CN1962949A - Lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparing method thereof - Google Patents
Lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparing method thereof Download PDFInfo
- Publication number
- CN1962949A CN1962949A CN 200610134460 CN200610134460A CN1962949A CN 1962949 A CN1962949 A CN 1962949A CN 200610134460 CN200610134460 CN 200610134460 CN 200610134460 A CN200610134460 A CN 200610134460A CN 1962949 A CN1962949 A CN 1962949A
- Authority
- CN
- China
- Prior art keywords
- lithium
- refrigerating machine
- corrosion inhibitor
- absorption type
- bromide
- 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
Landscapes
- Sorption Type Refrigeration Machines (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a lithium bromide absorbing-typed refrigerator inhibitor and preparing method, which comprises the following parts: 0.05-0.10mol/l lithium hydroxide, 100-500mg/l polyvalent heteropoly compound and 50-300mg/l antimony compound. The preparing method comprises the following steps: (1) adding lithium hydroxide in the lithium bromide solution to stir 1-2h; adjusting the pH value of lithium bromide solution at 9-10.5; (2) adding 100-500mg/l polyvalent heteropoly compound in the lithium bromide solution to stir 2-4h; (3) adding 50-300mg/l antimony compound in the lithium bromide solution to stir 2-4h under 25-80 Deg C.
Description
Technical field
The invention belongs to the metal corrosion and protection field, relate to a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparation method thereof
Background technology
Lithium-bromide absorption-type refrigerating machine is with H
2O-LiBr is that working medium is right, H
2O is a refrigeration agent, and LiBr is an absorption agent.Lithium-bromide absorption-type refrigerating machine has advantages such as the cold regulation range is wide, thermo-efficiency is high, energy consumption is low, pollution-free, can utilize low potential heat to be power, avoids the waste of industrial exhaust heat.Yet lithium bromide water solution is the very strong medium of a kind of aggressiveness, and metals such as carbon steel, copper and copper-nickel alloy are had very strong corrodibility.Do not contain under the situation of inhibiter, metallic corrosion speed is along with the rising of the concentration of lithium-bromide solution and temperature and increase.When temperature was lower than 160 ℃, corrosion speed changed little, and temperature is when surpassing 160 ℃, and metallic corrosion speed increases rapidly.For solving the lithium-bromide absorption-type refrigerating machine etching problem, most economical effective way is to add inhibiter in lithium-bromide solution, and inhibiter commonly used mainly contains Li
2CrO
4, Li
2MoO
4(Na
2MoO
4), LiNO
3With BTA etc.For improving lithium-bromide absorption-type refrigerating machine thermo-efficiency, the nineties in 20th century, refrigeration industry research is added one or more groups producer and solution heat exchanger on the basis of economic benefits and social benefits formula unit, exploitation triple effect and multiple-effect formula lithium-bromide absorption-type refrigerating machine.The triple effect unit is compared with economic benefits and social benefits formula unit, and coefficient of refrigerating performance (COP) value has improved 0.3, and energy-output ratio has saved 19%.Triple effect unit work top temperature surpasses 180 ℃, and lithium-bromide solution concentration is also higher, and the corrosion of unit being made material is more serious.Chromate corrosion inhibitors is toxic, and concentration is wayward, easily brings out pitting; Molybdate solubleness in lithium-bromide solution is low, is difficult for keeping effective concentration; The nitrate poor heat stability is easily decomposed, and can combine with the free hydrogen atom in the aqueous solution and produces ammonia, brings out the stress corrosion crack of metal; Thermally-stabilised poor under the organism hot conditionss such as BTA, easy decomposition and degeneration.Thereby the inhibiter that uses in the economic benefits and social benefits formula lithium-bromide absorption-type refrigerating machine has been not suitable for using in triple effect and multiple-effect formula unit, needs the new inhibiter of exploitation, and at present also fewer to the research that is applicable to the triple effect lithium-bromide absorption type corrosion inhibitor for refrigerating machine.
Summary of the invention
The present invention is directed to the problems referred to above, a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparation method thereof has been proposed, develop the novel corrosion inhibitor that in the high-temperature high concentration lithium-bromide solution, metallic substance such as carbon steel, copper-nickel alloy and copper is had outstanding corrosion inhibition, have inhibition efficiency height, characteristics that toxicity is low.
Technical scheme of the present invention is, a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine is made up of lithium hydroxide, polynary heteropoly compound and antimony containing compounds, and their concentration in lithium-bromide solution is:
Lithium hydroxide 0.05～0.10mol/L
Polynary heteropoly compound 100～500mg/L
Antimony containing compounds 50～300mg/L
The anion structure formula of above-mentioned polynary heteropoly compound is [X
aZ
bM
cO
d]
N-, wherein X is a central atom,
Comprise: P, Si, B, Fe, Cu and Zn, Z comprises: Mg, Co, Ni, Cu, Zn, V, Nb and Ta, and M is a transiting group metal elements, comprising: Mo and W, a, b, c and d are integer.Polynary heteropoly compound can be a kind of heteropoly compound, also can be the mixture of multiple heteropoly compound, and polynary heteropoly compound is phosphorus tungsten vanadium heteropolyacid or the phosphorus tungsten vanadium heteropolyacid salt with Keggin structure.Antimony containing compounds can be the oxide compound or the halogenide of antimony, also can be their mixture, and described antimony containing compounds is antimonous oxide or bromize antimony.
Prepare the method for a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine of right, finish by following steps:
(1) lithium hydroxide is added in the lithium-bromide solution, stir 1-2h, regulating lithium-bromide solution pH value is 9～10.5;
(2) the many first heteropoly compounds of 100～500mg/L are added in the lithium-bromide solution, stir 2-4h;
(3) 50～300mg/L antimony containing compounds is added in the lithium-bromide solution, stir 2-4h;
Above-mentioned steps is all carried out under 25-80 ℃.
The pH value of regulating lithium-bromide solution with an amount of lithium hydroxide is 9 ~ 10.5, can make metallic substance such as carbon steel, copper-nickel alloy and copper be in passivation region.Heteropoly compound has strong oxidizing property, easily is reduced agent and is reduced to and has the heteroatomic heteropoly compound of mixed valence, promotes metal passivation in the metallic surface by electrochemical reaction.Contain sb oxide and form adsorption film, contain antimony halogenide and then be reduced to simple substance antimony, participate in the metal passivation process by electrochemical reaction in the metallic surface.Combine experiment confirms to have synergistic effect between polynary heteropoly compound and the antimony containing compounds.The present invention is not only applicable to the triple effect lithium-bromide absorption-type refrigerating machine, also is applicable to the environment that other uses halide salt aqueous solution.
The invention has the beneficial effects as follows that this inhibiter can generate the multiple rete that is made of passive film and adsorption film in metallic surfaces such as carbon steel, copper-nickel alloy and copper, the retardance corrosion of metal has very high inhibition efficiency in the high-temperature high concentration lithium-bromide solution.
Description of drawings
To be carbon steel contain corrosion speed in the 55%LiBr solution of inhibiter of the present invention in differing temps to Fig. 1.
To be carbon steel contain corrosion speed inhibition efficiency in the 55%LiBr solution of inhibiter of the present invention in differing temps to Fig. 2.
Fig. 3 is that the scanning electron microscope (SEM) of soaking the carbon steel sample surface of 200h in 160 ℃ the 55%LiBr solution that contains inhibiter of the present invention is observed photo.
Fig. 4 is the electronic spectrum (EDX) that soaks the carbon steel sample surface of 200h in 160 ℃ the 55%LiBr solution that contains inhibiter of the present invention.
Fig. 5 soaks X-ray diffraction (XRD) analytical results on the carbon steel sample surface of 200h in 160 ℃ the 55%LiBr solution that contains inhibiter of the present invention.
Embodiment
At first prepare the lithium-bromide solution of the predetermined concentration of lithium-bromide absorption-type refrigerating machine needs, taking by weighing an amount of lithium hydroxide reagent adds in the lithium-bromide solution, stir 1h, make the pH value of solution value reach 9 ~ 10.5, take by weighing an amount of polynary heteropoly compound again and add in the lithium-bromide solution, stir 2h, take by weighing an amount of antimony containing compounds then and add in the lithium-bromide solution, stir 4h, finally obtain containing the lithium-bromide solution of inhibiter of the present invention.
Example 1
At first compound concentration is 55% lithium-bromide solution, takes by weighing an amount of lithium hydroxide reagent and adds in the lithium-bromide solution, stirs 1h, makes lithium hydroxide concentration reach 0.07mol/L, takes by weighing an amount of H again
4[PW
11VO
40] add in the lithium-bromide solution, stir 2h, make H
4[PW
11VO
40] concentration is 300mg/L, takes by weighing an amount of Sb then
2O
3Add in the lithium-bromide solution, stir 4h, make Sb
2O
3Concentration reaches 200mg/L.Experiment material is a straight carbon steel, and specification is 3 * 2 * 0.33cm.Used sample is polished to 1000# step by step through abrasive paper for metallograph, cleans with deionized water and dehydrated alcohol again, dries up, and places moisture eliminator standby.
Weight-loss method is adopted in experiment, and after sample was weighed, the immersion of constant temperature in the 55%LiBr of the high purity nitrogen deoxygenation solution 200h at preset temperature took out sample, removes corrosion product, weighs.Calculate corrosion speed v according to following formula:
v(μm/a)＝8.76×10
4×ΔW/(S×t×ρ) (1)
Wherein, Δ W-weight loss, mg;
The S-specimen surface is long-pending, cm
2
The t-soak time, h;
P-experiment material density, g/cm
3
Again by formula (2) calculate the inhibition efficiency η of inhibiter to carbon steel:
η(％)＝100×(v
0-v)/v
0 (2)
Wherein, v
0-corrosion speed (solution is 55%LiBr+0.07mol/L LiOH here) when not containing inhibiter;
Corrosion speed when v-contains inhibiter.
Weightless test test result and inhibition efficiency calculation result are shown in Fig. 1 and Fig. 2 respectively.When solution temperature was 180 ℃, corrosion of Carbon Steel speed was 21.32 μ m/a, and inhibition efficiency reaches 88.2%.
Claims (7)
1, a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine is characterized in that, is made up of lithium hydroxide, polynary heteropoly compound and antimony containing compounds, and their concentration in lithium-bromide solution is:
Lithium hydroxide 0.05～0.10mol/L
Polynary heteropoly compound 100～500mg/L
Antimony containing compounds 50～300mg/L
2. according to claims 1 described a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine, it is characterized in that the anion structure formula of described polynary heteropoly compound is [X
aZ
bM
cO
d]
N-, wherein X is a central atom, comprising: P, Si, B, Fe, Cu and Zn, and Z comprises: Mg, Co, Ni, Cu, Zn, V, Nb and Ta, and M is a transiting group metal elements, comprising: Mo and W, a, b, c and d are integer.
3. a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine according to claim 1 and 2 is characterized in that, described polynary heteropoly compound can be a kind of heteropoly compound, also can be the mixture of multiple heteropoly compound.
4, a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine according to claim 1 is characterized in that, described antimony containing compounds can be the oxide compound or the halogenide of antimony, also can be their mixture.
5, according to claim 1 or 4 described a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine, it is characterized in that described antimony containing compounds is antimonous oxide or bromize antimony.
6, a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine according to claim 3 is characterized in that, described polynary heteropoly compound is phosphorus tungsten vanadium heteropolyacid or the phosphorus tungsten vanadium heteropolyacid salt with Keggin structure.
7, prepare the method for claims 1 described a kind of lithium-bromide absorption type corrosion inhibitor for refrigerating machine, it is characterized in that, finish by following steps:
(1) lithium hydroxide is added in the lithium-bromide solution, stir 1-2h, regulating lithium-bromide solution pH value is 9～10.5;
(2) the many first heteropoly compounds of 100～500mg/L are added in the lithium-bromide solution, stir 2-4h;
(3) 50～300mg/L antimony containing compounds is added in the lithium-bromide solution, stir 2-4h; Above-mentioned steps is all carried out under 25-80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610134460 CN1962949A (en) | 2006-11-28 | 2006-11-28 | Lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610134460 CN1962949A (en) | 2006-11-28 | 2006-11-28 | Lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1962949A true CN1962949A (en) | 2007-05-16 |
Family
ID=38082173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610134460 Pending CN1962949A (en) | 2006-11-28 | 2006-11-28 | Lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1962949A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965670A (en) * | 2012-11-19 | 2013-03-13 | 镇江市富来尔制冷工程技术有限公司 | Lithium bromide absorption refrigerator high-efficiency corrosion inhibitor and preparation method thereof |
| CN111928518A (en) * | 2020-08-10 | 2020-11-13 | 江苏富来尔科技发展有限公司 | Method for removing potassium and sodium ions in regenerated lithium bromide solution |
-
2006
- 2006-11-28 CN CN 200610134460 patent/CN1962949A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965670A (en) * | 2012-11-19 | 2013-03-13 | 镇江市富来尔制冷工程技术有限公司 | Lithium bromide absorption refrigerator high-efficiency corrosion inhibitor and preparation method thereof |
| CN102965670B (en) * | 2012-11-19 | 2014-08-20 | 镇江市富来尔制冷工程技术有限公司 | Lithium bromide absorption refrigerator high-efficiency corrosion inhibitor and preparation method thereof |
| CN111928518A (en) * | 2020-08-10 | 2020-11-13 | 江苏富来尔科技发展有限公司 | Method for removing potassium and sodium ions in regenerated lithium bromide solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yanhua et al. | Research on anti-corrosion property of rare earth inhibitor for X70 steel | |
| CN103756649B (en) | A kind of anti-icing fluid for solar water heater and preparation method thereof | |
| CN101928075B (en) | Closed-type circulating cooling water system inhibiter and preparation method thereof | |
| CN101487117B (en) | Preparation of aluminum alloy surface fluoroaluminate conversion film | |
| CN100595328C (en) | Composition for surface treatment of light metal and its composite material | |
| CN104058511A (en) | Non-phosphorus composite corrosion and scale inhibitor used for circulating water | |
| CN107937893B (en) | Environment-friendly passivation solution for aluminum or aluminum alloy and preparation method and treatment process thereof | |
| CN101607766A (en) | A kind of preparation that is used for the corrosion inhibiting and descaling agent of high alkaline high chlorine circulating cooling water | |
| CN103695927A (en) | Corrosion inhibitor | |
| CN101624238A (en) | Scale and corrosion inhibiting agent for circular cooling water of oxygen preparation plant as well as method and application thereof | |
| CN102250592B (en) | The antifreeze heat-eliminating medium of long effective environmental protection type wind power equipment | |
| CN107142092B (en) | Modified graphene ethylene glycol type engine coolant | |
| CN103484847A (en) | Phosphating solution and phosphating method | |
| CN106756922A (en) | It is a kind of for the black chemical oxidation liquid of steel and its application | |
| CN104513998A (en) | Corrosion inhibitor composition, applications thereof, and method using same to perform acid-washing on equipment | |
| JPH0192386A (en) | Hermetically sealed circulation type absorption refrigerator and absorbing solution for absorption refrigerator | |
| CN104451634B (en) | Aluminum and aluminum alloy passivation solution, preparation method and using method thereof | |
| Baboukani et al. | Investigation the effects of Na2MoO4 as an inhibitor on electrochemical corrosion behavior of 316L stainless steel in LiBr solution | |
| CN101514458B (en) | Inhibitor in aqueous heat exchange medium for La-Fe-Si series room temperature magnetic refrigeration materials | |
| DE60220552T2 (en) | Composition of a heat transfer fluid | |
| CN1962949A (en) | Lithium-bromide absorption type corrosion inhibitor for refrigerating machine and preparing method thereof | |
| TWI503422B (en) | Ferritic stainless steel excellent in corrosion resistance and workability | |
| JP2947793B2 (en) | Corrosion control solution and method for refrigeration system | |
| CN102153212B (en) | Composite corrosion and scale inhibitor containing benzotriazole | |
| CN101157998A (en) | Tin-brass alloy containing rare earth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |