JP6218407B2 - Absorption refrigerator operation method - Google Patents
Absorption refrigerator operation method Download PDFInfo
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- JP6218407B2 JP6218407B2 JP2013057157A JP2013057157A JP6218407B2 JP 6218407 B2 JP6218407 B2 JP 6218407B2 JP 2013057157 A JP2013057157 A JP 2013057157A JP 2013057157 A JP2013057157 A JP 2013057157A JP 6218407 B2 JP6218407 B2 JP 6218407B2
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- absorption
- corrosion
- absorption liquid
- ascorbate
- refrigerator
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- 238000010521 absorption reaction Methods 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 9
- 239000007788 liquid Substances 0.000 claims description 33
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 31
- 235000010323 ascorbic acid Nutrition 0.000 claims description 16
- 239000011668 ascorbic acid Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229940072107 ascorbate Drugs 0.000 claims description 13
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 description 27
- 230000007797 corrosion Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 8
- 235000010378 sodium ascorbate Nutrition 0.000 description 8
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 8
- 229960005055 sodium ascorbate Drugs 0.000 description 8
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- -1 oxo acid salt Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000000994 L-ascorbates Chemical class 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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- 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]
- Y02B30/62—Absorption based systems
Landscapes
- Sorption Type Refrigeration Machines (AREA)
Description
本発明は、吸収式冷暖房機等として使用される吸収式冷凍機技術に関するものであり、吸収液としてリチウムブロマイド（ＬｉＢｒ）水溶液を使用する吸収式冷凍機の運転方法に関する。 The present invention relates to an absorption refrigerator technology used as absorption air conditioners or the like, a method of operation of the suction Osamushiki refrigerator that uses a lithium bromide (LiBr) solution as an absorbing solution.
リチウムブロマイド（ＬｉＢｒ）水溶液を吸収液とし、たとえば、アノード型インヒビターを吸収液に含有して運転される吸収式冷凍機がある。リチウムブロマイド（ＬｉＢｒ）水溶液を吸収液として、運転される吸収式冷凍機では、その循環系内の機器に接続部等から空気が系内に侵入する場合がある。この空気に含まれる酸素は、吸収液内に溶け込み酸化剤として働く。このような新たに侵入した酸素により、局部腐食等が進行しやすい状況となる。このような吸収式冷凍機の運転・維持管理にあたっては、局部腐食が過度に進行し、吸収液の循環系統内に酸素を含む空気が混入するような状態に達すると、直に運転を停止し、専任のサービス員を呼んでメンテナンスが行われる。この場合、酸素は、吸収液内に溶解し酸化剤として働き腐食の要因となる。なお、従来のＬｉＢｒ水溶液で用いる鉄用のインヒビターは、アノード反応抑制型（酸化剤タイプ）であるため、空気混入時には、鉄材に孔食、隙間腐食等の局部腐食を起こしやすい。 There is an absorption refrigerator that is operated by using an aqueous solution of lithium bromide (LiBr) as an absorption liquid, for example, containing an anode type inhibitor in the absorption liquid. In an absorption refrigerating machine that is operated using a lithium bromide (LiBr) aqueous solution as an absorbing liquid, air may enter the equipment in the circulation system from a connection portion or the like. Oxygen contained in the air dissolves in the absorbing solution and acts as an oxidizing agent. Such newly invaded oxygen is likely to cause local corrosion and the like. When operating and maintaining such an absorption chiller, if local corrosion progresses excessively and reaches a state where oxygen-containing air enters the absorption fluid circulation system, the operation is immediately stopped. The maintenance is performed by calling a dedicated service person. In this case, oxygen dissolves in the absorbing solution and acts as an oxidizing agent, causing corrosion. In addition, since the inhibitor for iron used with the conventional LiBr aqueous solution is an anode reaction suppression type (oxidizer type), it is easy to cause local corrosion, such as pitting corrosion and crevice corrosion, in an iron material at the time of air mixing.
そこで特許文献１には、このような吸収液に、中心原子が硫黄である還元性を有するオキソ酸塩を含有させることにより、吸収液に含まれる酸素を還元除去し、系内を防触することが有効であることが示されている。 Therefore, in Patent Document 1, such an absorbing solution contains a reducing oxo acid salt whose central atom is sulfur, thereby reducing and removing oxygen contained in the absorbing solution to prevent the inside of the system from being touched. Has been shown to be effective.
しかし、上述の吸収液に中心原子が硫黄である還元性を有するオキソ酸塩を含有させると、鉄材に対する防触効果はある程度得られるものの、前記鉄材よりも耐腐食性が高いと考えられており、薄肉に設けられる銅材からなる銅材部が存在するような場合、前記オキソ酸による銅材に対する防触効果が十分とは言えない事象が発生する場合があることを本発明者らは見出した。また、このような事情により、吸収式冷凍機の耐久性が低下する場合があり、保守点検にも労力を要する場合があった。 However, it is considered that the anti-corrosion effect on the iron material can be obtained to some extent when the above-mentioned absorbing liquid contains a reducing oxo acid salt whose central atom is sulfur, but the corrosion resistance is higher than that of the iron material. The present inventors have found that when there is a copper material portion made of a copper material provided in a thin wall, an event that the anti-corrosion effect on the copper material by the oxo acid may not be sufficient may occur. It was. In addition, due to such circumstances, the durability of the absorption chiller may be reduced, and labor may be required for maintenance and inspection.
そこで、本発明の目的は、吸収式冷凍機の内部において、さらに高い防触性能を図る技術を提供することにある。 Then, the objective of this invention is providing the technique which aims at the further higher anti-corrosion performance in the inside of an absorption refrigerator.
上記目的を達成するための本発明の吸収式冷凍機の運転方法の特徴構成は、吸収液の循環系に銅材部を有するとともに、前記吸収液がリチウムブロマイド（ＬｉＢｒ）を含有する吸収式冷凍機の運転方法であって、前記循環系に於ける減圧状態が破れ、酸素が前記循環系に混入した場合に、前記吸収液にアスコルビン酸塩を投入する点にある。 The characteristic configuration of the operation method of the absorption refrigerator of the present invention for achieving the above object is that the absorption refrigeration has a copper material part in the circulation system of the absorption liquid and the absorption liquid contains lithium bromide (LiBr). The operation method of the machine is that ascorbate is added to the absorption liquid when the decompressed state in the circulation system is broken and oxygen is mixed into the circulation system .
上記構成によると、前記吸収液は、アスコルビン酸塩により、中心原子が硫黄である還元性を有するオキソ酸塩よりも高い還元能力に基づく強い防触効果を発揮できることがわ
かった。また、このアスコルビン酸塩によると、吸収液の吸収性能に大きな影響を与えることもないので、吸収式冷凍機用として好適に用いることができるようになった。
吸収式冷凍機を構成する部材には、高い伝熱性の要求される部分で銅製の部材が利用され、特に伝熱性を高めるために薄肉に形成された銅管などが、熱交換器を構成する銅部材として用いられている。前記吸収液がアスコルビン酸塩を含有することで吸収液が高い防触性を備えたので、吸収式冷凍機に伝熱性の高い薄肉の銅部材を用いたとしても、優れた長期耐久性を発揮することとなる。
According to the above Symbol configuration, the absorbing fluid by ascorbate, central atom were found to be exhibited strong anti-corrosion effect based on high reducing ability than oxo acid salts having reducing properties is sulfur. Moreover, according to this ascorbate, since it does not have a big influence on the absorption performance of an absorption liquid, it came to be able to use suitably for absorption type refrigerators.
Copper members are used in the parts that make up the absorption chiller, where high heat transfer is required, and copper pipes that are formed thin to increase heat transfer make up the heat exchanger. It is used as a copper member. Since the absorption liquid contains ascorbate, the absorption liquid has high anti-corrosion properties, so even if a thin copper member with high heat conductivity is used in the absorption refrigerator, it exhibits excellent long-term durability. Will be.
アスコルビン酸塩の含有量は、少なすぎると効果が少なく、長期使用に耐えないという事情から、２５０ｐｐｍ以上とすることが望ましく、含有量が多すぎても、添加量の増加に伴う防触効果の向上が乏しくなり（効果が飽和し）、また、吸収液の物性に影響が生じる懸念もあることから、1％以下とすることが望ましい。なお、さらに望ましくは５００ｐｐｍ以上１％以下である。 The content of ascorbic acid salt, less effect is too small, the circumstance that not withstand long-term use, it is desirable to be at least 250 ppm, even too much content, proof tactile effect with increasing amount It is desirable to set the content to 1% or less because there is a concern that the improvement of the property will be poor (the effect will be saturated) and the physical properties of the absorbent will be affected. More desirably, the content is 500 ppm or more and 1% or less.
