JPH02294383A - Absorbing solution of absorption refrigerator - Google Patents
Absorbing solution of absorption refrigeratorInfo
- Publication number
- JPH02294383A JPH02294383A JP1113725A JP11372589A JPH02294383A JP H02294383 A JPH02294383 A JP H02294383A JP 1113725 A JP1113725 A JP 1113725A JP 11372589 A JP11372589 A JP 11372589A JP H02294383 A JPH02294383 A JP H02294383A
- Authority
- JP
- Japan
- Prior art keywords
- group
- metals
- lithium
- alkali metal
- aqueous solution
- 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.)
- Pending
Links
- 238000010521 absorption reaction Methods 0.000 title claims description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 10
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 150000002823 nitrates Chemical class 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003842 bromide salts Chemical class 0.000 claims 3
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 34
- 230000007797 corrosion Effects 0.000 abstract description 32
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 abstract description 18
- 239000000243 solution Substances 0.000 abstract description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- MOOYSSSIVSFZQA-UHFFFAOYSA-N [Li].[Mo] Chemical compound [Li].[Mo] MOOYSSSIVSFZQA-UHFFFAOYSA-N 0.000 description 7
- 150000001649 bromium compounds Chemical class 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- -1 OK lithium oxide Chemical class 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- SWFPCDJSMKKRFW-UHFFFAOYSA-N [Cr].[Li] Chemical compound [Cr].[Li] SWFPCDJSMKKRFW-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- PNEHEYIOYAJHPI-UHFFFAOYSA-N lithium tungsten Chemical compound [Li].[W] PNEHEYIOYAJHPI-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- COKMLVOGWBEPNX-UHFFFAOYSA-N 1-(dipropylamino)ethanol Chemical compound CCCN(C(C)O)CCC COKMLVOGWBEPNX-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- KEDNSMBVYXSBFC-UHFFFAOYSA-N 6-bromo-2-chloroquinoline-4-carbonyl chloride Chemical compound C1=C(Br)C=C2C(C(=O)Cl)=CC(Cl)=NC2=C1 KEDNSMBVYXSBFC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IBXOPEGTOZQGQO-UHFFFAOYSA-N [Li].[Nb] Chemical compound [Li].[Nb] IBXOPEGTOZQGQO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FEEFWFYISQGDKK-UHFFFAOYSA-J hafnium(4+);tetrabromide Chemical compound Br[Hf](Br)(Br)Br FEEFWFYISQGDKK-UHFFFAOYSA-J 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229940105965 yttrium bromide Drugs 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、吸収式冷凍機用吸収液に係り，臭化リチウム
などのハロゲン化アルカリ金属の水溶液を吸収液として
用いるもので，特に防食性能を良くするのに好適な吸収
式冷凍機用吸収液に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an absorption liquid for an absorption refrigerator, and uses an aqueous solution of an alkali metal halide such as lithium bromide as the absorption liquid. This invention relates to an absorption liquid for an absorption refrigerator suitable for improving the temperature.
一般に吸収式冷凍機は、吸収液として臭化リチウム液を
使用している．臭化リチウムは，食品と同様にハロゲン
化アルカリ金属の塩であり、金ノ―（に対して強い腐食
性をもっている．そのため、従来から水酸化リチウムに
よるＰＨｙＡ整をするとともに，クロム酸リチウム、モ
リブデン酸リチウムなどの複酸化物や、硝酸リチウムな
どの防食剤を含有させている。Absorption refrigerators generally use lithium bromide liquid as the absorption liquid. Lithium bromide is a salt of an alkali metal halide, just like in food, and is highly corrosive to gold. Therefore, in addition to lithium hydroxide for PHyA adjustment, lithium chromate and molybdenum Contains double oxides such as lithium oxide and anticorrosive agents such as lithium nitrate.
