JP2708857B2 - Absorption refrigerator - Google Patents
Absorption refrigeratorInfo
- Publication number
- JP2708857B2 JP2708857B2 JP1064407A JP6440789A JP2708857B2 JP 2708857 B2 JP2708857 B2 JP 2708857B2 JP 1064407 A JP1064407 A JP 1064407A JP 6440789 A JP6440789 A JP 6440789A JP 2708857 B2 JP2708857 B2 JP 2708857B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium bromide
- bromide solution
- solution
- absorption refrigerator
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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]
- Y02B30/62—Absorption based systems
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は吸収冷凍機〔吸収式ヒートポンプも含むもの
とする〕に係り、特に冷媒として水、吸収液として臭化
リチウム溶液、腐食抑制剤としてクロム酸リチウムを用
いている吸収冷凍機に関するものである。The present invention relates to an absorption refrigerator (also including an absorption heat pump), particularly water as a refrigerant, a lithium bromide solution as an absorption liquid, and chromium as a corrosion inhibitor. The present invention relates to an absorption refrigerator using lithium oxide.
（ロ）従来の技術 吸収冷凍機の従来技術として、特開昭53−17589号公
報、又は特開昭59−56066号公報（米国特許第4487036
号）にもみられるように、冷媒として水、吸収液として
臭化リチウム溶液を用いている吸収冷凍機において、臭
化リチウム溶液中に腐食抑制剤としてクロム酸リチウム
を添加しているものがある。第１表に吸収液の主な組成
を示す。(B) Conventional technology As a conventional technology of an absorption refrigerator, JP-A-53-17589 or JP-A-59-56066 (U.S. Pat.
As described in the above, there is an absorption refrigerator using water as a refrigerant and a lithium bromide solution as an absorption liquid, wherein lithium chromate is added to a lithium bromide solution as a corrosion inhibitor. Table 1 shows the main composition of the absorbing solution.
（ハ）発明が解決しようとする課題 しかし、前述した吸収冷凍機において、吸収冷凍機の
運転に伴い臭化リチウム溶液の稀釈と濃縮が繰り返され
ると共に、臭化リチウム溶液の加熱沸騰と冷却とが繰り
返され、臭化リチウム溶液の使用につれて吸収液内に白
濁沈殿物〔主成分はクロム酸塩（Li3CrO4等）〕が析出
する欠点があった。この白濁沈殿物の粒径は１μｍ以下
のものであり、この白濁沈殿物が吸収冷凍機の低温熱交
換器や散布装置として用いられているトレー内で詰まり
吸収液の循環を阻害するので、吸収冷凍機の冷凍能力が
著しく低下していた。 (C) Problems to be Solved by the Invention However, in the above-mentioned absorption refrigerator, the dilution and concentration of the lithium bromide solution are repeated with the operation of the absorption refrigerator, and the heating and boiling and cooling of the lithium bromide solution are repeated. It was repeated, and there was a defect that a cloudy precipitate (mainly chromate (Li 3 CrO 4, etc.)) precipitated in the absorbing solution as the lithium bromide solution was used. The particle size of the cloudy sediment is 1 μm or less, and the cloudy sediment is clogged in a tray used as a low-temperature heat exchanger of an absorption refrigerator or used as a spraying device. The refrigerating capacity of the refrigerator was significantly reduced.
本発明は前述した従来技術の課題にかんがみてなされ
たものであり、吸収液中での前記白濁沈殿物の析出を極
力抑えることのできる吸収冷凍機を提供するものであ
る。The present invention has been made in view of the above-mentioned problems of the related art, and provides an absorption refrigerator capable of minimizing the precipitation of the cloudy precipitate in the absorption liquid.
（ニ）課題を解決するための手段 本発明は、前述した課題を解決するために、冷媒とし
て水、吸収液として臭化リチウム溶液、腐食抑制剤とし
てクロム酸リチウムを用いている吸収冷凍機において、
前記臭化リチウム溶液中にホウ素あるいはホウ素化合物
を添加したものである。(D) Means for Solving the Problems In order to solve the above-mentioned problems, the present invention relates to an absorption refrigerator using water as a refrigerant, a lithium bromide solution as an absorbing solution, and lithium chromate as a corrosion inhibitor. ,
It is obtained by adding boron or a boron compound to the lithium bromide solution.
（ホ）作 用 本発明の吸収冷凍機においては、臭化リチウム溶液中
にホウ素あるいはホウ素化合物が添加されているので、
吸収冷凍機の運転に伴い、臭化リチウム溶液を稀釈、濃
縮、及び加熱沸騰、冷却する際の臭化リチウム溶液への
影響をホウ素あるいはホウ素化合物により緩衝すること
ができ、クロム酸リチウムの腐食抑制作用を損なうこと
なく臭化リチウム溶液内での白濁沈殿物（クロム酸塩
等）の析出を抑えることが可能になる。(E) Operation In the absorption refrigerator of the present invention, since boron or boron compound is added to the lithium bromide solution,
With the operation of the absorption refrigerator, the effect of diluting, concentrating, heating and boiling and cooling the lithium bromide solution on the lithium bromide solution can be buffered with boron or a boron compound, thereby suppressing the corrosion of lithium chromate. It becomes possible to suppress the precipitation of cloudy precipitates (chromate and the like) in the lithium bromide solution without impairing the action.
（ヘ）実施例 以下、本発明の吸収冷凍機について説明する。(F) Example Hereinafter, an absorption refrigerator of the present invention will be described.
図において、（１），（２），（３），（４），
（５），（６），（７），（８），（９）はそれぞれ高
温発生器、低温発生器、凝縮器、蒸発器、吸収器、冷媒
ポンプ、吸収液ポンプ、高温熱交換器、低温熱交換器
で、それぞれが管路で接続されて冷媒〔水〕と吸収液
〔臭化リチウム溶液〕の循環路が形成されている。尚、
臭化リチウム溶液中には腐食抑制剤としてクロム酸リチ
ウムが添加されている。しかし、このような吸収冷凍機
においては、その吸収冷凍機の使用について吸収液中に
白濁沈殿物が析出していた。しかし、クロム酸リチウム
の添加されている臭化リチウム溶液ではホウ素あるいは
ホウ素化合物が添加されると前記白濁沈殿物の析出を抑
えられることが見出された。この実験結果を第２表に示
す。In the figure, (1), (2), (3), (4),
(5), (6), (7), (8), and (9) are a high-temperature generator, a low-temperature generator, a condenser, an evaporator, an absorber, a refrigerant pump, an absorbent pump, a high-temperature heat exchanger, The low-temperature heat exchangers are connected by pipes to form a circulation path for the refrigerant [water] and the absorbing liquid [lithium bromide solution]. still,
Lithium chromate is added to the lithium bromide solution as a corrosion inhibitor. However, in such an absorption refrigerator, a cloudy precipitate was deposited in the absorption solution for use of the absorption refrigerator. However, it has been found that in a lithium bromide solution to which lithium chromate is added, the precipitation of the cloudy precipitate can be suppressed when boron or a boron compound is added. Table 2 shows the results of this experiment.
この結果はホウ素化合物〔H3BO3をLiOHで中和した
液〕の添加後１分間煮沸し、その後冷却した場合の臭化
リチウム溶液中の沈殿物の析出量を第１表に示してい
る。 Table 1 shows the amount of precipitates in the lithium bromide solution when the boron compound [a solution obtained by neutralizing H 3 BO 3 with LiOH] was boiled for 1 minute and then cooled. .
この実験結果により、臭化リチウム溶液において、沈
殿物の析出がホウ素化合物によって抑えられたことが示
された。The experimental results showed that the precipitation of the precipitate was suppressed by the boron compound in the lithium bromide solution.