吸収式冷凍機が吸収液の循環系に銅材部を有するとともに、吸収液がリチウムブロマイド（ＬｉＢｒ）を含有すると、吸収液の性能は極めて高いのに対して、吸収液の循環する循環路における腐食性の面で、長期耐久性に改善の余地があったが、前記吸収液にアスコルビン酸塩を含有することによって、アスコルビン酸塩の高い防触性能に基づき、前記循環路における腐食の発生が抑制されるとともに、長期耐久性が改善されるにいたった。 With absorption Osamushiki refrigerator has a copper material portion into the circulation of the absorption liquid, the absorption liquid containing lithium bromide (LiBr), the performance of the absorbent whereas very high, the circulation path for circulating the absorbing liquid There was room for improvement in long-term durability in terms of corrosivity, but by containing ascorbate in the absorption liquid, the occurrence of corrosion in the circulation path based on the high anticorrosion performance of ascorbate As a result, the long-term durability was improved.
吸収液の循環系における減圧状態が破れたことを察知することができれば、その循環系に酸素が混入した状況を知ることができる。酸素が混入してしまうと、吸収液の循環系に銅材部を有する場合、その循環系内の構成部材が腐食傾向に進むが、前記吸収液にアスコルビン酸塩を投入することによって、混入してしまった酸素を還元除去することによって、系内が腐食傾向に進むのを効果的に抑制することができ、吸収式冷凍機の運転状況を良好に維持することができるようになる。 If it is possible to infer that the reduced pressure is broken in the circulatory system of the intake Osamueki we can know the situation where oxygen is mixed into the circulation system. If oxygen is mixed, when the absorption material circulation system has a copper part, the components in the circulation system tend to corrode, but by introducing ascorbate into the absorption liquid, By reducing and removing the oxygen that has been lost, it is possible to effectively prevent the inside of the system from proceeding to a corrosion tendency, and it is possible to maintain the operating state of the absorption refrigeration machine satisfactorily.
したがって、吸収式冷凍機の内部における防触性を高めることができ、吸収式冷凍機をより耐久性高く用いることができるようになった。 Therefore, the anti-corrosion property inside the absorption refrigerator can be increased, and the absorption refrigerator can be used with higher durability.
以下に、本発明の吸収式冷凍機を説明し、併せて、吸収式冷凍機用の吸収液、および、吸収式冷凍機の運転方法を説明する。なお、以下に好適な実施形態を記すが、これら実施形態はそれぞれ、本発明をより具体的に例示するために記載されたものであって、本発明の趣旨を逸脱しない範囲において種々変更が可能であり、本発明は、以下の記載に限定されるものではない。 Below, the absorption refrigerator of this invention is demonstrated, and the absorption liquid for absorption refrigerators, and the operating method of an absorption refrigerator are demonstrated collectively. Preferred embodiments will be described below, but these embodiments are described in order to more specifically illustrate the present invention, and various modifications can be made without departing from the spirit of the present invention. The present invention is not limited to the following description.
〔吸収式冷凍機〕
図１に、対応する吸収式冷凍機１の一例を示す。
この吸収式冷凍機１は、所謂、二重効用式の吸収式冷凍機であり、凝縮器２、低温再生器３、高温再生器４、吸収器５、蒸発器６等を、所定の経路７で接続して構成されている。さらに、上記の主要な機器の他に、熱交換器８、溶液ポンプ９、冷媒ポンプ１０等が備えられて構成されている。
[Absorption type refrigerator]
FIG. 1 shows an example of a corresponding absorption refrigerator 1.
This absorption refrigerator 1 is a so-called double effect absorption refrigerator, and a
さて、このような吸収式冷凍機１にあっては、減圧状態に維持される吸収液循環系統１１が備えられ、この吸収液循環系統１１内を、吸収液として、アノード型インヒビターを含有したリチウムブロマイド（ＬｉＢｒ）水溶液が吸収液として循環する構成とされている。そして、本願においては、前記吸収液にアスコルビン酸ナトリウムを含有させておく。これにより、前記吸収液による防触効果が発揮され、吸収液の循環系における腐食が抑制される。 Now, in such an absorption refrigerator 1, the absorption liquid circulation system 11 maintained in a depressurized state is provided, and the inside of the absorption liquid circulation system 11 is used as an absorption liquid to contain lithium containing an anode type inhibitor. A bromide (LiBr) aqueous solution is circulated as an absorbing solution. In the present application, sodium ascorbate is contained in the absorption liquid. Thereby, the anti-corrosion effect by the said absorption liquid is exhibited, and the corrosion in the circulation system of an absorption liquid is suppressed.
ここで、アノード型インヒビターは、本発明の要部を構成するものではないが、吸収式冷凍機１の一部構成機器を成す鉄材（ステンレス鋼を除く）に対して酸化剤的に働く添加剤であり、鉄材を不動態化させて水素の発生を抑えることができると考えられるものである。具体的には、マンガン酸組成物（たとえばＬｉＯＨ＋Ｌｉ2ＭｏＯ4＋ＬｉＮＯ3のような組成物）が好適に用いられている。 Here, the anode-type inhibitor does not constitute a main part of the present invention, but an additive that acts as an oxidant on iron materials (except for stainless steel) that constitute a part of the absorption refrigerator 1. Therefore, it is considered that the generation of hydrogen can be suppressed by passivating the iron material. Specifically, a manganic acid composition (for example, a composition such as LiOH + Li 2 MoO 4 + LiNO 3 ) is preferably used.
〔吸収式冷凍機の運転方法〕
また、本願の吸収式冷凍機の運転方法を行う場合には、上記構成に追加して、図１に破線で記載の以下の構成を備えることができる。つまり、減圧状態に維持される吸収液循環系統１１が備えられ、この吸収液循環系統１１内を、吸収液として、アノード型インヒビターおよびアスコルビン酸ナトリウムを含有したリチウムブロマイド（ＬｉＢｒ）水溶液が吸収液として循環する構成とされている。そして、前記吸収式冷凍機１に、先に説明した吸収液循環系統１１の減圧状態を監視する監視機構１２を備える。これは、機器が正常な運転状態にあるか、循環系内の接続部等からこの系統内に外気の空気が混入したかどうかを、系の減圧状態の変化から検出するものである。さらに、この監視機構１２により、減圧状態が破られた状態が検出された場合に、吸収液循環系統内に、アスコルビン酸ナトリウムを投入する投入機構１３を備える。即ち、吸収式冷凍機１にとって、過酷な条件となっている高温再生器４や低温再生器３や、他の投入に適した部位に、上記アスコルビン酸ナトリウムを投入することにより、混入した空気中の酸素を、投入されたアスコルビン酸に消費させることによって、腐食の進行を抑制できるようになっている。投入されるアスコルビン酸ナトリウムは、好適には水溶液として供給される。
[Operation method of absorption refrigerator]
Moreover, when performing the operating method of the absorption refrigerator of this application, in addition to the said structure, the following structures described with a broken line in FIG. 1 can be provided. That is, the absorption liquid circulation system 11 maintained in a reduced pressure state is provided. The absorption liquid circulation system 11 is used as an absorption liquid, and an aqueous solution of lithium bromide (LiBr) containing an anodic inhibitor and sodium ascorbate is used as the absorption liquid. It is configured to circulate. The absorption refrigerator 1 is provided with a
したがって、本願の吸収式冷凍機１にあっては、所定の状態に維持されながら運転されてきた吸収式冷凍機１において、接続部等から空気が混入した場合に、この状態が検出され、系の溶液内に前記アスコルビン酸ナトリウムが投入される。このようにすると、系内への酸素の混入にも係わらず、孔食等の発生を抑えることができる。 Therefore, in the absorption refrigeration machine 1 of the present application, in the absorption refrigeration machine 1 that has been operated while being maintained in a predetermined state, this state is detected when air is mixed in from a connection portion or the like, and the system The sodium ascorbate is charged into the solution. In this way, it is possible to suppress the occurrence of pitting corrosion or the like regardless of the mixing of oxygen into the system.
以上が、本願の吸収式冷凍機の運転方法を採用する構成の吸収式冷凍機１の構成であるが、このようなメンテナンスの有効性に関するデータについて説明する。 The above is the configuration of the absorption chiller 1 configured to employ the operation method of the absorption chiller of the present application, and data regarding the effectiveness of such maintenance will be described.
〔アスコルビン酸に防触効果の実証試験〕
上記吸収液をフラスコに封入した試験装置を作成し、銅片を１か月間浸漬して放置し、その銅片の腐食速度を調べたところ図２に示すようになった。図中、「添加剤」として、「なし」と記載のものは、アノード型インヒビターを含有したリチウムブロマイド（ＬｉＢｒ）水溶液をそのまま吸収液としたものであり、「添加剤」として「亜硫酸水素Ｎａ」、「アスコルビン酸Ｎａ」とあるのは、それぞれ、「亜硫酸水素Ｎａ」、「アスコルビン酸Ｎａ」を、前記吸収液に添加してあることを示し、その添加量を「添加量」として示すものである。「雰囲気」として、Ａｒ脱気とあるのは、フラスコ内を脱気してＡｒ置換した状態を意味し、Ａｒ＋０．５％Ｏ2とあるものは、フラスコ内を脱気して、０．５％Ｏ2含有Ａｒガスで置換した状態を意味する。
[Verification test of anticorrosion effect on ascorbic acid]
A test apparatus in which the above-mentioned absorbing solution was sealed in a flask was prepared, and the copper piece was immersed for one month and allowed to stand. The corrosion rate of the copper piece was examined, and the result was as shown in FIG. In the figure, “None” as “additive” refers to an aqueous solution of lithium bromide (LiBr) containing an anode-type inhibitor as an absorbent, and “addition” is “hydrogen sulfite Na”. , "Na ascorbate" means that "Na bisulfite" and "Na ascorbate" are added to the absorption liquid, respectively, and the addition amount is shown as "addition amount". is there. As the “atmosphere”, Ar deaeration means a state in which the flask is degassed and substituted with Ar, and Ar + 0.5% O 2 is degassed in the flask and 0.5% It means a state where it is substituted with Ar gas containing% O 2 .
図より、アスコルビン酸ナトリウムを用いた場合には、中心原子が硫黄である還元性を有するオキソ酸塩を用いた場合に比べて高い防触性能を示していることがわかる。また、アスコルビン酸塩が、吸収液に２５０ｐｐｍ以上添加されている場合に高い防触性能が発揮されていることが別途実験より明らかになっており、アスコルビン酸塩を吸収液に２５０ｐｐｍ以上添加しておくことで、吸収式冷凍機内部の銅管部における腐食を有効に抑制することができることが分かった。なお、防触性能に関して添加量に上限はないが、効果の持続性、吸収液の吸収性能に対する影響、コスト面等の実用性の面から１％以下程度とすることが好ましい。さらに好ましくは５００ｐｐｍ以上１％以下程度である。 From the figure, it can be seen that when sodium ascorbate is used, the anti-corrosion performance is higher than when the reducing oxo acid salt whose central atom is sulfur is used. In addition, it has been clarified from experiments that when the ascorbate is added to the absorption liquid in an amount of 250 ppm or more, high anti-corrosion performance has been demonstrated. Ascorbate is added to the absorption liquid in an amount of 250 ppm or more. It was found that the corrosion in the copper pipe part inside the absorption refrigerator can be effectively suppressed by placing it. In addition, although there is no upper limit to the addition amount with respect to the anti-corrosion performance, it is preferably about 1% or less from the standpoint of practicality such as the sustainability of the effect, the effect on the absorption performance of the absorbent and the cost. More preferably, it is about 500 ppm or more and 1% or less.
〔別実施形態〕
上記実施形態では、アスコルビン酸塩としてアスコルビン酸ナトリウムを用いたが、カリウム塩、カルシウム塩等の他の塩でもよく上記構成に限られるものではない。
また、インヒビターとして、マンガン酸組成物に代表されるアノード型インヒビターを用いたが、これに限るものではない。また、銅の腐食防止を主な目的としたが、ほかの金属に対する防触効果も明らかなので、吸収式冷凍機一般に適用できることが明らかである。
さらに、従来の中心原子が硫黄である還元性を有するオキソ酸塩として、例えば、亜硫酸ナトリウムなどの亜硫酸塩又は亜硫酸水素塩等を追加で含有することを妨げるものではない。
[Another embodiment]
In the above embodiment, sodium ascorbate is used as the ascorbate, but other salts such as potassium salt and calcium salt may be used, and the present invention is not limited to the above configuration.