また、最近では、ペンゾトリアゾール，アルカノールア
ミン類などの有機性防食剤と水酸化アルカリ金属を複合
させたものもある．
このような技術として，例えば、特開昭６３−１０１１
５２号公報が挙げられる．
〔発明が解決しようとする課題〕
従来から使用されている防食剤の硝酸リチウム，クロム
酸リチウム，モリブデン酸リチウムなどは、鋼材の全面
腐食に対しては極めて有効であるが、図面に示す硝酸リ
チウムのように局部腐食を促す傾向をもっている．
ここで、図面は、横軸に硝酸リチウムの濃度（ｐｐｍ）
、縦軸に腐食麓（■／ｄｒｎ”）をとり、臭化リチウム
６５％，水酸化リチウム０．２％の吸収液における１６
０℃，２００時間の腐食試験のデータにより、酸化性防
食剤の過大が局部腐食を誘発する傾向を示している。Recently, there are also products that combine organic anticorrosive agents such as penzotriazole and alkanolamines with alkali metal hydroxide. As such technology, for example, Japanese Patent Application Laid-Open No. 63-1011
Publication No. 52 is mentioned. [Problem to be solved by the invention] Conventionally used anticorrosive agents such as lithium nitrate, lithium chromate, and lithium molybdate are extremely effective against general corrosion of steel materials. It has a tendency to promote local corrosion. Here, the drawing shows the concentration of lithium nitrate (ppm) on the horizontal axis.
, the corrosion foot (■/drn”) is plotted on the vertical axis.
Data from a 200 hour corrosion test at 0°C shows that too much oxidizing corrosion inhibitor tends to induce localized corrosion.
また，水酸化アルカリ金属、例えばＯＫ酸化リチウムは
単独では十分な防食効果は望めない。Furthermore, alkali metal hydroxide, such as OK lithium oxide, alone cannot provide a sufficient anticorrosion effect.
有機性防食剤のペンゾトリアゾールは，臭化リチウムの
高濃度溶液には難溶性であり、また５アルカノールアミ
ン類も単独では吸収液中での防食効果は不十分である。Penzotriazole, an organic anticorrosive agent, is poorly soluble in a high concentration solution of lithium bromide, and penta-alkanolamines alone have insufficient anticorrosion effect in the absorption liquid.
本発明は、上記従来技術における課題を解決するために
なされたもので、防食性能の良好な吸収液を提供し、機
器の腐食による大気の漏洩事故を防止しうる吸収式冷凍
機用吸収液を提供することを、その目的とするものであ
る。The present invention has been made in order to solve the above-mentioned problems in the prior art, and provides an absorption liquid for absorption refrigerating machines that can provide an absorption liquid with good anti-corrosion performance and prevent air leakage accidents due to corrosion of equipment. Its purpose is to provide.
ｃａｉＩ＋１を解決するための手段〕
上記目的を達成するために、本発明の吸収式冷凍機用吸
収液の第１の発明の構成は、ハロゲン化アルカリ金属の
水溶液に、イットリウム族，チタン族，バナジウム族，
およびクロム族の金属のうち１種または２種以上を、こ
れら金属の硝酸塩，臭化物、および複酸化物として添加
するものとし、その添加斌を，水溶液に対して前記金属
としての総斌が、０．０ １〜０．１ウェイトパーセン
トとなるようにしたものである．
また，本発明の吸収式冷凍機用吸収液の第２の発明の構
成は、ハロゲン化アルカリ金属の水溶液に、イットリウ
ム族，チタン族，バナジウム族，およびクロム族の金属
のうち１種または２種以上を、これら金属の硝酸塩，臭
化物、および複酸化物として，その金属の総量が水溶液
に対して、０．０１〜０．１ウェイトパーセント含むと
ともに，水酸化アルカリ金属を、０．１〜０．５ウェイ
トパーセント含むものである．
さらに．本発明の吸収式冷凍機用吸収液の第３の発明の
構成は、ハロゲン化アルカリ金属の水溶液に，イットリ
ウム族，チタン族，バナジウム族、およびクロム族の金
属のうち１種または２種以上を、これら金属の硝酸塩，
臭化物、および複酸化物として，その金属の総量が水溶
液に対して、０．０１〜０．１ウェイトパーセント含み
、かつ、水酸化アルカリ金属を、０．１〜０．５ウェイ
トパーセント含み、さらに，アルキルアミノアルカノー
ルおよびアルカノールアミンを、０．０１〜０．５ウェ
イトパーセント含むものである．
なお、本発明を開発した考え方に沿って技術的手段を説