次に、ホウ素の臭化リチウム溶液への作用を確認する
ために行った実験結果について説明する。第２図は新し
い臭化リチウム溶液にホウ素を添加して吸収冷凍機に使
用したとき、新しい臭化リチウム溶液を吸収冷凍機に使
用したとき、及び再生された臭化リチウム溶液を吸収冷
凍機に使用したときの運転時間の経過に対する稀液のア
ルカリ度（稀液１中のLiOHの量、単位はmol）の変化
を示したものである。ここで、上記稀液は、吸収器
（５）から高温発生器（１）へ送られる臭化リチウム溶
液である。Next, the results of experiments performed to confirm the effect of boron on a lithium bromide solution will be described. Fig. 2 shows the results when boron is added to a new lithium bromide solution and used in an absorption refrigerator, when a new lithium bromide solution is used in an absorption refrigerator, and when a regenerated lithium bromide solution is used in an absorption refrigerator. The change in alkalinity (the amount of LiOH in the dilute solution 1, the unit is mol) of the dilute solution with the elapse of the operation time when used is shown. Here, the dilute solution is a lithium bromide solution sent from the absorber (5) to the high temperature generator (1).
第２図の実験結果から明らかなように、ホウ素を添加
した新しい吸収液の場合には、直線（Ａ）で示されてい
るように、運転時間が長くなった場合にも、ほとんどア
ルカリ度は変化しない。これに対し、直線（Ｂ），
（Ｃ）で示されているように、ホウ素が添加されていな
い臭化リチウム溶液、及び再生された臭化リチウム溶液
の場合には、運転時間の経過に伴いアルカリ度が低下す
る。As is clear from the experimental results in FIG. 2, in the case of the new absorbing solution to which boron was added, as shown by the straight line (A), even when the operation time was long, almost the alkalinity was maintained. It does not change. On the other hand, the straight line (B),
As shown in (C), in the case of the lithium bromide solution to which boron has not been added and the regenerated lithium bromide solution, the alkalinity decreases with the elapse of the operation time.
又、第３図は、ホウ素を添加した新しい臭化リチウム
溶液、新しい臭化リチウム溶液、及び再生された臭化リ
チウム溶液をそれぞれ吸収冷凍機に使用したときの運転
時間の経過に対する濃液のアルカリ度の変化を示したも
のである。ここで、上記濃液は、低温発生器（２）から
吸収器（５）へ送られる臭化リチウム溶液である。FIG. 3 is a graph showing the concentration of the alkaline solution of the concentrated solution with respect to the operation time when a new lithium bromide solution containing boron, a new lithium bromide solution, and a regenerated lithium bromide solution were used in an absorption refrigerator. It shows a change in the degree. Here, the concentrated liquid is a lithium bromide solution sent from the low-temperature generator (2) to the absorber (5).
第３図の実験結果から明らかなように、ホウ素を添加
した新しい吸収液の場合には、直線（Ｄ）で運転時間の
経過に伴いアルカリ度が僅かに上昇する。これに対し、
直線（Ｅ），（Ｆ）で示されているように、ホウ素が添
加されていない臭化リチウム溶液、及び再生された臭化
リチウム溶液の場合には、運転時間の経過に伴いアルカ
リ度が低下する。As is clear from the experimental results shown in FIG. 3, in the case of the new absorbent containing boron, the alkalinity slightly increases with the elapse of the operation time on the straight line (D). In contrast,
As shown by the straight lines (E) and (F), in the case of the lithium bromide solution to which boron was not added and the regenerated lithium bromide solution, the alkalinity decreased with the elapse of the operation time. I do.
上記実験結果より、臭化リチウム溶液において、吸収
冷凍機の運転に伴うアルカリ度の低下がホウ素によって
抑えられることが示された。The above experimental results show that in the lithium bromide solution, the decrease in alkalinity due to the operation of the absorption refrigerator is suppressed by boron.