Moreover, although the anode type | mold inhibitor represented by the manganic acid composition was used as an inhibitor, it is not restricted to this. Although the main purpose is to prevent copper corrosion, the anti-corrosion effect against other metals is clear, so it is clear that it can be applied to absorption refrigerators in general.
Furthermore, it does not preclude the addition of, for example, sulfites such as sodium sulfite or hydrogen sulfites as conventional oxoacid salts having sulfur as the central atom.
本発明によると、吸収式冷凍機の内部における防触性を高めることができ、吸収式冷凍機をより耐久性高く用いることができるようになった。 According to the present invention, the anti-corrosion property inside the absorption refrigerator can be enhanced, and the absorption refrigerator can be used with higher durability.
１ ：吸収式冷凍機
２ ：凝縮器
３ ：低温再生器
４ ：高温再生器
５ ：吸収器
６ ：蒸発器
７ ：経路
８ ：熱交換器
９ ：溶液ポンプ
１０ ：冷媒ポンプ
１１ ：吸収液循環系統
１２ ：監視機構
１３ ：投入機構
1: Absorption type refrigerator 2: Condenser 3: Low temperature regenerator 4: High temperature regenerator 5: Absorber 6: Evaporator 7: Path 8: Heat exchanger 9: Solution pump 10: Refrigerant pump 11: Absorbing liquid circulation system 12: Monitoring mechanism 13: Input mechanism
Claims (1)
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| JP2013057157A JP6218407B2 (en) | 2013-03-19 | 2013-03-19 | Absorption refrigerator operation method |
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| JP6218407B2 true JP6218407B2 (en) | 2017-10-25 |
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| JP2848672B2 (en) * | 1990-05-21 | 1999-01-20 | オルガノ株式会社 | High-temperature water-based corrosion inhibitor |
| JPH0735433A (en) * | 1993-07-22 | 1995-02-07 | Osaka Gas Co Ltd | Absorption type cooler or heater and corrosion preventing method |
| JP3218156B2 (en) * | 1993-10-27 | 2001-10-15 | 大阪瓦斯株式会社 | Operating method of absorption refrigerator and absorption liquid |
| JP3547265B2 (en) * | 1996-09-11 | 2004-07-28 | 大阪瓦斯株式会社 | Absorption refrigerator maintenance method and absorption refrigerator |
| JPH10260173A (en) * | 1997-03-19 | 1998-09-29 | Mitsubishi Heavy Ind Ltd | Measuring method for refrigerant for refrigerating machine |
| JPH1114206A (en) * | 1997-06-23 | 1999-01-22 | Matsushita Electric Ind Co Ltd | Manufacture of compressor and outdoor unit |
| JP2000179973A (en) * | 1998-10-05 | 2000-06-30 | Osaka Gas Co Ltd | Operating method for absorption hot and chilled water generator and aqueous composition therefor |
| JP2003042588A (en) * | 2001-07-26 | 2003-02-13 | Rinnai Corp | Absorption type cooling and heating machine |
| JP2003082481A (en) * | 2001-09-12 | 2003-03-19 | Miura Co Ltd | Method for suppressing corrosion of nonpassivated metallic body, and method for suppressing corrosion of boiler |
| JP2003294333A (en) * | 2002-04-02 | 2003-10-15 | Sharp Corp | Stirling engine |
| CN1227492C (en) * | 2003-03-11 | 2005-11-16 | 张跃 | Main body of absorbing air-conditioner |
| US7313926B2 (en) * | 2005-01-18 | 2008-01-01 | Rexorce Thermionics, Inc. | High efficiency absorption heat pump and methods of use |
| US20070241309A1 (en) * | 2006-04-13 | 2007-10-18 | Julius Uradnisheck | Composition for controlling exposure to oxygen |
| JP2008267667A (en) * | 2007-04-18 | 2008-11-06 | Hitachi Building Systems Co Ltd | Absorption liquid for absorption chiller / heater and absorption chiller / heater |
| CN102239229A (en) * | 2008-11-07 | 2011-11-09 | 纳幕尔杜邦公司 | Absorption cycle utilizing ionic compounds and/or non-ionic absorbents as working fluids |
| JP2012510042A (en) * | 2008-11-26 | 2012-04-26 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Absorption cycle system with double absorption circuit |
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