熱が発生するため、熱交換管３６を介して熱的に接続されているエアコン室外機等の冷熱機器（冷熱需要）に対し、冷熱の利用が可能である。
このときの熱のやり取りは以下の通りである。
吸着器（吸着熱＋顕熱）：１１３［ｋＪ］
蒸発器（冷熱）：８８［ｋＪ］
In FIG. 3, the valve V3 is opened (valves V1, V2, and V4 are closed), the evaporator 30 and the adsorber 20 are connected, and the heat of adsorption when water vapor (heat medium) is adsorbed to the adsorber 20 is shown. It uses hot water. At this time, since cold heat is generated in the evaporator 30, cold heat can be used for the cold heat equipment (cold heat demand) such as an air conditioner outdoor unit that is thermally connected via the heat exchange pipe 36.
The heat exchange at this time is as follows.
Adsorber (adsorption heat + sensible heat): 113 [kJ]
Evaporator (cold heat): 88 [kJ]
図２及び図３に示す給湯モードにおいて、Ｎ１［回］の操作で蓄熱反応器の反応が全て完了したとすると、以下に示す温熱２０１［ｋＪ］が生成する。
消費した熱エネルギー：１１３［ｋＪ］×Ｎ１
生成した熱エネルギー（温熱）：２０１［ｋＪ］×Ｎ１
よって、この給湯モードの場合、蓄熱した熱量に対して、ＣＯＰ＝１．７８での給湯が可能であることが分かる。また、このときの冷熱生成ＣＯＰは、下記のようになる。
冷熱生成ＣＯＰ＝（４５［ｋＪ］＋８８［ｋＪ］）／（１１３［ｋＪ］）
＝１．１８
In the hot water supply mode shown in FIG. 2 and FIG. 3, if all the reactions of the heat storage reactor are completed by the operation of N1 [times], the following heat 201 [kJ] is generated.
Consumed heat energy: 113 [kJ] × N1
Generated thermal energy (heat): 201 [kJ] × N1
Therefore, in this hot water supply mode, it can be seen that hot water supply with COP = 1.78 is possible with respect to the amount of heat stored. Further, the cold-generated COP at this time is as follows.
Cold heat generation COP = (45 [kJ] +88 [kJ]) / (113 [kJ])
= 1.18
次に、給湯温度の高い給湯を行なう場合を説明する。
この給湯モードでは、図４に示すように、バルブＶ１を開き（バルブＶ２〜Ｖ４は閉状態）、蒸発器３０と蓄熱反応器１０とを接続し、蒸発器からの水蒸気(熱媒)の供給により蓄熱反応器で発熱反応させる。その後、この反応熱を給湯部５０において直接熱交換し、高温にて給湯する。この場合、上記の給湯モード（ｃ）で蓄熱反応器との間の熱交換により直接給湯を行なうほか、給湯モード（ｄ）〜（ｅ）のように、給湯モード（ａ）や（ｂ）で得られた温水をさらに蓄熱反応器との間の熱交換により昇温して給湯してもよい。
Next, the case where hot water supply with high hot water supply temperature is performed will be described.
In this hot water supply mode, as shown in FIG. 4, the valve V1 is opened (valves V2 to V4 are closed), the evaporator 30 and the heat storage reactor 10 are connected, and water vapor (heat medium) is supplied from the evaporator. To cause an exothermic reaction in a heat storage reactor. Thereafter, the reaction heat is directly exchanged in the hot water supply section 50, and hot water is supplied at a high temperature. In this case, in addition to directly performing hot water supply by heat exchange with the heat storage reactor in the hot water supply mode (c), as in the hot water supply modes (d) to (e), the hot water supply modes (a) and (b) The obtained hot water may be further heated to supply hot water by heat exchange with the heat storage reactor.
次に、外部からの加熱により蓄熱反応器を再生する場合を説明する。
この給湯モードでは、図５に示すように、バルブＶ２を開き（バルブＶ１、Ｖ３、Ｖ４は閉状態）蓄熱反応器１０と凝縮器４０とを接続し、燃焼器である外部熱源６０からの熱で蓄熱反応器１０を加熱する。加熱温度は、化学蓄熱材の再生温度に照らし、例えば４５０℃とすることができる。蓄熱反応器の化学蓄熱材の再生温度の４５０℃まで昇温するのに必要な顕熱をＱ１［ｋＪ］とすると、下記の「（１１３［ｋＪ］×Ｎ１）＋Ｑ１［ｋＪ］」のうち、４５［ｋＪ］×Ｎ１の熱を凝縮熱として給湯に利用することができる。
蓄熱反応器：（１１３［ｋＪ］×Ｎ１）＋Ｑ１［ｋＪ］
凝縮器：４５［ｋＪ］×Ｎ１
この給湯モードでは、高温の給湯あるいは多量の給湯が必要な場合に、外部熱源を利用して蓄熱作用を行なうものである。すなわち、外部熱源６０からの熱を蓄熱反応器１０に投入して化学蓄熱材を再生し蓄熱する。このとき放出される熱媒を凝縮器４０で凝縮し、この凝縮熱を給湯部５０において水と熱交換し、温水として回収する。その後は、蓄熱反応器の化学蓄熱材は再生されているため、化学蓄熱材の反応熱を中心とした熱利用が可能である。
Next, a case where the heat storage reactor is regenerated by heating from the outside will be described.
In this hot water supply mode, as shown in FIG. 5, the valve V2 is opened (valves V1, V3, and V4 are closed), the heat storage reactor 10 and the condenser 40 are connected, and heat from the external heat source 60 that is a combustor is connected. The heat storage reactor 10 is heated. The heating temperature can be set to 450 ° C., for example, in light of the regeneration temperature of the chemical heat storage material. Assuming that the sensible heat required to raise the regeneration temperature of the chemical heat storage material of the heat storage reactor to 450 ° C. is Q1 [kJ], among the following “(113 [kJ] × N1) + Q1 [kJ]”, The heat of 45 [kJ] × N1 can be used as hot water for condensation.
Thermal storage reactor: (113 [kJ] × N1) + Q1 [kJ]
Condenser: 45 [kJ] × N1
In this hot water supply mode, when a hot water supply or a large amount of hot water supply is required, an external heat source is used to perform a heat storage action. That is, the heat from the external heat source 60 is input into the heat storage reactor 10 to regenerate and store the chemical heat storage material. The heat medium released at this time is condensed by the condenser 40, and this condensed heat is heat-exchanged with water in the hot water supply section 50 and recovered as hot water. After that, since the chemical heat storage material of the heat storage reactor is regenerated, heat utilization centering on the reaction heat of the chemical heat storage material is possible.
また、図５のように蓄熱反応器の化学蓄熱材の再生が終了した後は、蓄熱反応器１０に溜まっている顕熱Ｑ［ｋＪ］を回収し、この顕熱を吸着器２０の再生に利用することができる。
具体的には、図６に示すように、バルブＶ４を開き（バルブＶ１〜Ｖ３は閉状態）、吸着器２０と凝縮器４０とを接続し、回収した顕熱Ｑを熱交換管１２を介して吸着器２０に与える。吸着器２０は、吸着されている熱媒を脱離し、脱離した熱媒は凝縮器４０に送られ凝縮される。ここで生成した凝縮熱を給湯部５０において水と熱交換し、温水として回収する。この給湯モードでは、回収した顕熱１１３［ｋＪ］、温度９０℃の温水を吸着器２０に投入する。吸着器２０は、給湯温度４５℃から９０℃まで昇温させるものとする。凝縮器４０では、吸着器での昇温に対応する凝縮熱が発生するため、給湯部５０において給湯温度４５℃の温水を回収する。吸着熱を４５［ｋＪ／ｍｏｌ］、吸着器２０の熱容量を０．５［ｋＪ／℃］とすると、吸着器で脱離した水量は１．９５［ｍｏｌ］となる。各器での熱のやり取りは、
吸着器（吸着熱＋顕熱）：１１３［ｋＪ］
凝縮器（凝縮熱）：８８［ｋＪ］
図５と図６の給湯モードを繰り返し行なうことで、給湯効率が高められる。
図５及び図６の給湯モードを繰り返し、Ｎ２［回］の操作を行なって蓄熱反応器の顕熱の回収が全て完了したとすると、以下に示す温熱［ｋＪ］が生成する。
顕熱回収による熱エネルギー：１１３［ｋＪ］×Ｎ２
生成した熱エネルギー(温熱)：（４５［ｋＪ］×Ｎ１）＋（２０１［ｋＪ］×Ｎ２）
Further, after the regeneration of the chemical heat storage material of the heat storage reactor is completed as shown in FIG. 5, the sensible heat Q [kJ] accumulated in the heat storage reactor 10 is recovered, and this sensible heat is used to regenerate the adsorber 20. Can be used.
Specifically, as shown in FIG. 6, the valve V4 is opened (valves V1 to V3 are closed), the adsorber 20 and the condenser 40 are connected, and the recovered sensible heat Q is passed through the heat exchange pipe 12. To the adsorber 20. The adsorber 20 desorbs the adsorbed heat medium, and the desorbed heat medium is sent to the condenser 40 to be condensed. The heat of condensation generated here is exchanged with water in the hot water supply section 50 and recovered as hot water. In this hot water supply mode, the recovered sensible heat 113 [kJ] and hot water having a temperature of 90 ° C. are put into the adsorber 20. The adsorber 20 is assumed to raise the temperature of the hot water supply from 45 ° C. to 90 ° C. In the condenser 40, heat of condensation corresponding to the temperature rise in the adsorber is generated, so hot water having a hot water supply temperature of 45 ° C. is collected in the hot water supply section 50. When the heat of adsorption is 45 [kJ / mol] and the heat capacity of the adsorber 20 is 0.5 [kJ / ° C.], the amount of water desorbed by the adsorber is 1.95 [mol]. The heat exchange in each unit is
Adsorber (adsorption heat + sensible heat): 113 [kJ]
Condenser (condensation heat): 88 [kJ]
By repeatedly performing the hot water supply mode of FIGS. 5 and 6, the hot water supply efficiency can be increased.
If the hot water supply mode of FIG.5 and FIG.6 is repeated and operation of N2 [times] is performed and all the recovery of the sensible heat of the heat storage reactor is completed, the following heat [kJ] is generated.
Thermal energy by sensible heat recovery: 113 [kJ] × N2
Generated thermal energy (heat): (45 [kJ] × N1) + (201 [kJ] × N2)
以上から、本実施形態では、４５℃の給湯において、図２、図３、図５、及び図６に示す給湯モードにより以下に示す給湯効率が達成される。
投入した熱エネルギー：１１３［ｋＪ］×（Ｎ１＋Ｎ２）
生成した熱エネルギー(温熱)：（２４６［ｋＪ］×Ｎ１）＋（２０１［ｋＪ］×Ｎ２）
よって、エネルギーの消費効率を示すＣＯＰ（Coefficient Of Performance）値は、下記式で表される（式中、Ｎ１＝４００回、Ｎ２＝１００回）。
このように、外部熱源を利用した給湯システムにおいて、高効率な給湯が可能となる。
ＣＯＰ＝｛（４５［ｋＪ］×Ｎ１）＋（２０１［ｋＪ］×Ｎ２）｝／（１１３［ｋＪ］×Ｎ２）
＝３．３７
From the above, in the present embodiment, in the hot water supply at 45 ° C., the hot water supply efficiency shown below is achieved by the hot water supply modes shown in FIG. 2, FIG. 3, FIG.
Input thermal energy: 113 [kJ] × (N1 + N2)
Generated thermal energy (warm heat): (246 [kJ] × N1) + (201 [kJ] × N2)
Therefore, a COP (Coefficient Of Performance) value indicating energy consumption efficiency is expressed by the following formula (where N1 = 400 times and N2 = 100 times).
Thus, in the hot water supply system using an external heat source, highly efficient hot water supply becomes possible.
COP = {(45 [kJ] × N1) + (201 [kJ] × N2)} / (113 [kJ] × N2)
= 3.37
また、このときの冷熱生成効率を示す冷熱生成ＣＯＰの値は、下記式で表される。
冷熱生成ＣＯＰ＝（蒸発器の冷熱生成量）／（顕熱量）
＝（８８［ｋＪ］×Ｎ２）／（１１３［ｋＪ］×Ｎ２）
＝０．７８
また、総蓄熱量は、下記の通りである。
総蓄熱量＝Ｎ１×１１３［ｋＪ］＝４００×１１３［ｋＪ］＝４５［ＭＪ］
Further, the value of the cold heat generation COP indicating the cold heat generation efficiency at this time is represented by the following equation.
Cold heat generation COP = (Cold heat generation amount of evaporator) / (Sensible heat amount)
= (88 [kJ] × N2) / (113 [kJ] × N2)
= 0.78
The total heat storage amount is as follows.
Total heat storage amount = N1 × 113 [kJ] = 400 × 113 [kJ] = 45 [MJ]
ここで、具体的な実施態様として、上記の総蓄熱量、及び顕熱１１．２５［ＭＪ］でのシステムを想定する。
蓄熱量０［ＭＪ］から完全に再生を行なう場合、５６．２５［ＭＪ］の熱を投入する。給湯需要（風呂を想定）に対して２８［ＭＪ］を利用することとし、１１．２５［ＭＪ］の顕熱回収時の増熱作用で風呂を沸かすとすると、
１１．２５［ＭＪ］×３．３７ ＝ 約３８［ＭＪ］
となり、２８［ＭＪ］の給湯が可能である。残りの１０［ＭＪ］で暖房利用が可能である。同時に、１１．２５［ＭＪ］×０．７８＝約８．８［ＭＪ］の冷房が利用可能になる。
顕熱回収時に風呂を沸かすとすると、図８の斜線部分を補うことが可能であるため、給湯と冷房又は暖房とを同時に利用する際に蓄熱反応器の再生を行なうことが望ましい。仮に冷暖房のエネルギーが不足するときは、蓄熱反応器から賄うことが望ましい。
Here, the system by said total heat storage amount and sensible heat 11.25 [MJ] is assumed as a concrete embodiment.