又、第４図は臭化リチウム溶液に塩酸（Hcl）を少量
ずつ滴下したときの中和滴定試験の結果を示した中和滴
定曲線を示したものであり、第４図から明らかなように
塩酸を約9.8ml滴下したとき臭化リチウム溶液のPHは急
激に低下し、吸収液はアルカリ性から酸性に変化する。
又、第５図はホウ素を添加した臭化リチウム溶液に塩酸
を滴下したときの中和滴定試験の結果を示したものであ
る。第５図の中和滴定曲線から明らかなようにホウ素が
添加された臭化リチウム溶液においては、ホウ素のアル
カリ緩衝作用により、アルカリ性から酸性への変化が緩
衝される。FIG. 4 shows a neutralization titration curve showing the results of a neutralization titration test when hydrochloric acid (Hcl) was added dropwise to the lithium bromide solution little by little. As is clear from FIG. When about 9.8 ml of hydrochloric acid is added dropwise, the pH of the lithium bromide solution drops sharply, and the absorbing solution changes from alkaline to acidic.
FIG. 5 shows the results of a neutralization titration test when hydrochloric acid was dropped into a lithium bromide solution to which boron was added. As is apparent from the neutralization titration curve in FIG. 5, in the lithium bromide solution to which boron is added, the change from alkaline to acidic is buffered by the alkali buffering action of boron.
しかし、前記ホウ素化合物の添加によって、クロム酸
リチウム添加の目的である腐食抑制作用が損なわれてい
れば、ホウ素化合物の添加の意味がない。However, if the addition of the boron compound impairs the corrosion inhibitory action, which is the purpose of adding lithium chromate, there is no point in adding the boron compound.
そこで、次に、クロム酸リチウムの添加されている55
％の臭化リチウム溶液中に鉄を浸漬させ、この液を200
時間加熱煮沸する実験を行なった。尚、前記臭化リチウ
ム溶液を加熱する容器の上部には蒸発した冷媒蒸気を凝
縮させるための冷却器が設けられており、前記臭化リチ
ウム溶液の濃度が吸収冷凍機の発生器内の臭化リチウム
溶液の濃度とほぼ同様に一定に保たれた。第３表に、各
試験液と試験液の汚濁度並びに鉄の様子との関係をまと
めた結果を示す。Therefore, next, lithium chromate is added 55
Iron in a 5% lithium bromide solution.
An experiment of heating and boiling for an hour was performed. In addition, a cooler for condensing the evaporated refrigerant vapor is provided at an upper portion of the container for heating the lithium bromide solution, and the concentration of the lithium bromide solution is determined by the concentration of the bromide in the generator of the absorption refrigerator. It was kept constant, almost similar to the concentration of the lithium solution. Table 3 shows the results summarizing the relationship between each test solution, the turbidity of the test solution, and the appearance of iron.
第３表により、ホウ素（Ｂ）が100PPM添加されている
臭化リチウム溶液では液の汚濁がなく、この臭化リチウ
ム溶液に浸漬されている鉄にも腐食の様子がないことが
確認された。 According to Table 3, it was confirmed that the lithium bromide solution to which 100 ppm of boron (B) was added did not cause contamination of the solution, and that the iron immersed in the lithium bromide solution did not corrode.
このため、ホウ素が臭化リチウム溶液に対して100PPM
以上添加されている本発明の吸収冷凍機では、クロム酸
リチウムの腐食抑制作用を損なうことなく、臭化リチウ
ム溶液内での白濁沈殿物の析出を抑え、白濁沈殿物によ
る吸収冷凍機の冷凍能力の低下を回避することができ、
腐食抑制作用の優れた吸収冷凍機を提供することができ
る。For this reason, boron is added to the lithium bromide solution at 100 PPM.
In the absorption refrigerator of the present invention added above, the precipitation of the cloudy precipitate in the lithium bromide solution is suppressed without impairing the corrosion inhibitory effect of lithium chromate, and the refrigerating capacity of the absorption refrigerator by the cloudy precipitate is reduced. Can be reduced,
An absorption refrigerator having excellent corrosion inhibiting action can be provided.