明すれば次のとおりである。Means for solving caiI+1] In order to achieve the above object, the structure of the first invention of the absorption liquid for an absorption refrigerator of the present invention is that yttrium group, titanium group, vanadium group, etc. are added to an aqueous solution of an alkali metal halide. family,
and chromium group metals shall be added as nitrates, bromides, and double oxides of these metals, and the amount of addition shall be such that the total amount of the metals in the aqueous solution is 0. .0 1 to 0.1 weight percent. Further, in the second aspect of the absorption liquid for an absorption refrigerator of the present invention, one or two metals from the yttrium group, the titanium group, the vanadium group, and the chromium group are added to the aqueous solution of the alkali metal halide. The above are nitrates, bromides, and double oxides of these metals, and the total amount of the metals in the aqueous solution is 0.01 to 0.1 weight percent, and the alkali metal hydroxide is 0.1 to 0.1 weight percent. It contains 5 weight percent. moreover. The third aspect of the structure of the absorption liquid for an absorption refrigerator of the present invention is that one or more metals from the yttrium group, titanium group, vanadium group, and chromium group are added to the aqueous solution of an alkali metal halide. , nitrates of these metals,
As bromides and double oxides, the total amount of the metals is 0.01 to 0.1 weight percent based on the aqueous solution, and the alkali metal hydroxide is 0.1 to 0.5 weight percent, and further, It contains 0.01 to 0.5 weight percent of alkylaminoalkanol and alkanolamine. The technical means based on the idea behind the invention will be explained as follows.
吸収液に対する鋼材の耐食性を向上させるには、鋼材の
表面に耐食性の保護皮膜を形成させればよいが、この皮
膜は、イットリウム族，チタン族，バナジウム族、およ
びクロム族の金属のうち１種または２種以上を含ませる
ことで良好な皮膜に改善される。In order to improve the corrosion resistance of steel materials against absorbing liquids, it is sufficient to form a corrosion-resistant protective film on the surface of the steel material. Alternatively, by including two or more kinds, a good film can be obtained.
また，気液境界部の耐食性の向上あるいは局部腐食の改
善には、アルキルアミノアルカノールまたはアルカノー
ルアミンのような揮発性防食剤による防食が好適で、こ
れらを吸収液に含ませることによって防食性能の良好な
吸収式冷凍機用吸収液を得るという目的は達成される．
〔作用〕
上記技術的手段により働きを、本発明を開発した考え方
に沿って説明する．
イットリウム族，チタン族，バナジウム族、およびクロ
ム族の金属について種々検討の結果、これらの金属は、
吸収式冷凍機等の鋼材の表面に形成される保護皮膜に浸
入して皮膜を緻密，均一化し耐食性を向上させる作用を
もっていることを見出だした．
そこで，これらの金属を吸収液に可溶な硝酸塩、臭化物
，および複酸化物の形で添加することを考えた．
また、吸収式冷凍機等の気液境界部の特に腐食されやす
い部位の防食には，揮発性の炭素Ｊｎ子３〜８個のアル
キルアミノアルカノールまたはアルカノールアミンを吸
収液に添加することによって鋼材表面への吸着形の気相
防食効果が期待できることを認めた．
さらに、これらの気相防食剤の効果を接液部の局部腐食
の抑制に利用するため、前記の防食剤と併用することを
考えた．
前記のイットリウム族，チタン族，バナジウム族、およ
びクロム族の金属のうち１種または２種以上の金属の、
硝酸塩，臭化物、および複酸化物の吸収液に対する添加
量は、これらの金属の総諷が０．０１ ウェイトパーセ
ント（以下ｗｔ％としるす）未満では十分な効果が得ら
れないので下限は０．０１ｗｔ％とした．また、０．１
ｗｔ％ を超えて添加しても効果に殆んど変化がみられ
ないので上限は０．１ｗｔ％とした．
次に、水酸化アルカリ金属の添加景は、０．１ｗｔ％未
満では効果不十分であり、０．５ｗｔ％を超える添加は
効果に殆んど変化が認められないので限定範囲を０．１
〜０．５ ｗ ｔ％ とした．次に、（Ｒ）−ＮＨｉ−
（（ＣＨｔ）ｎＯＨ）（ただし、Ｒは、Ｃａｒｔｅ＋１
で表わされるアルキル基、ｍはＯ〜２の整数、ｎは整数
）で表わされるアルキルアミノアル力一ノール、および
、
（ＨＯ（ＣＨｚ）ｎ）−ＮＨａ−（ただし、ｍはＯ〜３
の整数、ｎは整数）で表わされるアルカノールアミンの
添加量は、吸収液に対し０．０１ｗｔ％未満では効果不
十分であり．０．５ｗｔ％ を超える添加は殆んど変化
が認められないため，限定範囲を０．０１〜０．５ｗｔ
％ とした．
ここで前記のイットリウム族，チタン族，バナジウム族
、およびクロム族の金属の、吸収液に可溶な硝酸塩、臭
化物、および複酸化物としては、硝酸イットリウム，臭
化イットリウム，臭化チタン，リチウムーチタン複酸化
物（Ｌ１２０・’ｌ’ ｒ Ｏ ！；ＬｔｚＴ▲０８）
，硝酸ジルコニウム，臭化ジルコニウム，リチウムージ
ルコン複酸化物（ＬｔｚＯ・Ｚ ｒ Ｏ ｚ ： Ｌ
．ｚ Ｚ ｒ Ｏ ａ ） ｖ臭化ハフニウム，臭化バ
ナジウム，リチウムバナジウム複酸化物（ＬｉｚＯ・ｖ
２０ｓ： ＬｔｚＶｚＯ７）ｔ ！Ｊチウムーニオブ複
酸化物（Ｌ＋ｚＯ ・Ｎ ｂｚｏｓ ： ２ ＬｔＮ
ｂ Ｏｓ）．リチウムークロム複酸化物（ＬｔｚＯ−Ｃ
ｒＯａ・Ｌｔ！ＣｒＯ４Ｌリチウムーモリブデン？Ｍ酸
化物（Ｌ，！○・Ｍ ｏ Ｏ ｓ：ＬｓｚＭｏ○４），
リチウムータングステン複酸化物（ＬｓｚＯ−Ｗｏ８；
Ｌ＋ｘＷＯａ）などがあげられる．
なお、複酸化物におけるリチウムはこれに限らずアルカ
リ金属であればよい．
次に、アルキルアミノアルカノールとしては、モノまた
はジエチルアミノエタノール，モノまたはジメチルアミ
ノエタノール、モノまたはジプロピルアミノエタール、
およびこれらのエタノールに替えるプロバノールなどが
挙げられる．また、アルカノールアミンとしては、モノ
，ジまたはトリエタノールアミン，およびこれらのエタ
ノールアミンに替るモノ，ジおよびトリメタノールアミ
ンと、モノ，ジおよびトリブロバノールアミンが挙げら
れる．
〔実施例〕
以下、本発明の実施例を説明する．
試験液として、＆１〜＆１４の１４種類の吸収液を調整
した．調合は、各金属の硝酸塩，臭化物、および複酸化
物に、予め水酸化アルカリ金属として水酸化リチウムを
０．３％溶解した５３％臭化リチウム溶液を加えて溶解
後，さらにアルキルアミノアルカノールおよびアルカノ
ールアミンの順に加えた。In addition, to improve corrosion resistance at the gas-liquid interface or to improve local corrosion, corrosion protection using volatile corrosion inhibitors such as alkylamino alkanols or alkanolamines is suitable, and by including these in the absorbent liquid, good corrosion protection performance can be achieved. The objective of obtaining a suitable absorption liquid for absorption refrigerators is achieved. [Operation] The operation of the above technical means will be explained in accordance with the idea behind the development of the present invention. As a result of various studies on yttrium group, titanium group, vanadium group, and chromium group metals, these metals are
It was discovered that it penetrates into the protective film formed on the surface of steel materials such as absorption refrigerators, making the film denser and more uniform, and improving corrosion resistance. Therefore, we considered adding these metals to the absorbent in the form of soluble nitrates, bromides, and double oxides. In addition, to prevent corrosion in the gas-liquid boundary areas of absorption refrigerators, etc., which are particularly susceptible to corrosion, the steel surface can be prevented by adding a volatile alkylaminoalkanol or alkanolamine containing 3 to 8 carbon atoms to the absorption liquid. It was confirmed that the vapor phase corrosion protection effect of the adsorbed type can be expected. Furthermore, in order to utilize the effects of these vapor-phase corrosion inhibitors to suppress local corrosion in wetted parts, we considered using them in combination with the above-mentioned corrosion inhibitors. One or more metals from the yttrium group, titanium group, vanadium group, and chromium group metals,
The lower limit of the amount of nitrates, bromides, and double oxides added to the absorbent liquid is 0.01 wt, since sufficient effects cannot be obtained if the total amount of these metals is less than 0.01 weight percent (hereinafter referred to as wt%). %. Also, 0.1
The upper limit was set at 0.1 wt% since there was almost no change in the effect even if added in excess of wt%. Next, regarding the addition of alkali metal hydroxide, if it is less than 0.1 wt%, the effect is insufficient, and if it is added more than 0.5 wt%, there is almost no change in the effect, so the limited range is set to 0.1 wt%.
~0.5 wt%. Next, (R)-NHi-
((CHt)nOH) (where R is Carte+1
an alkyl group represented by, m is an integer of O~2, n is an integer), and an alkylaminoalkyl group represented by (HO(CHz)n)-NHa- (where m is an integer of O~3
If the amount of alkanolamine added (n is an integer) is less than 0.01 wt% with respect to the absorption liquid, the effect is insufficient. Addition of more than 0.5 wt% causes almost no change, so the limited range is set at 0.01 to 0.5 wt%.
%. Here, the nitrates, bromides, and double oxides of metals from the yttrium group, titanium group, vanadium group, and chromium group that are soluble in the absorption liquid include yttrium nitrate, yttrium bromide, titanium bromide, and lithium. Titanium double oxide (L120・'l' r O!; LtzT▲08)
, zirconium nitrate, zirconium bromide, lithium-zircon double oxide (LtzO.ZrOz: L
．． z Z r O a ) v Hafnium bromide, vanadium bromide, lithium vanadium double oxide (LizO・v
20s: LtzVzO7)t! J thiium niobium double oxide (L+zO ・N bzos : 2 LtN
bOs). Lithium-chromium double oxide (LtzO-C
rOa・Lt! CrO4L lithium-molybdenum? M oxide (L,!○・M o O s: LszMo○4),
Lithium-tungsten double oxide (LszO-Wo8;
L+xWOa), etc. Note that the lithium in the double oxide is not limited to this, and any alkali metal may be used. Next, the alkylaminoalkanol includes mono- or diethylaminoethanol, mono- or dimethylaminoethanol, mono- or dipropylaminoethanol,
and probanol, which can be used as a substitute for these ethanols. Examples of alkanolamines include mono-, di-, and triethanolamines, mono-, di-, and trimethanolamines that can replace these ethanolamines, and mono-, di-, and tribrobanolamines. [Examples] Examples of the present invention will be described below. As test liquids, 14 types of absorption liquids, &1 to &14, were prepared. The preparation involves adding and dissolving a 53% lithium bromide solution in which 0.3% lithium hydroxide is dissolved in advance as an alkali metal hydroxide to the nitrate, bromide, and double oxide of each metal, and then alkylaminoalkanol and alkanol. The amines were then added.
比較用の吸収液としては水酸化リチウム０．３％．硝酸
リチウム０．０５％ を添加した５３％臭化リチウム溶
液を調整した。The absorption liquid for comparison was 0.3% lithium hydroxide. A 53% lithium bromide solution to which 0.05% lithium nitrate was added was prepared.
吸収液は、Ｎｌｍｌは硝酸イットリウムを、＆２はリチ
ウムーチタン複酸化物を、＆３は硝酸ジルコニウムを、
魔４は臭化ハウニウムを、Ｎα５はリチウムーバナジウ
ム複酸化物を，Ｎａ６はリチウムーニオブ複酸化物を、
ｈ７はリチウムークロム複酸化物を，ＮＱ８はりチウム
ーモリブデン複酸化物を、翫９はリチウムータングステ
ン複酸化物を、それぞれ添加したものである．また，Ｎ
ａｌＯは，リチウムーモリブデン複酸化物を溶解したの
ち、ジエチルアミノエタノールを加えた．ＮＱ１１は，
リチウムーモリブデン複酸化物を溶解したのち，ジエタ
ノールアミンを加えた。The absorption liquid is yttrium nitrate for Nlml, lithium-titanium double oxide for &2, zirconium nitrate for &3,
Magic 4 is haunium bromide, Nα5 is lithium vanadium double oxide, Na6 is lithium niobium double oxide,
H7 has a lithium-chromium double oxide added, NQ8 has a lithium-molybdenum double oxide added, and H9 has a lithium-tungsten double oxide added. Also, N
For alO, diethylaminoethanol was added after dissolving lithium-molybdenum double oxide. NQ11 is
After dissolving the lithium-molybdenum double oxide, diethanolamine was added.
Ｎα１２〜１４には、これらの化合物を複合添加した試
験液も加えた。すなわち，Ｎα１２は、リチウムーバナ
ジウム複酸化物とりチウムーモリブデン複酸化物との等
斌を，ＮＱ１３は、リチウムーモリブデン複酸化物とり
チウムータングステン複酸化物との等量を、ＮＱ１４は
，リチウムーモリブデン複酸化物にジエチルアミノエタ
ノールとジエタノールアミンとの等量を加えたものであ
る。Ｎα１５は，比較用吸収液である．
なお，各金属の化合物の添加斌は、金ｌｉｔとして０．
０４％、複合添加の場合は０．０２％づつとした．また
、アルキルアミノアルカノールおよびアルカノールアミ
ンの添加斌は０．１％、複合添加の場合は０．０５％づ
つとした．
腐食試験片は、炭素鋼８８４１材で，縦１０Ｘ横５０×
厚さ２ＲＩＩｌの大きさの板状としエメリー＃４００仕
上後脱脂した．
腐食試験は，ガラスアンプル中に臭化リチウムとして６
５％に濃縮した試験液１ ０ ｍ Ｑが試験片の約７０
％を浸漬するように真空状態で封入し、１６０℃で２０
０時間腐食試験を行い、炭素鋼の腐食量を重量減少より
求めた．
その結果、凪１〜＆９，ＮＱ１２およびＮＩｌ１３の本
発明の吸収液中での炭素鋼の腐食量は１００〜１５０ｘ
／ｄｍ”で，Ｎａｌ５の従来の比較用吸収掖中での炭素
鋼の腐食量３２０■／ ｄ ｍ ２にくらべ１／３〜１
／２の小さい結果を得た．また、ＮｎｌＯ＝＆１１およ
び魔１４の揮発性防錆剤を添加した本発明の吸収液によ
る腐食坩は５０Ｎ／Ｑ前後とさらに小さい値であった．
〔発明の効果〕
以上詳細に説明したように、本発明によれば、防食性能
の良好な吸収液を提供し、機器の腐食による大気の漏洩
事故を防止しつる吸収式冷凍機用吸収液を提供すること
ができる．
言い換えれば、吸収液の腐食性が著しく抑制されるため
，吸収式冷凍機におこる腐食による大気漏洩事故が減少
し機械の信頼を著しく向上させる効果がある．A test solution containing a combination of these compounds was also added to Nα12 to Nα14. That is, Nα12 is the equivalence between lithium-vanadium double oxide and lithium-molybdenum double oxide, NQ13 is the equivalence between lithium-molybdenum double oxide and thiium-tungsten double oxide, and NQ14 is the equivalence between lithium-vanadium double oxide and lithium-molybdenum double oxide. It is made by adding equal amounts of diethylaminoethanol and diethanolamine to molybdenum double oxide. Nα15 is an absorption liquid for comparison. The addition rate of each metal compound is 0.0% as gold lit.
0.04%, and 0.02% in case of combined addition. Further, the addition rate of alkylaminoalkanol and alkanolamine was 0.1%, and in the case of combined addition, 0.05% each. The corrosion test piece is made of carbon steel 8841 material, 10 x 50 x horizontal.
It was shaped into a plate with a thickness of 2 RIIl, finished with emery #400, and then degreased. Corrosion tests were carried out using lithium bromide as lithium bromide in glass ampoules.
10 m Q of the test solution concentrated to 5% is approximately 70 m Q of the test piece.
% in vacuum, and heated at 160℃ for 20 minutes.
A 0-hour corrosion test was conducted, and the amount of corrosion of the carbon steel was determined from the weight loss. As a result, the amount of corrosion of carbon steel in the absorption liquid of the present invention of Nagi1~&9, NQ12 and NIl13 was 100~150x
/dm", the amount of corrosion of carbon steel in the conventional comparison absorption tank of Nal5 is 320cm2 to 1/3~1
We obtained a small result of /2. Furthermore, the corrosion crucible produced by the absorption liquid of the present invention to which NnlO=&11 and a volatile rust preventive of 14 was added had an even smaller value of around 50 N/Q.
[Effects of the Invention] As explained in detail above, according to the present invention, an absorbent liquid with good anti-corrosion performance is provided, and an absorbent liquid for a hanging absorption refrigerating machine that prevents atmospheric leakage accidents due to corrosion of equipment is provided. can be provided. In other words, since the corrosiveness of the absorption liquid is significantly suppressed, air leakage accidents due to corrosion that occur in absorption chillers are reduced, and the reliability of the machine is significantly improved.
Claims (1)
ム族の金属のうち１種または２種以上を、 これら金属の硝酸塩、臭化物、および複酸化物として添
加するものとし、 その添加量を、水溶液に対して前記金属としての総量が
、０．０１〜０．１ウェイトパーセントとなるようにし
た。 ことを特徴とする吸収式冷凍機用吸収液。 ２、ハロゲン化アルカリ金属の水溶液に、 イットリウム族、チタン族、バナジウム族、およびクロ
ム族の金属のうち１種または２種以上を、これら金属の
硝酸塩、臭化物、および複酸化物として、その金属の総
量が水溶液に対して、０．０１〜０．１ウェイトパーセ
ント含むとともに、 水酸化アルカリ金属を、０．１〜０．５ウェイトパーセ
ント含む ことを特徴とする吸収式冷凍機用吸収液。 ３、ハロゲン化アルカリ金属の水溶液に、 イットリウム族、チタン族、バナジウム族、およびクロ
ム族の金属のうち１種または２種以上を、これら金属の
硝酸塩、臭化物、および複酸化物として、その金属の総
量が水溶液に対して、０．０１〜０．１ウェイトパーセ
ント含み、かつ、水酸化アルカリ金属を、０．１〜０．
５ウェイトパーセント含み、 さらに、アルキルアミノアルカノールおよびアルカノー
ルアミンを、０．０１〜０．５ウェイトパーセント含む ことを特徴とする吸収式冷凍機用吸収液。[Claims] 1. One or more metals from the yttrium group, titanium group, vanadium group, and chromium group are added to an aqueous solution of an alkali metal halide, and nitrates, bromides, and double oxides of these metals are added. The amount of addition was such that the total amount of the metal was 0.01 to 0.1 weight percent relative to the aqueous solution. An absorption liquid for absorption refrigerators characterized by the following. 2. Add one or more metals from the yttrium group, titanium group, vanadium group, and chromium group to an aqueous solution of alkali metal halides as nitrates, bromides, and double oxides of these metals. An absorption liquid for an absorption refrigerator, characterized in that the total amount thereof is 0.01 to 0.1 weight percent based on the aqueous solution, and 0.1 to 0.5 weight percent of alkali metal hydroxide. 3. Add one or more metals from the yttrium group, titanium group, vanadium group, and chromium group to an aqueous solution of alkali metal halides as nitrates, bromides, and double oxides of these metals. The total amount contains 0.01 to 0.1 weight percent based on the aqueous solution, and 0.1 to 0.1 weight percent of alkali metal hydroxide.
5 weight percent, and further contains alkylaminoalkanol and alkanolamine at 0.01 to 0.5 weight percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1113725A JPH02294383A (en) | 1989-05-08 | 1989-05-08 | Absorbing solution of absorption refrigerator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1113725A JPH02294383A (en) | 1989-05-08 | 1989-05-08 | Absorbing solution of absorption refrigerator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02294383A true JPH02294383A (en) | 1990-12-05 |
Family
ID=14619558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1113725A Pending JPH02294383A (en) | 1989-05-08 | 1989-05-08 | Absorbing solution of absorption refrigerator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02294383A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156679A (en) * | 1991-06-20 | 1992-10-20 | W. R. Grace & Co.-Conn. | Air-detrainer for hydraulic cement compositions |
| AU648002B2 (en) * | 1991-06-20 | 1994-03-31 | W.R. Grace & Co.-Conn. | Cement admixture and defoaming agent |
| JPH0914783A (en) * | 1995-06-30 | 1997-01-17 | Kawasaki Heavy Ind Ltd | Absorbing liquid for absorption refrigerator and absorbing liquid-transfer unit therefor |
| US8597826B2 (en) | 2004-12-07 | 2013-12-03 | Lg Chem, Ltd. | Nonaqueous electrolyte comprising oxyanion and lithium secondary battery using the same |
-
1989
- 1989-05-08 JP JP1113725A patent/JPH02294383A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156679A (en) * | 1991-06-20 | 1992-10-20 | W. R. Grace & Co.-Conn. | Air-detrainer for hydraulic cement compositions |
| AU648002B2 (en) * | 1991-06-20 | 1994-03-31 | W.R. Grace & Co.-Conn. | Cement admixture and defoaming agent |
| JPH0914783A (en) * | 1995-06-30 | 1997-01-17 | Kawasaki Heavy Ind Ltd | Absorbing liquid for absorption refrigerator and absorbing liquid-transfer unit therefor |
| US8597826B2 (en) | 2004-12-07 | 2013-12-03 | Lg Chem, Ltd. | Nonaqueous electrolyte comprising oxyanion and lithium secondary battery using the same |
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