When completely regenerating from a heat storage amount of 0 [MJ], heat of 56.25 [MJ] is input. Suppose that 28 [MJ] is used for hot water supply demand (assuming a bath), and the bath is boiled due to the heat increase during sensible heat recovery of 11.25 [MJ],
11.25 [MJ] × 3.37 = about 38 [MJ]
Thus, hot water supply of 28 [MJ] is possible. Heating can be used with the remaining 10 [MJ]. At the same time, cooling of 11.25 [MJ] × 0.78 = about 8.8 [MJ] becomes available.
If the bath is boiled during sensible heat recovery, the shaded area in FIG. 8 can be compensated. Therefore, it is desirable to regenerate the heat storage reactor when hot water supply and cooling or heating are used simultaneously. If the air conditioning energy is insufficient, it is desirable to cover the heat storage reactor.
次に、具体的な実施態様として、蓄熱量４５［ＭＪ］からの利用を想定する。
給湯需要（風呂を想定）に対して２８［ＭＪ］を利用することにすると、
２８［ＭＪ］／１．７８（温熱生成ＣＯＰ）＝１５．７［ＭＪ］
の蓄熱エネルギーが放出されると同時に、
１５．７［ＭＪ］×１．１８（冷熱生成ＣＯＰ）＝１８．５［ＭＪ］
の冷熱利用が可能になる。ここで、４５［ＭＪ］の蓄熱がなされていた場合、図９に示されるように、冷房利用時、冷暖房利用なしの時は、約３日分の給湯と冷房が可能である。つまり、顕熱回収を含めて４日に１度、冷房利用時に蓄熱することが望ましい。
また、暖房利用時は、温熱を６０＋２８＝８８［ＭＪ］の利用となるため、８８［ＭＪ］／１．７８（温熱生成ＣＯＰ）＝４９．４［ＭＪ］となり、一回の蓄熱では１日分を賄えない場合があるが、いずれのタイミングで蓄熱し顕熱回収しても高効率なため、蓄熱量が０に近づいたときに蓄熱すればよい。
Next, the utilization from the heat storage amount 45 [MJ] is assumed as a specific embodiment.
If you decide to use 28 [MJ] for hot water demand (assuming a bath)
28 [MJ] /1.78 (thermally generated COP) = 15.7 [MJ]
At the same time as the heat storage energy is released
15.7 [MJ] × 1.18 (cold heat generation COP) = 18.5 [MJ]
It becomes possible to use cold energy. Here, when heat storage of 45 [MJ] is performed, as shown in FIG. 9, hot water supply and cooling for about three days are possible when using air conditioning and when not using air conditioning. That is, it is desirable to store heat at the time of cooling use once every four days including sensible heat recovery.
In addition, when heating is used, the heat is 60 + 28 = 88 [MJ], so that 88 [MJ] /1.78 (heat generation COP) = 49.4 [MJ]. Although it may not be possible to cover the heat, it is efficient even if heat is stored at any timing and sensible heat recovery is performed. Therefore, heat storage may be performed when the heat storage amount approaches zero.
本実施形態の給湯システムでは、上記したように化学蓄熱材を用いた蓄熱反応器を備えることで、給湯需要に応じた所望の高温、中温の給湯が選択可能であり、所望の給湯を効率よく取り出すことが可能である。また、一旦給湯した後に追い炊きする場合、燃焼器等の外部熱源を使用せずに追い炊きが可能であり、また蓄熱反応器を利用した構成であることで、追い炊き時にも増熱効果が得られる。 In the hot water supply system of the present embodiment, by providing a heat storage reactor using a chemical heat storage material as described above, it is possible to select desired high and medium temperature hot water supply according to hot water supply demand, and efficiently supply the desired hot water supply. It is possible to take it out. In addition, when cooking after hot water supply, it is possible to cook without using an external heat source such as a combustor, and because it has a configuration using a heat storage reactor, it has a heat increasing effect even during cooking. can get.
また、本実施形態の給湯システムでは、電気エネルギーや動力エネルギーのみならず、化石燃料を用いることが可能である。さらに、貯湯槽を設ける必要がないため、装置の大幅な小型化を図ることができる。 Further, in the hot water supply system of the present embodiment, not only electric energy and power energy but also fossil fuel can be used. Furthermore, since it is not necessary to provide a hot water storage tank, the apparatus can be significantly reduced in size.
上記の実施形態では、化学蓄熱材としてＣａＯを、水を吸着する吸着材として物理吸着材であるシリカゲルを用いた場合を中心に説明したが、これらに限られず、ＣａＯ及びシリカゲル以外の上記した他の化学蓄熱材、吸着材を用いた場合にも、上記実施形態と同様の効果を奏することができる。 In the above embodiment, the case where CaO is used as a chemical heat storage material and silica gel as a physical adsorbent is used as an adsorbent for adsorbing water has been mainly described. However, the present invention is not limited thereto, and the above-described other than CaO and silica gel. Even when the chemical heat storage material and the adsorbent are used, the same effects as in the above embodiment can be obtained.
１０・・・蓄熱反応器
２０・・・吸着器
３０・・・蒸発器
４０・・・凝縮器
５０・・・給湯部（給湯需要）
６０・・・熱源
７０・・・冷熱機器（冷熱需要）
DESCRIPTION OF SYMBOLS 10 ... Thermal storage reactor 20 ... Adsorber 30 ... Evaporator 40 ... Condenser 50 ... Hot-water supply part (hot-water supply demand)
60 ... Heat source 70 ... Cold heat equipment (cold heat demand)
Claims (14)
前記蒸発器から熱媒が供給され、供給された熱媒を吸着する吸着器と、
前記蒸発器から熱媒が供給され、供給された熱媒が固定化されるときに該熱媒の蒸発潜熱以上の反応熱を放出し、該熱媒が脱離するときに蓄熱する化学蓄熱材を備え、前記吸着器の再生温度以上の熱を前記吸着器に放熱可能な蓄熱反応器と、
前記吸着器から熱媒が供給され、供給された熱媒を凝縮する凝縮器と、
前記吸着器、前記蓄熱反応器、及び前記凝縮器の少なくとも１つと熱的に接続されて熱交換することで給湯する給湯部と、
を備えた給湯装置。 An evaporator for evaporating the heating medium;
A heat medium is supplied from the evaporator, and an adsorber that adsorbs the supplied heat medium;
A chemical heat storage material that stores a heat when a heat medium is supplied from the evaporator, releases the reaction heat equal to or greater than the latent heat of evaporation of the heat medium when the supplied heat medium is fixed, and stores when the heat medium is desorbed A heat storage reactor capable of dissipating heat above the regeneration temperature of the adsorber to the adsorber;
A condenser for supplying a heat medium from the adsorber and condensing the supplied heat medium;
A hot water supply section that is thermally connected to at least one of the adsorber, the heat storage reactor, and the condenser to supply hot water by heat exchange;
Hot water supply device equipped with.
前記凝縮器は、前記吸着器から脱離した熱媒を凝縮し、かつ前記給湯部は、前記凝縮器での凝縮熱を水と熱交換することで給湯する請求項１又は請求項２に記載の給湯装置。 The adsorber desorbs the heat medium when it is heated by the reaction heat supplied from the evaporator to the heat storage reactor and released from the heat storage reactor, and is supplied from the evaporator Adsorbing a heat medium, the hot water supply unit supplies hot water by exchanging heat of adsorption of the adsorber with water,
The said condenser condenses the heat medium desorbed from the said adsorber, and the said hot water supply part supplies hot water by exchanging heat of condensation in the condenser with water. Water heater.
前記給湯部から所定の閾値温度未満の給湯温度で給湯するときには、前記給湯部は、前記吸着器において熱媒が吸着するときの吸着熱を水と熱交換し、かつ前記凝縮器において熱媒を凝縮させるときの凝縮熱を水と熱交換することで給湯する請求項１〜請求項１３のいずれか１項に記載の給湯装置。 When hot water is supplied from the hot water supply unit at a hot water supply temperature equal to or higher than a predetermined threshold temperature, a heat medium is supplied from the evaporator to the heat storage reactor, and the hot water supply unit exchanges heat of reaction of the heat storage reactor with water. Hot water supply
When hot water is supplied from the hot water supply unit at a hot water supply temperature less than a predetermined threshold temperature, the hot water supply unit exchanges heat of adsorption with water when the heat medium is adsorbed in the adsorber, and the heat medium is supplied to the condenser. The hot water supply device according to any one of claims 1 to 13, wherein hot water is supplied by exchanging heat of condensation when condensed with water.
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