（ト）発明の効果 上記本発明の吸収冷凍機においては、腐食抑制剤とし
てクロム酸リチウムが添加されている吸収液中にホウ素
あるいはホウ素化合物が添加されているため、クロム酸
リチウムの腐食抑制作用を損なうことなく吸収液中での
白濁沈殿物の析出を極力抑えることができ、この結果、
耐食性に優れ、腐食抑制剤による弊害のない吸収冷凍機
を提供することができる。(G) Effect of the Invention In the absorption refrigerator of the present invention, since boron or a boron compound is added to the absorption solution to which lithium chromate is added as a corrosion inhibitor, the corrosion inhibition effect of lithium chromate is provided. The precipitation of cloudy precipitate in the absorbing solution can be suppressed as much as possible without impairing the
It is possible to provide an absorption refrigerator having excellent corrosion resistance and no harm caused by the corrosion inhibitor.
第１図は本発明の吸収冷凍機の概略構成説明図、第２図
は希液の運転時間とアルカリ度との関係図、第３図は濃
液の運転時間とアルカリ度との関係図、第４図は臭化リ
チウム溶液の中和滴定曲線、第５図はホウ素を添加した
臭化リチウム溶液の中和滴定曲線である。 （９）……低温熱交換器。FIG. 1 is a schematic diagram illustrating the structure of an absorption refrigerator according to the present invention, FIG. 2 is a diagram showing the relationship between the operation time of a dilute solution and alkalinity, FIG. FIG. 4 is a neutralization titration curve of a lithium bromide solution, and FIG. 5 is a neutralization titration curve of a lithium bromide solution to which boron is added. (9) Low temperature heat exchanger.
Claims (1)
溶液、腐食抑制剤としてクロム酸リチウムを用いている
吸収冷凍機において、前記臭化リチウム溶液中にホウ素
あるいはホウ素化合物が添加されていることを特徴とす
る吸収冷凍機。1. An absorption refrigerator using water as a refrigerant, a lithium bromide solution as an absorbing solution, and lithium chromate as a corrosion inhibitor, wherein boron or a boron compound is added to the lithium bromide solution. An absorption refrigerator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1064407A JP2708857B2 (en) | 1988-06-30 | 1989-03-15 | Absorption refrigerator |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16345588 | 1988-06-30 | ||
| JP63-163455 | 1988-06-30 | ||
| JP1064407A JP2708857B2 (en) | 1988-06-30 | 1989-03-15 | Absorption refrigerator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0285655A JPH0285655A (en) | 1990-03-27 |
| JP2708857B2 true JP2708857B2 (en) | 1998-02-04 |
Family
ID=26405522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1064407A Expired - Fee Related JP2708857B2 (en) | 1988-06-30 | 1989-03-15 | Absorption refrigerator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2708857B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547600A (en) * | 1995-05-05 | 1996-08-20 | Carrier Corporation | Absorption refrigeration system working fluid with molybdate, borate, silicate inhibitor blend |
| US6004475A (en) * | 1996-06-27 | 1999-12-21 | Fmc Corporation | Corrosion inhibiting solutions for refrigeration systems comprising heteropoly complex anions of transition metal elements |
| US6004476A (en) * | 1997-07-26 | 1999-12-21 | Fmc Corporation | Corrosion inhibiting solutions and processes for refrigeration systems comprising heteropoly complex anions of transition metal elements additional additives |
| US6758988B1 (en) | 1999-09-07 | 2004-07-06 | Fmc Corporation | Corrosion inhibiting solutions for absorption systems |
| US6620341B1 (en) | 1999-12-23 | 2003-09-16 | Fmc Corporation | Corrosion inhibitors for use in oil and gas wells and similar applications |
-
1989
- 1989-03-15 JP JP1064407A patent/JP2708857B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0285655A (en) | 1990-03-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |